U.S. patent application number 14/855223 was filed with the patent office on 2016-01-07 for method and apparatus for continuously applying nanolaminate metal coatings.
The applicant listed for this patent is Modumetal, Inc.. Invention is credited to Christina A. Lomasney.
Application Number | 20160002813 14/855223 |
Document ID | / |
Family ID | 51538617 |
Filed Date | 2016-01-07 |
United States Patent
Application |
20160002813 |
Kind Code |
A1 |
Lomasney; Christina A. |
January 7, 2016 |
Method and Apparatus for Continuously Applying Nanolaminate Metal
Coatings
Abstract
Described herein are apparatus and methods for the continuous
application of nanolaminated materials by electrodeposition.
Inventors: |
Lomasney; Christina A.;
(Seattle, WA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Modumetal, Inc. |
Seattle |
WA |
US |
|
|
Family ID: |
51538617 |
Appl. No.: |
14/855223 |
Filed: |
September 15, 2015 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US14/31101 |
Mar 18, 2014 |
|
|
|
14855223 |
|
|
|
|
61802102 |
Mar 15, 2013 |
|
|
|
Current U.S.
Class: |
205/96 ;
204/229.4; 204/229.5 |
Current CPC
Class: |
B82Y 40/00 20130101;
C25D 21/12 20130101; C25D 5/08 20130101; C25D 21/10 20130101; C25D
3/30 20130101; C25D 7/0614 20130101; C25D 3/34 20130101; C25D 5/20
20130101; C25D 3/22 20130101; C25D 3/56 20130101; C25D 7/0607
20130101; C23C 18/1653 20130101; C23C 18/1689 20130101; C25D 3/12
20130101; C25D 5/18 20130101; C25D 3/20 20130101; C25D 5/10
20130101; C25D 3/42 20130101; C25D 7/04 20130101; C25D 3/44
20130101; C25D 3/04 20130101; C25D 3/38 20130101; C25D 3/48
20130101; C25D 3/46 20130101; C25D 17/06 20130101; C25D 17/00
20130101; C25D 17/007 20130101; C25D 5/12 20130101; C25D 3/54
20130101 |
International
Class: |
C25D 17/06 20060101
C25D017/06; C25D 7/04 20060101 C25D007/04; C25D 3/56 20060101
C25D003/56; C25D 3/12 20060101 C25D003/12; C25D 3/20 20060101
C25D003/20; C25D 3/22 20060101 C25D003/22; C25D 3/48 20060101
C25D003/48; C25D 3/46 20060101 C25D003/46; C25D 3/44 20060101
C25D003/44; C25D 3/38 20060101 C25D003/38; C25D 3/34 20060101
C25D003/34; C25D 3/30 20060101 C25D003/30; C25D 3/04 20060101
C25D003/04; C25D 3/54 20060101 C25D003/54; C25D 3/42 20060101
C25D003/42; C25D 5/12 20060101 C25D005/12; C25D 5/20 20060101
C25D005/20; C25D 17/00 20060101 C25D017/00; C25D 21/10 20060101
C25D021/10; C25D 21/12 20060101 C25D021/12; C25D 7/06 20060101
C25D007/06 |
Claims
1. An apparatus for electrodepositing a nanolaminate coating
comprising: at least a first electrodeposition cell through which a
conductive workpiece is moved at a rate, a rate control mechanism
that controls the rate the workpiece is moved through the
electrodeposition cell; an optional mixer for agitating an
electrolyte during the electrodeposition process; an optional flow
control unit for applying the electrolyte to the workpiece; an
electrode; and a power supply controlling the current density
applied to the workpiece in a time varying manner as it moves
through the cell.
2. The apparatus of claim 1, wherein controlling the current
density in a time varying manner comprises applying two or more
different current densities to the workpiece as it moves through
the electrodeposition cell.
3. The apparatus of claim 2, wherein controlling the current
density in a time varying manner comprises applying an offset
current, so that the workpiece remains cathodic when it is moved
through the electrodeposition cell and the electrode remains
anodic.
4. The apparatus of claim 1, wherein the time varying manner
comprises one or more of: varying the baseline current, pulse
current modulation and reverse pulse current modulation.
5.-7. (canceled)
8. The apparatus of claim 1, further comprising a first location,
from which the workpiece is moved to the electrodeposition cell,
and/or a second location, for receiving the workpiece after it has
moved through the electrodeposition cell, wherein the first and/or
second location comprises a spool or a spindle, and wherein the
workpiece is a wire, rod, sheet or tube that can be wound on said
spool or around said spindle.
9.-13. (canceled)
14. The apparatus of claim 1, further comprising one or more
locations between the first location and the electrodeposition
cell, where the workpiece is contacted with one or more of: a
solvent, an acid, a base, an etchant, and a rinsing agent to remove
said solvent, acid, base, or etchant.
15. (canceled)
16. A method of electrodepositing a nanolaminate coating
comprising: moving a workpiece through an apparatus comprising at
least a first electrodeposition cell at a rate, where the
electrodeposition cell comprises an electrode and an electrolyte
comprising salts of two or more different electrodepositable
metals; and controlling the mixing rate and/or the current density
applied to the workpiece in a time varying manner as it moves
through the cell, thereby electrodepositing a nanolaminate
coating.
17. The method of claim 16, wherein controlling the current density
in a time varying manner comprises applying two or more different
current densities to the workpiece by varying one or more of the
baseline current, pulse current modulation and reverse pulse
current modulation as the workpiece moves through the
electrodeposition cell, wherein the workpiece is a wire, rod, sheet
or tube.
18. The method of claim 17, wherein controlling the current density
in a time varying manner comprises applying an offset current, so
that the workpiece remains cathodic when it is moved through the
electrodeposition cell and the electrode remains anodic.
19. (canceled)
20. The method of claim 16, wherein each electrodeposition cell
further comprises a mixer and/or an ultrasonic agitator, and the
method further comprises agitating the electrolyte with the mixer
and/or agitator continuously or in a non-continuous fashion to
control the mixing rate at a single rate or at varying rates.
21.-22. (canceled)
23. The method of claim 16, wherein the apparatus further comprises
a first location, from which the workpiece is moved to the
electrodeposition cell, and/or a second location, for receiving the
workpiece after it has moved through the electrodeposition cell,
the method further comprising moving the workpiece from the first
location to the electrodeposition cell and/or moving the workpiece
from the electrodeposition cell to the second location, wherein the
rate the workpiece is moved through the electrodeposition cell is
controlled.
24. The method of claim 23, wherein the apparatus further
comprises: (i) one or more locations between the first location and
the electrodeposition cell, and the method further comprises
contacting the workpiece with one or more of: a solvent, an acid, a
base, and an etchant, and rinsing to remove said solvent, acid,
base, and etchant; and/or (ii) one or more locations between the
electrodeposition cell and said second location, and the method
further comprises contacting the workpiece with one or more of: a
solvent, an acid, a base, a passivation agent, and a rinsing agent
to remove the solvent, acid base, and passivation agent.
25.-29. (canceled)
30. The method of claim 17, wherein electrodepositing a
nanolaminate coating comprises: the electrodeposition of a layered
composition, individual layers comprising one or more different
elements independently selected from Ag, Al, Au, Be, Co, Cr, Cu,
Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, Pd, Pt, Re, Rh, Sb, Sn, Pb, Ta,
Ti, W, V, Zn and Zr, wherein each of said elements is present at
greater than 0.001% by weight; or the electrodeposition of an alloy
comprising two or more different metals selected from the group
consisting of: Zn and Fe, Zn and Ni, Co and Ni, Ni and Fe, Ni and
Cr, Ni and Al, Cu and Zn, Cu and Sn or a composition comprising Al,
Ni and Co.
31.-32. (canceled)
33. The method according to claim 17, wherein the nanolaminate
coating comprises at least one portion consisting of a plurality of
layers, wherein each of said layers has a thickness in a range from
about 5 nm to about 250 nm, and wherein the nanolaminate coating
comprises a plurality of first layers and second layers that differ
in structure or composition, and which may have discrete or diffuse
interfaces between the first and second layers.
34.-38. (canceled)
39. The method of claim 33, wherein each said first layer comprises
nickel in a range independently selected from 1%-5%, 5%-7%, 7%-10%,
10%-15%, 15%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-55%, 55%-60%,
60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%,
92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%, 97%-98% or 98%-99%,
and the balance of the layer is cobalt and/or chromium.
40. The method of claim 33, wherein each second layer comprises
cobalt and/or chromium or each second layer comprises iron in the
range from 1% to 35% and the balance of the layer is nickel.
41. The method of claim 33, wherein each said first layer comprises
nickel or zinc in a range independently selected from 1%-5%, 5%-7%,
7%-10%, 10%-15%, 15%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-55%,
55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%,
90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%, 97%-98% or
98%-99%, and the balance of the layer comprises iron.
42.-46. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 61/802,102, filed Mar. 15, 2013, which is
incorporated by reference herein in its entirety.
BACKGROUND
[0002] Nanolaminate materials have become widely studied over the
past several decades. As a result some desirable advanced
performance characteristics of those materials have been discovered
and their potential application in numerous fields recognized.
While the potential application of nanolaminated materials in
numerous areas, including civil infrastructure, automotive,
aerospace, electronics, and other areas has been recognized, the
materials are on the whole not available in substantial quantities
due to the lack of a continuous process for their production.
SUMMARY
[0003] Described herein are apparatus and methods for the
continuous application of nanolaminated materials by
electrodeposition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 shows a continuous processing apparatus for the
application of nanolaminated coatings configured for conductive
materials that can be rolled.
DETAILED DESCRIPTION
1.0 Definitions
[0005] "Electrolyte" as used herein means an electrolyte bath,
plating bath, or electroplating solution from which one or more
metals may be electroplated.
[0006] "Workpiece" means an elongated conductive material or loop
of conductive material.
[0007] "Nanolaminate" or "nanolaminated" as used herein refers to
materials or coatings that comprise a series of layers less than 1
micron.
[0008] All compositions given as percentages are given as percent
by weight unless stated otherwise.
2.0 Electrodeposition Apparatus for Continuous Application of
Nanolaminated Coatings
[0009] The continuous application of nanolaminate coatings on
conductive materials can be accomplished using an electrodeposition
apparatus comprising: [0010] at least a first electrodeposition
cell 1 through which a conductive workpiece 2, which serves as an
electrode in the cell, is moved at a rate, [0011] a rate control
mechanism that controls the rate the workpiece is moved through the
electrodeposition cell; [0012] an optional mixer for agitating
electrolyte during the electrodeposition process (shown
schematically in FIG. 1 as item 3); [0013] a counter electrode 4;
and [0014] a power supply 8 controlling the current density applied
to the workpiece in a time varying manner as it moves through the
cell.
[0015] The rate control mechanism (throughput control mechanism)
may be integral to one or more drive motors or the conveying system
(e.g., rollers, wheels, pulleys, etc., of the apparatus), or housed
in associated control equipment; accordingly, it is not shown in
FIG. 1. Similarly the counter electrode may have a variety of
configurations including, but not limited to, bars, plates, wires,
baskets, rods, conformal anodes and the like, and accordingly is
shown generically as a plate 4 at the bottom of the
electrodeposition cell 1 in FIG. 1. The counter electrode, which
functions as an anode except during reverse pulses, may be inert or
may be active, in which case the anode will contain the metal
species that is to be deposited and will dissolve into solution
during operation.
[0016] Power supply 8 may control the current density in a variety
of ways including applying two or more, three or more or four or
more different average current densities to the workpiece as it
moves through the electrodeposition cell. In one embodiment the
power supply can control the current density in a time varying
manner that includes applying an offset current, so that the
workpiece remains cathodic when it is moved through the
electrodeposition cell and the electrode remains anodic even though
the potential between the workpiece and the electrode varies. In
another embodiment the power supply varies the current density in a
time varying manner which comprises varying one or more of: the
maximum current, baseline current, minimum current, frequency,
pulse current modulation and reverse pulse current modulation.
[0017] The workpiece may be introduced to the electrolyte by
immersion in said electrolyte or by spray application of the
electrolyte to the workpiece. The application of the electrolyte to
the workpiece may be modulated. The rate by which the workpiece is
moved through the electrolyte may also be modulated.
[0018] Mixing of electrolyte in the electrodeposition cell is
provided by solution circulation, a mechanical mixer and/or
ultrasonic agitators. While bulk mixing can be provided by the
mixer 3, which can be controlled or configured to operate at
variable speeds during the electrodeposition process, the apparatus
may optionally include one or more ultrasonic agitators which are
shown schematically as blocks 5 in the apparatus of FIG. 1. The
ultrasonic agitators of the apparatus may be configured to operate
independently in a continuous or in a non-continuous fashion (e.g.,
in a pulsed fashion). In one embodiment the ultrasonic agitators
may operate at about 17,000 to 23,000 Hz. In another embodiment
they may operate at about 20,000 Hz. Mixing of the electrolyte may
also occur in a separate reservoir and the mixed electrolyte may
contact the workpiece by immersion or by spray application. Instead
of one or more salts of a metal to be electroplated, the
electrolyte may comprise two or more, three or more or four or more
different salts of electrodepositable metals.
[0019] The apparatus may include a location from which the
workpiece material is supplied (e.g., a payoff reel) and a location
where the coated workpiece is taken up (e.g., a take-up reel, which
may be part of a strip puller for conveying a workpiece through the
apparatus). Accordingly, the apparatus may comprise a first
location 6, from which the workpiece is moved to the
electrodeposition cell and/or a second location 7 for receiving the
workpiece after it has moved through the electrodeposition cell.
Location 6 and location 7 are shown as spindles with reels in FIG.
1, however, they may also consist of racks for storing lengths of
materials, folding apparatus, and even enclosures with one or more
small openings, from which a workpiece (e.g., a wire, cable, strip
or ribbon) is withdrawn or into which a coated workpiece is
inserted.
[0020] In one embodiment the first and/or second location comprises
a spool or a spindle. In such an embodiment the apparatus may be
configured to electrodeposit a nanolaminate coating on a continuum
of connected parts, wire, rod, sheet or tube that can be wound on
the spool or around the spindle.
[0021] The apparatus may further comprise an aqueous or a
non-aqueous electrolyte. The electrolyte may comprise salts of two
or more, three or more or four or more electrodepositable
metals.
[0022] In addition to the above-mentioned components, the apparatus
may comprise one or more locations for treatment of the workpiece
prior or subsequent to electrodeposition. In one embodiment the
apparatus further includes one or more locations, between the first
location and the electrodeposition cell, where the workpiece is
contacted with one or more of: a solvent, an acid, a base, an
etchant, and/or a rinsing agent to remove the solvent, acid, base,
or etchant. In another embodiment the apparatus further includes
one or more locations between the electrodeposition cell and a
second location, where the coated workpiece is subject to one or
more of: cleaning with solvent, cleaning with acid, cleaning with
base, passivation treatments and rinsing.
3.0 Electrodeposition Process for the Continuous Application of
Nanolaminated Coatings on Workpieces
[0023] 3.1 Workpieces
[0024] Workpieces may take a variety of forms or shapes. Workpieces
may be, for example, in the form of wire, rod, tube, or sheet stock
(e.g., rolls or folded sheets). Workpieces may be metal or other
conductive strip, sheet or wire. Workpieces may also comprise a
series of discrete parts that may be, for example, affixed to a
sheet or webbing (e.g., metal netting or flexible screen) so as to
form a sheet-like assembly that can be introduced into the
electrodeposition cell in the same manner as substantially flat
sheets that are to be coated with a nanolaminate by
electrodeposition. Workpieces which are a series of discrete parts
connected to form a strip must be connected by a conductive
connector.
[0025] Virtually any material may be used as a workpiece, provided
it can be rendered conductive and is not negatively affected by the
electrolyte. The materials that may be employed as workpieces
include, but are not limited to, metal, conductive polymers (e.g.,
polymers comprising polyaniline or polypyrrole), or non-conductive
polymers rendered conductive by inclusion of conductive materials
(e.g., metal powders, carbon black, graphene, graphite, carbon
nanotubes, carbon nanofibers, or graphite fibers) or electroless
application of a metal coating.
[0026] 3.2 Continuous Electrodeposition of Nanolaminate
Coatings
[0027] Nanolaminate coatings may be continuously electrodeposited
by a method comprising: [0028] moving a workpiece through an
apparatus comprising at least a first electrodeposition cell at a
rate, where the electrodeposition cell comprises an electrode and
an electrolyte comprising salts of one or more metals to be
electrodeposited; and [0029] controlling the mixing rate and/or the
current density applied to the workpiece in a time varying manner
as the workpiece moves through the cell, thereby electrodepositing
a nanolaminate coating.
[0030] By controlling the current density applied to the workpiece
in a time varying manner, nanolaminate coatings having layers
varying in elemental composition and/or the microstructure of the
electrodeposited material can be prepared. In one set of
embodiments, controlling the current density in a time varying
manner comprises applying two or more, three or more or four or
more different current densities to the workpiece as it moves
through the electrodeposition cell. In another embodiment,
controlling the current density in a time varying manner includes
applying an offset current, so that the workpiece remains cathodic
when it is moved through the electrodeposition cell and the
electrode remains anodic, even though the potential between the
workpiece and the electrode varies in time to produce
nanolamination. In another embodiment controlling the current
density in a time varying manner comprises varying one or more of:
the baseline current, pulse current modulation and reverse pulse
current modulation.
[0031] Nanolaminated coatings may also be formed on the workpiece
as it passes through the electrodeposition cell by controlling the
mixing rate in a time varying manner. In one embodiment,
controlling the mixing rate comprises agitating the electrolyte
with a mixer (e.g., impeller or pump) at varying rates. In another
embodiment, controlling the mixing rate comprises agitating the
electrolyte by operating an ultrasonic agitator in a time varying
manner (e.g., continuously, non-continuously, with a varying
amplitude over time, or in a series of regular pulses of fixed
amplitude). In another embodiment, controlling the mixing rate
comprises pulsing a spray application of the electrolyte to the
workpiece.
[0032] In another embodiment, the nanolaminate coatings may be
formed by varying both the current density and the mixing rate
simultaneously or alternately in the same electrodeposition
process.
[0033] Regardless of which parameters are varied to induce
nanolaminations in the coating applied to the workpiece as it is
moved through the electrodeposition cell, the rate at which the
workpiece passes through the cell represents another parameter that
can be controlled. In one embodiment rates that can be employed are
in a range of about 1 to about 300 feet per minute. In other
embodiments, the rates that can be employed are greater than about
1, 5, 10, 30, 50, 100, 150, 200, 250 or 300 feet per minute, or
from about 1 to about 30 feet per minute, about 30 to about 100
feet per minute, about 100 to about 200 feet per minute, about 200
to about 300 feet per minute, or more than about 300 feet per
minute. Faster rates will alter the time any portion of the
workpiece being plated remains in the electrodeposition cell.
Accordingly, the rate of mass transfer (rate of electrodeposition)
that must be achieved to deposit the same nanolaminate coating
thickness varies with the rate the workpiece is moved through the
cell. In addition, where processes employ variations in current
density to achieve nanolamination, the rate the variation in
current density occurs must also be increased with an increasing
rate of workpiece movement through the electrodeposition cell.
[0034] In one embodiment, the electrodeposition process may further
include a step of moving the workpiece from a first location to the
electrodeposition cell. In another embodiment, the
electrodeposition process may further include a step of moving the
workpiece from the electrodeposition cell to a second location for
receiving the workpiece after electrodeposition of the nanolaminate
coating. As such, the method may further comprise both moving the
workpiece from a first location to the electrodeposition cell and
moving the workpiece from the electrodeposition cell to the second
location.
[0035] 3.3 Electrolytes and Nanolaminate Coating Compositions and
Structures
[0036] Continuous electrodeposition of nanolaminate coatings can be
conducted from either aqueous or non-aqueous electrolytes
comprising salts of the metals to be electrodeposited.
[0037] In one embodiment, electrodepositing a nanolaminate coating
comprises the electrodeposition of a layered composition comprising
one or more, two or more, three or more or four or more different
elements independently selected from Ag, Al, Au, Be, Co, Cr, Cu,
Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Sn, Pb,
Ta, Ti, W, V, Zn and Zr, wherein each of said independently
selected metals is present at greater than about 0.1, about 0.05,
about 0.01, about 0.005 or about 0.001% by weight. In one such
embodiment, electrodepositing a nanolaminate coating comprises
electrodeposition of a layered composition comprising two or more
different elements independently selected from Ag, Al, Au, Be, Co,
Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb,
Sn, Pb, Ta, Ti, W, V, Zn and Zr, wherein each of said independently
selected metals is present at greater than about 0.005 or about
0.001% by weight. In another such embodiment, electrodepositing a
nanolaminate coating comprises the electrodeposition of layers
comprising two or more different metals, where the two or more
different metals comprise: Zn and Fe, Zn and Ni, Co and Ni, Ni and
Fe, Ni and Cr, Ni and Al, Cu and Zn, Cu and Sn, or a composition
comprising Al and Ni and Co (AlNiCo). In any of those embodiments
the nanolaminate coating may comprise at least one portion
consisting of a plurality of layers, wherein each of said layers
has a thickness in a range selected independently from: about 5 nm
to about 250 nm, from about 5 nm to about 25 nm, from about 10 nm
to about 30 nm, from about 30 nm to about 60 nm, from about 40 nm
to about 80 nm, from about 75 nm to about 100 nm, from about 100 nm
to about 120 nm, from about 120 nm to about 140 nm, from about 140
nm to about 180 nm, from about 180 nm to about 200 nm, from about
200 nm to about 225 nm, from about 220 nm to about 250 nm, or from
about 150 nm to about 250 nm.
[0038] In another embodiment, the electrodeposited nanolaminate
coating compositions comprise a plurality of first layers and
second layers that differ in structure or composition. The first
layers and second layers may have discrete or diffuse interfaces at
the boundary between the layers. In addition, the first and second
layers may be arranged as alternating first and second layers.
[0039] In embodiments where the electrodeposited nanolaminate
coatings comprise a plurality of alternating first layers and
second layers, those layers may comprise two or more, three or
more, four or more, six or more, eight or more, ten or more, twenty
or more, forty or more, fifty or more, 100 or more, 200 or more,
500 or more, 1,000 or more, 1,500 or more, 2,000 or more, 3,000 or
more, 5,000 or more or 8,000 or more alternating first and second
layers independently selected for each multilayer coating.
[0040] In one embodiment each first layer and each second layer
comprises, consists essentially of, or consists of two, three, four
or more elements independently selected from: Ag, Al, Au, Be, Co,
Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb,
Sn, Pb, Ta, Ti, W, V, Zn and Zr. In another embodiment, each first
layer and each second layer comprises, consists essentially of, or
consists of two, three, four or more elements independently
selected from: Ag, Al, Au, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Sb,
Sn, Mn, Pb, Ta, Ti, W, V, and Zn. In another embodiment, each first
layer and each second layer comprises, consists essentially of, or
consists of two, three, four or more elements independently
selected from: Al, Au, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Sn, Mn,
Ti, W, V, and Zn.
[0041] In one embodiment each first layer comprises nickel in a
range independently selected from about 1% to about 5%, about 5% to
about 7%, about 7% to about 10%, about 10% to about 15%, about 15%
to about 20%, about 20% to about 30%, about 30% to about 40%, about
40% to about 50%, about 50% to about 55%, about 55% to about 60%,
about 60% to about 65%, about 65% to about 70%, about 70% to about
75%, about 75% to about 80%, about 80% to about 85%, about 85% to
about 90%, about 90% to about 92%, about 92% to about 93%, about
93% to about 94%, about 94% to about 95%, about 95% to about 96%,
about 96% to about 97%, about 97% to about 98% or about 98% to
about 99%. In such an embodiment, each second layer may comprise
cobalt and/or chromium in a range independently selected from about
1% to about 35%, about 1% to about 3%, about 2% to about 5%, about
5% to about 10%, about 10% to about 15%, about 15% to about 20%,
about 20% to about 25%, about 25% to about 30% or about 30% to
about 35%.
[0042] In one embodiment each first layer comprises nickel in a
range independently selected from about 1% to about 5%, about 5% to
about 7%, about 7% to about 10%, about 10% to about 15%, about 15%
to about 20%, about 20% to about 30%, about 30% to about 40%, about
40% to about 50%, about 50% to about 55%, about 55% to about 60%,
about 60% to about 65%, about 65% to about 70%, about 70% to about
75%, about 75% to about 80%, about 80% to about 85%, about 85% to
about 90%, about 90% to about 92%, about 92% to about 93%, about
93% to about 94%, about 94% to about 95%, about 95% to about 96%,
about 96% to about 97%, about 97% to about 98% or about 98% to
about 99%, and the balance of the layer comprises cobalt and/or
chromium. In such an embodiment, each second layer may comprise
cobalt and/or chromium in a range selected independently from about
1% to about 35%, about 1% to about 3%, about 2% to about 5%, about
5% to about 10%, about 10% to about 15%, about 15% to about 20%,
about 20% to about 25%, about 25% to about 30% or about 30% to
about 35%, and the balance of the layer comprises nickel. In such
embodiments, first and second layers may additionally comprise
aluminum.
[0043] In one embodiment each first layer comprises nickel in a
range independently selected from about 1% to about 5%, about 5% to
about 7%, about 7% to about 10%, about 10% to about 15%, about 15%
to about 20%, about 20% to about 30%, about 30% to about 40%, about
40% to about 50%, about 50% to about 55%, about 55% to about 60%,
about 60% to about 65%, about 65% to about 70%, about 70% to about
75%, about 75% to about 80%, about 80% to about 85%, about 85% to
about 90%, about 90% to about 92%, about 92% to about 93%, about
93% to about 94%, about 94% to about 95%, about 95% to about 96%,
about 96% to about 97%, about 97% to about 98% or about 98% to
about 99%, and the balance of the layer comprises aluminum. In such
an embodiment, each second layer may comprise aluminum in a range
selected independently from about 1% to about 35%, about 1% to
about 3%, about 2% to about 5%, about 5% to about 10%, about 10% to
about 15%, about 15% to about 20%, about 20% to about 25%, about
25% to about 30% or about 30% to about 35%, and the balance of the
layer comprises nickel.
[0044] In one embodiment each first layer comprises nickel in a
range independently selected from about 1% to about 5%, about 5% to
about 7%, about 7% to about 10%, about 10% to about 15%, about 15%
to about 20%, about 20% to about 30%, about 30% to about 40%, about
40% to about 50%, about 50% to about 55%, about 55% to about 60%,
about 60% to about 65%, about 65% to about 70%, about 70% to about
75%, about 75% to about 80%, about 80% to about 85%, about 85% to
about 90%, about 90% to about 92%, about 92% to about 93%, about
93% to about 94%, about 94% to about 95%, about 95% to about 96%,
about 96% to about 97%, about 97% to about 98% or about 98% to
about 99%, and the balance of the layer comprises iron. In such an
embodiment, each second layer may comprise iron in a range
independently selected from about 1% to about 35%, about 1% to
about 3%, about 2% to about 5%, about 5% to about 10%, about 10% to
about 15%, about 15% to about 20%, about 20% to about 25%, about
25% to about 30% or about 30% to about 35%, and the balance of the
layer comprises nickel.
[0045] In one embodiment each first layer comprises zinc in a range
independently selected from about 1% to about 5%, about 5% to about
7%, about 7% to about 10%, about 10% to about 15%, about 15% to
about 20%, about 20% to about 30%, about 30% to about 40%, about
40% to about 50%, about 50% to about 55%, about 55% to about 60%,
about 60% to about 65%, about 65% to about 70%, about 70% to about
75%, about 75% to about 80%, about 80% to about 85%, about 85% to
about 90%, about 90% to about 92%, about 92% to about 93%, about
93% to about 94%, about 94% to about 95%, about 95% to about 96%,
about 96% to about 97%, about 97% to about 98%, about 98% to about
99%, about 99% to about 99.5%, about 99.2% to about 99.7%, or about
99.5% to about 99.99%, and the balance of the layer comprises iron.
In such an embodiment, each second layer may comprise iron in a
range independently selected from about 0.01% to about 35%, about
0.01% to about 0.5%, about 0.3% to about 0.8%, about 0.5% to about
1.0%, about 1% to about 3%, about 2% to about 5%, about 5% to about
10%, about 10% to about 15%, about 15% to about 20%, about 20% to
about 25%, about 25% to about 30% or about 30% to about 35%, and
the balance of the layer comprises zinc.
[0046] In any of the foregoing embodiments the first and/or second
layers may each comprise one or more, two or more, three or more,
or four or more elements selected independently for each first and
second layer from the group consisting of Ag, Al, Au, Be, Co, Cr,
Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt, Re, Rh, Sb, Sn,
Pb, Ta, Ti, W, V, Zn and Zr.
[0047] 3.4 Pre to about and Post-Electrodeposition Treatments
[0048] Prior to electrodeposition, or following electrodeposition,
methods of continuously electrodepositing a nanolaminate coating
may include further steps of pre-electrodeposition or
post-electrodeposition treatment.
[0049] Accordingly, the apparatus described above may further
comprise one or more locations between the first location and the
electrodeposition cell, and the method may further comprise
contacting the workpiece with one or more of: a solvent, an acid, a
base, an etchant, or a rinsing solution (e.g., water) to remove
said solvent, acid, base, or etchant. In addition, the apparatus
described above may further comprise one or more locations between
the electrodeposition cell and a second location, and the method
may further comprise contacting the workpiece with one or more of:
a solvent, an acid, a base, a passivation agent, or a rinse
solution (e.g., water) to remove the solvent, acid, base or
passivation agent.
4.0 Nanolaminated Articles Prepared by Continuous
Electrodeposition
[0050] The process and apparatus described herein may be adapted
for the preparation of articles comprising, consisting essentially
of, or consisting of nanolaminated materials by the use of a
workpiece to which the coating applied during electrodeposition
does not adhere tightly. The article may be obtained after removal
of the workpiece from the electrodeposition process by separating
the coating from the workpiece. In addition, where the workpiece is
not flat, 3-dimensional articles may be formed as reliefs on the
contoured surface of the workpiece.
4.0 Certain Embodiments
[0051] 1. An apparatus for electrodepositing a nanolaminate coating
comprising:
[0052] at least a first electrodeposition cell (e.g., one or more,
two or more, three or more, four or more electrodeposition cells)
through which a conductive workpiece is moved at a rate,
[0053] a rate control mechanism that controls the rate the
workpiece is moved through the electrodeposition cell(s);
[0054] each electrodeposition cell optionally comprising a mixer
for agitating an electrolyte in its respective electrodeposition
cell during the electrodeposition process;
[0055] each electrodeposition cell optionally comprising a flow
control unit for applying an electrolyte to the workpiece;
[0056] an electrode; and
[0057] a power supply controlling the current density applied to
the workpiece in a time varying manner as it moves through the
cell(s).
2. The apparatus of embodiment 1, wherein controlling the current
density in a time varying manner comprises applying two or more,
three or more or four or more different current densities to the
workpiece as it moves through the electrodeposition cell(s). 3. The
apparatus of embodiment 2, wherein controlling the current density
in a time varying manner comprises applying an offset current, so
that the workpiece remains cathodic when it is moved through the
electrodeposition cell(s) and the electrode remains anodic. 4. The
apparatus of any of embodiments 1 or 2, wherein the time varying
manner comprises one or more of: varying the baseline current,
pulse current modulation and reverse pulse current modulation. 5.
The apparatus of any of the preceding embodiments, wherein one or
more of the electrodeposition cell(s) further comprises an
ultrasonic agitator. 6. The apparatus of embodiment 5, wherein each
ultrasonic agitator independently operates continuously or in a
pulsed fashion. 7. The apparatus of any of the preceding
embodiments, wherein each mixer operates independently to variably
mix an electrolyte placed in its respective electrodeposition
cell(s). 8. The apparatus of any of the preceding embodiments,
further comprising a first location, from which the workpiece is
moved to the electrodeposition cell(s), and/or a second location,
for receiving the workpiece after it has moved through one or more
of the electrodeposition cell(s). 9. The apparatus of embodiment 8,
wherein the first and/or second location comprises a spool or a
spindle. 10. The apparatus of embodiment 9 wherein the workpiece is
a wire, rod, sheet or tube that can be wound on said spool or
around said spindle. 11. The apparatus of any of the preceding
embodiments, wherein any one or more of said electrodeposition
cell(s) comprises an aqueous electrolyte. 12. The apparatus of any
of embodiments 1-10, wherein any one or more of said
electrodeposition cell(s) comprises a non-aqueous electrolyte. 13.
The apparatus of any preceding embodiment, wherein said
electrolyte(s) comprises salts of two or more, three or more or
four or more electrodepositable metals. 14. The apparatus of any of
the preceding embodiments further comprising one or more locations
between the first location and the electrodeposition cell(s), where
the workpiece is contacted with one or more of: a solvent, an acid,
a base, an etchant, and a rinsing agent to remove said solvent,
acid, base, and/or etchant. 15. The apparatus of any of the
preceding embodiments further comprising one or more locations
between the electrodeposition cell(s) and said second location,
where the coated workpiece is subject to one or more of: cleaning
with solvent, cleaning with acid, cleaning with base, passivation
treatments, and rinsing. 16. A method of electrodepositing a
nanolaminate coating comprising:
[0058] moving a workpiece through an apparatus comprising at least
a first electrodeposition cell (one, two, three, four, five, or
more electrodeposition cell(s)) at a rate, where the
electrodeposition cell(s) comprises an electrode and an electrolyte
comprising salts of two or more, three or more, or four or more
different electrodepositable metals; and
[0059] controlling the mixing rate and/or the current density
applied to the workpiece in a time varying manner as it moves
through the cell(s), thereby electrodepositing a nanolaminate
coating.
17. The method of embodiment 16, wherein controlling the current
density in a time varying manner comprises applying two or more,
three or more, or four or more different current densities to the
workpiece as it moves through the electrodeposition cell(s). 18.
The method of embodiment 16 or 17, wherein controlling the current
density in a time varying manner comprises applying an offset
current, so that the workpiece remains cathodic when it is moved
through the electrodeposition cell(s) and the electrode remains
anodic. 19. The method of embodiments 16 or 17, wherein the time
varying manner comprises one or more of: varying the baseline
current, pulse current modulation and reverse pulse current
modulation. 20. The method of any of embodiments 16-19, wherein one
or more electrodeposition cell(s) optionally comprises a mixer,
each of which mixer is independently operated at a single rate or
at varying rates to agitate the electrolyte within its respective
electrodeposition cell. 21. The method of any of embodiments 16-20,
wherein one or more electrodeposition cell(s) optionally comprises
an ultrasonic agitator, each of which is independently operated
continuously or in a non-continuous fasion to control the mixing
rate. 22. The method of any of embodiments 16-21, further
comprising controlling the rate the workpiece is moved through the
electrodeposition cell(s). 23. The method of any of embodiments
16-22, wherein the apparatus further comprises a first location,
from which the workpiece is moved to the electrodeposition cell(s),
and/or a second location for receiving the workpiece after it has
moved through the electrodeposition cell(s), the method further
comprising moving the workpiece from the first location to the
electrodeposition cell(s) and/or moving the workpiece from the
electrodeposition cell(s) to the second location. 24. The method of
embodiment 23, wherein the apparatus further comprises one or more
locations between the first location and the electrodeposition
cell(s), and the method further comprises contacting the workpiece
with one or more of: a solvent, an acid, a base, and an etchant,
and rinsing to remove said solvent, acid, base, or etchant at one
or more of the locations between the first location and the
electrodeposition cell(s). 25. The method of embodiments 23 or 24,
wherein the apparatus further comprises one or more locations
between the electrodeposition cell(s) and said second location, and
the method further comprises contacting the workpiece with one or
more of: a solvent, an acid, a base, a passivation agent, and a
rinsing agent to remove the solvent, acid base and/or passivation
agent at one or more locations between the electrodeposition
cell(s) and said second location. 26. The method of any of
embodiments 16-25, wherein said workpiece is comprised of a metal,
a conductive polymer or a non-conductive polymer rendered
conductive by inclusion of conductive materials or electroless
application of a metal. 27. The method of any of embodiments 16-26,
wherein the workpiece is a wire, rod, sheet or tube. 28. The method
of any of embodiments 16-27, wherein the electrolyte(s) is/are
aqueous electrolyte(s). 29. The method of any of embodiments 16-27,
wherein the electrolyte(s) is/are a non-aqueous electrolyte(s). 30.
The method of any of embodiments 16-29, wherein electrodepositing a
nanolaminate coating comprises the electrodeposition of a layered
composition comprising one or more, two or more, three or more or
four or more different elements independently selected from Ag, Al,
Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt,
Re, Rh, Sb, Sn, Pb, Ta, Ti, W, V, Zn and Zr, wherein each of said
independently selected metals is present at greater than 0.1, 0.05,
0.01, 0.005 or 0.001% by weight. 31. The method of any of
embodiments 16-29, wherein electrodepositing a nanolaminate coating
comprises the electrodeposition of a layered composition comprising
two or more different elements independently selected from Ag, Al,
Au, Be, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Nb, Nd, Ni, P, Pd, Pt,
Re, Rh, Sb, Sn, Pb, Ta, Ti, W, V, Zn and Zr, wherein each of said
independently selected metals is present at greater than about 0.1,
0.05, 0.01, 0.005 or 0.001% by weight. 32. The method of embodiment
31, wherein said two or more different metals comprise: Zn and Fe,
Zn and Ni, Co and Ni, Ni and Fe, Ni and Cr, Ni and Al, Cu and Zn,
Cu and Sn or a composition comprising Al and Ni and Co. 33. The
method according to any of embodiments 16-32, wherein the
nanolaminate coating comprises at least one portion consisting of a
plurality of layers, wherein each of said layers has a thickness in
a range selected independently from about 5 nm to about 250 nm,
from about 5 nm to about 25 nm, from about 10 nm to about 30 nm,
from about 30 nm to about 60 nm, from about 40 nm to about 80 nm,
from about 75 nm to about 100 nm, from about 100 nm to about 120
nm, from about 120 nm to about 140 nm, from about 140 nm to about
180 nm, from about 180 nm to about 200 nm, from about 200 nm to
about 225 nm, from about 220 nm to about 250 nm, or from about 150
nm to about 250 nm. 34. The method of any of embodiments 16-33,
wherein the nanolaminate coating composition comprises a plurality
of first layers and second layers that differ in structure or
composition, and which may have discrete or diffuse interfaces
between the first and second layers. 35. The method of embodiment
34 wherein the first and second layers are arranged as alternating
first and second layers. 36. The method of embodiment 35, wherein
said plurality of alternating first layers and second layers
comprises two or more, three or more, four or more, six or more,
eight or more, ten or more, twenty or more, forty or more, fifty or
more, 100 or more, 200 or more, 500 or more, 1,000 or more, 1,500
or more, 2,000 or more, 4,000 or more, 6,000 or more, or 8,000 or
more alternating first and second layers independently selected for
each multilayer coating. 37. The method of any of embodiments
34-36, wherein each first layer comprises nickel in a range
independently selected from 1%-5%, 5%-7%, 7%-10%, 10%-15%, 15%-20%,
20%-30%, 30%-40%, 40%-50%, 50%-55%, 55%-60%, 60%-65%, 65%-70%,
70%-75%, 75%-80%, 80%-85%, 85%-90%, 90%-92%, 92%-93%, 93%-94%,
94%-95%, 95%-96%, 96%-97%, 97%-98% or 98%-99%. 38. The method of
embodiment 37, wherein each second layer comprises cobalt and/or
chromium in a range independently selected from 1%-35%, 1%-3%,
2%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25%-30% or 30%-35%. 39.
The method of any of embodiments 34-36, wherein each first layer
comprises nickel in a range independently selected from 1%-5%,
5%-7%, 7%-10%, 10%-15%, 15%-20%, 20%-30%, 30%-40%, 40%-50%,
50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%,
85%-90%, 90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%,
97%-98% or 98%-99%, and the balance of the layer is cobalt and/or
chromium. 40. The method of embodiment 39, wherein each second
layer comprises cobalt and/or chromium in a range selected
independently from 1%-35%, 1%-3%, 2%-5%, 5%-10%, 10%-15%, 15%-20%,
20%-25%, 25%-30% or 30%-35%, and the balance of the layer is
nickel. 41. The method of any of embodiments 34-36, wherein each
first layer comprises nickel in a range independently selected from
1%-5%, 5%-7%, 7%-10%, 10%-15%, 15%-20%, 20%-30%, 30%-40%, 40%-50%,
50%-55%, 55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%,
85%-90%, 90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%,
97%-98% or 98%-99%, and the balance of the layer comprises iron.
42. The method of embodiment 41, wherein each second layer
comprises iron in a range independently selected from 1%-35%,
1%-3%, 2%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25%-30% or
30%-35%, and the balance of the layer comprises nickel. 43. The
method of any of embodiments 34-36, wherein each first layer
comprises zinc in a range independently selected from 1%-5%, 5%-7%,
7%-10%, 10%-15%, 15%-20%, 20%-30%, 30%-40%, 40%-50%, 50%-55%,
55%-60%, 60%-65%, 65%-70%, 70%-75%, 75%-80%, 80%-85%, 85%-90%,
90%-92%, 92%-93%, 93%-94%, 94%-95%, 95%-96%, 96%-97%, 97%-98%,
98%-99%, 99%-99.5%, 99.2%-99.7%, or 99.5%-99.99%, and the balance
of the layer comprises iron. 44. The method of embodiment 43,
wherein each second layer comprises iron in a range independently
selected from 0.01%-35%, 0.01%-0.5%, 0.3%-0.8%, 0.5%-1.0%, 1%-3%,
2%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25%-30% or 30%-35%, and
the balance of the layer comprises zinc. 45. The method of any of
embodiments 34-36, wherein one or more of said first and/or second
layers comprises one or more, two or more, three or more or four or
more elements selected independently for each first and second
layer from the group consisting of Ag, Al, Au, C, Cr, Cu, Fe, Mg,
Mn, Mo, Sb, Si, Sn, Pb, Ta, Ti, W, V, Zn and Zr. 46. A product
produced by the method of any of embodiments 16-44.
* * * * *