U.S. patent application number 11/194222 was filed with the patent office on 2007-02-01 for article having patterned decorative coating.
This patent application is currently assigned to Vapor Technologies Inc.. Invention is credited to Bryce Anton, Patrick Sullivan, Richard P. Welty.
Application Number | 20070026205 11/194222 |
Document ID | / |
Family ID | 36889286 |
Filed Date | 2007-02-01 |
United States Patent
Application |
20070026205 |
Kind Code |
A1 |
Anton; Bryce ; et
al. |
February 1, 2007 |
Article having patterned decorative coating
Abstract
An article having a decorative, visibly-patterned, multi-colored
surface appearance includes a substrate and a first coating
provided by vapor deposition above at least a portion of the
substrate, the coating comprising a first material having a first
color. The coating comprises a random arrangement of penetrations
through which a portion of an underlying surface is visible, the
underlying surface comprising a second material having a second
color that differs from the first color. The penetrations form a
decorative pattern comprising features distinguishable to an
unaided human eye.
Inventors: |
Anton; Bryce; (Longmont,
CO) ; Welty; Richard P.; (Boulder, CO) ;
Sullivan; Patrick; (Longmont, CO) |
Correspondence
Address: |
FOLEY & LARDNER LLP
777 EAST WISCONSIN AVENUE
MILWAUKEE
WI
53202-5306
US
|
Assignee: |
Vapor Technologies Inc.
|
Family ID: |
36889286 |
Appl. No.: |
11/194222 |
Filed: |
August 1, 2005 |
Current U.S.
Class: |
428/195.1 |
Current CPC
Class: |
B05D 5/06 20130101; C23C
4/02 20130101; C23C 14/0015 20130101; B05D 1/32 20130101; C23C
14/58 20130101; C23C 16/56 20130101; B05D 5/067 20130101; Y10T
428/24802 20150115; C23C 16/26 20130101; C23C 14/0641 20130101;
C23C 16/006 20130101; B05D 7/52 20130101 |
Class at
Publication: |
428/195.1 |
International
Class: |
G03G 7/00 20060101
G03G007/00 |
Claims
1. An article having a decorative, visibly-patterned, multi-colored
surface appearance comprising: a substrate; and a first coating
provided by vapor deposition above at least a portion of the
substrate, the coating comprising a first material having a first
color; wherein the coating comprises a random arrangement of
penetrations through which a portion of an underlying surface is
visible, the underlying surface comprising a second material having
a second color that differs from the first color, wherein the
penetrations form a decorative pattern comprising features
distinguishable to an unaided human eye.
2. The article of claim 1, wherein the first coating is deposited
by a physical vapor deposition process or a chemical vapor
deposition process performed within a vacuum chamber at
sub-atmospheric pressure.
3. The article of claim 2, wherein the physical vapor deposition
process or chemical vapor deposition process comprises cathodic arc
evaporation.
4. The article of claim 2, wherein the physical vapor deposition
process or chemical vapor deposition process comprises a
hot-filament PECVD process.
5. The article of claim 1, wherein the first material comprises a
metal.
6. The article of claim 5, wherein the first material further
comprises at least one material selected from the group consisting
of nitrogen, oxygen, and carbon.
7. The article of claim 6, wherein the first material comprises at
least one material selected from the group consisting of zirconium,
scandium, titanium, chromium, hafnium, carbon, and an anodized
layer comprising a metal.
8. The article of claim 1, further comprising a second coating
provided intermediate the first coating and the substrate, the
second coating comprising the underlying surface.
9. The article of claim 8, wherein the second material comprises a
metal.
10. The article of claim 9, wherein the second material further
comprises at least one material selected from the group consisting
of nitrogen, oxygen, and carbon.
11. The article of claim 10, wherein the second material comprises
at least one material selected from the group consisting of
zirconium, titanium, chromium, hafnium, and scandium.
12. The article of claim 11, wherein the first material comprises
at least one of zirconium and scandium.
13. The article of claim 8, wherein the second material comprises
zirconium, oxygen, and carbon and the first material comprises
zirconium and nitrogen.
14. The article of claim 8, wherein the second material comprises
diamond-like carbon.
15. A method for producing an article having a decorative coating
comprising: depositing at least a first coating layer onto at least
a portion of a surface of a substrate using a physical or chemical
vapor deposition method in a vacuum chamber at sub-atmospheric
pressure, the first coating layer comprising a first material
having a first color; and patterning the first coating layer using
a non-uniform patterning process to form a patterned coating layer
having penetrations through which a portion of an underlying
surface is visible, the underlying surface comprising a second
material and having a second color that is visually contrasting to
the first color; wherein the patterned first coating layer
comprises a decorative pattern comprising features distinguishable
by an unaided human eye.
16. The method of claim 15, wherein at least one of the first
material and the second material comprises diamond-like carbon.
17. The method of claim 15, wherein the first material comprises a
metal.
18. The method of claim 17, wherein the first material further
comprises at least one material selected from the group consisting
of nitrogen, oxygen, and carbon.
19. The method of claim 18, wherein the first coating layer is
deposited using one of a cathodic arc evaporation process and a
hot-filament PECVD method.
20. The method of claim 18, wherein the first material comprises at
least one element selected from the group consisting of zirconium,
scandium, titanium, chromium, hafnium, and carbon.
21. The method of claim 15, wherein the first material comprises an
anodized layer comprising a metal.
22. The method of claim 15, wherein the patterning process
comprises an etching process.
23. The method of claim 15, wherein the patterning process
comprises a lift-off process.
24. The method of claim 15, wherein the patterning process
comprises a tumbling or vibratory finishing process.
25. The method of claim 15, wherein the patterning process
comprises forming a non-continuous masking layer, the masking layer
having penetrations through which a portion of the first coating
layer is exposed.
26. The method of claim 25, wherein the patterning process
comprises removing portions of the first coating layer under the
penetrations in the masking layer.
27. The method of claim 25, wherein the penetrations in the masking
layer are formed by means of a wire or fiber brush.
28. The method of claim 25, wherein the penetrations in the masking
layer are formed by a photolithographic process.
29. The method of claim 25, wherein the penetrations in the masking
layer are formed by non-uniform application of a masking
material.
30. The method of claim 29, wherein the masking material is applied
non-uniformly by means of a stamp or stencil.
31. The method of claim 29, wherein the masking material is applied
non-uniformly by means of at least one of a silk-screening process
and a spraying process.
32. The method of claim 25, wherein the penetrations in the masking
layer are created by means of a mass finishing operation handling
at least ten parts simultaneously.
33. The method of claim 15, further comprising depositing at least
a second coating layer onto the substrate prior to the deposition
of the first coating layer, the second coating layer comprising the
second material.
34. The method of claim 33, wherein the second material comprises a
metal.
35. The method of claim 34, wherein the second material further
comprises at least one member of the group consisting of nitrogen,
oxygen, and carbon.
36. The method of claim 35, wherein the second material comprises
at least one member of the group consisting of zirconium, titanium,
chromium, hafnium or scandium.
37. The method of claim 33, wherein the second material comprises
zirconium, oxygen, and carbon, and wherein the first material
comprises zirconium and nitrogen.
38. The method of claim 33, wherein the second material comprises
carbon.
39. The method of claim 38, wherein the first material comprises
carbon.
40. The method of claim 33, wherein the second material comprises
an anodized layer comprising a metal.
41. A method for producing an article having a decorative surface
comprising: depositing a first layer of material on a substrate
using a vapor deposition method, the first layer of material
comprising a first material having a first color; depositing a
second layer of material on the first layer of material using a
vapor deposition method, the second layer of material comprising a
second material having a second color that differs from the first
color; and removing portions of the second layer of material to
form apertures extending through the second layer, the apertures
arranged in a random configuration; wherein portions of the first
layer are visible through the apertures such that a decorative
pattern is formed on the article.
42. The method of claim 41, wherein the step of removing portions
of the second layer of material comprises a masking process.
43. The method of claim 41, wherein the masking process comprises
providing a mask above the second layer of material, the mask
comprising at least one of an ink, a photoresist, a paint, a
lacquer, a wax, and a metal.
44. The method of claim 41, wherein the step of removing portions
of the second layer of material comprises at least one of an
etching process, a lift-off process, and a tumbling or vibratory
finishing process.
45. The method of claim 41, wherein the step of removing portions
of the second layer of material comprises forming a non-continuous
masking layer, the masking layer having penetrations through which
a portion of the first coating layer is exposed.
46. The method of claim 45, wherein the step of removing portions
of the second layer of material comprises removing portions of the
second layer of material under the penetrations in the masking
layer.
47. The method of claim 45, wherein the penetrations in the masking
layer are formed by non-uniform application of a masking
material.
48. The method of claim 45, wherein the penetrations in the masking
layer are created by means of a mass finishing operation handling
at least ten parts simultaneously.
49. The method of claim 41, wherein the first material comprises a
metal and at least one material selected from the group consisting
of nitrogen, oxygen, and carbon.
50. The method of claim 49, wherein the first material comprises at
least one of zirconium, titanium, chromium, hafnium and
scandium.
51. The method of claim 41, wherein the first coating layer is
deposited using at least one of a hot-filament PECVD method and a
cathodic arc evaporation process.
52. The method of claim 41, wherein the first material comprises an
anodized layer comprising a metal.
53. The method of claim 41, wherein the second material comprises a
metal and at least one member of the group consisting of nitrogen,
oxygen, and carbon.
54. The method of claim 43, wherein the second material comprises
zirconium, titanium, chromium, hafnium or scandium.
55. The method of claim 41, wherein the second material comprises
zirconium, oxygen, and carbon, and wherein the first material
comprises zirconium and nitrogen.
56. The method of claim 41, wherein at least one of the first
material and the second material comprises diamond-like carbon.
57. The method of claim 41, wherein the second material comprises
carbon.
58. The method of claim 56, wherein the first material comprises
carbon.
Description
BACKGROUND
[0001] The present invention relates generally to articles having
decorative coatings or finishes provided thereon and methods of
producing such articles. More specifically, the present invention
relates to articles and methods for producing articles which have
multi-tone coatings provided thereon.
[0002] Colored coatings have been provided on articles using
physical vapor deposition (PVD) or chemical vapor deposition (CVD)
methods. PVD coatings are at present available in a range of colors
on such commercial products as plumbing products, home hardware
such as doorknobs and hinges, automotive products, recreational
products, and various other products.
[0003] PVD and CVD decorative coatings in general offer many
performance advantages such as high hardness, abrasion resistance,
corrosion resistance, chemical resistance, etc. as compared to
conventional polymer and electroplated coatings. Although PVD and
CVD coatings are available in a variety of colors, presently
available PVD and CVD coatings generally have a uniform color over
the entire substrate surface. It may be desirable, however, for
certain applications to use a PVD or CVD coating having a
visibly-patterned, multi-color appearance (e.g., for creating
products having, for example, streaked, speckled, marbled,
"antique", "aged", or "distressed" finishes, or having decorative
or informational digitized images incorporated into the surface
finish).
[0004] Conventional methods for creating patterned decorative
finishes on products such as those mentioned above generally
utilize polymer coatings for either coloration or protection. It is
known to use paints, lacquers, etc. to create patterned finishes
directly on a substrate surface. It is also known to thermally,
chemically, and/or mechanically treat substrate surfaces to produce
patterned finishes, but such treated surfaces are often not durable
and require a polymer topcoat for protection against abrasion and
corrosion. Polymer coatings may be susceptible to abrasion,
solvents, and household chemicals, and may develop pinholes through
which corrosion of the substrate can initiate.
[0005] PVD coatings, in contrast, are generally very hard and
resistant to abrasion and chemical attack, and are superior to
polymer-based coatings for many applications. While patterned PVD
and CVD coatings have been used in the electronics industry for
purposes of fabricating printed and integrated circuits, such
coatings have not conventionally been used to provide decorative
coatings (e.g., visibly-patterned, multi-colored decorative
coatings). Such patterned PVD and CVD coatings are generally made
of materials selected for their electronic (as opposed to
decorative) properties and are used to produce non-decorative
patterns that are too small to be visible to the human eye without
magnification. In addition, such patterning processes often handle
only flat substrates and a single substrate at a time, which would
be unsuitable for the mass-production of consumer products.
[0006] It would be advantageous to provide a decorative coating or
finish for an article that is provided using PVD and/or CVD methods
that has a patterned appearance, which will not rub or scrub off in
normal use, which is scratch and corrosion resistant, can withstand
common household chemicals and solvents, and does not age or
degrade in sunlight or under exposure to outdoor conditions. It
would also be advantageous to provide articles having decorative
coatings which provide an aesthetically-pleasing appearance that is
visible to the unaided human eye and that are produced using
methods which are suitable for mass-production. It would be
desirable to provide coatings, articles, and methods which exhibit
any one or more of these or other advantageous features as may be
understood by those of ordinary skill in the art reviewing this
document.
SUMMARY
[0007] An exemplary embodiment relates to an article having a
decorative, visibly-patterned, multi-colored surface appearance
that includes a substrate and a first coating provided by vapor
deposition above at least a portion of the substrate, the coating
comprising a first material having a first color. The coating
comprises a random arrangement of penetrations through which a
portion of an underlying surface is visible, the underlying surface
comprising a second material having a second color that differs
from the first color. The penetrations form a decorative pattern
comprising features distinguishable to an unaided human eye.
[0008] Another exemplary embodiment relates to a method for
producing an article having a decorative coating that includes
depositing at least a first coating layer onto at least a portion
of a surface of a substrate using a physical or chemical vapor
deposition method in a vacuum chamber at sub-atmospheric pressure,
the first coating layer comprising a first material having a first
color. The method also includes patterning the first coating layer
using a non-uniform patterning process to form a patterned coating
layer having penetrations through which a portion of an underlying
surface is visible, the underlying surface comprising a second
material and having a second color that is visually contrasting to
the first color. The patterned first coating layer comprises a
decorative pattern comprising features distinguishable by an
unaided human eye.
[0009] Another exemplary embodiment relates to a method for
producing an article having a decorative surface that includes
depositing a first layer of material on a substrate using a vapor
deposition method, the first layer of material comprising a first
material having a first color; depositing a second layer of
material on the first layer of material using a vapor deposition
method, the second layer of material comprising a second material
having a second color that differs from the first color; and
removing portions of the second layer of material to form apertures
extending through the second layer. The apertures are the apertures
arranged in a random configuration. Portions of the first layer are
visible through the apertures such that a decorative pattern is
formed on the article.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a photograph of an article having a decorative
coating provided thereon according to an exemplary embodiment.
[0011] FIG. 2 is a photograph of an article having a decorative
coating provided thereon according to an exemplary embodiment.
[0012] FIG. 3 is a flow diagram illustrating steps in a method of
producing an article having a decorative coating according to an
exemplary embodiment.
[0013] FIGS. 4-9 are schematic cross-sectional views of a portion
of an article having a decorative coating provided thereon
illustrating steps in the exemplary method represented by the flow
diagram of FIG. 3.
[0014] FIG. 10 is a flow diagram illustrating steps in a method of
producing an article having a decorative coating according to an
exemplary embodiment.
[0015] FIGS. 11-15 are schematic cross-sectional views of a portion
of an article having a decorative coating provided thereon
illustrating steps in the exemplary method represented by the flow
diagram of FIG. 10.
[0016] FIG. 16 is a photograph of an article having a decorative
coating provided thereon according to an exemplary embodiment.
[0017] FIG. 17 is a photograph of an article having a decorative
coating provided thereon according to an exemplary embodiment.
[0018] FIG. 18 is a flow diagram illustrating steps in a method of
producing an article having a decorative coating according to an
exemplary embodiment.
[0019] FIGS. 19-22 are schematic cross-sectional views of a portion
of an article having a decorative coating provided thereon
illustrating steps in the exemplary method represented by the flow
diagram of FIG. 18.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0020] According to an exemplary embodiment, an article or product
is provided that includes a decorative coating with a
visibly-patterned, multi-colored appearance provided thereon. Any
of a variety of articles or products may be produced using the
methods described below in the various exemplary embodiments,
including, but not necessarily limited to, plumbing components
(e.g., faucets, handles, nozzles, sinks, drain flanges, stop
valves, pipes, tub drains, etc.), home hardware (e.g., doorknobs,
hinges, drawer/cabinet pulls, etc.), bath hardware (towel bars,
safety "grab" bars, etc.), windows and doors (e.g., shower doors,
etc.), automotive products (e.g., automotive trim parts, emblems,
wheel covers, etc.), knives, medical instruments, tableware,
recreational products, sporting goods (e.g., golf clubs, ice
skates, etc.), indoor or outdoor lighting products (e.g., lamps,
fixtures, etc.) weatherproof informational signs, and any of a
variety of other products or articles. It should be noted that the
present invention does not pertain to microprocessors or the
fabrication of electronic chips and the like.
[0021] According to one exemplary embodiment, at least one coating
or layer of material is provided (e.g., deposited using a PVD
and/or CVD process) on a substrate, after which a masking material
is applied on top of the coating. The masking material is then
patterned by a random or non-uniform modification process, forming
penetrations (e.g., apertures or holes) which leave a portion of
the underlying coating exposed. The exposed portion of the coating
is subsequently removed by chemical etching, leaving randomly or
non-uniformly arranged penetrations through which an underlying
coating layer or substrate surface having a contrasting color is
visible.
[0022] In this manner, an article having a decorative coating with
a visibly-patterned multi-colored appearance may be provided that
includes at least one coating material deposited on a substrate by
a vacuum deposition process. According to various exemplary
embodiments, the at least one coating may be provided (e.g.,
deposited) by a PVD technique such as cathodic arc evaporation or
sputtering, or by a CVD method such as hot-filament or ion-beam
PECVD.
[0023] The coating may be patterned by etching, using the patterned
masking layer which is resistant to the etching process, to remove
the coating in areas unprotected by the mask. The masking layer is
subsequently removed using a solvent, uncovering the un-etched
regions of the coating surface. The coating material is selected to
have a color which is visually contrasting to the underlying
surface exposed by the etching process. Regions of contrasting
color may alternatively be produced by anodizing or otherwise
chemically or physically modifying the unmasked regions of the
coating in such a way as to produce regions having a color
contrasting from that of the masked regions. The underlying surface
may be the substrate surface, or may be an underlying coating layer
selected to have a desired decorative appearance and/or to provide
other desired properties.
[0024] According to other exemplary embodiments, the coating may be
patterned by providing the coating on top of a patterned masking
layer having penetrations which expose a portion of the substrate
surface (or a surface of another underlying layer). After providing
the coating, the masking layer is dissolved in a solvent, thereby
loosening and removing the coating material deposited on top of the
masking material while leaving in place the coating deposited on
the portion of the substrate surface exposed through the
penetrations in the masking layer. This latter type of process may
be referred to as a "lift-off" process.
[0025] The patterned masking layer that may be used for either an
etching or a lift-off process may be formed by depositing a layer
of a masking material non-uniformly on a substrate, as by
stenciling, or by depositing the masking material uniformly over
the substrate surface and subsequently patterning it by a
non-uniform removal process such as barrel tumbling in finishing
media, which removes portions of the masking layer, forming
penetrations (e.g., apertures or holes) through which portions of
the underlying surface is exposed. A variety of methods for forming
decoratively-patterned masking layers according to the various
exemplary embodiments will be described below in more detail.
[0026] As used herein, the term "substrate" refers to all or a
portion of an article underlying the decorative coating, and may
include any surface protection or preparation layers such as
electroplating or polymer basecoats. According to various exemplary
embodiments, the substrate may include materials such as metals
(e.g., brass, zinc, stainless steel, tin, copper, iron-based
alloys, etc.), plastics (e.g., thermoset or thermoplastic materials
such as a polyolefin or acrylonitrile-butadiene-styrene (ABS)
material, etc.), ceramics, glasses (e.g., architectural type glass
(e.g., shower doors, etc.), and/or composites (e.g., metal matrix
materials, polymer matrix materials, ceramic and glass matrix
materials, carbon graphite matrix materials, fiber reinforced
composites, and the like).
[0027] Substrates may be electroplated with corrosion-resistant
and/or surface-leveling layers comprising, for example, nickel,
chromium, copper, cobalt, zinc, cadmium, tin, lead, gold, brass,
bronze, rhodium, platinum, nickel-tin alloys, and other known
electroplating materials. Substrates may also include protective
and/or surface-leveling polymer layers, anodized layers of the
substrate material or of an applied coating, or any other known
surface-preparation material that is compatible with vacuum
deposition and patterning processes.
[0028] The term "decorative coating" as used herein refers to
coatings that provide a desired surface appearance to an article
(e.g., to coatings that have a patterned, multi-colored visual
appearance). In some embodiments, in addition to providing a
desired surface appearance, the decorative coating may also provide
various utilitarian features such as some degree of abrasion,
scratch, tarnish, and/or corrosion resistance to an underlying
substrate. Such coatings may also be employed for other functional
purposes, such as to increase the strength of a cutting edge or to
improve the wear resistance of a surface (e.g., in cases in which
the appearance of the coating contributes to its consumer marketing
appeal).
[0029] The terms "pattern" and "patterned" refer to a coating or
mask comprising a layer that has penetrations (e.g., apertures or
holes) through which an underlying coating layer or substrate of a
different (e.g., contrasting) color is visible. The term
"visibly-patterned" refers to a patterned coating or layer in which
at least some features (regions) of the pattern are of sufficient
size and/or have sufficient color contrast from surrounding
features to be readily distinguished by a human eye without
magnification, for example, but without limitation, features larger
than around 1 mm extent in least one linear dimension. Such visible
features may also be made up of smaller dots or shaped pixels which
are individually indistinguishable to a human eye, but which
together form distinguishable features. The term "decorative
pattern" refers to a pattern selected at least in part to have a
desired aesthetically-appealing appearance. The term "informational
pattern" refers to a pattern selected to provide a visually
distinguishable display of text or of a digitized image, which may
also be decorative.
[0030] The terms "random" and "non-uniform" when used herein to
refer to the arrangement of apertures or holes formed in a layer of
material is intended to mean an arrangement in which the specific
locations of apertures or holes is not predetermined prior to
patterning. Various techniques for obtaining such random or
non-uniform arrangements are described below in greater detail.
Such arrangements are unlike those used, for example, in masks used
in the manufacture of microprocessors and the like, which have a
set or predetermined pattern when provided on a wafer or the like
(e.g., so that features such as conductive lines, vias, and the
like will line up properly to provide the desired
functionality).
[0031] It should be understood by those reviewing this disclosure
that larger distinguishable patterns (e.g., an image of an animal)
may be formed while using random patterning techniques. For
example, a substrate may be covered with a mask having a cutout
formed therein. The cutout may have a desired shape (e.g., an image
of an animal). The portion of the substrate not covered by the mask
(corresponding to the cutout) may be patterned in a random or
non-uniform fashion to have apertures extending through the
substrate. When the mask is removed, the portion covered by the
mask will not be patterned (e.g., will not have apertures extending
therethrough) and the portion of the substrate not covered by the
mask will have random or non-uniform patterning therein. An
observer of the substrate will then see an image (e.g., an animal)
defined by the random or non-uniform patterning.
[0032] The term "contrasting color" refers to a second color which
is visually distinguishable from a first color by an unaided human
eye under normal outdoor or indoor lighting conditions.
[0033] FIGS. 1 and 2 are photographs of articles 10 and 20 produced
using a method 100 for providing decorative coatings or finishes
according to an exemplary embodiment. FIG. 3 is a flow diagram
illustrating exemplary steps of method 100, and FIGS. 4-9 are
schematic cross-sectional views of an article 200 illustrating the
steps in method 100.
[0034] In a step 110 shown in FIG. 4, a first layer or coating 220
comprising a material 222 is provided on a substrate 210 comprising
a material 212. According to an exemplary embodiment, material 222
is a relatively dark-colored material. For example, material 222
may be an oxy-carbide or oxy-carbo-nitride of zirconium that is
applied to substrate 210 using a cathodic arc evaporation process
carried out in a vacuum chamber at sub-atmospheric pressure using
known processes. According to another exemplary embodiment,
material 222 is a diamond-like carbon (DLC) coating applied by
hot-filament PECVD in a low-pressure vacuum deposition process.
Various other materials may also be used for layer 220 as will be
described below.
[0035] In a step 120 shown in FIG. 5, a second layer or coating 230
of material 232 is provided above layer 220. According to an
exemplary embodiment, material 232 has a different color (e.g., is
lighter-colored) than material 222. For example, material 232 may
be a material such as zirconium nitride applied on layer 220 by
cathodic arc evaporation.
[0036] According to an exemplary embodiment, layers 220 and 230
have thicknesses of between approximately 0.3 and 0.5 microns.
According to other exemplary embodiments, layers greater than 0.5
microns or less than 0.3 microns thick may be employed. For
example, thicker coatings (e.g., in a range from around 0.5 to 5
microns) may be utilized in cases in which the coating is required
to perform some function such as scratch or corrosion protection in
addition to providing a decorative appearance. It should also be
noted that the thickness of layer 220 may be the same as or may
differ from the thickness of layer 230 according to various
exemplary embodiments.
[0037] Subsequent to providing layer 230, article 200 is removed
from the vacuum chamber and coated with a relatively thin mask or
masking layer 240 (e.g., comprising a material 242 such as a
waterproof permanent ink) in a step 130 shown in FIG. 6. According
to an exemplary embodiment, layer 240 has a thickness of between
approximately 0.1 microns and 0.5 microns. According to various
other exemplary embodiments, the thickness of the masking layer may
be between approximately 0.01 microns and 50 microns.
[0038] In a step 140 shown in FIG. 7, a portion of layer 240 is
removed (e.g., layer 240 is randomly or non-uniformly patterned).
According to an exemplary embodiment, article 200 is placed in a
barrel-tumbler with plastic tumbling media and tumbled until layer
240 is partially, but not totally, removed and a portion of layer
230 is exposed. For example, according to an exemplary embodiment,
plastic tumbling media having an average diameter of between
approximately 10 mm and 20 mm are utilized in a tumbling operation
for between approximately 3 and 15 minutes to remove a portion of
layer 240.
[0039] As shown in FIG. 7, a number of apertures or holes 244
(e.g., penetrations) are formed in layer 240 during this process
(leaving regions or areas 246 of layer 240 masking or covering
portions of layer 230). It should be noted that apertures 244 may
have any of a variety of shapes and sizes depending on processing
conditions and other factors. By selection of the tumbling media
material, carrier liquid, fill levels, and other known parameters,
visible features may be produced through non-uniform removal of
layer 240. According to other exemplary embodiments, the masking
layer may be patterned to produce a desired repeating pattern
(e.g., it may be deposited having an interference pattern (e.g.,
color may be controlled by controlling the thickness of a layer
such as an oxide layer, such that there will be an "apparent" color
even if the material is transparent due to interference of light),
a pattern may be applied by silk screen methods, by a
photolithographic process, by a spraying process (e.g., spray
painting), by a stamp or stencil, by laser patterning, or by any
other suitable method). According to another exemplary embodiment,
instead of spraying on a mask material, the etchant may be sprayed
onto a mask material to form a pattern in the mask.
[0040] In a step 150 shown in FIG. 8, the exposed portions of layer
230 (i.e., those portions of layer 230 underlying apertures 244
formed in layer 240) are removed in an etching process. According
to an exemplary embodiment, article 200 is placed in an etching
solution which dissolves layer 230 in the exposed areas, forming
apertures 234 (e.g., penetrations, holes, etc.) in layer 230
through which the darker layer 220 is visible. Regions or areas 236
of layer 230 that were covered by regions 246 of layer 240 during
the etching process remain above layer 230.
[0041] In a step 160 shown in FIG. 9, layer 240 is removed (i.e.,
the portion of layer 240 remaining above layer 230 after step 140).
Layer 240 is removed by use of an organic solvent (e.g., acetone,
TCE, etc.) or an etchant (acidic or alkaline) formulated to
selectively remove such layer without harming other layers.
[0042] According to another exemplary embodiment, only a single
vacuum-deposited layer is employed. FIG. 10 is a flow diagram
showing steps in such a method 300, and FIGS. 11-15 are schematic
cross-sectional views of steps in the manufacture of an article 400
using method 300.
[0043] In a step 310 shown in FIG. 11, a layer or coating 420
including a material 422 is provided above a substrate 410
comprising a material 412. According to an exemplary embodiment,
layer 420 is a layer of an oxy-carbide of zirconium deposited
directly on a substrate surface by cathodic arc evaporation.
[0044] Subsequent to providing layer 420, article 400 is removed
from the vacuum chamber and coated with a relatively thin mask or
masking layer 440 (e.g., made of a material 442 such as a
waterproof permanent ink) in a step 320 shown in FIG. 12. According
to an exemplary embodiment, layer 440 has a thickness of between
approximately 0.5 microns and 5.0 microns. According to various
other exemplary embodiments, the thickness of the masking layer may
be between approximately 0.01 microns and 50 microns.
[0045] In a step 330 shown in FIG. 13, a portion of layer 440 is
removed as described above with respect to FIG. 7. A number of
apertures or holes 444 are formed in layer 440 during this process
(leaving regions or areas 446 of layer 440 masking or covering
portions of layer 420). It should be noted that apertures 244 may
have any of a variety of shapes and sizes depending on processing
conditions and other factors. By selection of the tumbling media
material, carrier liquid, fill levels, and other known parameters,
visible features may be produced through non-uniform removal of
layer 440. According to other exemplary embodiments, the masking
layer may be patterned to produce a desired repeating pattern
(e.g., it may be deposited having an interference pattern (e.g.,
color may be controlled by controlling the thickness of a layer
such as an oxide layer, such that there will be an "apparent" color
even if the material is transparent due to interference of light),
a pattern may be applied by silk screen methods, by a
photolithographic process, by a spraying process (e.g., spray
painting), by a stamp or stencil, by laser patterning, or by any
other suitable method). According to another exemplary embodiment,
instead of spraying on a mask material, the etchant may be sprayed
onto a mask material to form a pattern in the mask.
[0046] In a step 340 shown in FIG. 14, the exposed portions of
layer 420 (i.e., those portions of layer 420 underlying apertures
444 formed in layer 440) are removed in an etching process.
According to an exemplary embodiment, article 400 is placed in an
etching solution which dissolves layer 420 in the exposed areas,
forming apertures 424 (e.g., penetrations, holes, etc.) in layer
420 through which substrate 410 is visible. Regions or areas 426 of
layer 420 that were covered by regions 446 of layer 440 during the
etching process remain above substrate 410.
[0047] In a step 350 shown in FIG. 15, layer 440 is removed (i.e.,
the portion of layer 440 remaining above layer 420 after step 340).
Layer 440 is removed by use of an organic solvent (e.g., acetone,
TCE, etc.) or an etchant (acidic or alkaline) formulated to
selectively remove such layer without harming other layers.
[0048] Methods 100 and 300 as described above with respect to FIGS.
3-15 may be used to form visibly-patterned layers that include
penetrations (e.g., apertures 234 and 424) through which an
underlying material (e.g., layer 220 in FIG. 9 and substrate 410 in
FIG. 15) may be seen. According to an exemplary embodiment, such
underlying materials have a different color than the overlying
layers of material. In this manner, articles having finishes that
appear to be streaked, speckled, marbled, "antique", "aged",
"distressed", or the like can be produced. The embodiment shown and
described with respect to FIGS. 3-9 utilizes a multiple-layer
deposition process, while the embodiment shown and described with
respect to FIGS. 10-15 utilizes a single-layer deposition process.
According to various other exemplary embodiments, a different
number of layers (e.g., three or more layers) may be provided
(e.g., deposited) and patterned as may be appropriate to provide
the desired surface characteristic or appearance.
[0049] According to yet another exemplary embodiment, a coating
layer may be patterned directly by mechanical or chemical treatment
to expose portions of an underlying surface having a different
color. In this manner, articles such as those illustrated
schematically in FIGS. 9 and 15 may be produced without the need to
use a masking layer. For example, a relatively dark layer of an
oxy-carbide of zirconium can be tumbled with plastic media in an
abrasive slurry for a controlled period of time in order to create
a decorative pattern of penetrations that exposes a portion of an
underlying surface having a different color (such as an underlying
layer of a nitride of zirconium). Textured surfaces may be buffed
with a polishing compound to remove the coating on high spots and
exposing portions of the underlying surface having a different
color. Non-uniform application of chemical etchants by means of a
brush, stamp, etc. may also be used to directly pattern colored
layers.
[0050] FIGS. 16 and 17 are photographs illustrating articles 30 and
40 produced using a method 500 for providing decorative coatings or
finishes according to an exemplary embodiment. According to an
exemplary embodiment, method 500 may be referred to as a "lift-off
process," as will be described in greater detail below. FIG. 18 is
a flow diagram illustrating exemplary steps of method 500, and
FIGS. 19-22 are schematic cross-sectional views of an article 600
showing steps in method 500.
[0051] In a step 510 shown in FIG. 19, a layer 640 (e.g., an
etch-masking layer comprising a material 642 similar to material
242 described above) is provided directly on a substrate 610 of
article 600.
[0052] In a step 520 shown in FIG. 20, layer 640 is patterned
(e.g., by a tumbling process) similar to layer 240 described above
with respect to FIG. 7. As a result of this process, apertures 644
are formed in layer 640, leaving behind regions or areas 646 that
mask or cover portions of substrate 610.
[0053] In a step 530 shown in FIG. 21, a layer 620 including a
material 622 may be provided above layer 640 and substrate 610 such
that material 622 is provided both above remaining portions 646 of
layer 640 and in apertures 644 formed therein (e.g., article 600
may be placed in a vacuum chamber and coated with layer 620).
According to an exemplary embodiment, layer 620 has a different
color from that of substrate 610.
[0054] In a step 540 shown in FIG. 22, remaining portions 646 of
layer 640 are removed (e.g., dissolved with a solvent or otherwise
removed) in such a way as to also remove that portion of layer 620
that was deposited on top of it, thereby forming visibly-patterned
penetrations in layer 620 through which the underlying substrate
surface having a different color can be seen. As shown in FIG. 22,
apertures 624 are formed in layer 620 due to removal of the
remaining portions 646 of layer 640 and the overlying portions of
layer 620. Regions or areas 626 of layer 620 which were provided in
apertures 644 in step 530 remain after the removal of portions 646
and mask or cover underlying regions of substrate 610.
[0055] While the embodiment shown and described with respect to
FIGS. 18-22 illustrates the provision of layer 640 directly on an
underlying substrate 610, according to another exemplary
embodiment, a substrate may include a layer of material provided
thereon prior to the provision of a mask layer (such as layer 640).
In this manner, the patterned layer 620 may be provided such that
aperture or penetrations formed therein allow an underlying layer
of material to be seen (as shown, for example, in FIG. 9, which
shows a patterned layer 230 provided above an underlying base-color
layer 220). Thus, this type of lift-off process is performed after
vacuum deposition of a base-color layer, such that the base-color
layer is visible through the penetrations formed in the top layer
by a lift-off process. Lift-off processes may be useful, for
example, to avoid the necessity of etching materials, such as DLC,
that are difficult to etch.
[0056] For example and not for purposes of limitation, known PVD
(physical vapor deposition) vacuum processes suitable for
practicing the methods described in the various exemplary
embodiments include cathodic arc evaporation, sputtering, thermal
and e-beam evaporation, and ion-beam sputtering, with cathodic arc
evaporation and sputtering being preferred PVD processes. Preferred
chemical vapor deposition (CVD) methods include hot-filament plasma
enhanced CVD (PECVD) methods and ion-beam PECVD methods, and
include plasma and ion source methods using ECR (electron-cyclotron
resonance), microwave, or radio-frequency excitation. PVD and CVD
methods may also in various exemplary embodiments be combined, for
example, by depositing a base-color layer of dark-grey or black
diamond-like carbon by a hot-filament PECVD method, then depositing
a ZrN coating layer by cathodic arc evaporation. According to one
exemplary embodiment, physical vapor deposition equipment as may be
used in conjunction with the method disclosed herein may include VT
3000 or VT 1500 batch coaters commercially available from Vapor
Technologies of Boulder, Colo.
[0057] Preferred materials for base-color layers (e.g., layer 220)
and patterned coating layers (e.g., layers 230, 420, and 620)
include such known materials as the nitrides, oxides, carbides,
oxy-nitrides, oxy-carbides, carbo-nitrides, and oxy-carbo-nitrides
of such metals as zirconium, titanium, hafnium, chromium, scandium,
and various alloys comprising such metals. Highly preferred
materials include those comprising zirconium, and in particular the
nitrides, oxy-carbides, and oxy-carbo-nitrides of zirconium and
zirconium alloys such as Zr--Ti and Zr--Sc. The terms nitrides,
oxides, carbides, oxy-nitrides, oxy-carbides, carbo-nitrides, and
oxy-carbo-nitrides of metals refer to compounds and mixtures of a
metal and the corresponding combination of reactive components
oxygen, nitrogen, and carbon. These terms refer to both
stoichiometric and non-stoichiometric compounds, referring to those
which have a deficit or excess of one or more reactive components
relative to the quantity required to combine in the formulaically
specified ratios. They also refer in particular to
sub-stoichiometric compounds having a deficit of one or more
reactive components.
[0058] Materials for base-color layers and patterned coating layers
also may include carbon, and in particular an amorphous, usually
hydrogenated, glassy and hard form of carbon known as diamond-like
carbon or DLC. DLC can be vacuum-deposited in a variety of known
ways including hot-filament or ion-beam PECVD, in which either
electron current from a hot filament, or an ion beam source, is
used to ionize a carbon-bearing gas such as methane or acetylene.
DLC is a semi-transparent material which becomes grayish to nearly
black in appearance as the layer thickness is increased. DLC is
advantageous as a base-color layer upon which zirconium-based or
other metal-based patterned layers may be deposited, since DLC is
not attacked by the etchants used for metal-based layers. Preferred
materials for base-color layers and patterned coating layers also
include anodized layers of such metals as aluminum, niobium,
titanium, zirconium, and hafnium. Anodization refers to
wet-chemical electrolytic processes by which a layer of a metal is
oxidized. Transparent anodized layers of controlled thicknesses
exhibit interference colors ranging through the entire interference
spectrum. Porous anodized layers may be dyed using known organic
dyes to produce durable colored finishes in a variety of colors
including black and grey.
[0059] Known etching methods include wet-chemical etching with
known acids, bases, and commercial etching solutions. It is also
known to etch such materials as ZrN, ZrOC, and the like using a
dilute solution of ammonium bifluoride. Etching may also be
accomplished using a plasma etching process in a vacuum system. In
some cases it is desirable to employ an etch-stop layer between the
underlying surface and the patterned layer, in order to prevent
over-etching of the underlying surface. Such an etch-stop layer is
particularly desirable when the two color layers are similar
materials and etched by the same processes. The etch-stop layer may
be of a transparent material such the underlying surface is visible
without removal of the etch-stop layer, or may be of a
non-transparent material which can be subsequently removed by a
process which does not damage the color layers. Chromium is a
possible candidate as an etch-stop material as it is not
aggressively etched by ammonium bifluoride and is galvanically
compatible with the zirconium compounds and the underlying plating
stack.
[0060] Mask materials (e.g., used to form mask layers 240, 440, and
640) may include any material that resists the modification process
used to modify the unmasked regions of the coating layer to be
patterned, and that can itself be patterned by the modification
process selected to create the desired pattern in the mask layer.
Suitable materials may include inks, photoresists, paints,
lacquers, waxes, and thin metal films.
[0061] Processes for randomly or non-uniformly patterning the
masking layer include known processes such as scratching, sanding,
buffing by wire, cloth, or abrasive wheel, tumbling in ceramic,
nutshell, plastic, or abrasive media, sandblasting, etc. Processes
such as photolithography (as by focused image or scanning laser
techniques) and ion-beam lithography may also be used.
[0062] A random or non-uniform patterned masking layer may be
deposited directly onto the substrate by spraying, condensation, or
coalescence of droplets or streaks of a masking material on the
coating surface, by applying a masking material through a
silk-screen or stencil, writing with a pen or marker containing an
masking material, stamping with a rubber stamp carrying a masking
material, and other known methods of applying such materials
non-uniformly to surfaces. A preferred method for non-uniform
application of a masking layer is to use a silk-screen created
using a photographic process. Such silk-screens can produce masking
layers comprising images such as geometric or random decorative
patterns, corporate logos, digitized images, and text. Such
silk-screened patterns may comprise smaller dots, or shaped pixels
of variable size, which are individually indistinguishable to the
human eye, but which collectively form patterns with visually
distinguishable features.
[0063] According to another exemplary embodiment, a non-uniform
modification process used to pattern a mask layer includes tumbling
or vibratory finishing in media such as plastic or ceramic pellets,
nutshells, abrasive media, and the like. One exemplary method for
creating a patterned masking layer comprises the steps of a)
applying waterproof masking layer uniformly or semi-uniformly over
the surface of the part, b) tumbling multiple parts in a barrel
partially filled with plastic tumbling media, preferably but non
necessarily with a carrier liquid, for a time period sufficient to
remove portions of the masking layer but not all of it. Desirable
accents in the pattern produced by tumbling may be produced by
applying the masking agent in a non-uniform manner such that the
masking layer is thicker in some regions and thinner or absent
altogether in other regions.
[0064] It should be noted that the various processes described
herein may be performed multiple times to obtain desired effects.
For example, multiple coatings having various colors may be applied
to an article to give an article a multi-colored surface appearance
(e.g., three or more different colors may be visible on the surface
of the article). Those of ordinary skill in the art reviewing this
disclosure will appreciate that any number of layers and
combinations of layers may be utilized depending on the desired
appearance of the article for a given application.
[0065] According to another exemplary embodiment, a patterning
process similar to those described above may be used in order to
prepare an article having one or more pictures, drawings, logos,
signs, or other information provided thereon. For example, a mask
material may be provided and patterned to include a logo, after
which an underlying layer may be etched to expose an underlying
surface in the pattern of the logo. It will be appreciated than any
number of variations are possible.
[0066] The following examples are provided for purposes of
illustration and not of limitation. Those of skill in the art
reviewing this document will appreciate that various other
combinations of methods and layer materials may be to produce
patterned decorative coatings on a substrate according to various
other exemplary embodiments. It will also be appreciated that
patterned coatings having more than two colors may be produced by
repeated application of the techniques and materials disclosed
herein.
EXAMPLE 1
[0067] According to a working example, a brass faucet handle was
electroplated with a duplex nickel and chromium plating stack to
provide it with a chromium-colored surface. A coating layer
including an oxy-carbide of zirconium was deposited on the part
using cathodic arc evaporation in a vacuum chamber at
sub-atmospheric pressure. A second coating layer of a
sub-stoichiometric nitride of zirconium was afterwards applied,
also using cathodic arc evaporation. An etch-mask layer of a water
resistant permanent ink was applied to the part. The part was
subjected to a tumbling or vibratory mass finishing operation using
plastic media to partially remove the ink. The part was then etched
in a dilute solution of ammonium bifluoride to remove the portion
of the top coating layer that is exposed in the areas where the
masking layer has been removed. Finally, the part was dipped in a
solvent (e.g., acetone, TCE, etc.) to remove the ink. The top
coating layer in the areas protected by the ink was still intact,
providing a visibly-patterned "aged pewter" surface appearance.
EXAMPLE 2
[0068] According to a theoretical example, an injection-molded
plastic shower spray housing is electroplated with a copper,
nickel, and chromium plating stack having a chromium-colored
surface. The part is mounted in a vacuum chamber and coated with a
dark grey layer of an oxy-carbide of zirconium having a thickness
of approximately 0.4 microns. The part is removed from the vacuum
chamber and a lacquer masking material is non-uniformly applied in
a streaked manner using an automated brushing system, leaving at
least a portion of the surface of the oxy-carbide layer exposed
through penetrations (uncovered areas) in the masking layer. The
part is then etched in a dilute solution of ammonium bifluoride to
remove the portion of the coating layer that is exposed. Finally,
the part is rinsed with a solvent to remove the lacquer masking
material, exposing the surface of the remaining, un-etched
oxy-carbide layer and providing a "distressed" finished with either
a dark background and chromium-colored highlights, or vice-versa
depending on the ratio of the surface areas of the masked and
unmasked areas of the coating surface.
EXAMPLE 3
[0069] According to another theoretical example, a zinc die-cast
bathtub spout is electroplated with a copper, nickel, and chromium
plating stack having a chromium-colored surface. A thin etch-mask
layer of a waterproof ink or an acrylic lacquer is applied to the
part. The part is then automatically or manually "wire-brushed" in
a random or streaked fashion using a motor-mounted wire or fiber
wheel, thus creating a scratch pattern in the etch mask layer which
exposes a portion of the chromium-colored substrate surface. The
part is mounted in a vacuum chamber, and coated with a layer of
dark-grey or black diamond-like carbon. The carbon may be deposited
by ion-beam or hot-filament PECVD and has a thickness of at least
about 0.2 microns and preferably at least about 0.3 microns to 0.5
microns or more, with thicker coatings providing darker colors. A
thin metal adhesion layer comprising, for example, zirconium may
optionally be deposited prior to the carbon. The part is then
removed from the vacuum system and placed in a solvent bath with
ultrasonic agitation. The masking layer is dissolved by the solvent
and the portion of the DLC layer deposited on top of the
unscratched areas of the masking layer is also removed. The DLC
deposited on the exposed portions of the substrate surface through
the scratches in the masking layer remains in place on the
substrate surface, forming a decorative gray or black accent
pattern reproducing the scratch pattern in the masking layer. Those
of skill in the art will appreciate that similar patterns may be
obtained using other dark-colored materials such as the
oxy-carbides and oxy-carbo-nitrides of zirconium.
EXAMPLE 4
[0070] According to another theoretical example, an
injection-molded plastic automotive trim part is first base-coated
with a polymer layer by a known process in order to provide a
level, glossy substrate surface. The part is mounted in a vacuum
chamber, and coated with a layer of dark-grey or black diamond-like
carbon by a hot-filament or ion-beam PECVD process. The part is
then coated with a layer of zirconium-titanium nitride using a
cathodic arc evaporation process. The part is removed from the
vacuum chamber, and a permanent ink masking material is applied to
the part through a patterned silk-screen, thus creating a
non-continuous masking layer having a selected pattern such as a
corporate logo, digitized image, or other decorative or
informational pattern. The part is then immersed in a dilute
ammonium bifluoride solution until the zirconium-titanium nitride
is removed in the areas unprotected by the masking layer, leaving
behind durable, bright gold-colored features having a visible
pattern on a dark gray or black background.
EXAMPLE 5
[0071] According to another theoretical example, a stainless steel
spoon is polished and cleaned by known methods, mounted in a vacuum
chamber, and coated by PECVD with a base-color layer of gray or
black DLC having a thickness preferably at least about 0.3 micron
to 1 micron. A thin metal adhesion layer comprising, for example,
zirconium may optionally be deposited prior to the carbon. A layer
of zirconium nitride is then deposited on top of the carbon layer
by cathodic arc evaporation. The part is removed from the vacuum
chamber, and a waterproof-ink masking layer is applied to the part.
The part is tumbled in a barrel with plastic tumbling media until
part, but not all, of the masking layer is removed. The part is
then immersed in a dilute ammonium bifluoride solution until the
zirconium nitride is removed in the areas not covered by the
masking layer. If the masked areas are relatively large compared to
the unmasked areas, a spoon having a patterned, decorative "brass
on black" appearance may be thereby for example produced. If the
masked areas are relatively small compared to the unmasked areas, a
spoon having a patterned, decorative "black antique" finish on
brass, for example, may thereby be produced.
EXAMPLE 6
[0072] According to another theoretical example, a brass doorknob
is electroplated with known materials, comprising for example a
nickel-tin alloy. The part is mounted in a vacuum chamber and
coated with a layer of zirconium nitride by cathodic arc
evaporation. The part is then coated by sputtering with a layer of
aluminum. The part is removed from the vacuum chamber and a masking
layer of permanent ink is applied and subsequently patterned in a
tumbling process as described above. The portion of the aluminum
coating which is exposed through the penetrations in the masking
layer is then black-anodized by a known electrochemical process.
The masking layer is removed with a solvent, and the un-anodized
portions of the aluminum layer are removed with an alkaline etching
agent, such as NaOH, that does not damage the underlying
zirconium-based layer. A durable decorative "black antique" finish,
for example, may thereby be produced.
EXAMPLE 7
[0073] According to a working example, a brass towel ring was
electroplated with a satin-textured nickel and chromium plating
stack having a chromium-colored surface. A coating layer including
a black colored oxy-carbide of zirconium was deposited on the part
using cathodic arc evaporation in a vacuum chamber at
sub-atmospheric pressure at a thickness of 0.4 microns. A layer of
copper was then applied using magnetron sputtering to a thickness
of 0.25 microns. The part was subjected to a vibratory mass
finishing operation using plastic media to partially remove the
copper, exposing a portion of the underlying zirconium oxy-carbide
layer. A final coating layer of a brass colored carbo-nitride of
zirconium was afterwards applied to a thickness of 0.15 microns,
also using cathodic arc evaporation. The copper lift-off layer was
then etched in a dilute solution of hydrogen peroxide and sulfuric
acid. Finally, the part was placed in an ultrasonic water bath to
remove the loosely adhered top zirconium carbo-nitride material
that was directly on top of the copper. The top zirconium
carbo-nitride layer in the areas where the copper was removed by
vibratory finishing remained intact, providing a visibly-patterned
"weathered brass" surface appearance.
EXAMPLE 8
[0074] According to another working example, a zinc faucet handle
base was electroplated with a copper, nickel and chromium plating
stack having a chromium-colored surface. A coating layer including
a gold-colored layer of zirconium nitride was deposited to a
thickness of 0.5 microns on the part using cathodic arc evaporation
in a vacuum chamber at sub-atmospheric pressure. Without venting
the vacuum chamber, a second coating layer of chromium was
afterwards applied, using magnetron sputtering, to a thickness of
0.2 microns. Finally, still without venting, a dark layer of
zirconium carbo-nitride was applied using cathodic arc evaporation
to a thickness of 0.5 microns. An etch-mask layer of a water
resistant permanent ink was applied to the part. The part was
subjected to a tumbling or vibratory mass finishing operation using
plastic media to partially remove the ink. The part was then etched
in a dilute solution of ammonium bifluoride to remove the portion
of the top dark coating layer that is exposed in the areas where
the masking layer has been removed. This first etch was impeded at
the chromium "etch-stop" layer. Subsequently, the part was dipped
in a solution of 5% sodium hydroxide where the exposed chromium
underwent anodic etching by holding the part at +8.0 volts relative
to a flat stainless steel electrode in the same bath. This final
etching step selectively etched the chromium; visually exposing in
areas the gold-colored zirconium nitride under-layer. Finally, the
part was rinsed in acetone to remove the ink. The top dark coating
layer in the areas protected by the ink remained intact, providing
a visibly-patterned "aged pewter" surface appearance.
[0075] It is important to note that the articles and methods shown
and described with respect to the various exemplary embodiments are
illustrative only. Although only a few embodiments have been
described in detail in this disclosure, those skilled in the art
who review this document will readily appreciate that many
modifications are possible (e.g., variations in sizes, dimensions,
structures, shapes and proportions of the various elements, values
of parameters, mounting arrangements, use of materials, colors,
orientations, etc.) without materially departing from the novel
teachings and advantages of the subject matter recited in the
claims. Accordingly, all such modifications are intended to be
included within the scope of the present invention as defined in
the appended claims. The order or sequence of any process or method
steps may be varied or re-sequenced according to other exemplary
embodiments. Other substitutions, modifications, changes and
omissions may be made in the design, operating conditions and
arrangement of the preferred and other exemplary embodiments
without departing from the scope of the present inventions as
expressed in the appended claims.
* * * * *