U.S. patent application number 11/198361 was filed with the patent office on 2005-12-08 for platinum surface coating and method for manufacturing the same.
Invention is credited to Zhou, Dao Min.
Application Number | 20050271895 11/198361 |
Document ID | / |
Family ID | 28794136 |
Filed Date | 2005-12-08 |
United States Patent
Application |
20050271895 |
Kind Code |
A1 |
Zhou, Dao Min |
December 8, 2005 |
Platinum surface coating and method for manufacturing the same
Abstract
An improved platinum surface coating and method for
manufacturing the improved platinum surface coating wherein the
platinum surface coating having a fractal surface coating of
platinum ["platinum gray"] with a increase in surface area of at
least 5 times when compared to shiny platinum of the same geometry
and also having improved resistance to physical stress when
compared to platinum black having the same surface area. The
process of electroplating the surface coating of platinum gray
comprising plating at a moderate rate, i.e., at a rate that is
faster than the rate necessary to produce shiny platinum and that
is less than the rate necessary to produce platinum black.
Inventors: |
Zhou, Dao Min; (Saugus,
CA) |
Correspondence
Address: |
Second Sight Medical Products, Inc.
12744 San Fernando Road Building3
Sylmar
CA
91342
US
|
Family ID: |
28794136 |
Appl. No.: |
11/198361 |
Filed: |
August 4, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11198361 |
Aug 4, 2005 |
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10226976 |
Aug 23, 2002 |
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60372062 |
Apr 11, 2002 |
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Current U.S.
Class: |
428/670 ;
205/112 |
Current CPC
Class: |
A61N 1/0543 20130101;
Y10T 428/12993 20150115; C25D 3/50 20130101; Y10T 428/12875
20150115; Y10S 428/935 20130101 |
Class at
Publication: |
428/670 ;
205/112 |
International
Class: |
B32B 015/00; C25D
005/00 |
Goverment Interests
[0002] This invention was made with government support under grant
No. R24EY12893-01, awarded by the National Institutes of Health.
The Government has certain rights in the invention.
Claims
What we claim is:
1. A platinum surface coating, comprising: a conductive substrate;
and a surface coating of platinum having a fractal
configuration.
2. The platinum surface coating of claim 1 wherein said surface
coating has at least 5 times the surface area of that for the
corresponding surface area resulting from the basic geometric
shape.
3. The platinum surface coating of claim 1 wherein said surface
coating has a surface area of less than 500 times the corresponding
surface area resulting from the basic geometric shape.
4. The platinum surface coating of claim 1 wherein said surface
coating has a surface area of less than 200 times the corresponding
surface are resulting from the basic geometric shape.
5. The platinum surface coating of claim 1 wherein said surface
coating has a thickness of at least 0.5 microns.
6. The platinum surface coating of claim 1 wherein said surface
coating has a thickness of at least 5 microns.
7. The platinum surface coating of claim 1 wherein said surface
coating has a thickness of at least 10 microns.
8. The platinum surface coating of claim 1 wherein said surface
coating has a thickness of at least 30 microns.
9. The platinum surface coating of claim 1 wherein said surface
coating has an adhesive strength as measured by critical load
greater than 35 millinewtons.
10. The platinum surface coating of claim 1 wherein said surface
coating appears gray in color.
11. The platinum surface coating of claim 1 wherein said surface
coating has a lightness (l*) greater than 30 on the CIELAB color
scale.
12. The platinum surface coating of claim 1 wherein said surface
coating has a color density (D) greater than 0.25 D but less than
1.3 D.
13. The platinum surface coating of claim 1 wherein said surface
coating of platinum comprises alloys of platinum and iridium or
rhodium.
14. The platinum surface coating of claim 1 wherein said surface
coating of platinum comprises alloys of platinum and gold,
tantalum, titanium or niobium.
15. The platinum surface coating of claim 1 wherein said conductive
substrate is platinum, platinum alloy, iridium, iridium oxide or
rhodium.
16. The platinum surface coating of claim 1 wherein said conductive
substrate is gold, tantalum, titanium, titanium nitride or
niobium.
17. A method for electroplating a platinum surface coating having a
rough surface, comprising: electroplating the surface of a
conductive substrate at a rate such that the particles of platinum
form on the conductive substrate faster than necessary to form
shiny platinum and slower than necessary to form platinum
black.
18. The method of claim 17 wherein at least a portion of said rough
surface coating has fractal geometry.
19. The method of claim 17 wherein said step of electroplating is
accomplished at a rate of more than 0.05 microns per minute, but
less than 1 micron per minute.
20. The method of claim 17 wherein the electroplating process is
controlled by electrode voltage.
21. The method of claim 20 wherein the voltage is constant
voltage.
22. The method of claim 20 wherein the controlled voltage causes at
least a partially diffusion-limited plating reaction.
23. The method of claim 17 wherein the electroplating is
accomplished at a rate of more than 0.05 microns per minute, but
less than 1 micron per minute.
24. The method of claim 17 wherein the voltage of the
electroplating process is less than 0.2 Volts and greater than -1
Volts vs. Ag/AgCl Reference electrode.
25. The method of claim 17 wherein the voltage of the
electroplating process is less than -0.45 Volts and greater than
-0.85 Volts vs. Ag/AgCl Reference electrode.
26. The method of claim 17 wherein the electroplating solution is
at least 3 mM but less than 30 mM ammonium hexachloroplatinate in
about 0.4 M disodium hydrogen phosphate.
27. A platinum surface coating prepared by the method of claim 17.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of application Ser. No.:
10/226,976, filed Aug. 23, 2002, which claims the benefit of U.S.
Provisional Application No. 60/372,062, filed Apr. 11, 2002, the
disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The field of the invention relates to platinum surface
coating and electroplating processes for deposition of
platinum.
[0005] 2. Description of Related Art
[0006] Platinum has often been used as a material for electrodes in
corrosive environments such as the human body due to its superior
electrical characteristics, biocompatibility and stability.
Platinum has many desirable qualities for use as an electrode for
electrical stimulation of body tissue. Since platinum has a smooth
surface and its surface area is limited by the geometry of the
electrode, it is not efficient for transferring electrical charge.
The platinum with a smooth surface is hereinafter called "shiny
platinum".
[0007] Electrodes for stimulating body tissue by electrical
stimulation are known in great variety. For the utility of an
implantable stimulation or sensing electrode--especially one
intended for long-term use in a tissue stimulator with a
non-renewable energy source and that, therefore, must require
minimal energy--a high electrode capacitance and correspondingly
low electrical impedance is of great importance. Furthermore,
without sufficiently low impedance, a large voltage may cause
polarization of both the electrode and the tissue to which the
electrode is attached forming possibly harmful byproducts,
degrading the electrode and damaging the tissue.
[0008] Because the ability of an electrode to transfer current is
proportional to the surface area of the electrode and because small
electrodes are necessary to create a precise signal to stimulate a
single nerve or small group of nerves, many in the art have
attempted to improve the ability of an electrode to transfer charge
by increasing the surface area of the electrode without increasing
the size of the electrode.
[0009] One approach to increase the surface area of a platinum
electrode without increasing the electrode size and therefore to
improve the ability of the electrode to transfer charge is to
electroplate platinum rapidly such that the platinum molecules do
not have time to arrange into a smooth, shiny surface. The rapid
electroplating forms a platinum surface which is commonly known as
"platinum black". Platinum black has a porous and rough surface
which is less dense and less reflective than shiny platinum. U.S.
Pat. No. 4,240,878 to Carter describes a method of plating platinum
black on tantalum.
[0010] Platinum black is more porous and less dense than shiny
platinum. Platinum black has weak structural and physical strength
and is therefore not suitable for applications where the electrode
is subject to even minimal physical stresses. Platinum black also
requires additives such as lead to promote rapid plating. Lead,
however, is a neurotoxin and cannot be used in biological systems.
Finally, due to platinum black's weak structure, the plating
thickness is quite limited. Thick layers of platinum black simply
fall apart.
[0011] For the foregoing reasons there is a need for an improved
platinum surface coating and process for electroplating the surface
to obtain an increased surface area for a given geometry and at the
same time the coating is structurally strong enough to be used in
applications where the platinum surface coating is subject to
physical stresses.
BRIEF SUMMARY OF INVENTION
[0012] The present invention is directed in part to a platinum
surface coating having increased surface area for greater ability
to transfer charge and also having sufficient physical and
structural strength to withstand physical stress.
[0013] This and other aspects of the present invention which may
become obvious to those skilled in the art through the following
description of the invention are achieved by an improved platinum
surface coating and method for preparing the improved platinum
surface coating having a fractal surface coating of platinum,
hereinafter called "platinum gray". Platinum gray has an increase
in surface area of at least 5 times compared to shiny platinum of
the same geometry. Platinum gray has at the same time an improved
resistance to physical stress when compared to platinum black. The
gray color is not considered a feature of the invention. It is a
means of describing the invention. The process of electroplating
the surface coating of platinum gray comprising plating at a
moderate rate, i.e., at a rate that is faster than the rate
necessary to produce shiny platinum and that is less than the rate
necessary to produce platinum black.
BRIEF DESCRIPTION OF DRAWINGS
[0014] FIG. 1 shows a platinum gray surface magnified 2000
times.
[0015] FIG. 2 shows a shiny platinum surface magnified 2000
times.
[0016] FIG. 3 shows a platinum black surface magnified 2000
times.
[0017] FIG. 4 shows color density (D) values and lightness (l*)
values for several representative samples of platinum gray,
platinum black and shiny platinum.
[0018] FIG. 5 shows a three-electrode electroplating cell with a
magnetic stirrer.
[0019] FIG. 6 shows a three-electrode electroplating cell in an
ultrasonic tank.
[0020] FIG. 7 shows a three-electrode electroplating cell with a
gas dispersion tube.
[0021] FIG. 8 shows an electroplating system with constant voltage
control or constant current control.
[0022] FIG. 9 shows an electroplating system with pulsed current
control.
[0023] FIG. 10 shows an electroplating system with pulsed voltage
control.
[0024] FIG. 11 shows an electroplating system with scanned voltage
control.
[0025] FIG. 12 shows an electrode platinum silicone array having 16
electrodes.
[0026] FIG. 13 shows the electrode capacitance for both plated and
unplated electrodes of varying diameter.
[0027] FIG. 14 shows a representative linear voltage sweep of a
representative platinum electrode.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Referring to FIG. 1, an illustrative example of a platinum
gray surface coating for an electrode is shown having a fractal
surface with a surface area increase of greater than 5 times the
surface area for a shiny platinum surface of the same geometry,
shown in FIG. 2, and an increase in strength over a platinum black
surface, shown in FIG. 3. FIGS. 1, 2, and 3 are images produced on
a Scanning Electron Microscope (SEM) at 2000.times. magnifications
taken by a JEOL JSM5910 microscope (Tokyo, Japan). Under this
magnification level it is observed that platinum gray is of a
fractal configuration having a cauliflower shape with particle
sizes ranging from 0.5 to 15 microns. Each branch of such structure
is further covered by smaller and smaller particles of similar
shape. The smallest particles on the surface layer may be in the
nanometer range. This rough and porous fractal structure increases
the electrochemically active surface area of the platinum surface
when compared to an electrode with a smooth platinum surface having
the same geometric shape.
[0029] The surface is pure platinum because no impurities or other
additives such as lead need to be introduced during the plating
process to produce platinum gray. This is especially advantages in
the field of implantable electrodes because lead is neurotoxin and
cannot be used in the process of preparing implantable electrodes.
Alternatively, other materials such as iridium, rhodium, gold,
tantalum, titanium or niobium could be introduced during the
plating process if so desired but these materials are not necessary
to the formation of platinum gray.
[0030] Platinum gray can also be distinguished from platinum black
and shiny platinum by measuring the color of the material on a
spectrodensitometer using the Commission on Illumination l*a*b*
color scale. l* defines lightness, a* denotes the red/green value
and b*, the yellow/blue value. The lightness value (called l*
Value) can range from 0 to 100, where white is 100 and black is
0--similar to grayscale. The a* value can range from +60 for red
and -60 for green, and the b* value can range from +60 for yellow
and -60 for blue. All samples measured have very small a* and b*
values (they are colorless or in the so called neutral gray zone),
which suggests that the lightness value can be used as grayscale
for Platinum coatings.
[0031] Referring to FIG. 4, the l*, a*, and b* values for
representative samples of platinum gray, platinum black and shiny
platinum are shown as measured on a color reflection
spectrodensimeter, X-Rite 520. Platinum gray's l* value ranges from
25 to 90, while platinum black and shiny platinum both have l*
values less than 25.
[0032] Referring to FIG. 4, color densities have also been measured
for representative samples of platinum gray, platinum black and
shiny platinum. Platinum gray's color density values range from 0.4
D to 1.3 D; while platinum black and shiny platinum both have color
density values greater than 1.3 D.
[0033] Platinum gray can also be distinguished from platinum black
based on the adhesive and strength properties of the thin film
coating of the materials. Adhesion properties of thin film coatings
of platinum gray and platinum black on 500 microns in diameter
electrodes have been measured on a Micro-Scratch Tester (CSEM
Instruments, Switzerland). A controlled micro-scratch is generated
by drawing a spherical diamond tip of radius 10 microns across the
coating surface under a progressive load from 1 millinewton to 100
millinewtons with a 400 micron scratch length. At a critical load
the coating will start to fail. Using this test it is found that
platinum gray can have a critical load of over 60 millinewtons
while platinum black has a critical load of less than 35
millinewtons.
[0034] Referring to FIGS. 5, 6, 7 and 8, a method to produce
platinum gray according to the present invention is described
comprising connecting a platinum electrode 2, the anode, and a
conductive substrate to be plated 4, the cathode, to a power source
6 with a means of controlling and monitoring 8 either the current
or voltage of the power source 6. The anode 2, cathode 4, a
reference electrode 10 for use as a reference in controlling the
power source 6 and an electroplating solution are placed in a
electroplating cell 12 having a means 14 for mixing or agitating
the electroplating solution. Power is supplied to the electrodes
with constant voltage, constant current, pulsed voltage, scanned
voltage or pulsed current to drive the electroplating process. The
power source 6 is modified such that the rate of deposition will
cause the platinum to deposit as platinum gray, the rate being
greater than the deposition rate necessary to form shiny platinum
and less than the deposition rate necessary to form platinum
black.
[0035] Referring to FIGS. 5, 6 and 7, the electroplating cell 12,
is preferably a 50 ml to 150 ml four neck glass flask or beaker,
the common electrode 2, or anode, is preferably a large surface
area platinum wire or platinum sheet, the reference electrode 10 is
preferably a Ag/AgCl electrode (silver, silver chloride electrode),
the conductive substrate to be plated 4, or cathode, can be any
suitable material depending on the application and can be readily
chosen by one skilled in the art. Preferable examples of the
conductive substrate to be plated 4 include but are not limited to
platinum, iridium, rhodium, gold, tantalum, titanium or
niobium.
[0036] The stirring mechanism is preferably a magnetic stirrer 14
as shown in FIG. 5, an ultrasonic tank 16 (such as the VWR
Aquasonic 50D) as shown in FIG. 6, or gas dispersion 18 with Argon
or Nitrogen gas as shown in FIG. 7. The plating solution is
preferably 3 to 30 mM (milimole) ammonium hexachloroplatinate in
disodium hydrogen phosphate, but may be derived from any
chloroplatinic acid or bromoplatinic acid or other electroplating
solution. The preferable plating temperature is approximately 24 to
26.degree. C.
[0037] Electroplating systems with pulsed current and pulsed
voltage control are shown in FIGS. 9 and 10 respectively. While
constant voltage, constant current, pulsed voltage or pulsed
current can be used to control the electroplating process, constant
voltage control of the plating process has been found to be most
preferable. The most preferable voltage range to produce platinum
gray has been found to be -0.45 Volts to -0.85 Volts. Applying
voltage in this range with the above solution yields a plating rate
in the range of about 1 micron per minute to 0.05 microns per
minute, the preferred range for the plating rate of platinum gray.
Constant voltage control also allows an array of electrodes in
parallel to be plated simultaneously achieving a fairly uniform
surface layer thickness for each electrode.
[0038] The optimal potential ranges for platinum gray plating are
solution and condition dependent. Linear voltage sweep can be used
to determine the optimal potential ranges for a specific plating
system. A representative linear voltage sweep is shown in FIG. 14.
During linear voltage sweep, the voltage of an electrode is scanned
cathodically until hydrogen gas evolution occurs which reveals
plating rate control steps of electron transfer 20 and diffusion
22. For a given plating system, it is preferable to adjust the
electrode potential such that the platinum reduction reaction has a
limiting current under diffusion control or mixed control 24
between diffusion and electron transfer but that does not result in
hydrogen evolution 26.
[0039] It has been found that because of the physical strength of
platinum gray, surface layers of thickness greater than 30 microns
can be plated. It is very difficult to plate shiny platinum in
layers greater than approximately several microns because the
internal stress of the dense platinum layer which will cause the
plated layer to peel off and the underlying layers cannot support
the above material. The additional thickness of the plate's surface
layer allows the electrode to have a much longer usable life.
[0040] The following example is illustrative of electroplating
platinum on a conductive substrate to form a surface coating of
platinum gray.
[0041] Electrodes with a surface layer of platinum gray are
prepared in the following manner using constant voltage plating. An
electrode platinum silicone array having 16 electrodes where the
diameter of the platinum discs on the array range from 510 to 530
microns, as shown in FIG. 12, is first cleaned electrochemically in
sulfuric acid and the starting electrode impedance is measured in
phosphate buffered saline solution. Referring to FIG. 5, the
electrodes are arranged in the electroplating cell such that the
plating electrode 2 is in parallel with the common electrode 4. The
reference electrode 10 is positioned next to the electrode 4. The
plating solution is added to the electroplating cell 12 and the
stirring mechanism 14 is activated.
[0042] A constant voltage is applied on the plating electrode 2 as
compared to the reference electrode 10 using an EG&G PAR M273
potentiostat 6. The response current of the plating electrode 2 is
recorded by a recording means 8. (The response current is measured
by the M273 potentiostat 6.) After a specified time, preferably
1-90 minutes, and most preferably 30 minutes, the voltage is
terminated and the electrode 4 is thoroughly rinsed in deionized
water.
[0043] The electrochemical impedance of the electrode array with
the surface coating of platinum gray is measured in a saline
solution. The charge/charge density and average plating
current/current density are calculated by integrating the area
under the plating current vs. time curve. Scanning Electron
Microscope (SEM)/Energy Dispersed Analysis by X-ray (EDAX.TM.)
analysis can be performed on selected electrodes. SEM Micrographs
of the plated surface can be taken showing its fractal surface.
Energy Dispersed Analysis demonstrates that the sample is pure
platinum rather than platinum oxide or some other materials.
[0044] From this example it is observed that the voltage range is
most determinative of the formation of the fractal surface of
platinum gray. For this system it observed that the optimal voltage
drop across the electrodes to produce platinum gray is
approximately -0.55 to -0.65 Volts vs. Ag/AgCl reference electrode
10. The optimal platinum concentration for the plating solution is
observed to be approximately 8 to 18 mM ammonium
hexachloroplatinate in 0.4 M (Mole) disodium hydrogen
phosphate.
[0045] FIG. 12 provides a perspective view of a retinal electrode
array for use with the present invention, generally designated 32,
comprising oval-shaped electrode array body 34, a plurality of
electrodes 36 made of a conductive material, such as platinum or
one of its alloys, but that can be made of any conductive
biocompatible material such as iridium, iridium oxide or titanium
nitride, and a single reference electrode 38 made of the same
material as electrode 36, wherein the electrodes are individually
attached to separate conductors 40 made of a conductive material,
such as platinum or one of its alloys, but which could be made of
any biocompatible conductive material, that is enveloped within an
insulating sheath 42, that is preferably silicone, that carries an
electrical signal to each of the electrodes 36.
[0046] A strain relief internal tab 44, defined by a strain relief
slot 46 that passes through the array body 34, contains a mounting
aperture 48 for fixation of the electrode array body 34 to the
retina of the eye or other neural interface by use of a surgical
tack. A reinforcing ring 50 is colored and opaque to facilitate
locating the mounting aperture 48 during surgery. A grasping handle
52 is located on the surface of electrode array body 34 to enable
its placement by a surgeon using forceps or by placing a surgical
tool into the hole formed by grasping handle 52. Grasping handle 52
avoids damage to the electrode body that might be caused by the
surgeon grasping the electrode body directly. The electrode array
32 is described in greater detail in U.S. patent application No.
2002/0111658 A1 filed Feb. 13, 2001 and entitled Implantable
Retinal Electrode Array Configuration for Minimal Retinal Damage
and Method of Reducing Retinal Stress, which is incorporated herein
by reference.
[0047] FIG. 13 shows the increase in electrode capacitance of
several electrodes of varying diameter for a polyimide array plated
according to the above example at -0.6 V vs. Ag/AgCl Reference
electrode for 30 minutes compared with unplated electrodes of the
same diameters. Because the electrode capacitance is proportional
to its surface area, the surface area increase, calculated from
electrode capacitance, is 60 to 100 times that of shiny platinum
for this array. It should be noted that shiny platinum exhibits
some roughness and has a surface area increase up to 3 times that
of the basic geometric shape. While it is simple to measure a
surface area change between two sample using capacitance, it is
difficult to compare a sample with the basic geometric shape.
[0048] As plating conditions, including but not limited to the
plating solution, surface area of the electrodes, pH, platinum
concentration and the presence of additives, are changed the
optimal controlling voltage and/or other controlling parameters
will also change according basic electroplating principles.
Platinum gray will still be formed so long as the rate of
deposition of the platinum particles is slower than that for the
formation of platinum black and faster than that for the formation
of shiny platinum.
[0049] While the invention is described in terms of a specific
embodiment, other embodiments could readily be adapted by one
skilled in the art. Accordingly, the scope of the invention is
limited only by the following claims.
* * * * *