# Patent

## Title
Process for cathodic protection of electrode materials

## Abstract

The present invention relates to a process for cathodic protection of electrode or electrode materials wherein negative bias is applied on the electrode. the negative bias is obtained by asymmetric current pulse. The asymmetric current pulse is obtained by performing negative phase with higher amplitude. The asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase. The asymmetric current pulse is obtained by performing negative phase with higher amplitude and with wider pulse width than that of the anodic phase. The present invention further relates to a process for cathodic protection of electrode or electrode materials, wherein negative bias is applied on the electrode, wherein the negative bias is obtained by asymmetric current pulse, wherein the asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase. The wider pulse width is obtained by pulse trains.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 11/881,254, entitled “Process for Cathodic Protection of Electrode Materials”, filed Jul. 26, 2007, which application claims the benefit of provisional Application No. 60/833,330, filed Jul. 26, 2006 and the benefit of provisional Application No. 60/833,386, filed Jul. 26, 2006, the disclosure of all of which is hereby incorporated by reference.


FEDERALLY SPONSORED RESEARCH
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.


FIELD OF THE INVENTION
The field of the invention relates to cathodic protection for electrode materials prone to corrosion including oxidation and anodic dissolution.
DESCRIPTION OF RELATED ART
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”.
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.
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.
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.
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.
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.
Titanium nitride (TiN) coating has been widely used as biomaterials for orthopedic prostheses, cardiac valves and as electrode materials for sensing and charge-injecting electrodes [1,2]. Titanium Nitride (TiN) offers several advantages including higher surface area providing by its columnar structure and capacitive charge-injection process. However, it was found that TiN can be passivited at a higher anodic voltage. The reaction of electrochemically passivation of TiN surface is irreversible. The resulting surface is less conductive. EDX results confirm that passivited TiN surface is oxygen rich. See M. Janders, U. Egert, M. Stelzle, and W. Nisch, “Novel thin film titanium nitride micro-electrodes with excellent charge transfer capability for cell stimulation and sensing applications,” 18th Annual international Conference of the IEEE Engineering in medicine and biology society, Amsterdam, pp. 245-247, 1996. M. Schaldach, M. Hubmann, A. Weikl, and R. Hardt, “Sputter-deposited TiN electrode coatings for superior sensing and pacing performance”, Pace, vol. 3, pp. 1891-1895, 1990. S. Logothetidis, E. I. Meletis, G. Stergioudis, and A. A. Adjattor, “Room temperature oxidation behavior of TiN thin films,” Thin Solid films, Vol. 336, pp 304-313, 1999. D. Zhou and R. Greenberg, “Tantalum capacitive microelectrode array for a neural prosthesis” in Chemical and Biological Sensors and Analytical methods II., (eds., Butler. M., Vanysek. P and Yamazoe. N., pp. 622-629, 2001.
BRIEF SUMMARY OF INVENTION
The present invention is directed cathodic protection for electrode materials prone to corrosion including oxidation and anodic dissolution. Metal electrode materials including noble metal, such as Pt will suffer from metal oxidation and dissolution during stimulation even by a charge balanced waveform within water window potentials. The metal dissolution not only causes the damage of electrodes, but also affects the biological tissue surfaces. This limits the lifetime of the medical implants for chronic applications.
Application of negative bias on stimulation electrodes, to prevent the anodic voltage excursion exceed +1.3V. The negative bias can be created by an asymmetric current pulse (negative phase has a higher amplitude and/or wider pulse width than that of anodic phase) or a negative DC bias. To avoid pH increase due to water reduction, the negative bias should be limited to keep the voltage excursion within the water window. Alternatively, TiN can be used for monophasic pulse as a cathode only. This method is also useful for other electrode materials, including Ti, TiN, Nb, Rh, Ir, Au and W.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a typical cyclic voltammogram of a TiN electrode.
FIG. 2 shows a linear polarization curve of a TiN electrode at a potential scan rate of 5 mV/sec.
FIG. 3 shows bode plots of a TiN electrode passivited with various anodic voltages. EIS were measured at AC 10 mV with no DC bias.
FIG. 4 shows an optical microscopic image shows darker TiN surface after anodically biased at a voltage above +1.5V.
FIG. 5 shows SEM micrograph (5a) a partially (at edge) delaminated and (5b) totally damaged TiN surfaces.
FIG. 6 shows a corroded Pt electrode surface (FIG. 6a) due to both Pt dissolution and Pt oxidation pulsed by a charge balanced waveform in comparison to a control surface (FIG. 6b).
FIG. 7 shows a comparison of Voltage excursions for various unbalanced pulse waveforms.
FIG. 8 shows an excursion change after 6 hour pulse stimulation for a +5% biased pulse.
FIG. 9 shows a voltage excursion changes after unbalanced pulse (+0.4%) stimulation for 6 hours.
FIG. 10 shows a voltage excursion change after −5% negatively biased waveform pulse stimulation for 6 hours.
FIGS. 11A and 11B show two typical surface images after 6 hour positively biased (+5%) waveform pulse stimulation.
FIGS. 12A and 12B show two typical electrode surfaces after 6 hour +0.4% biased waveform pulse stimulation.
FIGS. 13A and 13B show two typical electrode surfaces after 6 hour −5% biased waveform pulse stimulation.
FIG. 14 shows an Edx spectrum for an electrode surface pulsed by a +5% biased waveform (FIG. 14A). Oxygen peak is detected, indicated Pt surface oxidation after pulsing (FIG. 14B).



DETAILED DESCRIPTION OF THE INVENTION
Metal electrode materials including noble metal, such as Pt will suffer from metal oxidation and dissolution during stimulation even by a charge balanced waveform within water window potentials. The metal dissolution not only causes the damage of electrodes, but also affects the biological tissue surfaces. This limits the lifetime of the medical implants for chronic applications.
Apply a negative bias on the stimulation electrodes, to prevent the anodic voltage excursion exceed +1.3V. This negative bias can be created by an asymmetric current pulse (negative phase has a higher amplitude and/or wider pulse width than that of anodic phase) or a negative DC bias. To avoid pH increase due to water reduction, the negative bias should be limited to keep the voltage excursion within the water window. Alternatively, TiN can be used for monophasic pulse as a cathode only. This method is also useful for other electrode materials, like Ti, TiN, Nb, Rh, Ir, Au and W.
The tests results show that TiN prone to oxidation and it will limit its usage for long term stimulation application.
FIG. 1 shows a typical cyclic voltammogram of a TiN electrode. FIG. 1 shows more specifically Cyclic voltammograms of a TiN electrode at a potential scan rate of 100 mV/sec.
No visible oxidation/reduction peaks occur within the water window of +/−1V. This suggests that if pulsed within water window, charge injection of TiN is through non-faradaic processes, i.e. mainly via a capacitive mechanism. At the voltage higher than −1V, the sharp increase in cathodic current is due to the hydrogen evaluation. At the voltage higher than +1V, the anodic current decreases with continuous potential scan. There is no gas evolution observed. This indicates that the TiN surface is passivited at the potential higher than +1V, instead of oxygen evolution reaction. Multiple CV measurements repeated on same TiN samples show that the reduced anodic current can't be recovered and this suggests that the passivation reaction is irreversible.
Linear polarization curves were measured to confirm TiN passivation observed in CV measurements and determine passivation potential at anodic voltage range as shown in FIG. 2. FIG. 2 shows more specifically linear polarization curve of a TiN electrode at a potential scan rate of 5 mV/sec.
The cathodic curve was scanned from open circuit potential to −2V while anodic curve was scanned from open circuit potential to +14V at a slow scan rate of 5 mV/sec. The predominate passivation peak at anodic scan phase was observed for all the TiN electrodes measured. It was found that the passivation starts from about +1.3 V which is in agreement with the results from CV measurements. At the voltage higher than +3 V, the TiN is totally passivited.
EIS measurements were conducted at open circuit potential with a 10 mV AC excitation potential. The frequency was scanned from 100 kHz to 1 Hz. The impedance changes with passivation voltage are shown in FIG. 3. FIG. 3 shows more specifically bode plots of a TiN electrode passivited with various anodic voltages. EIS were measured at AC 10 mV with no DC bias.
The electrode impedance increased dramatically while the passivation voltage increased from 2 V to 14V. The electrode impedance at 1000 Hz is increased from initially 20 kohm to 1800 kohm at +14V. EIS measurements also confirmed that the passivited TiN can not been reduced by applied a cathodic voltage or cathodic current pulse.
The passivited TiN surface has a darker brown color in comparison to its control surface, as shown in FIG. 4. This darken surface appears brittle and has a poor adhesion to Si substrate. FIG. 4 shows more specifically an optical microscopic image shows darker TiN surface after anodically biased at a voltage above +1.5V.
EDX examinations were carried out to compare surface elements changes before and after TiN passivation. For the TiN surface before passivation, a roughly TiN ratio of 1:1 is detected. However, after passivation, increased oxygen concentration was detected. The higher the passivation voltage, the higher the oxygen concentration on TiN surface. This suggested that passivation will result in the replacement of nitrogen by oxygen, i.e. oxidation of TiN to TiOx. For some TiN surface anodically biased to higher than +5V, a Ti:O ratio of 1:2 was detected, indicates a formation of TiO2. The oxidation of TiN maybe due to its void boundaries of columnar structure for an easy oxygen diffusion or overstoichiometry of TiN with loosely bound nitrogen to titanium are prone to be oxidized.
Gentle gassing of the TiN electrode surface generated by cathodic voltage bias did not damage electrode in terms of Qinj and adhesion. However, if the surface is passivited, Qinj is lost and gassing generated on the electrode surface will damage TiN coating. FIGS. 5(a) and (b) show a slightly damaged and a total damaged TiN surface due to gassing on the passivited surfaces. FIGS. 5 (a) and 5 (b) more specifically SEM micrographs show (a) a partially at edge delaminated and (b) damaged TiN surfaces.
Metal electrode materials including noble metal, such as Pt will suffer from metal oxidation and dissolution during stimulation even by a charge balanced waveform within water window potentials. The metal dissolution not only causes the damage of electrodes, but also affects the biological tissue surfaces. This limits the lifetime of the medical implants for chronic applications.
FIG. 6 shows a corroded Pt electrode surface (FIG. 6a) due to both Pt dissolution and Pt oxidation pulsed by a charge balanced waveform in comparison to a control surface (FIG. 6b).
Metal oxidation and dissolution are anodic electrochemical reactions. During pulse stimulation, metal dissolution occurs at the anodic phase when the electrode voltage is positive against the return electrode. The positive voltage remains on the electrode after the anodic pulse completed and decades as the built-up charge disperses. Using cathodic first charge balanced waveform will pull the electrode voltage towards negative direction, the metal oxidation and dissolution will be naturally reduced. More effectively, by applying a negative bias on the electrode, the metal dissolution can be minimized or prevented depending on the degree of the biases. The negative bias will keep the anodic voltage as low as possible or the period of anodic voltage to which electrode subjected as short as possible. To avoid pH increase due to water reduction, the negative bias should be limited to keep the voltage excursion within the water window.
The negative bias is created by a charge unbalanced waveform or by a dc current. One example of such waveform is the one with larger negative current amplitude than that of the anodic current for the pulses with same pulse width. The other example is that a wider negative pulse than that of the anodic pulse with same current amplitudes. The third example is the combination of above examples: a wider and a larger negative pulse than that of anodic pulse. This method is also useful for other electrode materials, like Ti, TiN, Nb, Rh, Ir, Au and W.
The tests results (see Table 1 and FIGS. 7-14) show that positive biased pulses cause severe corrosion of the Pt electrode while the negatively biased pulse protected the electrode surface. The corrosion of Pt electrodes is measured as the metal dissolution and metal oxidation.
FIG. 7 shows a comparison of Voltage excursions for various unbalanced pulse waveforms. Negatively biased waveform causes the electrode voltage shifted towards negative direction and provide a cathodic protection for Pt dissolution and oxidation.
FIG. 8 shows Voltage excursion changes after 6 hour pulse stimulation for a +5% biased pulse. The electrode voltage increased after Pt surface oxidation. Pt oxide is less conductive than that Pt.
FIG. 9 shows Voltage excursion changes after unbalanced pulse (+0.4%) stimulation for 6 hours. The voltage increase is due to Pt surface oxidation.
FIG. 10 shows Voltage excursion changes after −5% negatively biased waveform pulse stimulation for 6 hours. No significant voltage changes after stimulation indicates minimal surface changes.
FIG. 11 shows two typical surface images after 6 hour positively biased (+5%) waveform pulse stimulation.
FIG. 12 shows two typical electrode surfaces after 6 hour +0.4% biased waveform pulse stimulation.
FIG. 13 shows two typical electrode surfaces after 6 hour −5% biased waveform pulse stimulation. The electrode surface appears no change after 6 hour stimulation.
FIG. 14 shows Edx spectrum for an electrode surface pulsed by a +5% biased waveform (FIG. 14a). Oxygen peak is detected, indicated Pt surface oxidation after pulsing. (FIG. 14b) Edx spectrum for an electrode surface pulsed by a −5% biased waveform. No oxygen peak is detected, indicated negative biased waveform prevented Pt surface oxidation.
Table 1 bellows contains Edx, ICP-MS and EIS results for electrodes pulsed by various biased waveforms. All electrode has a 250 um diameter, polished Pt surface as electrode surface. The pulse has a 1 ms pulse width, 60 Hz and a charge density of 0.35 mC/cm2.











TABLE 1








Pt in





Oxygen
test




concentration
solution
Rs (ohm)


Electrode
Bias
form Edx
by ICP-MS
Ave ini


arrays
Condition
(atomic %)
(ppm)*
Rs = 1378 ohm



















#199
  +5%
67%
0.67
2840


200
  +5%

0.42
2899


203
+0.4%, no
67%
0.0071
4490



bias


204
+0.4%, no

0.0070
4215



bias


201
−0.5%
 0%
0.0008
1341


157
−0.5%

0.0010
1477





*ICP-MS detection limit: 0.00002 ppm. Measured in 10 ml solution, pulsed 6 hr with 5 250 um electrodes.






Table 2 shows the results of a Chip long-term stimulation, PtG-5B Chip long-term stimulation, 4 Groups/4 Arrays per Group/5 Electrodes per Array, Pulsed by 5B chip at 0.35 mC/cm^2, 1-1-1 ms, 60 Hz, shorting for 2 ms at 11 ms if any, 10 mM PBS at 37° C., large Pt common electrode, Pt grey on Thin-film/polyimide arrays, 200 um in diameter











TABLE 2





Array
Array ID
# of E
Days
Observations















Anodic Bias-no Shorting(150k Rb/+(3-5) % bias)











5.1
ABM27#7
5
570
5E Stopped on 11/09/05


5.2
ABL07 #8
5
>771
Increased Rs/Decreased Caps


5.3
ABN18 #6
5
>771
Increased Rs/Decreased Caps


5.4
ABN05 #7
5
>771
Increased Rs/Decreased Caps







Cathodic Bias-no Shorting(150k Rb/−(3-5) % bias)











8.1
ABL03 #7
5
>771
No Significant Change


8.2
ABN27 #6
5
>771


8.3
ABN17#5
5
>771


8.4
ABN02 #7
5
>771







Anodic Bias-Shorting(11-2 ms Sh/+(3-5) % bias)











9.1
ABL06 #5
5
>771
No Significant Change


9.2
ABM27#8
5
>771


9.3
ABN18 #5
5
>771


9.4
ABN05 #6
5
>771







Cathodic Bias-Shorting(11-2 ms Sh/−(3-5) % bias)











12.1
ABM 22 #6
5
>771
No Significant Change


12.2
ABL 06 #6
5
>771


12.3
ABN 10 #6
5
>771


12.4
ABL 20 #7
5
>771









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.

## Claims

1. A process for cathodic protection of electrode or electrode materials, wherein negative bias is applied on the electrode, wherein the negative bias is obtained by asymmetric current pulse, wherein the asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase.

2. The process according to claim 1 wherein first charged balanced waveform pulls the electrode voltage towards the negative direction.

3. The process according to claim 1 wherein the negative bias is obtained by asymmetric current pulse.

4. The process according to claim 3 wherein the asymmetric current pulse is obtained by performing negative phase with higher amplitude.

5. The process according to claim 4 wherein the negative phase has higher amplitude from 1-15%.

6. The process according to claim 4 wherein the negative phase has higher amplitude from 3-7%.

7. The process according to claim 4 wherein the negative phase has higher amplitude from 4-6%.

8. The process according to claim 3 wherein the asymmetric current pulse is obtained by performing negative phase with wider pulse width than that of the anodic phase.

9. The process according to claim 8 wherein the pulse width is wider by 1-15%.

10. The process according to claim 8 wherein the pulse width is wider by 3-7%.

11. The process according to claim 8 wherein the pulse width is wider by 4-6%.

12. The process according to claim 11 wherein the asymmetric current pulse is obtained by performing negative phase with higher amplitude by 1-15% and with wider pulse width by 1-15% than that of the anodic phase.

13. The process according to claim 1 wherein the asymmetric current pulse is obtained by performing negative phase with higher amplitude and with wider pulse width than that of the anodic phase.

14. The process according to claim 3 wherein the asymmetric current pulse is obtained by a negative DC bias.

15. The process according to claim 1 wherein the negative bias is limited to kept the voltage excursion within the water window.

16. The process according to claim 1 wherein electrode material comprising TiN is used for monophasic pulse as a cathode.

17. The process according to claim 1 wherein electrode materials comprising Pt, Pd, Ti, TiN, Nb, Rh, Ir, IrO2, Au, or W, or mixtures or oxides or alloys thereof are used for monophasic pulse as a cathode.

18. The process according to claim 16 wherein the wider pulse width is obtained by pulse trains.

19. The process according to claim 16 wherein each pulse train has a negative phase with higher amplitude and/or wider pulse width than that of the anodic phase.