Title of Invention

PROCESS FOR MAKING MICROPOROUS LAYER ASSEMBLY

Abstract One embodiment includes a process including coating a first microporous layer onto a first decal and curing the first microporous layer and the first decal.
Full Text MICROPOROUS LAYER ASSEMBLY AND METHOD OF MAKING THE
SAME
TECHNICAL FIELD
[0001] The field to which the disclosure generally relates includes fuel
cell layers including microporous layers and products including the same and
methods of making the same.
BACKGROUND
[0002] Hydrogen is a very attractive fuel because it is clean and can be
used to efficiently produce electricity in a fuel cell. The automotive industry
expends significant resources in the development of hydrogen fuel cells as a
source of power for vehicles. Such vehicles would be more efficient and
generate fewer emissions than today's vehicles employing internal
combustion engines.
[0003] A hydrogen fuel cell is an electro-chemical device that includes
an anode and a cathode with an electrolyte therebetween. The anode
receives hydrogen-rich gas or pure hydrogen and the cathode receives
oxygen or air. The hydrogen gas is oxidized in the anode to generate
protons and electrons. The protons pass through the electrolyte to the
cathode. The protons react with the oxygen and the electrons in the cathode
to generate water. The electrons from the anode cannot pass through the
electrolyte, and thus are directed through a load to perform work before being
sent to the cathode. The work may be used to operate a vehicle, for example.

[0004] Proton exchange membrane (PEM) fuel cells are popular for
vehicle applications. The PEM fuel cell generally includes a solid-polymer-
electrolyte proton-conducting membrane, such as a perfluorosulfonic acid
membrane. The anode and cathode typically include finely divided catalytic
particles, usually platinum (Pt), supported on carbon particles and mixed with
an ionomer. The catalytic mixture is deposited on opposing sides of the
membrane. The combination of the anode catalytic mixture, the cathode
catalytic mixture, and the membrane define a membrane electrode assembly
(MEA). MEAs are relatively expensive to manufacture and require certain
conditions for effective operation. These conditions include proper water
management and humidification, and control of catalyst poisoning
constituents, such as carbon monoxide (CO).
[0005] Several fuel cells are typically combined in a fuel cell stack to
generate the desired power. The fuel cell stack includes a series of flow field
or bipolar plates positioned between the MEAs in the stack. The bipolar
plates include an anode side and a cathode side for adjacent fuel cells in the
stack. The fuel cell stack receives an anode hydrogen reactant gas that flows
into the anode side of the stack Anode gas flow channels are provided on
the anode side of the bipolar plates that allow the anode gas to flow to the
anode side of the MEA. The fuel cell stack receives a cathode reactant gas,
typically a flow of air forced through the stack by a compressor. Cathode gas
flow channels are provided on the cathode side of the bipolar plates that allow
the cathode gas to flow to the cathode side of the MEA. Not all of the oxygen
is consumed by the stack and some of the air is output as a cathode exhaust
gas that may include liquid water as a stack by-product. The bipolar plates

may also include flow channels for a cooling fluid. An automotive fuel cell
stack, for example, may include about two hundred or more bipolar plates.
SUMMARY OF EXEMPLARY EMBODIMENTS OF THE INVENTION
[0006] One embodiment includes a process including coating a first
microporous layer onto a first decal and curing the first microporous layer and
the first decal.
[0007] Other exemplary embodiments of the invention will become
apparent from the detailed description provided hereinafter. It should be
understood that the detailed description and specific examples, while
disclosing exemplary embodiments of the invention, are intended for purposes
of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Exemplary embodiments of the present invention will become
more fully understood from the detailed description and the accompanying
drawings, wherein:
[0009] FIG. 1 illustrates a process according to one embodiment.
[0010] FIG. 2 illustrates a process according to one embodiment.
[0011] FIG. 3 illustrates a process according to one embodiment.
[0012] FIG. 4 illustrates a process according to one embodiment.
[0013] FIG. 5 illustrates a process according to one embodiment.
[0014] FIG. 6 illustrates a product according to one embodiment.
[0015] FIG. 7 illustrates a product according to one embodiment.
[0016] FIG. 8 illustrates a product according to one embodiment.

[0017] FIG. 9 is a graph of potential versus current density.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0018] The following description of the embodiment(s) is merely
exemplary in nature and is in no way intended to limit the invention, its
application, or uses.
[0019] In one embodiment, a method is provided for fabricating an MEA
25 having microporous layers. Referring to FIG. 1, a decal blank 26 is
provided. In one embodiment the decal blank 26 may be expanded
polytetrafluoroethylene (ePTFE), polytetrafluoroethylene (PTFE), or Kapton
polyimide film (poly(4,4'-oxydiphenylene-pyromellitimide)) (available from
Dupont). Then a first microporous layer 22 is coated onto the decal 26. In
one embodiment, the first microporous layer 22 may be coated by using a
microporous layer ink. In one embodiment, the first microporous layer 22 may
be coated by Meyer rod and then allowed to dry. Next the decal 26 with the
first microporous layer 22 may be placed in an oven and cured at a first
temperature. In one embodiment, the first temperature may be the glass
transition temperature (Tg) of a polymer in the microporous layer ink. In one
embodiment, the polymer in the microporous layer ink may be a
fluoropolymer. After a suitable curing time, for example about 15 minutes to
about 60 minutes, the decal 26 with the first microporous layer 22 may be
cooled to room temperature.
[0020] Referring to FIG. 2, a cathode electrode or cathode catalyst
layer 18 is then coated over the first microporous layer 22. The first
microporous layer 22 may adhere to the cathode catalyst layer 18. In one

embodiment, the catalyst layer 18 may be coated using a catalyst ink.
Referring to FIG. 3, a membrane 12 is then provided over the cathode catalyst
layer 18. In one embodiment, the membrane 12 may be a polymer electrolyte
membrane. The decal 26 with the first microporous layer 22 and the cathode
catalyst layer 18 is hot pressed to the membrane 12 such that the cathode
catalyst layer 18 is in contact with a first face 14 of the membrane 12. As
shown in FIG. 4, the decal 26 then may be peeled away if desired and the first
microporous layer 22 and the cathode catalyst layer 18 remain attached to the
membrane 12. Conditions of temperature, pressure, and time for hot pressing
known in the art may be used. For example, the hot pressing conditions may
include a pressing time of 4 minutes at 295°F and 250 psi.
[0021] The process just described may then be repeated with a second
decal blank 27, a second microporous layer 24, and an anode electrode or
anode catalyst layer 20. As shown in FIG. 5, the second microporous layer
24 and the anode catalyst layer 20 may be hot pressed to a second face 16 of
the membrane 12. Then the second decal 27 is peeled away. In another
embodiment, the decal 26 with the first microporous layer 22 and the cathode
electrode 18, and the decal 27 with the second microporous layer 24 and the
anode electrode 20, may be simultaneously hot pressed to opposite sides of
the membrane 12.
[0022] As shown in FIGS. 6-7, a cross-sectional view of the resulting
product 10 shows, starting from the bottom, the first microporous layer 22, the
cathode catalyst layer 18, the membrane 12, the anode catalyst layer 20, and
the second microporous layer 24. In one embodiment, the thickness of the
first and second microporous layers 22, 24 may be about 2 urn to about 100

µm. In another embodiment, the thickness of the first and second
microporous layers 22, 24 may be about 15 µm to about 40 µm. FIGS. 6-7
may be described as an MEA 25 with microporous layers 22, 24. Referring to
FIG. 6, in one embodiment the membrane 12 may extend past the
microporous layers 22, 24 and the catalyst layers 18, 20. Referring to FIG. 7,
in one embodiment the membrane 12 and the microporous layers 22, 24 may
extend past the catalyst layers 18, 20. In various embodiments, the
membrane 12 and the microporous layers 22, 24 may or may not have the
same active area. In various embodiments, the electrodes 18, 20 and the
microporous layers 22, 24 may or may not have the same active area.
[0023] Referring to FIG. 8, in one embodiment a first gas diffusion
media layer 52 may be positioned over the first microporous layer 22, and a
second gas diffusion media layer 54 may be positioned over the second
microporous layer 24. Referring still to FIG. 8, in one embodiment, the
product 10 may be a fuel cell 28 including the MEA 25 with microporous
layers 22, 24 adhered to the catalyst layers 18, 20, respectively, as described
above. The fuel cell 28 may include at least one bipolar plate 30. The bipolar
plate 30 may have a first face 32 and a second face 34. The bipolar plate 14
may include two sheets 36 and 38. The two sheets 38 and 38 may be
machined or stamped. The two sheets 36 and 38 may be welded together. A
reactant gas flow field comprising flow channels 40 and lands 42 is defined in
the first face 32. Cooling fluid flow channels 44 may be provided over the
second face 34.
[0024] Referring still to FIG. 8, in one embodiment of the invention the
fuel cell 28 may include two bipolar plates 30, a first fuel cell bipolar plate 46

and a second fuel cell bipolar plate 48. The bipolar plates 46, 48 may include
a variety of materials including, but not limited to, a metal, metal alloy, and/or
electrically conductive composite. In one embodiment, the bipolar plates 46,
48 may be stainless steel. In one embodiment, a method includes positioning
the first bipolar plate 46 over the first gas diffusion media 52, and positioning
the second bipolar plate 48 over the second gas diffusion media 54.
[0025] A soft goods portion 50 is provided between the first bipolar
plate 46 and the second bipolar plate 48. The soft goods portion 50 may
include the polymer electrolyte membrane 12 comprising the first face 14 and
the second face 16. The cathode electrode 18 may adhere to the first face 14
of the polymer electrolyte membrane 12, and the first microporous layer 22
may adhere to the cathode electrode 18. The first gas diffusion media layer
52 may overlie the first microporous layer 22. The first gas diffusion media
layer 52 may be hydrophobic. The first bipolar plate 46 may overlie the first
gas diffusion media layer 52.
[0026] The anode electrode 20 may adhere to the second face 16 of
the polymer electrolyte membrane 12, and the second microporous layer 24
may adhere to the anode electrode 20. The second gas diffusion media layer
54 may underlie the second microporous layer 24. The second gas diffusion
media layer 54 may be hydrophobic. The second bipolar plate 48 may
underlie the second gas diffusion media layer 54.
[0027] Referring again to the microporous layers 22, 24, in one
embodiment the microporous layer 22 or 24 may include a plurality of
particles, for example including graphitized carbon or carbon blacks and a
binder. In one embodiment the binder may include a hydrophobic agent or

polymer such as, but not limited to, polyvinylidene fluoride (PVDF),
fluoroethylene propylene (FEP), polytetrafluoroethylene (PTFE), or other
organic or inorganic hydrophobic materials. The particles and binder may be
included in a liquid phase which may be, for example, a mixture of an organic
solvent and water to provide dispersion. In various embodiments, the solvent
may include at least one of 2-propanol, 1-propanol or ethanol, etc. In one
embodiment, the microporous layers 22, 24 may have a thickness ranging
from about 2 to about 100 micrometers, may include 60-90 weight percent
particles and 10-40 weight percent binder. The microporous layers 22, 24
may have an average pore size ranging from about 50 nm to about 100 nm.
[0028] In another embodiment, a microporous layer ink was formed by
mixing the following in a jar mill at 120 rpm with 30 ml grinding media for
about 20 hours: 2.4 g acetylene black, 37 ml deionized H2O, 32 ml isopropyl
alcohol, and 0.2 g (NH4)2CO3. Then 2.21 g of a 36 wt% polyvinylidene
fluoride (PVDF) solution in IPA was added to the microporous layer ink. The
bottle was then shaken by hand. Then the mixture was coated onto an
expanded PTFE decal with a Meyer Rod, size 70. The decal was allowed to
air dry and then was placed in an oven preheated to 150°C and allowed to
soak for 1 hour. After curing the polymer, the decal and microporous layer
combination was coated with an appropriate catalyst ink and the MEA was
fabricated in the traditional decal transfer process. In one embodiment,
appropriate substitute materials for acetylene black may include, but are not
limited to, XC-72, Black pearls, and Ketjen Black. In another embodiment,
appropriate substitute materials for PVDF may include, but are not limited to,
any fluorinated polymer that has a melting point below that of the decal

material, for example fluorinated ethylenepropylene (FEP) and fluorinated
acrylates. In another embodiment, appropriate substitute materials for the
pH-adjusting material, (NH4)2CO3, may include, but are not limited to, a basic
component that does not poison ionomer, for example NH4OH.
[0029] FIG. 9 shows a comparison of an embodiment of the invention
with other fuel cell arrangements. The polarization curve shown is run on a
50 cm2 platform, and the testing conditions are as follows: 270 kpa absolute,
100%inlet RH, 60°C cell temperature, and 2/2 stoichiometry of hydrogen and
air. This condition is running fully saturated at the inlets and there is liquid
water being condensed in the cell as water is being produced; thus this
condition stresses the ability of the microporous layer and diffusion media to
remove water. The embodiment of the invention represented in FIG. 9 is a
fuel cell 28 with the first microporous layer 22 on the MEA 25, and is
represented by the lines with square markers. The lines with triangle markers
represent a fuel cell with a commercially available freestanding microporous
layer. The lines with circle markers represent a fuel cell with the microporous
layer formed over the diffusion media layer, which is known in the art. The
data points corrected by the high frequency resistance (HFR), which are
designated as the "IR Free" curves, show that there is no additional transport
resistance for the microporous layer on the MEA compared with the
microporous layer on the diffusion media layer. As shown in FIG. 9, the fuel
cell with the microporous layer on the MEA performs as well as the fuel cell
with the microporous layer on the diffusion media up to a current density of
about 1.2 A/cm2 and performs better than the commercially available
freestanding microporous layer at a current density greater than 1.2 A/cm2.

[0030] During fuel cell operation, many stresses may be placed upon
the MEA 25. For example, the MEA may take up water, stretch, shrink,
compress, feel tension, and so forth. In one embodiment, the microporous
layers 22, 24 may add durability to the MEA 25 or the fuel cell 28 when the
catalyst layers 18, 20 are coated directly over the microporous layers 22, 24.
The microporous layers 22, 24 may lend mechanical support to the MEA 25.
In other embodiments, the microporous layers 22, 24 may slow down the
drying-out process of the MEA 25 and may protect the MEA 25 from
catastrophic failure. The microporous layers 22, 24 may protect the
membrane 12 from being punctured by fibers from the diffusion media layers
52, 54. In another embodiment, the catalyst layers 18, 20 coated over the
microporous layers 22, 24 may contribute to water management within the
fuel cell 28 by creating a tight interface without voids. This may aid in water
removal from the fuel cell 28.
[0031] In various embodiments, the membrane 12 may comprise a
variety of different types of membranes. In one embodiment, the membrane
12 may be a perfluorinated sulfonic: acid polymer electrolyte in which the
entire membrane structure has ionic exchange characteristics. These
membranes are commercially available, and a typical example of a
commercial sulfonic perfluorocarbon proton conductive membrane is sold by
E. I. DuPont D Nemours & Company' under the trade designation NAFION.
Other such membranes are available from Asahi Glass and Asahi Chemical
Company. The use of other types of membranes 12, such as, but not limited
to, perfluorinated cation-exchange membranes, hydrocarbon based cation-

exchange membranes as well as anion-exchange membranes are also within
the scope of the invention.
[0032] In one embodiment, the first gas diffusion media layer 52 or the
second gas diffusion media layer 54 may include any electrically conductive
porous material. In various embodiments, the gas diffusion media layer 52 or
54 may include non-woven carbon fiber paper or woven carbon cloth which
may be treated with a hydrophobic material, such as, but not limited to,
polymers of polyvinylidene fluoride (PVDF), fluouroethylene propylene, or
polytetrafluoroethylene (PTFE). The gas diffusion media layer 52 or 54 may
have an average pore size ranging from 5 to 40 µm. The gas diffusion media
layer 52 or 54 may have a thickness ranging from about 100 to about 500 µm.
[0033] In one embodiment, the cathode electrode 18 and the anode
electrode 20 (cathode layer and anode layer) may be catalyst layers which
may include catalyst particles such as platinum, and an ion conductive
material such as a proton conducting ionomer, intermingled with the particles.
The proton conductive material may be an ionomer such as a perfluorinated
sulfonic acid polymer. The catalyst materials may include metals such as
platinum, palladium, and mixtures of metals such as platinum and
molybdenum, platinum and cobalt, platinum and ruthenium, platinum and
nickel, platinum and tin, other platinum transition-metal alloys, and other fuel
cell electrocatalysts known in the art. The catalyst materials may be finely
divided if desired. The catalyst materials may be unsupported or supported
on a variety of materials such as, but not limited to, finely divided carbon
particles.

[0034] When the terms "over", "overlying", "overlies", or "under",
"underlying", "underlies" are used with respect to the relative position of a first
component or layer with respect to a second component or layer, such shall
mean that the first component or layer is in direct contact with the second
component or layer, or that additional layers or components are interposed
between the first component or layer and the second component or layer.
[0035] The above description of embodiments of the invention is merely
exemplary in nature and, thus, variations thereof are not to be regarded as a
departure from the spirit and scope of the invention.

CLAIMS
What is claimed is:
1. A process comprising:
coating a first microporous layer onto a first decal; and
curing the first microporous layer and the first decal.
2. A process as set forth in claim 1 further comprising:
coating a first catalyst layer over the first microporous layer so
that the first catalyst is adhered to the first microporous layer.
3. A process as set forth in claim 2 further comprising:
providing a membrane comprising a first face and a second
face; and
hot pressing the first microporous layer and the first catalyst
layer to the first face of the membrane.
4. A process as set forth in claim 3 further comprising:
coating a second microporous layer onto a second decal;
curing the second microporous layer and the second decal;
coating a second catalyst layer over the second microporous
layer; and
hot pressing the second microporous layer and the anode
catalyst layer to the second face of the membrane.

5. A process as set forth in claim 2 further comprising:
coating a second microporous layer onto a second decal;
curing the second microporous layer and the second decal;
coating a second catalyst layer over the second microporous
layer;
providing a membrane comprising a first face and a second
face; and
simultaneously hot pressing the first microporous layer and the
first catalyst layer to the first face of the membrane, and the second
microporous layer and the anode catalyst layer to the second face of the
membrane.
6. A process as set forth in claim 5 wherein the first decal and the
second decal comprise one of expanded polytetrafluoroethylene (ePTFE),
polytetrafluoroethylene (PTFE), or poly(4,4'-oxydiphenylene-pyromellitimide).
7. A process as set forth in claim 1 wherein the first microporous
layer and the first decal are cured at the glass transition temperature of a
polymer in the first microporous layer.
8. A process as set forth in claim 5 wherein the second
microporous layer and the second decal are cured at the glass transition
temperature of a polymer in the second microporous layer.

9. A process as set forth in claim 3 wherein the membrane
comprises a polymer electrolyte membrane.
10. A process as set forth in claim 5 wherein the first and second
catalyst layers comprise catalyst particles and an ion conductive material.
11. A process as set forth in claim 5 wherein the first and second
microporous layers comprise carbon black.
12. A process as set forth in claim 5 further comprising:
removing the first decal and providing a first gas diffusion media
layer over the first microporous layer;
providing a first bipolar plate over the first gas diffusion media
layer, wherein the first bipolar plate includes a plurality of lands and channels;
removing the second decal and providing a second gas diffusion
media layer over the second microporous layer; and
providing a second bipolar plate over the second gas diffusion
media layer, wherein the second bipolar plate includes a plurality of lands and
channels.
13. A process as set forth in claim 1 wherein the first microporous
layer comprises at least one of graphitized carbon or carbon black and a
hydrophobic agent.

14. A process as set forth in claim 13 wherein the hydrophobic
agent comprises a fluorocarbon.
15. A product comprising:
a decal; and
a microporous layer overlying the decal.
16. A product as set forth in claim 15 further comprising a catalyst
layer adhered to the microporous layer.
17. A product as set forth in claim 16 further comprising a
membrane overlying the catalyst layer.
18. A product as set forth in claim 16 wherein the catalyst layer
comprises catalyst particles and an ion conductive material.
19. A product as set forth in claim 15 wherein the microporous layer
comprises at least one of carbon black or graphitized carbon.
20. A product as set forth in claim 19 wherein the microporous layer
further comprises at least one of polyvinylidene fluoride, fluoroethylene
propylene, polytetrafluoroethylene, organic hydrophobic material, or inorganic
hydrophobic material.

21. A product as set forth in claim 15 wherein the microporous layer
has an average pore size ranging from about 50 to about 100.
22. A product comprising a microporous layer adhered to a catalyst
layer.
23. A product as set forth in claim 22 further comprising a
membrane overlying the catalyst layer.
24. A product as set forth in claim 23 further comprising a gas
diffusion media layer overlying the microporous layer.
25. A product as set forth in claim 24 further comprising a bipolar
plate overlying the gas diffusion media layer, wherein the bipolar plate
includes a plurality of lands and channels.

One embodiment includes a process including coating a first microporous layer onto a first decal and curing the first microporous layer and
the first decal.

Documents:

1-KOL-2009-(14-01-2013)-ABSTRACT.pdf

1-KOL-2009-(14-01-2013)-CLAIMS.pdf

1-KOL-2009-(14-01-2013)-CORRESPONDENCE.pdf

1-KOL-2009-(14-01-2013)-DESCRIPTION (COMPLETE).pdf

1-KOL-2009-(14-01-2013)-DRAWINGS.pdf

1-KOL-2009-(14-01-2013)-FORM 1.pdf

1-KOL-2009-(14-01-2013)-FORM 2.pdf

1-KOL-2009-(14-01-2013)-FORM 3.pdf

1-KOL-2009-(14-01-2013)-FORM 5.pdf

1-KOL-2009-(14-01-2013)-OTHERS.pdf

1-KOL-2009-(14-01-2013)-PETITION UNDER RULE 137.pdf

1-kol-2009-abstract.pdf

1-KOL-2009-ASSIGNMENT-1.1.pdf

1-KOL-2009-ASSIGNMENT.pdf

1-KOL-2009-CANCELLED PAGES.pdf

1-kol-2009-claims.pdf

1-KOL-2009-CORRESPONDENCE-1.1.pdf

1-KOL-2009-CORRESPONDENCE-1.2.pdf

1-KOL-2009-CORRESPONDENCE-1.3.pdf

1-KOL-2009-CORRESPONDENCE-1.4.pdf

1-kol-2009-correspondence.pdf

1-kol-2009-description (complete).pdf

1-kol-2009-drawings.pdf

1-KOL-2009-EXAMINATION REPORT.pdf

1-kol-2009-form 1.pdf

1-KOL-2009-FORM 18-1.1.pdf

1-kol-2009-form 18.pdf

1-kol-2009-form 2.pdf

1-kol-2009-form 3.pdf

1-kol-2009-form 5.pdf

1-KOL-2009-GPA-1.1.pdf

1-kol-2009-gpa.pdf

1-KOL-2009-GRANTED-ABSTRACT.pdf

1-KOL-2009-GRANTED-CLAIMS.pdf

1-KOL-2009-GRANTED-DESCRIPTION (COMPLETE).pdf

1-KOL-2009-GRANTED-DRAWINGS.pdf

1-KOL-2009-GRANTED-FORM 1.pdf

1-KOL-2009-GRANTED-FORM 2.pdf

1-KOL-2009-GRANTED-FORM 3.pdf

1-KOL-2009-GRANTED-FORM 5.pdf

1-KOL-2009-GRANTED-SPECIFICATION-COMPLETE.pdf

1-KOL-2009-OTHERS.pdf

1-KOL-2009-PETITION UNDER RULE 137.pdf

1-KOL-2009-REPLY TO EXAMINATION REPORT.pdf

1-kol-2009-specification.pdf

1-KOL-2009-TRANSLATED COPY OF PRIORITY DOCUMENT-1.1.pdf

1-KOL-2009-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract_1-kol-2009.jpg


Patent Number 260748
Indian Patent Application Number 1/KOL/2009
PG Journal Number 21/2014
Publication Date 23-May-2014
Grant Date 20-May-2014
Date of Filing 01-Jan-2009
Name of Patentee GM GLOBAL TECHNOLOGY OPERATIONS, INC.
Applicant Address 300 GM RENAISSANCE CENTER DETROIT, MICHIGAN
Inventors:
# Inventor's Name Inventor's Address
1 HUBERT A. GASTEIGER PIAZZA 185TH ART. REG FOLGORE, 15 57128 LIVORNO
2 JEANETTE E. OWEJAN 5185 COUNTY ROAD 36 HONEOYE, NEW YORK 14471
PCT International Classification Number C25D5/48
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/972,865 2008-01-11 U.S.A.