U.S. patent application number 09/998277 was filed with the patent office on 2003-06-05 for hydrogen storage material including a modified ti-mn2 alloy.
Invention is credited to Chao, Benjamin, Myasnikov, Vitaliy, Stetson, Ned T., Tan, Zhaosheng, Yang, Jun.
Application Number | 20030103861 09/998277 |
Document ID | / |
Family ID | 25544995 |
Filed Date | 2003-06-05 |
United States Patent
Application |
20030103861 |
Kind Code |
A1 |
Stetson, Ned T. ; et
al. |
June 5, 2003 |
Hydrogen storage material including a modified Ti-Mn2 alloy
Abstract
A modified Ti--Mn.sub.2 hydrogen storage alloy. The alloy
generally is comprised of Ti and Mn. A generic formula for the
alloy is: Ti.sub.Q-XZr.sub.XMn.sub.Z-YA.sub.Y, where A is generally
one or more of V, Cr, Fe, Ni and Al. Most preferably A is one or
more of V, Cr, and Fe. The subscript Q is preferably between 0.9
and 1.1, and most preferably Q is 1.0. The subscript X is between
0.0 and 0.35, more preferably X is between 0.1 and 0.2, and most
preferably X is between 0.1 and 0.15. The subscript Y is preferably
between 0.3 and 1.8, more preferably Y is between 0.6 and 1.2,and
most preferably Y is between 0.6 and 1.0. The subscript Z is
preferably between 1.8 and 2.1,and most preferably Z is between 1.8
and 2.0. The alloys are generally single phase materials,
exhibiting a hexagonal C.sub.14 Laves phase crystalline
structure.
Inventors: |
Stetson, Ned T.; (Lake
Orion, MI) ; Yang, Jun; (Dearborn, MI) ; Chao,
Benjamin; (Troy, MI) ; Myasnikov, Vitaliy;
(West Bloomfield, MI) ; Tan, Zhaosheng; (Troy,
MI) |
Correspondence
Address: |
Energy Conversion Devices, Inc.
2956 Waterview Dr.
Rochester Hills
MI
48309
US
|
Family ID: |
25544995 |
Appl. No.: |
09/998277 |
Filed: |
November 30, 2001 |
Current U.S.
Class: |
420/417 ;
420/421; 420/900 |
Current CPC
Class: |
C22C 14/00 20130101;
C22C 22/00 20130101; C01B 3/0031 20130101; Y02E 60/10 20130101;
H01M 4/383 20130101; Y02E 60/32 20130101 |
Class at
Publication: |
420/417 ;
420/421; 420/900 |
International
Class: |
C22C 014/00 |
Claims
We claim:
1. A hydrogen storage material comprising: a hydrogen storage alloy
having the formula Ti.sub.Q-XZr.sub.XMn.sub.Z-YA.sub.Y, wherein A
is one or more elements selected from the group consisting of V,
Cr, Fe, Ni, and Al; Q is between 0.9 and 1.1 X is between 0 and
0.35, Y is between 0.3 and 1.8, and Z is between 1.8 and 2.1.
2. The hydrogen storage material of claim 1, wherein A one or more
elements selected from the group consisting of V, Cr, Fe, and
Ni.
3. The hydrogen storage material of claim 1, wherein X is between
0.1 and 0.2.
4. The hydrogen storage material of claim 1, wherein X is between
0.1 and 0.15.
5. The hydrogen storage material of claim 1, wherein Y is between
0.6 and 1.2
6. The hydrogen storage material of claim 1, wherein Y is between
0.7 and 1.0.
7. The hydrogen storage material of claim 1, wherein said hydrogen
storage alloy is a single phase material.
8. The hydrogen storage material of claim 7, wherein said hydrogen
storage alloy exhibits a hexagonal C.sub.14 Laves phase crystalline
structure.
9. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.9Zr.sub.0 1Mn.sub.1 3V.sub.0.45Ni.sub.0.26.
10. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.8Zr.sub.0.2Mn.sub.1.25V.sub.0
4Cr.sub.0.3Fe.sub.0.06.
11. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.8Zr.sub.0.2Mn.sub.1.25V.sub.0 4Fe.sub.0.36.
12. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.7Zr.sub.0.3Mn.sub.1 5V.sub.0.3Ni.sub.0.17.
13. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.8Zr.sub.0.2Mn.sub.1 3V.sub.0.45Ni.sub.0 26.
14. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.95Zr.sub.0.05Mn.sub.1 3V.sub.0 45Ni.sub.0
26.
15. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.9Zr.sub.0.1Mn.sub.1 28V.sub.0
3Cr.sub.0.25Ni.sub.0.17.
16. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.8Zr.sub.0 2Mn.sub.1 31V.sub.0 25Cr.sub.0
3Ni.sub.0 14.
17. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.9Zr.sub.0 1Mn.sub.0.6V.sub.0 2Cr.sub.1
08Ni.sub.0 12.
18. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.8Zr.sub.0.2Mn.sub.1 31V.sub.0.25Cr.sub.0
30Fe.sub.0.14.
19. The hydrogen storage material of claim 1, wherein said all
Ti.sub.0.84Zr.sub.0.15Mn.sub.1 28V.sub.0 25Cr.sub.0.18Fe.sub.0
25Al.sub.0.06.
20. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.85Zr.sub.0 15Mn.sub.1 5V.sub.0.3Fe.sub.0
23Al.sub.0 06.
21. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.87Zr.sub.0 13Mn.sub.1 29V.sub.0 17Cr.sub.0
18Fe.sub.0.24Al.sub.0.06.
22. The hydrogen storage material of claim 1, wherein said alloy
comprises Ti.sub.0.87Zr.sub.0.13Mn.sub.1 23V.sub.0.16Cr.sub.0
17Fe.sub.0.23Al.sub.0.06.
23. The hydrogen storage material of claim 1, wherein said hydrogen
storage alloy is in powder form.
24. The hydrogen storage material of claim 23, wherein said
hydrogen storage alloy powder is physically bonded to a support
means.
25. The hydrogen storage material of claim 24, wherein hydrogen
storage alloy powder is physically bonded to said support means by
compaction and/or sintering.
26. The hydrogen storage material of claim 24, wherein said support
means comprises at least one selected from the group consisting of
mesh, grid, matte, foil, foam and plate.
27. The hydrogen storage material of claim 24, wherein said support
means is formed from a metal.
28. The hydrogen storage material of claim 27, wherein said support
means is formed from one or more metals selected from the group
consisting of Ni, Al, Cu, Fe and mixtures or alloys thereof.
29. The hydrogen storage material of claim 24, wherein said storage
material comprises said hydrogen storage alloy powder physically
bonded to said support means and spirally wound into a coil.
30. The hydrogen storage material of claim 24, wherein said storage
material comprises said hydrogen storage alloy powder physically
bonded to said support means, a plurality of which are stacked as
disks or plates.
Description
FIELD OF THE INVENTION
[0001] The instant invention relates generally to hydrogen storage
materials and more specifically to hydrogen storage materials
including a modified TiMn.sub.2 alloy. The hydrogen storage
materials also include a support means such as a metal mesh, grid,
matte, foil, foam or plate.
BACKGROUND OF THE INVENTION
[0002] In the past considerable attention has been given to the use
of hydrogen as a fuel or fuel supplement. While the world's oil
reserves are rapidly being depleted, the supply of hydrogen remains
virtually unlimited. Hydrogen can be produced from coal, natural
gas and other hydrocarbons, or formed by the electrolysis of water.
Moreover hydrogen can be produced without the use of fossil fuels,
such as by the electrolysis of water using nuclear or solar energy.
Furthermore, hydrogen, although presently more expensive than
petroleum, is a relatively low cost fuel. Hydrogen has the highest
density of energy per unit weight of any chemical fuel and is
essentially non-polluting since the main by-product of burning
hydrogen is water.
[0003] While hydrogen has wide potential application as a fuel, a
major drawback in its utilization, especially in mobile uses such
as the powering of vehicles, has been the lack of acceptable
lightweight hydrogen storage medium. Conventionally, hydrogen has
been stored in a pressure-resistant vessel under a high pressure or
stored as a cryogenic liquid, being cooled to an extremely low
temperature. Storage of hydrogen as a compressed gas involves the
use of large and heavy vessels. In a steel vessel or tank of common
design only about 1% of the total weight is comprised of hydrogen
gas when it is stored in the tank at a typical pressure of 136
atmospheres. In order to obtain equivalent amounts of energy, a
container of hydrogen gas weighs about thirty times the weight of a
container of gasoline. Additionally, transfer is very difficult,
since the hydrogen is stored in a large-sized vessel; amount of
hydrogen stored in a vessel is limited, due to low density of
hydrogen. Furthermore, storage as a liquid presents a serious
safety problem when used as a fuel for motor vehicles since
hydrogen is extremely flammable. Liquid hydrogen also must be kept
extremely cold, below -253.degree. C., and is highly volatile if
spilled. Moreover, liquid hydrogen is expensive to produce and the
energy necessary for the liquefaction process is a major fraction
of the energy that can be generated by burning the hydrogen.
[0004] Alternatively, certain metals and alloys have been known to
permit reversible storage and release of hydrogen. In this regard,
they have been considered as a superior hydrogen-storage material,
due to their high hydrogen-storage efficiency. Storage of hydrogen
as a solid hydride can provide a greater volumetric storage density
than storage as a compressed gas or a liquid in pressure tanks.
Also, hydrogen storage in a solid hydride presents fewer safety
problems than those caused by hydrogen stored in containers as a
gas or a liquid. Solid-phase metal or alloy system can store large
amounts of hydrogen by absorbing hydrogen with a high density and
by forming a metal hydride under a specific temperature/pressure or
electrochemical conditions, and hydrogen can be released by
changing these conditions. Metal hydride systems have the advantage
of high-density hydrogen-storage for long periods of time, since
they are formed by the insertion of hydrogen atoms to the crystal
lattice of a metal. A desirable hydrogen storage material must have
a high storage capacity relative to the weight of the material, a
suitable desorption temperature/pressure, good kinetics, good
reversibility, resistance to poisoning by contaminants including
those present in the hydrogen gas and be of a relatively low cost.
If the material fails to possess any one of these characteristics
it will not be acceptable for wide scale commercial
utilization.
[0005] The hydrogen storage capacity per unit weight of material is
an important consideration in many applications, particularly where
the hydride does not remain stationary. A low hydrogen storage
capacity relative to the weight of the material reduces the mileage
and hence the range of a vehicle making the use of such materials.
A low desorption temperature is desirable to reduce the amount of
energy required to release the hydrogen. Furthermore, a relatively
low desorption temperature to release the stored hydrogen is
necessary for efficient utilization of the available exhaust heat
from vehicles, machinery, or other similar equipment.
[0006] Good reversibility is needed to enable the hydrogen storage
material to be capable of repeated absorption-desorption cycles
without significant loss of its hydrogen storage capabilities. Good
kinetics are necessary to enable hydrogen to be absorbed or
desorbed in a relatively short period of time. Resistance to
contaminants to which the material may be subjected during
manufacturing and utilization is required to prevent a degradation
of acceptable performance.
[0007] The prior art hydrogen storage materials include a variety
of metallic materials for hydrogen-storage, e.g., Mg, Mg--Ni,
Mg--Cu, Ti--Fe, Ti--Ni, Mm-Ni and Mm-Co alloy systems (wherein, Mm
is Misch metal, which is a rare-earth metal or combination/alloy of
rare-earth metals). None of these prior art materials, however, has
had all of the required properties required for a storage medium
with widespread commercial utilization.
[0008] Of these materials, the Mg alloy systems can store
relatively large amounts of hydrogen per unit weight of the storage
material. However, heat energy must be supplied to release the
hydrogen stored in the alloy, because of its low hydrogen
dissociation equilibrium pressure at room temperature. Moreover,
release of hydrogen can be made, only at a high temperature of over
250.degree. C. along with the consumption of large amounts of
energy.
[0009] The rare-earth (Misch metal) alloys have their own problems.
Although they typically can efficiently absorb and release hydrogen
at room temperature, based on the fact that it has a hydrogen
dissociation equilibrium pressure on the order of several
atmospheres at room temperature, their hydrogen-storage capacity
per unit weight is lower than any other hydrogen-storage material
and they are very expensive.
[0010] The Ti--Fe alloy system which has been considered as a
typical and superior material of the titanium alloy systems, has
the advantages that it is relatively inexpensive and the hydrogen
dissociation equilibrium pressure of hydrogen is several
atmospheres at room temperature. However, since it requires a high
temperature of about 350.degree. C. and a high pressure of over 30
atmospheres for initial hydrogenation, the alloy system provides
relatively low hydrogen absorption/desorption rate. Also, it has a
hysteresis problem which hinders the complete release of hydrogen
stored therein.
[0011] Under the circumstances, a variety of approaches have been
made to solve the problems of the prior art and to develop an
improved material which has a high hydrogen-storage efficiency, a
proper hydrogen dissociation equilibrium pressure and a high
absorption/desorption rate.
[0012] In this regard, Ti--Mn alloy system has been reported to
have a high hydrogen-storage efficiency and a proper hydrogen
dissociation equilibrium pressure, since it has a high affinity for
hydrogen and low atomic weight to allow large amounts of
hydrogen-storage per unit weight.
[0013] Unfortunately there is still a need in the art for a low
cost, high hydrogen-storage efficiency, good dissociation
equilibrium pressure, high absorption/desorption, rate room
temperature hydrogen storage alloy.
SUMMARY OF THE INVENTION
[0014] The instant invention is a hydrogen storage material which
includes a modified Ti--Mn.sub.2 hydrogen storage alloy. The alloy
generally is comprised of Ti and Mn. A generic formula for the
alloy is: Ti.sub.Q-XZr.sub.XMn.sub.Z-YA.sub.Y, where A is generally
one or more of V, Cr, Fe, Ni and Al. Most preferably A is one or
more of V, Cr, and Fe. The subscript Q is preferably between 0.9
and 1.1, and most preferably Q is 1.0. The subscript X is between
0.0 and 0.35, more preferably X is between 0.1 and 0.2, and most
preferably is between 0.1 and 0.15. The subscript Y is preferably
between 0.3 and 1.8, more preferably Y is between 0.6 and 1.2,and
most preferably Y is between 0.6 and 1.0. The subscript Z is
preferably between 1.8 and 2.1,and most preferably Z is between 1.8
and 2.0. The alloys are generally single phase materials,
exhibiting a hexagonal C.sub.14 Laves phase crystalline
structure.
[0015] The hydrogen storage material is comprised of the hydrogen
storage alloy powder physically bonded to a support means by
compaction and/or sintering. The support means is at least one of
mesh, grid, matte, foil, foam or plate and is preferably formed
from a metal such as one or more of Ni, Al, Cu, Fe and mixtures or
alloys thereof. The hydrogen storage alloy powder which is bonded
to the support means can be spirally wound into a coil or a
plurality of them can be stacked as disks or plates.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1, is a Pressure-Composition-Temperature (PCT) graph
for several hydrogen storage alloys of the instant invention;
[0017] FIG. 2 is a PCT graph of alloy TA-34 of the instant
invention;
[0018] FIG. 3 is an X-ray diffraction (XRD) analysis of alloy TA-34
of the instant invention;
[0019] FIG. 4 is a PCT graph of alloy TA-56 of the instant
invention;
[0020] FIG. 5 is a PCT graph of alloy TA-56D of the instant
invention;
[0021] FIG. 6 shows an embodiment of the instant invention where
the support means bonded with the hydrogen storage alloy material
is spirally wound into a coil; and
[0022] FIG. 7 shows an alternate embodiment of the instant
invention where the support means bonded with the hydrogen storage
alloy material is assembled as a plurality of stacked disks.
DETAILED DESCRIPTION OF THE INVENTION
[0023] One aspect of the instant invention is a modified
Ti--Mn.sub.2 hydrogen storage alloy. The alloy generally is
comprised of Ti and Mn. A generic formula for the alloy is:
Ti.sub.Q-XZr.sub.XMn.sub.Z-YA.sub.Y, where A is generally one or
more of V, Cr, Fe, Ni and Al. Most preferably A is one or more of
V, Cr, and Fe. The subscript Q is preferably between 0.9 and 1.1,
and most preferably Q is 1.0. The subscript X is between 0.0 and
0.35, more preferably X is between 0.1 and 0.2, and most preferably
X is between 0.1 and 0.15. The subscript Y is preferably between
0.3 and 1.8, more preferably Y is between 0.6 and 1.2, and most
preferably Y is between 0.6 and 1.0. The subscript Z is preferably
between 1.8 and 2.1,and most preferably Z is between 1.8 and 2.0.
The alloys are generally single phase materials, exhibiting a
hexagonal C.sub.14 Laves phase crystalline structure. Preferred
alloys are shown in Table 1.
[0024] These alloys have average storage capacity, ranging from 1
to 2 weight percent. They also have excellent room temperature
kinetics. FIG. 1, is a Pressure-Composition-Temperature (PCT) graph
for several of the alloys of the instant invention plotting
pressure in Torr on the y-axis versus weight percent of stored
hydrogen on the x-axis. Specifically shown are the desorption PCT
curves for TA-1, TA-9, TA-10 and TA-11 at 30.degree. C. FIG. 2 is a
PCT graph of TA-34 at 30.degree. C. (the .diamond-solid. symbol)
and 45.degree. C. (the .circle-solid. symbol) plotting pressure in
Torr on the y-axis versus weight percent of stored hydrogen on the
x-axis. As can be seen, these alloys have very good plateau
pressures at room temperature. The plateau pressures at 30.degree.
C., the maximum storage capacity and the reversible storage
capacity (also at 30.degree. C.) of most of the alloys of Table 1
are shown in Table 2. It should be noted that alloys TA-34, TA-35,
TA-56 and TA-56D are lower cost alloys which have reduced V and Cr
content and can be made using commercially available ferrovavadium
and ferrochromium alloys. FIG. 3 is an X-ray diffraction (XRD)
analysis of alloy TA-34. As can be seen analysis of the XRD plot,
the alloys of the instant invention have a hexagonal C.sub.14 Laves
phase crystalline structure.
[0025] FIG. 4 is a PCT graph of TA-56 at 30.degree. C. (adsorption
is solid line, desorption is the dashed line) plotting pressure in
Bar on the y-axis versus weight percent of stored hydrogen on the
x-axis. FIG. 5 is a PCT graph of TA-56D at 30.degree. C.
(adsorption is dashed line, desorption is the solid line) plotting
pressure in Bar on the y-axis versus weight percent of stored
hydrogen on the x-axis.
1TABLE 1 Alloy # Ti Zr V Cr Mn Fe Ni Al TA-1 0.9 0.1 0.45 -- 1.3 --
0.26 -- TA-2 0.8 0.2 0.4 0.3 1.25 0.06 -- -- TA-4 0.8 0.2 0.4 --
1.25 0.36 -- -- TA-5 0.7 0.3 0.3 -- 1.5 -- 0.17 -- TA-9 0.8 0.2
0.45 -- 1.3 -- 0.26 -- TA-10 0.95 0.05 0.45 -- 1.3 -- 0.26 -- TA-11
0.9 0.1 0.3 0.25 1.28 -- 0.17 -- TA-12 0.8 0.2 0.25 0.3 1.31 --
0.14 -- TA-16 0.9 0.1 0.2 1.08 0.6 -- 0.12 -- TA-23 0.8 0.2 0.25
0.30 1.31 0.14 -- -- TA-34 0.84 0.15 0.25 0.18 1.28 0.25 -- 0.06
TA-35 0.85 0.15 0.03 -- 1.5 0.23 -- 0.06 TA-56 0.87 0.13 0.17 0.18
1.29 0.24 -- 0.06 TA-56D 0.87 0.13 0.16 0.17 1.23 0.23 -- 0.06
[0026]
2TABLE 2 Max % H.sub.2 Conc. Rev. % H.sub.2 Conc. Plateau Pressure
Alloy # (H/(H + M)) (H/(H + M)) (Torr) TA-1 1.84 1.6 2400 TA-2
>1.57 1.6 1130 TA-4 >1.56 1.6 3030 TA-5 1.83 1.5 660 TA-9
>1.55 1.6 1180 TA-10 2.0 1.6 5590 TA-11 1.78 1.5 7000 TA-12 1.9
1.72 2500 TA-16 1.75 1.19 5000 TA-23 1.99 1.71 1300 TA-34 1.87 1.55
1600 TA-56 1.84 1.7 7200 TA-56D 1.9 1.68 5700
[0027] The present invention includes a metal hydride hydrogen
storage means for storing hydrogen within a container or tank. In
one embodiment of the present invention, the storage means
comprises the afore described hydrogen storage alloy material
physically bonded to a support means. Generally, the support means
can take the form of any structure that can hold the storage alloy
material. Examples of support means include, but are not limited
to, mesh, grid, matte, foil, foam and plate. Each may exist as
either a metal or non-metal.
[0028] The support means may be formed from a variety of materials
with the appropriate thermodynamic characteristics that can provide
the necessary heat transfer mechanism. These include both metals
and non-metals. Preferable metals include those from the group
consisting of Ni, Al, Cu, Fe and mixtures or alloys thereof.
Examples of support means that can be formed from metals include
wire mesh, expanded metal and foamed metal.
[0029] The hydrogen storage alloy material may be physically bonded
to the support means by compaction and/or sintering processes. The
alloy material is first converted into a fine powder. The powder is
then compacted onto the support means. The compaction process
causes the powder to adhere to and become an integral part of the
support means. After compaction, the support means that has been
impregnated with alloy powder is preheated and then sintered. The
preheating process liberates excess moisture and discourages
oxidation of the alloy powder. Sintering is carried out in a high
temperature, substantially inert atmosphere containing hydrogen.
The temperature is sufficiently high to promote
particle-to-particle bonding of the alloy material as well as the
bonding of the alloy material to the support means.
[0030] The support means/alloy material can be packaged within the
container/tank in many different configurations. FIG. 6 shows a
configuration where the support means/alloy material is spirally
wound into a coil. FIG. 7 shows an alternate configuration where
the support means/alloy material is assembled in the container as a
plurality of stacked disks. Other configurations are also possible
(e.g. stacked plates).
[0031] Compacting and sintering alloy material onto a support means
increases the packing density of the alloy material, thereby
improving the thermodynamic and kinetic characteristics of the
hydrogen storage system. The close contact between the support
means and the alloy material improves the efficiency of the heat
transfer into and out of the hydrogen storage alloy material as
hydrogen is absorbed and desorbed. In addition, the uniform
distribution of the support means throughout the interior of the
container provides for an even temperature and heat distribution
throughout the bed of alloy material. This results in a more
uniform rates of hydrogen absorption and desorption throughout the
entirety thereof, thus creating a more efficient energy storage
system.
[0032] One problem when using just alloy powder (without a support
means) in hydrogen storage beds is that of self-compaction due to
particle size reduction. That is, during repeated hydriding and
dehydriding cycles, the alloy materials expand and contract as they
absorb and desorb hydrogen. Some alloy materials have been found to
expand and contract by as much as 25% in volume as a result of
hydrogen introduction into and release from the material lattice.
As a result of the dimensional change in the alloy materials, they
crack, undergo fracturing and break up into finer and finer
particles. After repeated cycling, the fine particles self-compact
causing inefficient hydrogen transfer as well as high stresses that
are directed against the walls of the storage container.
[0033] However, the processes used to attach the alloy material
onto the support means keeps the alloy particles firmly bonded to
each other as well as to the support means during the absorption
and desorption cycling. Furthermore, the tight packaging of the
support means within the container serves as a mechanical support
that keeps the alloy particles in place during the expansion,
contraction and fracturing of the material.
[0034] While the invention has been described in connection with
preferred embodiments and procedures, it is to be understood that
it is not intended to limit the invention to the described
embodiments and procedures. On the contrary it is intended to cover
all alternatives, modifications and equivalence which may be
included within the spirit and scope of the invention as defined by
the claims appended hereinafter.
* * * * *