U.S. patent application number 17/231754 was filed with the patent office on 2021-10-21 for antimicrobial steel and related methods.
The applicant listed for this patent is Northwestern University. Invention is credited to Yip-Wah Chung, Erica Marie Hartmann, Dieter Isheim, Arman Mohammad Khan, Semyon Vaynman, Qian Wang.
Application Number | 20210324505 17/231754 |
Document ID | / |
Family ID | 1000005537800 |
Filed Date | 2021-10-21 |
United States Patent
Application |
20210324505 |
Kind Code |
A1 |
Chung; Yip-Wah ; et
al. |
October 21, 2021 |
ANTIMICROBIAL STEEL AND RELATED METHODS
Abstract
A method of reducing viability of a microbe is provided. An
illustrative method comprises contacting a microbe with an
antimicrobial surface comprising a copper-alloy steel comprising an
iron matrix and copper nanoprecipitates distributed throughout the
iron matrix, wherein the copper-alloy steel comprises: Cu in a
range from 0.5 weight % to 5.0 weight %; C in a range from 0.03
weight % to 0.10 weight %; Mn in a range from 0.20 weight % to 5.0
weight %; Ni in a range from 0.0 weight % to 6.0 weight %; Al in a
range from 0.0 weight % to 4.0 weight %; Nb in a range from 0.0
weight % to 0.10 weight %; Si in a range from 0.0 weight % to 2.0
weight %; Mo in a range from 0.0 weight % to 2.0 weight %; Ti in a
range from 0.0 weight % to 2.0 weight %; V in a range from 0.0
weight % to 2.0 weight %; Cr in a range from 0.0 weight % to 8.0
weight %; and a balance of Fe. The antimicrobial surfaces are also
provided.
Inventors: |
Chung; Yip-Wah; (Wilmette,
IL) ; Wang; Qian; (Mt. Prospect, IL) ;
Hartmann; Erica Marie; (Chicago, IL) ; Khan; Arman
Mohammad; (Evanston, IL) ; Vaynman; Semyon;
(Highland Park, IL) ; Isheim; Dieter; (Chicago,
IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Northwestern University |
Evanston |
IL |
US |
|
|
Family ID: |
1000005537800 |
Appl. No.: |
17/231754 |
Filed: |
April 15, 2021 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
63011646 |
Apr 17, 2020 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C22C 38/08 20130101;
C22C 38/06 20130101; C22C 38/04 20130101; C22C 38/14 20130101; C22C
38/02 20130101; C22C 38/12 20130101; C22C 38/16 20130101 |
International
Class: |
C22C 38/16 20060101
C22C038/16; C22C 38/04 20060101 C22C038/04; C22C 38/08 20060101
C22C038/08; C22C 38/06 20060101 C22C038/06; C22C 38/02 20060101
C22C038/02; C22C 38/12 20060101 C22C038/12; C22C 38/14 20060101
C22C038/14 |
Claims
1. A method of reducing viability of a microbe, the method
comprising contacting a microbe with an antimicrobial surface
comprising a copper-alloy steel comprising an iron matrix and
copper nanoprecipitates distributed throughout the iron matrix,
wherein the copper-alloy steel comprises: Cu in a range from 0.5
weight % to 5.0 weight %; C in a range from 0.03 weight % to 0.10
weight %; Mn in a range from 0.20 weight % to 5.0 weight %; Ni in a
range from 0.0 weight % to 6.0 weight %; Al in a range from 0.0
weight % to 4.0 weight %; Nb in a range from 0.0 weight % to 0.10
weight %; Si in a range from 0.0 weight % to 2.0 weight %; Mo in a
range from 0.0 weight % to 2.0 weight %; Ti in a range from 0.0
weight % to 2.0 weight %; V in a range from 0.0 weight % to 2.0
weight %; Cr in a range from 0.0 weight % to 8.0 weight %; and a
balance of Fe.
2. The method of claim 1, wherein the copper iron alloy does not
comprise S, P, Co, Sn, and N.
3. The method of claim 1, wherein the copper iron alloy comprises
Fe, Cu, C, Mn, and one or more of Ni, Al, Nb, Si, Mo, Ti, V, and
Cr.
4. The method of claim 1, wherein the copper iron alloy comprises
Fe, Cu, C, Mn, Ni, and optionally, Cr.
5. The method of claim 1, wherein the copper iron alloy comprises
Fe, Cu, C, Mn, Ni, Al and, optionally, Cr.
6. The method of claim 1, wherein the copper iron alloy comprises
Fe, Cu, C, Mn, Ni, Nb, Si, and optionally, Cr.
7. The method of claim 1, wherein the copper alloy steel comprises
Fe, Cu, C, Mn, Ni, Al, Nb, Si, and optionally, Cr.
8. The method of claim 1, wherein the copper alloy steel comprises
Fe, Cu, C, Mn, Ni, Nb, Si, Ti, and optionally, Cr.
9. The method of claim 1, wherein the copper alloy steel is
characterized by an average center-to-center spacing .lamda.
between neighboring copper nanoprecipitates in a range of from 5 nm
to 200 nm.
10. The method of claim 1, wherein the copper nanoprecipitates are
bcc copper nanoprecipitates.
11. The method of claim 1, wherein the iron matrix is ferritic,
martensitic, or partially martensitic.
12. The method of claim 1, wherein the antimicrobial surface is
textured.
13. The method of claim 1, wherein the contacting is carried out in
an environment in which microbes are present, or are suspected of
being present, in quantities that are more likely than not to
result in an infection of a mammalian subject due to the
microbes.
14. The method of claim 1, wherein the contacting is carried out in
an indoor environment.
15. The method of claim 1, wherein the antimicrobial surface is
part of an article configured for regular contact with a human body
part.
16. The method of claim 15, wherein the human body part is a
hand.
17. The method of claim 1, wherein the microbe is a virus.
18. The method of claim 17, wherein the virus is SARS-CoV-2.
19. An antimicrobial surface comprising a copper-alloy steel
comprising an iron matrix and copper nanoprecipitates distributed
throughout the iron matrix, wherein the copper-alloy steel
comprises: Cu in a range from 0.5 weight % to 5.0 weight %; C in a
range from 0.03 weight % to 0.10 weight %; Mn in a range from 0.20
weight % to 5.0 weight %; Ni in a range from 0.0 weight % to 6.0
weight %; Al in a range from 0.0 weight % to 4.0 weight %; Nb in a
range from 0.0 weight % to 0.10 weight %; Si in a range from 0.0
weight % to 2.0 weight %; Mo in a range from 0.0 weight % to 2.0
weight %; Ti in a range from 0.0 weight % to 2.0 weight %; V in a
range from 0.0 weight % to 2.0 weight %; Cr in a range from 0.0
weight % to 8.0 weight %; and a balance of Fe.
20. The antimicrobial surface of claim 19, wherein the
antimicrobial surface is part of an article configured for regular
contact with a human body part.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. provisional
patent application No. 63/011,646 that was filed Apr. 17, 2020, the
entire contents of which are incorporated herein by reference.
BACKGROUND
[0002] Stainless steels are used in hospitals, health care
facilities, public transportation, appliances, food manufacturing
and service, etc. because of their corrosion resistance and clean
appearance. However, stainless steels have little or no
antimicrobial properties, rendering them ineffective against the
transmission of pathogens. SARS-CoV-2 coronavirus is known to
survive several days on stainless steel surfaces. Thus, touching
contaminated surfaces is likely to spread COVID-19 infection.
SUMMARY
[0003] Provided are antimicrobial surfaces and related methods.
[0004] An illustrative method of reducing viability of a microbe
comprises contacting a microbe with an antimicrobial surface
comprising a copper-alloy steel comprising an iron matrix and
copper nanoprecipitates distributed throughout the iron matrix,
wherein the copper-alloy steel comprises: Cu in a range from 0.5
weight % to 5.0 weight %; C in a range from 0.03 weight % to 0.10
weight %; Mn in a range from 0.20 weight % to 5.0 weight %; Ni in a
range from 0.0 weight % to 6.0 weight %; Al in a range from 0.0
weight % to 4.0 weight %; Nb in a range from 0.0 weight % to 0.10
weight %; Si in a range from 0.0 weight % to 2.0 weight %; Mo in a
range from 0.0 weight % to 2.0 weight %; Ti in a range from 0.0
weight % to 2.0 weight %; V in a range from 0.0 weight % to 2.0
weight %; Cr in a range from 0.0 weight % to 8.0 weight %; and a
balance of Fe. The antimicrobial surfaces are also provided.
[0005] Other principal features and advantages of the disclosure
will become apparent to those skilled in the art upon review of the
following drawings, the detailed description, and the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Illustrative embodiments of the disclosure will hereafter be
described with reference to the accompanying drawings.
[0007] FIG. 1 shows an atom probe image of a copper alloy steel
comprising a ferritic matrix and copper nanoprecipitates
distributed throughout the ferritic matrix. The copper alloy steel
comprises from 1.5 weight % to 4.5 weight % copper.
[0008] FIG. 2 shows the evolution of the number of H.sub.2O.sub.2,
hydroxyl radicals, oxygen, and water molecules as a function of
time at room temperature from a surface of a bcc Cu nanoprecipitate
in an illustrative antimicrobial surface.
[0009] FIG. 3 illustrates flat and textured controlled
antimicrobial surfaces.
[0010] FIG. 4 illustrates the bactericidal properties of
illustrative antimicrobial surfaces.
DETAILED DESCRIPTION
[0011] The present antimicrobial surfaces comprise a copper alloy
steel comprising an iron matrix and copper nanoprecipitates
distributed throughout the iron matrix. The crystal structure of
the iron of the iron matrix may be ferritic, martensitic, or
partially martensitic. The copper of the copper alloy steel is
generally present in the iron matrix at an amount in a range of
from 0.5 weight % to 5.0 weight % as compared to the total weight
of the copper alloy steel. This includes from 0.5 weight % to 4.0
weight %, from 1.0 weight % to 4.0 weight %, from 0.5 weight % to
3.0 weight %, and from 1.0 weight % to 3.0 weight %. The copper
alloy steel generally comprises other elements in addition to the
copper and the carbon and iron of the matrix. These other elements
may include Mn, Ni, Al, Nb, Si, Mo, Ti, V, and combinations
thereof. Illustrative amounts (in weight %) of these elements are
as follows: C may range from 0.03 to 0.10; Mn may range from 0.20
to 5.0; Ni may range from 0.0 to 6.0; Al may range from 0.0 to 4.0;
Nb may range from 0.0 to 0.10; Si, Mo, Ti, and V may each range
(independently) from 0.0 to 2.0. In all cases, the balance is iron.
Chromium is another element which may be added to the copper alloy
steel, including in amounts (in weight %) of from 0.0 to 8.0. The
addition of chromium (Cr) is further described below.
[0012] Thus, in embodiments, the copper alloy steel comprises or
consists of Fe, Cu, C, Mn, and one or more of Ni, Al, Nb, Si, Mo,
Ti, V, and Cr. In embodiments, the copper alloy steel comprises or
consists of Fe, Cu, C, Mn, Ni, and optionally, Cr. In embodiments,
the copper alloy steel comprises or consists of Fe, Cu, C, Mn, Ni,
Al and, optionally, Cr. In embodiments, the copper alloy comprises
or steel consists of Fe, Cu, C, Mn, Ni, Nb, Si, and optionally, Cr.
In embodiments, the copper alloy steel comprises or consists of Fe,
Cu, C, Mn, Ni, Al, Nb, Si, and optionally, Cr. In embodiments, the
copper alloy steel comprises or consists of Fe, Cu, C, Mn, Ni, Nb,
Si, Ti, and optionally, Cr. In each of these embodiments, the
amounts of each element may be within the ranges described
above.
[0013] In embodiments, certain elements are not present in the
copper alloy steel (or in the antimicrobial surface), i.e., in
these embodiments, the copper alloy steel does not comprise these
elements. These include one, more than one, or all, of S, P, Co,
Sn, and N.
[0014] In embodiments, the copper alloy steel has one of the
compositions shown in Table 1, below. However, in each of these
embodiments, chromium may be present in the amounts described
above. In such embodiments, the copper alloy steel may be
considered to consist of the elements shown below at the amounts
shown below.
TABLE-US-00001 TABLE 1 Illustrative Compositions for Copper Alloy
Steels. Amounts are weight %. Cu C Mn Ni Al Nb Si Ti Fe 1.29 0.05
0.50 2.70 0.6 0.0 0.0 0.0 Balance 2.48 0.06 0.52 2.58 0.59 0.06
0.51 0.0 Balance 2.50 0.06 1.47 2.59 0.54 0.06 0.52 0.0 Balance
2.50 0.05 1.50 4.00 1.00 0.0 0.0 0.0 Balance 3.00 0.05 3.00 4.00
1.50 0.07 0.53 0.0 Balance 4.00 0.05 4.00 4.00 1.00 0.07 0.48 0.0
Balance 1.49 0.03 0.49 0.84 0.0 0.06 0.40 0.03 Balance 1.30 0.06
0.50 0.90 0.0 0.06 0.39 0.10 Balance 0.94 0.07 0.87 0.49 0.0 0.07
0.30 0.03 Balance
[0015] The antimicrobial surface may consist of any of the copper
alloy steels described herein.
[0016] An atom probe tomography image of a copper alloy steel
comprising 2.5 weight % copper is shown in FIG. 1. The copper alloy
steel was formed as described in Kapoor, M. et al., Acta Materialia
73 (2014) 56-74 (hereby incorporated by reference in its entirety),
with solution treatment at 950.degree. C., followed by
water-quenching and aging at 500.degree. C. for 2 hours. As shown
in FIG. 1, the copper is in the form of the nanoprecipitates,
although some copper may be present outside of the
nanoprecipitates, including in solid solution. These
nanoprecipitates are generally spherical in shape, but the term
"spherical" encompasses irregularly shaped nanoprecipitates as well
as nanoprecipitates having a more elongated morphology. All of the
nanoprecipitates in the copper alloy steel of FIG. 1 may be
considered spherical. The copper nanoprecipitates may be
characterized by an average radius. (By "average" it is meant an
average value over a representative number of nanoprecipitates. The
average value may be obtained from atom probe images such as that
shown in FIG. 1.) The average radius for the copper alloy steel of
FIG. 1 is 2.0.+-.0.6 nm. However, in general, the average radius
may vary depending upon the amount of copper in the copper alloy
steel and heat treatment. In embodiments, the copper alloy steel
has an average radius in a range of from 0.5 nm to 20 nm. This
includes an average radius in a range of from 0.5 nm to 10 nm, and
from 0.5 nm to 5 nm.
[0017] The average center-to-center spacing .lamda. between
neighboring Cu nanoprecipitates also depends upon the amount of
copper in the copper alloy steel and heat treatment. The value of
.lamda. is given by
d 2 .times. 3 .times. .pi. 4 .times. f , ##EQU00001##
wherein d is the average nanoprecipitate diameter and f is the
volume fraction. However, in embodiments, .lamda. is in a range of
from 5 nm to 200 nm, from 10 nm to 150 nm, and from 25 nm to 100
nm. Comparing the average nanoprecipitate radius and the average
.lamda. to the size of a microbe such as SARS-CoV-2 (having a
diameter of about 120 nm), it is clear that a microbe on a surface
of the copper alloy steel will be in contact with many copper atoms
simultaneously.
[0018] The copper nanoprecipitates in the copper alloy steel may be
further characterized by their crystal structure. In embodiments,
the crystal structure is bcc, i.e., the copper nanoprecipitates are
bcc copper nanoprecipitates. Theoretical calculations were
conducted to examine the interaction of microbes coming into direct
contact with copper atoms at the surfaces of bcc copper
nanoprecipitates. As an example, molecular dynamics simulation
using the large-scale atomic/molecular massively parallel simulator
(LAMMPS) was conducted on the interaction between a bcc Cu (111)
stepped surface and 150 hydrogen peroxide (H.sub.2O.sub.2)
molecules at room temperature (H.sub.2O.sub.2 is produced by human
cells and many bacteria species). FIG. 2 displays the evolution of
the number of H.sub.2O.sub.2, hydroxyl radicals, molecular oxygen,
and water molecules as a function of time. The fragmentation of
H.sub.2O.sub.2 upon contact with Cu is almost immediate, producing
hydroxyl radicals, oxygen, and water. These changes are accompanied
by the oxidation of Cu to form Cu.sup.+, strongly suggestive of
Fenton-like chemical reactions. The process appears to reach steady
state after about 60 ps and is indicative of the occurrence of a
back-reaction, i.e., formation of H.sub.2O.sub.2 from initial
reaction products. Both H.sub.2O.sub.2 and hydroxyl radicals are
reactive oxygen species that play an important role in
antimicrobial action.
[0019] As noted above, the methods of Kapoor, M. et al. may be used
to form the copper alloy steels. Other methods which may be used
are those described in Fine, M. E., et al., Metallurgical and
Materials Transactions A, Vol. 41A, December 2010, (hereby
incorporated by reference in its entirety). Some embodiments of
such copper alloy steels have been used as weather steels for civil
infrastructure applications, such as bridges, due to their
low-temperature toughness, weldability, and weather resistance.
However, these copper alloy steels have not previously been
considered for use in the very different application of
antimicrobial steels.
[0020] As noted above, the copper alloy steel may further comprise
an amount of chromium (Cr). The amount may be selected to provide
enough Cr so that a chromium oxide layer forms on a surface of the
copper alloy steel (thereby inhibiting rust formation) but not so
much Cr that the incorporation of copper and copper
nanoprecipitates into the chromium oxide layer is prevented. As
noted above, the amount may be in a range of from 0.0 weight % to
8.0 weight %.
[0021] In embodiments, a surface of the copper alloy steel is
textured. Different types of texture may be used and a variety of
known techniques may be used to achieve such texture types such as
buffing, etching, laser machining, forging, forming, milling,
polishing, rolling, turning, etc. The texture type (e.g.,
morphology and dimensions) may be selected to increase (e.g.,
maximize) the amount of surface area of the microbe in contact with
the antimicrobial surface. Thus, the texture type may depend upon
the target microbe. Illustrative texture types include grooves (one
dimensional (1D) texture type), pillars (2D), dimples (2D texture
type), and the like in any density and distribution. Such texture
types effectively provide the surface having a plurality of ridges
(1D)/peaks (2D) separated by a plurality of channels (1D)/valleys
(2D). A cross-section of these texture types is shown in the right
image of FIG. 3. The width of the channel/valley and the height of
the peak-to-valley (ridge-to-channel) (both of which may be an
average value) be selected to increase (e.g., maximize) the amount
of surface area of the microbe in contact with the antimicrobial
surface. This may be achieved by using texture type dimensions
(e.g., the width/height described above) that match the diameter of
the target microbe. As shown in FIG. 3, for SARS-CoV-2 coronavirus,
dimensions of about 100 nm are particularly useful to maximize
contact. In other embodiments, the surface of the copper alloy
steel is untextured, i.e., flat.
[0022] The present antimicrobial surfaces are characterized by
antimicrobial properties which are exhibited upon contact with a
microbe. Without wishing to be bound to a particular theory, these
antimicrobial properties may include an ability to induce
dissociation of certain components, e.g., proteins, of the
microbes, thereby reducing, including destroying, the viability of
the microbes. By way of example, molecular simulations were
conducted examining the interactions of a molecular model of the
S-protein of SARS-CoV-2 coronavirus with an illustrative
antimicrobial surface and for a control surface free of copper. The
control surface free of copper may have the same composition as the
antimicrobial surface except is free of copper. Such a control
surface may be referred to as a comparative surface. The
simulations showed that the S-protein quickly dissociates in the
presence of copper.
[0023] The present antimicrobial surfaces may be used against
microbes of any variety. The microbes include any bacteria, e.g.,
an Escherichia coli (E. coli) bacterium. The microbes include any
virus, e.g., SARS-CoV-2 coronavirus, or .PHI.-6. Contact between
the antimicrobial surfaces and the microbes may result from, e.g.,
touching, splattering, spilling, spraying, etc., the antimicrobial
surface with any material (e.g., a fluid, a sample, another
surface, etc.) containing the microbes. Use of the antimicrobial
surfaces effectively provides a method of reducing microbe
viability, reducing infection due to a microbe, reducing
transmission of such an infection, and the like.
[0024] The antimicrobial properties and efficacy of the present
antimicrobial surfaces against microbes may be quantified in a
variety of ways. However, such properties/efficacy can refer to a
number of colony forming units (CFUs) (or percentage thereof)
measured in a sample containing a target microbe after the sample
and antimicrobial surface have been in contact for a particular
period of time. This is illustrated in FIG. 4 showing the CFUs
obtained from a sample of E. coli HCB84 after contact with two
different illustrative antimicrobial surfaces, one comprising 2.5
wt % copper and one comprising 4.0 weight % copper, for 30 minutes.
The results for control surfaces are also shown, including a
copper-free "control" and pure copper "Cu". Clearly, the CFUs for
the illustrative antimicrobial surfaces are less than that of the
copper-free control surface. Remarkably, the CFUs for the
illustrative antimicrobial surfaces are less than 10 CFUs, a factor
30 less than that of the copper-free control surface. Moreover, the
CFUs for the illustrative antimicrobial surfaces are nearly the
same as that of pure copper. Another way to reference the
antimicrobial properties/efficacy of the antimicrobial surfaces is
to measure a half-life of a target microbe or a % kill of a target
microbe. For example, the antimicrobial surface may be
characterized by a half-life of a target microbe (e.g., SARS-CoV-2)
on the antimicrobial surface that is shorter than the half-life of
the target microbe on steel having a composition that is the same
as the copper alloy steel except is free of copper. The half-life
may be shorter by a factor of at least 5.
[0025] Due to their antimicrobial properties, the present
antimicrobial surfaces are used in environments in which microbes
are present, or are suspected of being present, including in
quantities that are more likely than not to result in infection of
a mammalian (e.g., human) subject. These environments include those
frequented by the public, such as hospitals and health care
facilities, schools, public transportation centers and vehicles,
public restroom facilities, recreation centers, shopping centers,
food service facilities, walkways of a bridge, etc. In embodiments,
the environment is an indoor environment, e.g., enclosed within one
or more walls such as a building, vehicle, tent, pavilion, etc.
They may also be used to make pet containers and chains.
[0026] In general, the present antimicrobial surfaces may be
incorporated into any article (which encompasses devices,
appliances, etc., and components thereof) in which steel (or other
materials, such as similar alloys and metals, glass, ceramics,
plastics, wood) is typically used and for which antimicrobial
properties are desired. In other words, the antimicrobial surfaces
may be used to replace steel (or a similar material as mentioned
above) in such articles in order to render the steel/materials
antimicrobial. However, the type of article is often one which is
configured for use by or contact with humans, including human body
parts such as hands, as well as fluids or samples from humans. Such
use generally refers to regular use, as opposed to incidental use.
Non-limiting examples of such articles include handles, hand-holds,
hand rails, doors, countertops, bed hardware, hardware in restroom
facilitates, etc. These are all surfaces which are touchable by
human body parts, e.g., hands, and which come into frequent contact
with members of the public. The articles do not include those used
in civil infrastructure applications, such as rebars in concrete.
In embodiments, the articles do not include bridges.
[0027] The present disclosure encompasses the antimicrobial
surfaces; articles, devices, appliances, and the like incorporating
such antimicrobial surfaces; and methods of making and using the
same.
[0028] The word "illustrative" is used herein to mean serving as an
example, instance, or illustration. Any aspect or design described
herein as "illustrative" is not necessarily to be construed as
preferred or advantageous over other aspects or designs. Further,
for the purposes of this disclosure and unless otherwise specified,
"a" or "an" means "one or more."
[0029] All numeric values of parameters in the present disclosure
are proceeded by the term "about" which means approximately. This
encompasses those variations inherent to the measurement of the
relevant parameter as understood by those of ordinary skill in the
art. This also encompasses the exact value of the disclosed numeric
value and values that round to the disclosed numeric value.
[0030] The foregoing description of illustrative embodiments of the
disclosure has been presented for purposes of illustration and of
description. It is not intended to be exhaustive or to limit the
disclosure to the precise form disclosed, and modifications and
variations are possible in light of the above teachings or may be
acquired from practice of the disclosure. The embodiments were
chosen and described in order to explain the principles of the
disclosure and as practical applications of the disclosure to
enable one skilled in the art to utilize the disclosure in various
embodiments and with various modifications as suited to the
particular use contemplated. It is intended that the scope of the
disclosure be defined by the claims appended hereto and their
equivalents.
* * * * *