U.S. patent application number 14/442412 was filed with the patent office on 2016-09-22 for separator media for electrochemical cells.
The applicant listed for this patent is E.I. DU PONT DE NEMOURS AND COMPANY. Invention is credited to Pankaj Arora, Hyun Sung Lim.
Application Number | 20160276640 14/442412 |
Document ID | / |
Family ID | 49627132 |
Filed Date | 2016-09-22 |
United States Patent
Application |
20160276640 |
Kind Code |
A1 |
Lim; Hyun Sung ; et
al. |
September 22, 2016 |
SEPARATOR MEDIA FOR ELECTROCHEMICAL CELLS
Abstract
A separator medium for electrochemical cells that contains at
least one nonwoven sheet of polymeric fibers. The nonwoven sheet
has a surface area of about 0.5 to about 1.5 m.sup.2/g and has a
maximum pore size that is equal to or more than 2.5 times the mean
flow pore size and more than 11 times the minimum pore size. The
sheet may be sulfonated to a level of 0.67% and demonstrates
superior tensile properties after sulfonation and relative to
previously known separators.
Inventors: |
Lim; Hyun Sung; (Midlothian,
VA) ; Arora; Pankaj; (Chesterfield, VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E.I. DU PONT DE NEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Family ID: |
49627132 |
Appl. No.: |
14/442412 |
Filed: |
November 8, 2013 |
PCT Filed: |
November 8, 2013 |
PCT NO: |
PCT/US13/69127 |
371 Date: |
May 13, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61726168 |
Nov 14, 2012 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 10/24 20130101;
H01M 2220/20 20130101; H01M 2220/10 20130101; H01G 9/02 20130101;
D04H 3/009 20130101; H01M 2/145 20130101; Y02E 60/10 20130101; D06M
11/54 20130101; D01F 6/04 20130101; H01M 2/162 20130101; H01M 10/26
20130101; Y02E 60/13 20130101; D01F 6/06 20130101; D04H 3/007
20130101; H01G 11/52 20130101; H01M 10/345 20130101; H01M 6/045
20130101; D04H 1/724 20130101; D01D 5/11 20130101; D04H 3/011
20130101 |
International
Class: |
H01M 2/16 20060101
H01M002/16; D04H 1/724 20060101 D04H001/724; H01M 6/04 20060101
H01M006/04; H01M 2/14 20060101 H01M002/14; H01M 10/26 20060101
H01M010/26 |
Claims
1. A separator medium for electrochemical cells comprising at least
one nonwoven sheet comprising polymeric fibers, wherein the
nonwoven sheet has a surface area of 0.5 to 1.5 m.sup.2/g and the
separator retains at least 70% of its machine direction (MD)
tensile strength relative to the medium when it is not subjected to
sulfonation.
2. The separator medium of claim 1, wherein the polymeric fibers
are sulfonated and contain at least 0.67% by weight of sulfur.
3. The separator medium of claim 1, wherein the polymeric fibers
comprise polymers selected from the group consisting of
polyolefins, polyesters, polyamides, polyaramids, polysulfones,
polyimides, fluorinated polymers and combinations thereof.
4. The separator medium of claim 3, wherein the polymeric fibers
are made from polyolefin polymers selected from the group
consisting of polyethylene, polypropylene, polybutylene and
polymethylpentene.
5. The separator medium of claim 1, wherein the polymeric fibers
have non-circular cross sections.
6. The separator medium of claim 1, wherein the polymeric fibers
are plexifilamentary fiber strands.
7. The separator medium of claim 1, wherein the nonwoven sheet is a
uniaxially stretched nonwoven sheet in the machine direction.
8. The separator medium of claim 1, wherein the nonwoven sheet has
a surface area of 0.5 to 1.0 m.sup.2/g.
9. The separator medium of claim 1, wherein the nonwoven sheet
consists of fibers that have a number average fiber diameter
greater than 1 micrometer for 100% of the fibers.
10. The separator medium of claim 1, wherein the nonwoven sheet has
an ammonia trapping capacity of 0.20 mmole/g and a machine
direction tensile strength retention of at least 16
newtons/centimeter (N/cm).
11. The separator medium of claim 1, wherein the nonwoven sheet has
a maximum pore size that is equal to or more than 2.5 times the
mean flow pore size and more than 11 times the minimum pore
size.
12. A process for producing a separator medium for electrochemical
cells comprising: flash spinning a solution of 12% to 24% by weight
polyethylene in a spin agent consisting of a mixture of normal
pentane and cyclopentane at a spinning temperature from 205.degree.
C. to 220.degree. C. to form plexifilamentary fiber strands and
collecting the plexifilamentary fiber strands into an unbonded web;
uniaxially stretching the unbonded web in the machine direction
between heated draw rolls at a temperature between 124.degree. C.
and 154.degree. C., positioned between 5 cm and 30 cm apart and
stretched between 3% and 25% to form the stretched web; and bonding
the stretched web between heated bonding rolls at a temperature
between 124.degree. C. and 154.degree. C. to form a nonwoven sheet
wherein the nonwoven sheet has a surface area of 0.5 to about 1.5
m.sup.2/g and a maximum pore size that is more than 2.5 times the
mean flow pore size and more than 11 times the minimum pore
size.
13. The process for producing the separator medium of claim 12,
further comprising sulfonating the nonwoven sheet after bonding the
stretched web.
14. An electrochemical cell of claim 1, wherein the cell is either
a battery or a capacitor.
15. An electrochemical cell, wherein the cell is an alkaline
battery comprising separator medium that further comprises at least
one nonwoven sheet comprising polymeric fibers wherein the nonwoven
sheet has a surface area of 0.5 to 1.5 m.sup.2/g and wherein the
nonwoven sheet has a maximum pore size that is equal to or more
than 2.5 times the mean flow pore size and more than 11 times the
minimum pore size, the polymeric fibers are sulfonated and contain
at least 0.67% by weight of sulfur and wherein the separator
retains at least 70% of its machine direction (MD) tensile strength
relative to the medium when it is not subjected to sulfonation.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to the field of separators for
electrochemical cells, and in particular alkaline batteries.
[0003] 2. Description of the Related Art
[0004] Alkaline batteries have become increasingly more popular
because of their high energy density. As such, these batteries are
increasingly used in applications normally reserved for the
traditional lead-acid battery systems.
[0005] In order to achieve extended battery life and efficiency in
alkaline systems, the use of battery separators is required. The
battery separators are located between the positive and negative
plates so as to provide, (1) a separation between the electrodes of
opposite charge, (2) an electrolyte reservoir, (3) a uniform
electrolyte distribution across the electrode surface so as to
permit uniform current density and (4) a space for electrode
expansion.
[0006] Battery separators used in alkaline batteries at present are
commonly formed of a polyolefin, preferably polypropylene,
polyamide or nylon non-woven sheet.
[0007] One of the major deficiencies in nickel metal hydride (NiMH)
battery systems is their high rate of self-discharge, that is,
continuously losing their charge during storage. The
"ammonia-shuttle" has major influence on the self-discharge. The
nitrogen containing impurities in Ni electrode are oxidized to form
nitrate which migrate through the separator to the cathode. The
nitrate is reduced to ammonia at the cathode. The ammonia again
passes through the separator and reaches the nickel electrode and
the shuttle is completed.
SUMMARY OF THE INVENTION
[0008] The present invention is directed to a separator medium for
electrochemical cell, where a electrochemical cell can be a battery
or a capacitor. In one embodiment, the medium comprises at least
one nonwoven sheet comprising polymeric fibers wherein the nonwoven
sheet has a surface area of about 0.5 to about 1.5 m.sup.2/g and
wherein the nonwoven sheet has a maximum pore size that is equal to
or more than 2.5 times the mean flow pore size and more than 11
times the minimum pore size.
[0009] The present invention is directed to a separator medium for
alkaline batteries, and in particular nickel metal hydride
batteries. In one embodiment, the medium comprises at least one
nonwoven sheet comprising polymeric fibers wherein the nonwoven
sheet has a surface area of about 0.5 to about 1.5 m.sup.2/g and
wherein the nonwoven sheet has a maximum pore size that is equal to
or more than 2.5 times the mean flow pore size and more than 11
times the minimum pore size. In a further embodiment, the polymeric
fibers are sulfonated and contain at least 0.67% by weight of
sulfur. In a further embodiment, the separator retains at least 70%
of its machine direction (MD) tensile strength relative to the
medium when it is not subjected to sulfonation.
[0010] The invention is further directed to a process for producing
a separator medium for electrochemical cells.
[0011] The invention is still further directed to an
electrochemical cell wherein the cell is an alkaline battery
comprising separator medium that further comprises at least one
nonwoven sheet comprising polymeric fibers wherein the nonwoven
sheet has a surface area of about 0.5 to about 1.5 m.sup.2/g and
wherein the nonwoven sheet has a maximum pore size that is equal to
or more than 2.5 times the mean flow pore size and more than 11
times the minimum pore size, the polymeric fibers are sulfonated
and contain at least 0.67% by weight of sulfur and wherein the
separator retains at least 70% of its machine direction (MD)
tensile strength relative to the medium when it is not subjected to
sulfonation.
DETAILED DESCRIPTION
[0012] Applicants specifically incorporate the entire contents of
all cited references in this disclosure. Further, when an amount,
concentration, or other value or parameter is given as either a
range, preferred range, or a list of upper preferable values and
lower preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of any upper range limit
or preferred value and any lower range limit or preferred value,
regardless of whether ranges are separately disclosed. Where a
range of numerical values is recited herein, unless otherwise
stated, the range is intended to include the endpoints thereof, and
all integers and fractions within the range. It is not intended
that the scope of the invention be limited to the specific values
recited when defining a range.
DEFINITIONS
[0013] The term "polymer" as used herein, generally includes but is
not limited to, homopolymers, copolymers (such as for example,
block, graft, random and alternating copolymers), terpolymers,
etc., and blends and modifications thereof. Furthermore, unless
otherwise specifically limited, the term "polymer" shall include
all possible geometrical configurations of the material. These
configurations include, but are not limited to isotactic,
syndiotactic, and random symmetries.
[0014] The term "polyolefin" as used herein, is intended to mean
any of a series of largely saturated polymeric hydrocarbons
composed only of carbon and hydrogen. Typical polyolefins include,
but are not limited to, polyethylene, polypropylene,
polymethylpentene, and various combinations of the monomers
ethylene, propylene, and methylpentene.
[0015] The term "polyethylene" as used herein is intended to
encompass not only homopolymers of ethylene, but also copolymers
wherein at least 85% of the recurring units are ethylene units such
as copolymers of ethylene and alpha-olefins. Preferred
polyethylenes include low-density polyethylene, linear low-density
polyethylene, and linear high-density polyethylene. A preferred
linear high-density polyethylene has an upper limit melting range
of about 130.degree. C. to 140.degree. C., a density in the range
of about 0.941 to 0.980 gram per cubic centimeter, and a melt index
(as defined by ASTM D-1238-57T Condition E) of between 0.1 and 100,
and preferably less than 4.
[0016] The term "polypropylene" as used herein is intended to
embrace not only homopolymers of propylene but also copolymers
where at least 85% of the recurring units are propylene units.
Preferred polypropylene polymers include isotactic polypropylene
and syndiotactic polypropylene.
[0017] The term "nonwoven sheet" as used herein means a structure
of individual fibers or threads that are positioned in a random
manner to form a planar material without an identifiable pattern,
as in a knitted fabric.
[0018] The term "plexifilament" as used herein means a
three-dimensional integral network or web of a multitude of thin,
ribbon-like, film-fibril elements of random length. Typically,
these have a mean film thickness of less than about 4 micrometers
and a median fibril width of less than about 25 micrometers. The
average film-fibril cross sectional area if mathematically
converted to a circular area would yield an effective diameter
between about 1 micrometer and 25 micrometers. In plexifilamentary
structures, the film-fibril elements intermittently unite and
separate at irregular intervals in various places throughout the
length, width and thickness of the structure to form a continuous
three-dimensional network.
[0019] "Sulfonation" refers to chemical binding of sulfur
containing moieties to at least a fraction of the polymer that the
fiber comprises. Sulfonation can be carried out by any method known
to one of skill in the art. For example, sulfonation can be carried
out using the vapor phase surface sulfonation of webs described in
U.S. Pat. No. 3,684,554. The basic process involves contacting the
dry polymer web with continuous blast of gaseous SO.sub.3 (2-15%
volume in dry inert gas) that can run continuously at high speed
(100-200 ft/sec). The sulfonated polymer web can be rinsed with DI
water. Sulfonation may also be carried out by the process of U.S.
Pat. No. 6,403,265 using concentrated sulfuric acid.
DESCRIPTION
[0020] The present invention overcomes the problems inherent in the
currently used separators and provides a wettable sheet material
with the desired tensile strength, ammonia absorption
characteristic, electrolyte absorption and electrical resistance
properties which is usable in alkaline batteries.
[0021] An object of the present invention is therefore to provide a
wettable sheet material useful as a separator in alkaline
batteries. Another object of the present invention is to provide a
sheet material which is wettable by electrolyte and has good
electrolyte absorption and ammonia absorption in an alkaline
battery system.
[0022] The present invention is therefore directed to a separator
medium for alkaline batteries, and in particular nickel metal
hydride batteries. In one embodiment, the medium comprises at least
one nonwoven sheet comprising polymeric fibers wherein the nonwoven
sheet has a surface area of about 0.5 to about 1.5 m.sup.2/g and
wherein the nonwoven sheet has a maximum pore size that is equal to
or more than 2.5 times the mean flow pore size and more than 11
times the minimum pore size. In a further embodiment, the polymeric
fibers are sulfonated and contain at least 0.67% by weight of
sulfur. In a further embodiment, the separator retains at least 70%
of its machine direction (MD) tensile strength relative to the
medium when it is not subjected to sulfonation.
[0023] The polymeric fibers may comprise polymers selected from the
group consisting of polyolefins, polyesters, polyamides,
polyaramids, polysulfones, polyimides, fluorinated polymers and
combinations thereof. When the polymeric fibers are made from
polyolefin the polymers may be selected from the group consisting
of polyethylene, polypropylene, polybutylene and
polymethylpentene.
[0024] Suitable polymers for use in the alkaline battery separator
also include aliphatic polyamide, semi-aromatic polyamide,
polyvinyl alcohol, cellulose, polyethylene terephthalate,
polypropylene terephthalate, polybutylene terephthalate,
polysulfone, polyvinylidene fluoride, polymethyl pentene,
polyphenylene sulfide, polyacetyl, polyacrylonitrile, polyurethane,
aromatic polyamide and blends, mixtures and copolymers thereof.
Polymers that are especially suitable for use in the alkaline
battery separator include polyvinyl alcohol, cellulose, aliphatic
polyamide and polysulfone.
[0025] The polymeric fibers can be plexifilamentary fiber strands.
The polymeric fibers may furthermore have non-circular cross
sections.
[0026] In a further embodiment, the nonwoven sheet is a uniaxially
stretched nonwoven sheet where the stretching has taken place in
the machine direction. The nonwoven sheet may furthermore have a
surface area of about 0.5 to about 1.0 m.sup.2/g.
[0027] In a still further embodiment the nonwoven sheet consists of
fibers that have a number average fiber diameter greater than 1
micrometer for 100% of the fibers.
[0028] The nonwoven sheet may have an ammonia trapping of 0.20
mmole/g and a machine direction tensile strength retention of at
least 16 Newtons/centimeter (N/cm.)
[0029] The invention is further directed to a process for producing
a separator medium for electrochemical cells. The process comprises
the steps of: [0030] (i) Flash spinning a solution of 12% to 24% by
weight polyethylene in a spin agent consisting of a mixture of
normal pentane and cyclopentane at a spinning temperature from
about 205.degree. C. to 220.degree. C. to form plexifilamentary
fiber strands and collecting the plexifilamentary fiber strands
into an unbonded web; [0031] (ii) Uniaxially stretching the
unbonded web in the machine direction between heated draw rolls at
a temperature between about 124.degree. C. and about 154.degree.
C., positioned between about 5 cm and about 30 cm apart and
stretched between about 3% and 25% to form the stretched web; and
[0032] (iii) Bonding the stretched web between heated bonding rolls
at a temperature between about 124.degree. C. and about 154.degree.
C. to form a nonwoven sheet wherein the nonwoven sheet has a
surface area of about 0.5 to about 1.5 m.sup.2/g and [0033] a
maximum pore size that is more than 2.5 times the mean flow pore
size and more than 11 times the minimum pore size.
[0034] The process for producing a separator medium may further
comprise sulfonating the nonwoven sheet after bonding the stretched
web.
[0035] The invention is further directed to an electrochemical cell
wherein the cell is an alkaline battery comprising separator medium
that further comprises at least one nonwoven sheet comprising
polymeric fibers wherein the nonwoven sheet has a surface area of
about 0.5 to about 1.5 m.sup.2/g and wherein the nonwoven sheet has
a maximum pore size that is equal to or more than 2.5 times the
mean flow pore size and more than 11 times the minimum pore size,
the polymeric fibers are sulfonated and contain at least 0.67% by
weight of sulfur and wherein the separator retains at least 70% of
its machine direction (MD) tensile strength relative to the medium
when it is not subjected to sulfonation.
[0036] The battery can be an alkaline primary battery, e.g.,
Zinc-Manganese Oxide or Zn--MnO.sub.2 battery in which the anode is
zinc and the cathode is manganese oxide (MnO.sub.2), or Zinc-Air
battery in which the anode is zinc and the cathode is air, or it
can be an alkaline secondary battery, e.g., a Nickel Cadmium
battery in which the anode is cadmium and the cathode is Nickel
oxy-hydroxide (NiOOH), Nickel Zinc or Ni--Zn battery in which the
anode is zinc and the cathode is NiOOH, Nickel Metal Hydride (NiMH)
battery in which the anode is metal hydride (e.g. LaNi.sub.5) and
the cathode is NiOOH or Nickel-Hydrogen or NiH.sub.2 battery in
which the anode is hydrogen (H.sub.2) and the cathode is NiOOH.
Other types of alkaline batteries include Zinc/Mercuric Oxide in
which the anode is zinc, and the cathode is mercury oxide (HgO),
Cadmium/Mercuric Oxide in which the anode is cadmium and the
cathode is mercury oxide, Zinc/Silver Oxide in which the anode is
zinc and the cathode is silver oxide (AgO), Cadmium/Silver Oxide in
which the anode is cadmium and the cathode is silver oxide. All of
these battery types use 30-40% potassium hydroxide as the
electrolyte.
[0037] The alkaline battery of this embodiment of the invention can
include a separator having an ionic resistance of less than about
300 milliohms-cm.sup.2, preferably less than 200
milliohms-cm.sup.2, most preferably less than 100 mohms-cm.sup.2,
as measured in 35% potassium hydroxide electrolyte solution at 1
KHz.
[0038] In some embodiments of the invention, it may be preferable
to crosslink the polymeric fine fibers in order to maintain the
porous structure and improve the structural integrity of the
separator in the electrolyte.
[0039] In some embodiments of the invention, it may be preferable
to coat the separators with surfactants prior to forming into a
battery in order to improve the wettability and wicking properties
in 30-40% KOH electrolyte. The surfactant is one that is stable in
a strong alkaline environment, such as an ionic surfactant.
Alternatively, the separators can undergo acrylic acid grafting to
improve the wettability of separators.
EXAMPLES
Test Methods
[0040] Ionic Resistance in KOH electrolyte is a measure of a
separator's resistance to the flow of ions, and was determined as
follows. Samples were cut into small pieces (1''.times.1'') and
soaked in 35% potassium hydroxide overnight to ensure thorough
wetting. Samples were sandwiched between two Teflon.RTM. shims with
a 1 cm.sup.2 window exposing the sample. The sandwich of
Teflon.RTM. shims and sample was placed in a resistance cell having
two platinum electrodes such that the window was facing the two
electrodes. The resistance was measured at 1 KHz using an HP
milliohmeter. The measurement was repeated without any separator
between the Teflon.RTM. shims. The difference between the two
readings is the resistance (milliohms) of the sample. The separator
resistance is then multiplied by the area of the electrodes (1
cm.sup.2 in this case) and the results are reported in
milliohms-cm.sup.2.
[0041] Basis Weight was determined by ASTM D-3776, which is hereby
incorporated by reference and reported in g/m.sup.2.
[0042] Porosity was calculated by dividing the basis weight of the
sample in g/m.sup.2 by the polymer density in g/cm.sup.3 and by the
sample thickness in micrometers and multiplying by 100 and
subsequently subtracting from 100%, i.e., percent
porosity=100-basis weight/(density.times.thickness).times.100.
[0043] Fiber Diameter was determined as follows. Ten scanning
electron microscope (SEM) images at 5,000.times. magnification were
taken of each fine fiber layer sample. The diameter of eleven (11)
clearly distinguishable fine fibers were measured from the
photographs and recorded. Defects were not included (i.e., lumps of
fine fibers, polymer drops, intersections of fine fibers). The
average (mean) fiber diameter for each sample was calculated.
[0044] Thickness was determined by ASTM D1777, which is hereby
incorporated by reference, and is reported in mils and converted to
micrometers.
[0045] Mean Flow Pore Size was measured according to ASTM
Designation E 1294-89, "Standard Test Method for Pore Size
Characteristics of Membrane Filters Using Automated Liquid
Porosimeter" which approximately measures pore size characteristics
of membranes with a pore size diameter of 0.05 .mu.m to 300 .mu.m
by using automated bubble point method from ASTM Designation F 316
using a capillary flow porosimeter (model number
CFP-34RTF8A-3-6-L4, Porous Materials, Inc. (PMI), Ithaca, N.Y.).
Individual samples (8, 20 or 30 mm diameter) were wetted with low
surface tension fluid (1,1,2,3,3,3-hexafluoropropene, or "Galwick,"
having a surface tension of 16 dyne/cm). Each sample was placed in
a holder, and a differential pressure of air was applied and the
fluid removed from the sample. The differential pressure at which
wet flow is equal to one-half the dry flow (flow without wetting
solvent) is used to calculate the mean flow pore size using
supplied software.
[0046] Tensile Strength was measured according to ASTM D5035-95,
"Standard Test Method for Breaking Force and Elongation of Textile
Fabrics (Strip Method)" and was reported in kg/cm.sup.2.
[0047] Surface Area was measure using a BET method. Branaur, Emmet
and Teller (BET) theory relates the amount of gas adsorption on a
solid surface to surface area. One gram of sample was placed in a
sample chamber and placed in liquid nitrogen to be degassed under
vacuum. After any surface adsorbed gases have been removed from the
sample surface, nitrogen is introduced to the sample. The volume of
nitrogen consumed by surface adsorption is measured and related to
surface area.
[0048] The ammonia trapping capacity was measured by ASTM D7129-09
"Standard test method for determination of ammonia trapping in a
grafted battery separator". The test measures amount of ammonia
retained by separator when a predetermined amount of separator and
ammonia hydroxide are conditioned under a controlled temperature
for a day.
[0049] Four different levels of sulfonation on the stretch bonded
nonwoven webs were carried out using the vapor phase surface
sulfonation of webs described in U.S. Pat. No. 3,684,554, issued
Aug. 15, 1972. The basic process involves contacting the dry
polymer web with continuous blast of gaseous SO.sub.3 (2-15% volume
in dry inert gas) that can run continuously at high speed (100-200
ft/sec). The sulfonated polymer web was rinsed with DI water.
[0050] The % sulfur on the sulfonated samples was measured by
Micro-Analysis, Inc, (Wilmington, Del.) Sulfur analyses are
performed by one of two procedures. In the Carlo Erba 1108 Sulfur
Autoanalyzer, samples are weighed on an electronic microbalance and
then introduced into the autoanalyzer which is maintained under a
positive pressure with the carrier gas of helium. Dynamic flash
combustion takes place at approximately 1400.degree. C. in an
oxygen atmosphere. Quantitative combustion is achieved by passing
the mixture of gases over tungstic anhydride on alumina to remove
any fluorine and then over the oxidizing agent tungstic anhydride.
The mixture is then passed over copper to remove excess oxygen and
to reduce the oxides of nitrogen to elemental nitrogen. The
resulting mixture is directed to the chromatographic column
containing Perapak PQS which is maintained at a constant
temperature in the range 60.degree. C.-80.degree. C., and the
individual components are separated and sulfur is eluted as sulfur
dioxide. The sulfur dioxide is measured with a thermal conductivity
detector whose signal feeds to a computer for data processing.
[0051] Using the LECO CHNS.cndot.932 analyzer, the products of
combustion in a CHNS analysis are CO.sub.2, H.sub.2O, NO.sub.x, and
SO.sub.x. The gases, which are carried through the system by the
helium carrier, are swept through the oxidation tube packed with
WO.sub.3 and copper. The copper removes excess oxygen to complete
the conversion to SO.sub.2. Oxides of Nitrogen are reduced to
N.sub.2. The gas mixture is swept through the H.sub.2O infrared
detection cell, and then passed through a water trap where H.sub.2O
is removed. The remaining gaseous mixture is then passed through
SO.sub.2, and CO.sub.2 IR cells, respectively. The SO.sub.2, and
CO.sub.2 are then removed and N.sub.2 is passed through a thermal
conductivity detector. The signals are fed to a computer for data
processing.
[0052] Examples 1 and 2 representing nonwoven sheets of the present
invention were made from flash spinning technology as disclosed in
U.S. Pat. No. 7,744,989, incorporated herein by reference with
additional thermal stretching prior to sheet bonding. Unbonded
nonwoven sheets were flash spun from a 20 weight percent
concentration of high density polyethylene having a melt index of
0.7 g/10 min (measured according to ASTM D-1238 at 190.degree. C.
and 2.16 kg load) in a spin agent of 60 weight percent normal
pentane and 40 weight percent cyclopentane. The unbonded nonwoven
sheets of Examples 1 and 2 were stretched and whole surface bonded.
The sheets were run between pre-heated rolls at 146.degree. C., two
pairs of bond rolls at 146.degree. C., one roll for each side of
the sheet, and backup rolls at 146.degree. C. made by formulated
rubber that meets Shore A durometer of 85-90 and two chill rolls.
Examples 1 and 2 were stretched 20% between two pre-heated rolls
with 10 cm span length at a rate 30.5 m/min at bonding temperature
of 146.degree. C. Example 1 was calendered under nip pressure at
500 PLI and Example 2 was made without the calendering. Comparative
Example A was Tyvek.RTM. 1056D (available from DuPont of
Wilmington, Del.), a commercial flash spun nonwoven sheet product
of basis weight 54.4 gsm. The sheet physical properties are given
in Tables 1 and 2.
[0053] Comparative Example B was prepared similarly to Examples 1
and 2, except without the sheet stretching. The unbonded nonwoven
sheet was whole surface bonded as disclosed in U.S. Pat. No.
7,744,989. Each side of the sheet was run over a smooth steam roll
at 359 kPa steam pressure and at a speed of 91 m/min.
[0054] Comparative Examples C and D are commercial
Spunbond-Meltblown-Spunbond (SMS) laminated products purchased from
Midwest Filtration Co. Cincinnati, Ohio and Comparative Example E
is a commercial nonwoven made of Polypropylene and is used as a
separator for NiMH batteries.
[0055] Tables 1 and 2 show how examples of this invention compared
to the comparative examples that were tested. Data in Tables 1 and
2 are for samples that were not sulfonated.
TABLE-US-00001 TABLE 1 Basis Thickness Porosity Weight (.mu.m) (%)
Sample (grams/meter.sup.2) @10 KPa (calculated) Example 1 37.3 91.4
57.5% Example 2 40.7 182.9 76.8% Comparative 54.2 172.7 67.2%
Example A Comparative 54.6 234.3 75.7% Example B Comparative 61.0
381.2 83.3% Example C Comparative 88.1 491.7 81.3% Example D
Comparative 63.8 144.2 53.8% Example E
TABLE-US-00002 TABLE 2 Mini- Maxi- mum Mean mum Maximum Maximum
Pore Pore Pore Pore Size/ Pore Size/ Surface Size Size Size Mean
Minimum Area Sample (.mu.m) (.mu.m) (.mu.m) Pore Size Pore Size
(m.sup.2g) Example 1 0.5 3.4 12.0 3.5 22.0 1.15 Example 2 0.6 8.3
22.6 2.7 37.7 0.72 Comparative 0.2 2.1 7.4 3.5 38.4 4.80 Example A
Comparative 0.4 2.9 10.0 3.4 22.9 3.43 Example B Comparative 6.5
9.8 20.7 2.1 3.2 0.41 Example C Comparative 4.3 7.7 23.7 3.1 5.6
0.47 Example D Comparative 3.4 13.3 36.1 2.7 10.5 0.22 Example
E
[0056] Table 3 shows the results obtained before and after
sulfonation. Examples 1-1 and 2-1 demonstrated superior ammonia
trapping ability after sulfonation with only a small loss in
tensile strength.
TABLE-US-00003 TABLE 3 Sulfur Ammonia MD Tensile content trapping
Strength Sample (%) (mmole/g) (N/cm) Example 1 0 0 38.8 Example 1-1
3.62 0.1679 25.7 Example 2 0 0 40.7 Example 2-1 2.02 0.4479 37.6
Comparative 0.0 0.0 22.1 Example C Comparative 1.5 0.176 9.9
Example C-1 Comparative 0.0 0.00 41.3 Example D Comparative 3.1
0.13 15.7 Example D-1
* * * * *