U.S. patent application number 14/759946 was filed with the patent office on 2015-12-10 for diaphragm cloth for water electrolyzer and manufacturing method therefor.
The applicant listed for this patent is TORAY INDUSTRIES, INC.. Invention is credited to Masaaki Takeda, Lili Yang, Youjuan Zhang.
Application Number | 20150354074 14/759946 |
Document ID | / |
Family ID | 51186198 |
Filed Date | 2015-12-10 |
United States Patent
Application |
20150354074 |
Kind Code |
A1 |
Yang; Lili ; et al. |
December 10, 2015 |
DIAPHRAGM CLOTH FOR WATER ELECTROLYZER AND MANUFACTURING METHOD
THEREFOR
Abstract
A diaphragm cloth for a water electrolyzer includes a woven
fabric, non-woven cloth or knitted fabric composed of
alkali-resistant fiber at a common use temperature of no less than
150.degree. C., an average pore size of the diaphragm cloth is less
than 10 .mu.m and, under conditions of pressure of 3 KPa, venting
quality of the diaphragm cloth is 2 L/cm.sup.2/min or less.
Inventors: |
Yang; Lili; (Nantong,
CN) ; Takeda; Masaaki; (Nantong, CN) ; Zhang;
Youjuan; (Nantong, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TORAY INDUSTRIES, INC. |
Tokyo |
|
JP |
|
|
Family ID: |
51186198 |
Appl. No.: |
14/759946 |
Filed: |
January 20, 2014 |
PCT Filed: |
January 20, 2014 |
PCT NO: |
PCT/CN2014/070896 |
371 Date: |
July 9, 2015 |
Current U.S.
Class: |
204/296 ;
204/295; 8/115.52 |
Current CPC
Class: |
D06M 2101/30 20130101;
C25B 13/08 20130101; Y02E 60/36 20130101; D06M 2101/22 20130101;
Y02E 60/366 20130101; C25B 1/10 20130101; D06M 10/00 20130101 |
International
Class: |
C25B 13/08 20060101
C25B013/08; D06M 10/00 20060101 D06M010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 18, 2013 |
CN |
201310026190.X |
Jul 8, 2013 |
CN |
201310284342.6 |
Claims
1-19. (canceled)
20. A diaphragm cloth for a water electrolyzer comprising a woven
fabric, non-woven cloth or knitted fabric composed of
alkali-resistant fiber at a common use temperature of no less than
150.degree. C., an average pore size of the diaphragm cloth is less
than 10 .mu.m and, under conditions of pressure of 3 KPa, venting
quality of the diaphragm cloth is 2 L/cm.sup.2/min or less.
21. The diaphragm cloth according to claim 20, wherein said
alkali-resistant fiber at a common use temperature of above
150.degree. C. is at least one selected from the group consisting
of polyphenylene sulfide fiber, polytetrafluoroethylene fiber,
poly(p-phenylene benzobisoxazole) fiber and
poly(ether-ether-ketone) fiber.
22. The diaphragm cloth according to claim 21, wherein said
alkali-resistant fiber at a common use temperature of no less than
150.degree. C. is polyphenylene sulfide fiber.
23. The diaphragm cloth according to claim 20, wherein the
alkali-resistant fiber at a common use temperature of above
150.degree. C. contains hydrophilic groups on its surface, and the
content of oxygen element on a surface of the fiber is 12 wt % or
more.
24. The diaphragm cloth according to claim 23, wherein said content
of oxygen element on the fiber surface is 15-40 wt %.
25. The diaphragm cloth according to claim 23, wherein said
hydrophilic groups are at least one selected from the group
consisting of carboxyl groups, carbonyl groups, hydroxyl groups and
formyl groups, and total content of the hydrophilic groups is
10-60% of the total content of the groups on the fabric
surface.
26. The diaphragm cloth according to claim 20, wherein pores with a
pore size of 0.2-10 .mu.m in the diaphragm cloth take up no less
than 60% of all pores.
27. The diaphragm cloth according to claim 20, wherein stiffness of
the diaphragm cloth in both warp and weft directions is no less
than 3 N.
28. The diaphragm cloth according to claim 20, wherein stiffness of
the diaphragm cloth in both warp and weft directions is no less
than 5 N.
29. The diaphragm cloth according to claim 22, wherein the
polyphenylene sulfide fiber contains no less than 20 wt % of
modified cross-section polyphenylene sulfide fiber.
30. The diaphragm cloth according to claim 29, wherein said
modified cross-section polyphenylene sulfide fiber is crossed,
latticed, polygonal, leaf-shaped, elliptic or flat cross-section
polyphenylene sulfide fiber.
31. The diaphragm cloth according to claim 20, wherein said woven
fabric is plain cloth.
32. The diaphragm cloth according to claim 31, wherein the plain
cloth has a cover factor of 2300 to 3000.
33. The diaphragm cloth according to claim 20, wherein said knitted
fabric is wrap-knitted fabric.
34. A method of manufacturing the diaphragm cloth according to
claim 20, comprising: weaving, non-weaving or knitting with
alkali-resistant fiber at a common use temperature of no less than
150.degree. C. to obtain high-temperature-resistant and
alkali-resistant woven fabric, non-woven cloth or knitted fabric,
refining and drying the woven fabric or knitted fabric after
weaving; and subjecting a surface of the obtained woven fabric,
non-woven cloth or knitted fabric to discharge modification to
obtain the diaphragm cloth.
35. The method according to claim 34, wherein said discharge
modification is plasma treatment or electric ironing treatment.
36. The method according to claim 35, wherein said plasma treatment
is vacuum plasma surface treatment or atmospheric pressure plasma
surface treatment.
37. The method according to claim 36, wherein, during the vacuum
plasma surface treatment, the process gas is selected from the
group consisting of oxygen, argon, a gas mixture of oxygen and
argon, carbon dioxide and air, pressure of a vacuum chamber is
5-100 Pa, and treatment intensity is 50-500 KWs/m.sup.2.
38. The method according to claim 36, wherein, during the
atmospheric pressure plasma surface treatment, the process gas is
air, and treatment intensity is 50-500 KWs/m.sup.2.
Description
TECHNICAL FIELD
[0001] This disclosure relates to a kind of diaphragm cloth for a
water electrolyzer and a manufacturing method therefor.
BACKGROUND
[0002] As the key material of a water electrolyzer, diaphragm cloth
is disposed between an anode and a cathode of the water
electrolyzer to prevent gas on the anode side from mixing with gas
on the cathode side and thus to ensure the purity of gas. Diaphragm
cloth has the following requirements on its properties: full
wettability by the electrolyte; small average pore size and high
gas-tightness; large porosity; certain mechanical strength and
stiffness; corrosion resistance to alkaline electrolyte,
high-temperature resistance, strong chemical stability and ease of
production.
[0003] At present, major factories of equipment that produces
hydrogen by alkaline water electrolysis in China still use asbestos
cloth as a diaphragm cloth. However, with the advance of
industrialization and the technical progress, during the production
practice, it is gradually recognized that the asbestos diaphragms
have some problems. First, due to the swelling property and
chemical instability of asbestos diaphragms, pure asbestos
diaphragms experience serious swelling in a specific operating
environment, particularly under a high current load so that the
mechanical strength of the diaphragms is reduced and the service
life thereof is shortened. Moreover, limited by the asbestos
material, the temperature of the electrolyte has to be controlled
below 90.degree. C. When the temperature of the electrolyte exceeds
90.degree. C., the corrosion to the asbestos diaphragms will be
aggravated so that the electrolyte is polluted and the service life
of the asbestos diaphragms is influenced. As a result, it is very
difficult to improve the efficiency of an electrolyzer by
increasing the temperature of the solution. In addition, the
asbestos material also has the problems of source reduction, high
price, and unstable quality. Comprehensively considering the above
reasons, the development and application of novel diaphragm
material which can replace the asbestos diaphragms has become a
very important issue in the industry. The manufacturers of
equipment for producing hydrogen by water electrolysis also
successively and actively explore high-performance novel diaphragm
material which is energy-saving, environmentally friendly and easy
to produce. However, due to the following problems, the so-called
novel diaphragm material still can not completely replace current
asbestos diaphragms.
[0004] CN101372752A discloses non-woven cloth made of common
polyphenylene sulfide fiber, where the non-woven cloth is
sulfonated with 90%-98% H.sub.2SO.sub.4 at 70-130.degree. C. for
20-40 min and then treated with 30% potassium hydroxide to finally
obtain a high-temperature-resistant diaphragm for an alkaline water
electrolyzer. As the non-woven cloth has a relatively high liquid
absorption rate, the non-woven cloth, after being treated by strong
acid, needs to consume a large amount of valuable water resource
and chemicals during a cleaning process and takes a long time to
clean, and the technological operation is complicated and easily to
pollute the environment. Meanwhile, such non-woven cloth is low in
safety and not suitable for industrial production.
[0005] In addition, CN101195944A discloses asbestos-free,
environmental and energy-saving diaphragm cloth which is woven
fabric made of one or more of poly(ether-ether-ketone) fiber,
polyphenylene sulfide fiber and polypropylene fiber. Although the
gas-tightness of this diaphragm cloth fulfills the standard
requirements of an asbestos diaphragm, the hydrophilicity of the
obtained diaphragm cloth is poor because the chemical fiber has
poor water absorption, and thus is unable to actually fulfill the
use requirements.
[0006] It could therefore be helpful to provide a diaphragm cloth
for a water electrolyzer with high gas-tightness and excellent ion
permeability and a manufacturing method of a diaphragm cloth for a
water electrolyzer with a simple process, lower energy use and
decreased environmental pollution.
SUMMARY
[0007] We provide a diaphragm cloth for a water electrolyzer
including a woven fabric, non-woven cloth or knitted fabric
composed of alkali-resistant fiber at a common use temperature of
no less than 150.degree. C.; an average pore size of the diaphragm
cloth is less than 10 .mu.m and, under conditions of pressure of 3
KPa, venting quality of the diaphragm cloth is 2 L/cm.sup.2/min or
less.
[0008] We also provide a method of manufacturing the diaphragm
cloth for a water electro-lyzer including a woven fabric, non-woven
cloth or knitted fabric composed of alkali-resistant fiber at a
common use temperature of no less than 150.degree. C.; an average
pore size of the diaphragm cloth is less than 10 .mu.m and, under
conditions of pressure of 3 KPa, venting quality of the diaphragm
cloth is 2 L/cm.sup.2/min or less, including weaving, non-weaving
or knitting with alkali-resistant fiber at a common use temperature
of no less than 150.degree. C. to obtain high-temperature-resistant
and alkali-resistant woven fabric, non-woven cloth or knitted
fabric, refining and drying the woven fabric or knitted fabric
after weaving, and subjecting a surface of the obtained woven
fabric, non-woven cloth or knitted fabric to discharge modification
to obtain the diaphragm cloth.
DETAILED DESCRIPTION
[0009] We provide a diaphragm cloth for a water electrolyzer,
wherein the diaphragm cloth is woven fabric, non-woven cloth or
knitted fabric composed of alkali-resistant fiber at a common use
temperature of no less than 150.degree. C.; the average pore size
of the diaphragm cloth is smaller than 10 .mu.m; and under the
condition of a pressure at 3 KPa, the venting quality of the
diaphragm cloth is 2 L/cm.sup.2/min or less.
[0010] If the average pore size and the venting quality of the
diaphragm cloth are controlled within the above ranges, high
gas-tightness of the diaphragm for a water electrolyzer can be
ensured. In this way, gas molecules and bubbles are difficult to
pass through. As a result, gas on the anode side can be prevented
from mixing with gas on the cathode side, the purity of gas and
good safety are ensured. From the perspective of ensuring the
separator fabric to stably have high gas-tightness for a long term,
preferably, the average pore size of the diaphragm cloth is less
than 5 .mu.m and the venting quality is 1.5 L/cm.sup.2/min or
less.
[0011] To ensure the diaphragm cloth has high gas-tightness and to
improve generation efficiency of gas and purity of the generated
gas, the average pore size is kept within a certain range and the
weaving conditions are controlled to improve the uniformity of the
pore size. In other words, preferably, the average pore size is
less than 10 .mu.m, and pores with a pore size of 0.2-10 .mu.m in
the diaphragm cloth take up no less than 60% of all pores; more
preferably, pores with a pore size of 0.2-10 .mu.m in the diaphragm
cloth take up no less than 80% of all pores; and particularly
preferably, the average pore size is less than 5 .mu.m, and pores
with a pore size of 0.2-5 .mu.m in the diaphragm cloth take up
above 60% of all pores.
[0012] The diaphragm cloth for a water electrolyzer is formed from
high-temperature-resistant and alkali-resistant fiber at a common
use temperature of no less than 150.degree. C., such fiber is
usually at least one of polyphenylene sulfide (PPS) fiber,
polytetrafluoroethylene (PTFE) fiber, poly(p-phenylene
benzobisoxazole) (PBO) fiber and poly(ether-ether-ketone) (PEEK)
fiber. Considering the requirement of use performance, cost and
hydrophilic processability, the polyphenylene sulfide (PPS) fiber
is preferred.
[0013] In addition, the cover factor of the fabric is a parameter
which characterizes the tightness of the fabric. The higher the
cover factor is, the tighter the fabric is, and the smaller the
venting quality and pore size are. The weave of the woven fabric is
plain weave, twill weave, satin weave, derivative weave and
multiple weave thereof, where the plain cloth has the most weaving
points and the largest tightness. From the perspective of better
fulfilling the gas-tightness requirement of the diaphragm cloth,
the plain cloth is preferred of the above mentioned woven fabric
plain cloth. When the diaphragm cloth is plain cloth, the cover
factor ranges from 2300 to 3000, preferably 2500 to 2900. If the
cover factor of the plain cloth is less than 2300, the
gas-tightness of the fabric is low due to insufficient tightness of
the fabric, thus the diaphragm cloth is difficult to prevent gas on
the cathode side and gas on the anode side from passing through,
and both the purity of gas and the safety thus can not be ensured.
On the other hand, if the cover factor of the plain cloth is more
than 3000, the higher requirements are proposed for a weaving
machine and the weaving is difficult. When the diaphragm cloth is
of multiple weave, for example, weft-backed, weft-tripled or
multi-layer fabric, the density of warps or wefts can be further
improved under limited conditions of weaving tightness, thereby
reducing the venting quality of the fabric and improving the
gas-tightness. When the diaphragm cloth is knitted fabric, the
cover factor of the knitted fabric is 0.7 to 1.5.
[0014] When in practical operation, if the diaphragm cloth for a
water electrolyzer can remain airtight for 2 min at a pressure of
no less than 200 mm H.sub.2O (2 KPa), the use requirement of
gas-tightness of the diaphragm cloth for a water electrolyzer can
be basically fulfilled. From the perspective of ensuring the
diaphragm cloth to have excellent gas-tightness, ion permeability
and diaphragm cloth processability, the diaphragm cloth for a water
electrolyzer preferably has gas-tightness remaining for 2 min at a
pressure of 250-450 mm H.sub.2O (2.5-4.5 KPa). If the gas-tightness
is less than 250 mm H.sub.2O (2.5 KPa), the basic requirement on
the diaphragm can not be fulfilled, and the purity of the generated
gas will be influenced. On the other hand, if the gas-tightness is
more than 450 mm H.sub.2O (4.5 KPa), it is likely to result in
difficult weaving and high cost; furthermore, the resistance of the
separator will be increased and the energy consumption for a unit
of gas generation is thus increased.
[0015] The diaphragm cloth for a water electrolyzer has high
stiffness. During mounting of the diaphragm, the high stiffness can
make the separator difficultly wrinkled during the cutting and
mounting process, so it is easier, more convenient and more
efficient to mount. Meanwhile, a size deviation caused in the
cutting process and a thickness deviation caused by wrinkling in
the mounting process of the diaphragm can be reduced. Thus, the
uniformity of the diaphragm in use is improved. In addition, during
operation of an electrolyzer, electrolyte flows in a space between
a polar plate and a diaphragm, and the high stiffness of the
diaphragm can make the diaphragm cloth generate a smaller
deformation when the diaphragm cloth suffering from pressure or
other external acting force so that the diaphragm cloth has a
smaller influence on the gas-tightness of the diaphragm,
electrolysis and voltage, and the stability of the system operation
can be thus ensured. The stiffness of the diaphragm cloth in both
warp and weft directions is no less than 3 N, preferably no less
than 5N.
[0016] To improve both ion permeability and working efficiency of
the diaphragm and achieve the goal of saving energy and reducing
consumption, we conducted studies from the perspective of improving
the hydrophilicity of the diaphragm. Specifically, in the diaphragm
cloth for a water electrolyzer, the high-temperature-resistant and
alkali-resistant fiber at a common use temperature of no less than
150.degree. C. contains hydrophilic groups on its surface, and the
content of oxygen element on the fiber surface is 12 wt % or more.
If the content of oxygen element on the fiber surface is less than
12 wt %, improvement in hydrophilicity of the diaphragm cloth is
low, and the diaphragm cloth cannot be completely wetted by the
electrolyte, resulting in poor ion permeability, large resistance
of the diaphragm cloth, low electrolysis efficiency and large
energy loss. Considering the balance between the hydrophilicity of
the diaphragm cloth and the processing cost, the content of oxygen
element on the fiber surface is preferably with 15-40 wt %, more
preferably within 15-30 wt %.
[0017] The type of hydrophilic groups and chemical bonds contained
on the surface of the high-temperature-resistant and
alkali-resistant fiber at a common use temperature of no less than
150.degree. C. is related to a processing method and the type of
processing gas. The hydrophilic groups are at least one of carboxyl
groups (COOH), carbonyl groups (C.dbd.O), hydroxyl groups (--OH),
formyl groups (CHO) or --SO.sub.x. Preferably, the hydrophilic
groups are at least one of carboxyl groups (COOH), carbonyl groups
(C.dbd.O), hydroxyl groups (--OH) or formyl groups (CHO), and the
total content of the hydrophilic groups takes up 10-60% of the
total content (mol number) of the groups on the fabric surface.
Considering the balance between the hydrophilicity of the diaphragm
and the processing cost, more preferably, the total content of the
hydrophilic groups takes up 20-50% of the total content (mol
number) of the groups on the fabric surface.
[0018] When the diaphragm cloth for a water electrolyzer is
composed of polyphenylene sulfide fiber, no less than 20 wt % of
the polyphenylene sulfide fiber is modified cross-section
polyphenylene sulfide fiber. As its specific surface area larger
than that of a circular cross-section, the modified cross-section
polyphenylene sulfide fiber may improve water absorption and water
conductivity of the fabric by wicking If the content of the
modified cross-section polyphenylene sulfide fiber is less than 20
wt %, the specific surface area of fiber in yarns will be reduced
so that improvement in water absorption and water conductivity of
the prepared diaphragm cloth is not significant, hydrophilicity of
the diaphragm cloth is poor, ion permeability and the effect of
energy saving are influenced.
[0019] The modified cross-section polyphenylene sulfide fiber may
be crossed, latticed, polygonal, leaf-shaped, elliptic or flat
cross-section polyphenylene sulfide fiber. From the perspective of
preparing diaphragm cloth with excellent hydrophilicity, the
modified cross-section polyphenylene sulfide fiber is preferably
crossed or polygonal cross-section polyphenylene sulfide fiber.
Among the polygonal cross-section polyphenylene sulfide fiber,
hexagonal cross-section polyphenylene sulfide fiber is
preferred.
[0020] The knitted fabric may be warp-knitted fabric. The
warp-knitted fabric is obtained from weaving polyphenylene sulfide
yarns or filaments by warp knitting equipment via warp knitting
processes. The number of yarns forming the warp-knitted fabric is
brought to be lower than that of yarns forming the woven fabric,
and the yarns are arranged in a same direction so that the water
absorption and water conductivity of the diaphragm cloth may be
improved. In addition, the warp-knitted fabric itself has a feature
of shrinkage, and due to the shrinkage of the warp-knitted fabric,
the diaphragm cloth may be allowed to have high density and high
gas-tightness.
[0021] The fabric for the diaphragm cloth for a water electrolyzer
is subjected to hydrophilic treatment so that the water absorption
of the diaphragm cloth for a water electrolyzer may be improved by
no less than 15%, compared with the fabric before treatment. If the
improvement rate of the water absorption is less than 15%, the
improvement effect of the hydrophilicity is poor. Considering the
balance between the hydrophilicity and the processability of the
diaphragm cloth, the improvement rate of the water absorption is
preferably 15-200%, more preferably 20-100%.
[0022] We further include a manufacturing method of the diaphragm
cloth for a water electrolyzer. In the manufacturing method,
high-temperature-resistant and alkali-resistant fiber at a common
use temperature of no less than 150.degree. C. are woven, non-woven
or knitted to obtain high-temperature-resistant and
alkali-resistant woven fabric, non-woven cloth or knitted fabric,
the woven fabric or knitted fabric are refined and dried after
weaving, and then the surface of the obtained woven fabric,
non-woven cloth or knitted fabric is subjected to discharge
modification to obtain the finished product.
[0023] The raw material of the non-woven cloth is preferably
polyphenylene sulfide fiber. The manufacturing method of non-woven
cloth made of polyphenylene sulfide fiber is as fol-lows: stretched
polyphenylene sulfide fiber is mixed with non-stretched
polyphenylene sulfide fiber in water at a certain proportion by
weight to form papermaking dispersion, then the wet-laid non-woven
cloth of polyphenylene sulfide fiber wet-laid obtained by a
wet-laid non-weaving process, then dried and calendered by a roll
calendar consisting of a steel roll and a paper roll, and the
surface (front side) of the non-woven cloth of polyphenylene
sulfide fiber is brought into contact with the steel roll and then
heated and pressurized to obtain single-side pressed non-woven
cloth; then, the inner side of non-woven cloth is brought into
contact with the steel roll and then heated and pressurized to
obtain double-side pressed non-woven cloth; and finally, the
surface of the double-side pressed non-woven cloth is subjected to
discharge modification.
[0024] The discharge modification increases the number of
hydrophilic groups on the surface of fabric by a physical
processing method and thus to further improve hydrophilicity of the
diaphragm cloth. Compared to a method of subjecting fabric to
hydrophilic treatment with a hydrophilic chemical reagent, this
method will not bring any burden to the environment and can
generate durability which ordinarily will not be generated by the
hydrophilic chemical reagent in the alkaline environment, and the
hydrophilicity may be remained after long-term use in the alkaline
environment.
[0025] The discharge modification is plasma treatment or electric
ironing treatment, preferably plasma treatment. After the fabric is
subjected to plasma treatment, the fiber surface of the fabric is
etched so that the surface area is increased. On the other hand,
active groups are generated on the fiber surface so that graft
copolymerization of hydrophilic monomers on the material surface is
caused. Accordingly, when applied in a water electrolyzer, the
fabric is easily wet by the electrolyte so that the hydrophilicity
of the diaphragm cloth is improved.
[0026] The plasma treatment is preferably vacuum plasma surface
treatment or atmospheric pressure plasma surface treatment. When
the vacuum plasma surface treatment is employed, a gas (process
gas) that forms plasma may be oxygen or argon, or a gas mixture of
oxygen and argon, or may be carbon dioxide or air. Generally, the
pressure of the used vacuum chamber is 5-100 Pa, and the treatment
intensity is 50-500 KWs/m.sup.2. When the treatment gas is oxygen,
after plasma surface treatment, oxygen-containing polar groups can
be formed on the fiber surface. Thus, the diaphragm cloth has
excellent hydrophilicity. When the process gas is argon, as argon
is an inert gas with high molecular energy and is easy to be
ionized, the fiber on the surface of the fabric is easily activated
to fully form polar groups. When the process gas is a gas mixture
of oxygen and argon, under the combined action of oxygen and argon,
the fiber on the surface of the plasma-ionized fabric is activated
first, to be grafted more easily when meeting the oxygen component.
To increase the number of formed hydrophilic groups and prolong
duration of their effects, the process gas is preferably a gas
mixture of oxygen and argon. In addition, as air contains oxygen,
nitrogen and carbon dioxide, when air is used as the process gas,
the plasma-treated fabric can also achieve excellent
hydrophilicity.
[0027] When the vacuum plasma surface treatment is employed, the
pressure in the used vacuum chamber is generally 5-100 Pa.
Considering treatment effect and energy consumption, the pressure
is preferably 30-70 Pa. The treatment intensity is 50-500
KWs/m.sup.2, preferably 80-300 KWs/m.sup.2. The treatment intensity
is calculated by the following formula:
treatment intensity=discharge power (KW).times.treatment duration
(s)/treatment area (m.sup.2), or
treatment intensity=discharge power (KW)/treatment rate
(m/s)/treatment breadth (m).
[0028] If the treatment intensity is less than 50 KWs/m.sup.2, the
energy of the charged particles of the plasma is low, thereby
leading to a weak cross-linking action on the fiber surface and
very few of hydrophilic groups generated on the fiber surface so
the finally formed diaphragm cloth is difficult to be fully wetted
by the electrolyte. If the treatment intensity is more than 500
KWs/m.sup.2, the treatment effect becomes stable when the treatment
intensity reaches about 500 KWs/m.sup.2 so that further increasing
the treatment intensity will increase the energy consumption rather
than improving the treatment effect. From the perspective of
allowing the number of hydrophilic groups on the fiber surface to
be saturated and avoiding waste of energy, the treatment intensity
is preferably 80-300 KWs/m.sup.2. In this case, the energy of the
charged particles is increased, and the cross-linking action can
play a full role.
[0029] When the atmospheric pressure plasma surface treatment is
employed and air is used as the process gas, the treatment
intensity is generally set as 50-500 KWs/m.sup.2. The treatment
intensity is calculated by the following formula:
treatment intensity=discharge power (KW)/treatment rate
(m/s)/treatment breadth (m).
[0030] If the treatment intensity is less than 50 KWs/m.sup.2,the
energy of the charged particles of the plasma is low, thereby
leading to a weak cross-linking action on the fiber surface and
very few of hydrophilic groups generated on the fiber surface so
the finally formed diaphragm cloth is difficult to be fully wetted
by electrolyte. If the treatment intensity is more than 500
KWs/m.sup.2, the treatment effect becomes stable when the treatment
intensity reaches about 500 KWs/m.sup.2 so that further increasing
the treatment intensity will increase the energy consumption rather
than improving the treatment effect. From the perspective of
allowing the number of hydrophilic groups on the fiber surface to
be saturated and avoiding waste of energy, the treatment intensity
is preferably 80-300 KWs/m.sup.2. In this case, the energy of the
charged particles is increased, and the cross-linking action can
play a full role.
[0031] In addition, during or after the plasma treatment, the
fabric surface can be subjected to graft modification with a graft
modification chemical reagent. For example, the fabric surface can
be grafted with carboxyl groups, acrylic groups, sulfonic groups or
the like.
[0032] The diaphragm cloth for a water electrolyzer has the
features of high gas-tightness and excellent ion permeability, also
has low cost, safety, environmental friendliness and light weight;
and the manufacturing method is rapid, high efficiency, no
pollution, simple operation and energy saving.
[0033] Alkali resistance, the common use temperature, the
hydrophilic groups and the total content (mol number) of the
hydrophilic groups are defined as follows: [0034] Alkali
resistance: the strength of fiber is still kept no less than 95% of
the original strength after the fiber is treated in 10% NaOH at
93.degree. C. for 7 days. [0035] Common use temperature: a
temperature at which the strength is to be reduced by half after
exposure for one hundred thousand hours. The common use temperature
is calculated by the Arrhenius equation. [0036] Hydrophilic groups:
atomic groups which are weakly bonded with water molecules by
bonding with hydrogen atoms.
[0037] The percentage of the total content of hydrophilic groups in
the total content (mol number) of groups on the fabric surface:
chemical components on the fiber surface are analyzed qualitatively
and quantitatively by an X-ray photoelectron spectroscopy (XPS),
then peak separation analysis is performed to Peak C, and the type
and mol concentration content of groups are judged according to the
result of peak separation, where oxygen-containing polar groups are
hydrophilic groups, and the sum of mol concentration percentages of
the hydrophilic groups is the percentage of the total content of
hydrophilic groups in the total content of groups on the fabric
surface.
EXAMPLES
[0038] Our cloth and methods will be further described by the
following examples. However, the scope of protection afforded by
this disclosure is not limited thereto.
[0039] In the examples, the physical properties of the fiber are
measured by the following methods or calculated by the following
formulae.
Cover Factor
[0040] (1) The cover factor of woven fabric is calculated by the
following formula:
[0040] CF=N.sub.W.times. {square root over
(D.sub.W)}+N.sub.f.times. {square root over (D.sub.f)},
[0041] wherein, N.sub.W denotes the warp density of the fabric
(yarns/inch);
[0042] D.sub.Wdenotes the fineness of warp filaments in the fabric
(dtex);
[0043] N.sub.f denotes the weft density of the fabric
(yarns/inch);
[0044] D.sub.f denotes the fineness of weft filaments in the fabric
(dtex). [0045] (2) The cover factor of knitted fabric is calculated
by the following formula: [0046] the cover factor of knitted fabric
is also referred to as a tightness factor, which is a ratio of the
square root of a TEX of yarns and a stitch length (L), i.e., a K
value, where the K value= {square root over (Tex)}/L .
Average Pore Size
[0047] According to the ASTMF316-03 standard, the pore size of
fabric is measured by a capillary flowing porosimeter (a product
from PMI; Model: CFP-1100-AE), and the working mode is set as a
wet-up/dry-down mode. The test environment is 20.+-.2.degree. C.
and 65.+-.4% RH. A fabric sample is placed into a sample chamber
and then wetted with silwick silicone fluid with a surface tension
of 19.1 dynes/cm. The bottom clamp of the sample chamber has a
porous metal disc insert with a diameter of 2.54 cm and a thickness
of 3.175 mm, while the top clamp of the sample chamber has a hole
with a diameter of 3.175 mm, thus the value of the average pore
size of the fabric can be directly read. An average value of two
times of measurement is used as the final average pore size
value.
[0048] The distribution condition of pore size and the ratio of
each pore size range can be directly read from the specific
measurement results, and the pore size ratio within a certain range
can be obtained by adding the measured values shown in the
measurement results.
Venting Quality
[0049] The venting quality is measured by a high-pressure air
permeability tester (a product from Technoworld; Model: WI70848) at
23.degree. C. and 50% RH. The specific measurement methods are as
follows: 17 circular samples each with a diameter of 10 cm are
stretched in a breadth direction of the fabric, the venting quality
of each sample is measured at 3 KPa, and an average value of 13
intermediate data is used as a final test result.
Gas-Tightness
[0050] The gas-tightness is measured in accordance with the Term
4.5.2 "Gas-tightness Measurement" of "Asbestos Diaphragm Cloth" of
the Chinese building material industry standard JC/T211-2009.
Water Absorption
[0051] The water absorption of diaphragm cloth before or after
hydrophilic treatment is measured in accordance with
GB/T21655.1-2008.
Water Absorption Rate
[0052] The water absorption rate is measured in accordance with the
Term 7.1.1 "Falling-drop Method" of JIS L1907-2010 "Water
Absorption Test Method of a Fiber Product."
Stiffness
[0053] The stiffness is measured by a fabric stiffness tester
(SASD-672-1) (J.A. KING & COMPANY) in accordance with the ASTM
D4032 stiffness test standard. The specific method is as follows:
warp and weft samples are prepared, and then tested on a stiffness
tester after the pressure is regulated to 324 KPa. The test
environment is 20.+-.2.degree. C. and 65.+-.4% RH, and the
humidification to the samples is performed for above 24 hours.
Requirements on sampling:
[0054] Warp: length*width=8 inch (204 mm)*4 inch (102 mm)
[0055] Weft: length*width=4 inch (102 mm)*8 inch (204 mm)
Hydrophilic group components and content of oxygen element
therein
[0056] Chemical components on the fiber surface are analyzed
qualitatively and quantitatively by an X-ray photoelectron
spectroscopy ("KRATOS" that is produced by SHIMAZU Co. Ltd.,;
Model: AXIS ULTRA HAS). The content of oxygen element on the fiber
surface is calculated according to the X-ray photoelectron energy
spectrum. The bonding capacity of each carbon/oxygen peak can be
apparently recognized according to the X-ray photoelectron energy
spectrum, thus the hydrophilic group components are determined.
Example 1
[0057] Warps and wefts are both woven with 20 s/6 polyphenylene
sulfide yarns to obtain plain cloth with a warp density of 39
yarns/inch and a weft density of 27 yarns/inch. After weaving, the
plain cloth is refined and dried, and then the surface of the
polyphenylene sulfide plain cloth is subjected to vacuum plasma
treatment, where the pressure in a vacuum chamber is 50 Pa, the
process gas is a gas mixture of oxygen and argon, and the treatment
intensity is 150 KWs/m.sup.2. Finally, diaphragm cloth for a water
electrolyzer with a cover factor of 2777.89 and an average pore
size of 3 .mu.m is obtained, wherein pores with a pore size of
0.2-10 .mu.m take up 90% of all pores, and the breaking strength of
the diaphragm cloth is 4008 N/5 cm and 3218 N/5 cm in warp and weft
directions, respectively.
[0058] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the polyphenylene
sulfide fiber surface of the diaphragm cloth contains
oxygen-containing hydrophilic groups, and the content of oxygen
element is 25 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 48% of the total content of groups on the fabric surface. The
physical properties of the separator diaphragm cloth for a water
electrolyzer in Example 1 are shown in Table 1.
Example 2
[0059] Warps and wefts are both woven with 20 s/4 polyphenylene
sulfide yarns to obtain plain cloth with a warp density of 47
yarns/inch and a weft density of 32 yarns/inch. After weaving, the
plain cloth is refined and dried, and then the surface of the
polyphenylene sulfide plain cloth is subjected to atmospheric
pressure plasma surface treatment, where the process gas is air,
and the treatment intensity is 150 KWs/m.sup.2. Finally, diaphragm
cloth for a water electrolyzer with a cover factor of 2705.82 and
an average pore size of 4 .mu.m is obtained, and wherein pores with
a pore size of 0.2-10 .mu.m take up 85% of all pores, and the
breaking strength of the diaphragm cloth is 2247 N/5 cm and 2110
N/5 cm in warp and weft directions, respectively.
[0060] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the polyphenylene
sulfide fiber surface of the diaphragm cloth contains
oxygen-containing hydrophilic groups, and the content of oxygen
element is 30 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O), hydroxyl groups (--OH) and
formyl groups (CHO), and the total content of the oxygen-containing
hydrophilic groups takes up 45% of the total content of surface
groups of the fabric. The physical properties of the diaphragm
cloth for a water electrolyzer in Example 2 are shown in Table
1.
Example 3
[0061] Crossed cross-section polyphenylene sulfide fiber is mixed
with circular cross-section polyphenylene sulfide fiber at a
proportion by weight of 20:80, and then 15 s/4 polyphenylene
sulfide yarns are obtained by a spinning process. Then, the
obtained polyphenylene sulfide yarns are used as warps and wefts
for weaving to form plain cloth with a warp density of 39
yarns/inch and a weft density of 28 yarns/inch. After weaving, the
polyphenylene sulfide plain cloth is refined and dried, and then
the surface of the plain cloth is subjected to atmospheric pressure
plasma surface treatment, where the process gas is air, and the
treatment intensity is 130 KWs/m.sup.2. Finally, diaphragm cloth
for a water electrolyzer with a cover factor of 2658.70 and an
average pore size of 5 .mu.m is obtained, wherein pores with a pore
size of 0.2-10 .mu.m take up 80% of all pores, and the breaking
strength of the diaphragm cloth is 2600 N/5 cm and 2216 N/5 cm in
warp and weft directions, respectively.
[0062] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the polyphenylene
sulfide fiber surface of the diaphragm cloth contains
oxygen-containing hydrophilic groups, and the content of oxygen
element is 20 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O), hydroxyl groups (--OH) and
formyl groups (CHO), and the total content of the oxygen-containing
hydrophilic groups takes up 43% of the total content of groups on
the fabric surface. The physical properties of the diaphragm cloth
for a water electrolyzer in Example 3 are shown in Table 1.
Example 4
[0063] Hexagonal cross-section polyphenylene sulfide fiber is mixed
with circular cross-section polyphenylene sulfide fiber at a
proportion by weight of 50:50, to obtain 220 dtex polyphenylene
sulfide fiber-mixed filaments. The obtained filaments are
warp-knitted to form knitted fabric with a longitudinal density of
89 rows/inch and a transverse density of 63 columns/inch. After
weaving, the polyphenylene sulfide knitted fabric is refined and
dried, and then the surface of the fabric is subjected to vacuum
plasma treatment, where the pressure in a vacuum chamber is 50 Pa,
the process gas is a gas mixture of oxygen and argon, and the
treatment intensity is 150 KWs/m.sup.2. Finally, diaphragm cloth
for a water electrolyzer with a cover factor of 1.3 and an average
pore size of 7 .mu.m is obtained, wherein pores with a pore size of
0.2-10 .mu.m take up 60% of all pores, and the breaking strength of
the diaphragm cloth is 2347 N/5 cm and 1540 N/5 cm in warp and weft
directions, respectively.
[0064] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the polyphenylene
sulfide fiber surface of the diaphragm cloth contains
oxygen-containing hydrophilic groups, and the content of oxygen
element is 11 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 21% of the total content of groups on the fabric surface. The
physical properties of the diaphragm cloth for a water electrolyzer
in Example 4 are shown in Table 1.
Example 5
[0065] Hexagonal cross-section polyphenylene sulfide fiber is mixed
with circular cross-section polyphenylene sulfide fiber at a
proportion by weight of 80:20, and then 20 s/6 polyphenylene
sulfide yarns are obtained by a spinning process. Then, the
obtained yarns are used as warps and wefts for weaving to form 3/3
twill-woven fabric with a warp density of 56 yarns/inch and a weft
density of 40 yarns/inch. After weaving, the 3/3 twill-woven fabric
is refined and dried, and then the surface of the fabric is
subjected to vacuum plasma treatment, where the pressure in a
vacuum chamber is 50 Pa, the process gas is air, and the treatment
intensity is 100 KWs/m.sup.2. Finally, diaphragm cloth for a water
electrolyzer with an average pore size of 8 .mu.m is obtained,
wherein pores with a pore size of 0.2-10 .mu.m take up 70% of all
pores, and the breaking strength of the diaphragm cloth is 4980 N/5
cm and 3600 N/5 cm in warp and weft directions, respectively.
[0066] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the polyphenylene
sulfide fiber surface of the diaphragm cloth contains
oxygen-containing hydrophilic groups, and the content of oxygen
element is 26 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 40% of the total content of surface groups of the fabric. The
physical properties of the diaphragm cloth for a water electrolyzer
in Example 5 are shown in Table 1.
Example 6
[0067] Warps and wefts are both woven with 440 dtex-60 f
polytetrafluoroethylene filaments to obtain plain cloth with a warp
density of 76 yarns/inch and a weft density of 62 yarns/inch. After
weaving, the plain cloth is refined and dried, and then the surface
of the plain cloth is subjected to vacuum plasma treatment, where
the pressure in a vacuum chamber is 50 Pa, the process gas is a gas
mixture of oxygen and argon, and the treatment intensity is 200
KWs/m.sup.2. Finally, diaphragm cloth for a water electrolyzer with
a cover factor of 2895 and an average pore size of 5 .mu.m is
obtained, wherein pores with a pore size of 0.2-10 .mu.m take up
75% of all pores, and the breaking strength of the diaphragm cloth
is 4008 N/5 cm and 3218 N/5 cm in warp and weft directions,
respectively.
[0068] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the
polytetrafluoroethylene fiber surface of the diaphragm cloth
contains oxygen-containing hydrophilic groups, and the content of
oxygen element is 20 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 38% of the total content of surface groups of the fabric. The
physical properties of the diaphragm cloth for a water electrolyzer
in Example 6 are shown in Table 1.
Example 7
[0069] Stretched polyphenylene sulfide fiber ("TORCON .RTM." from
TORAY; Specification: S301) with a fineness of 1.0 dtex (10 .mu.m
in diameter) and a cutting length of 6 mm and non-stretched
polyphenylene sulfide fiber ("TORCON.RTM." from TORAY;
Specification: S111) with a fineness of 3.0 dtex (17 .mu.m in
diameter) and a cutting length of 6 mm are dispersed in water at a
proportion by weight of 60:40 to form papermaking dispersion. A
140-mesh papermaking net for handmade paper is provided on the
bottom, and the dispersion is fed at a rate of 80 g/m.sup.2 by a
small paper machine (from KUMAGAI RIKI KOGYO Co., Ltd.) with a size
of 25 cm.times.25 cm and a height of 40 cm. Then, water is added
into the dispersion to make the total amount of the dispersion to
be 20 L, and the dispersion is fully stirred by a stirrer. Water in
the small paper machine is drained, and the residual wet-laid paper
on the papermaking net is transferred to a piece of filter paper.
The described wet-laid paper and the filter paper are put into a
rotary dryer (ROTARY DRYER DR-200 from KUMAGAI RIKI KOGYO Co.,
Ltd.) together for drying (a temperature of 100.degree. C., a rate
of 0.5 m/min, a length of 1.25 m and a duration of 2.5 min) for one
time to obtain wet-laid non-woven cloth of polyphenylene sulfide
fiber. At this moment, one side in contact with a roll of the dryer
is used as surface (front side), and another side not in contact
with the roll of the dryer is used as an inner side. Calendering is
performed under a steel roll temperature of 200.degree. C., a line
pressure of 490 N/cm and a roller rotation speed of 5 m/min by a
hydraulic three-roll calender (from Ligun Company; Model: IH type
H3RCM) consisting of a steel roll and a paper roll. The surface
(front side) of the wet-laid non-woven cloth of polyphenylene
sulfide fiber is brought into contact with the steel roll and then
heated and pressurized to obtain single-side pressed non-woven
cloth. Then, the inner side of the wet-laid non-woven cloth is
brought into contact with the steel roll and then heated and
pressurized to obtain double-side pressed non-woven cloth. Then,
the surface of the double-side pressed non-woven cloth is subjected
to vacuum plasma treatment, where the pressure in a vacuum chamber
is 50 Pa, the process gas is a gas mixture of oxygen and argon, and
the treatment intensity is 150 KWs/m.sup.2. Finally, diaphragm
cloth for a water electrolyzer with a volume density of 0.94 and an
average pore size of 8 .mu.m is obtained, wherein pores with a pore
size of 0.2-10 .mu.m take up 80% of all pores, and the breaking
strength of the diaphragm cloth is 151 N/5 cm and 143 N/5 cm in
warp and weft directions, respectively.
[0070] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the
polytetrafluoroethylene fiber surface of the diaphragm cloth
contains oxygen-containing hydrophilic groups, and the content of
oxygen element is 25 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 48% of the total content of surface groups of the fabric. The
physical properties of the diaphragm cloth for a water electrolyzer
in Example 7 are shown in Table 1.
Example 8
[0071] Stretched polyphenylene sulfide fiber ("TORCON.RTM." from
TORAY; Specification: S301) with a fineness of 1.0 dtex (10 .mu.m
in diameter) and a cutting length of 6 mm and non-stretched
polyphenylene sulfide fiber ("TORCON.RTM." from TORAY;
Specification: S111) with a fineness of 3.0 dtex (17 .mu.m in
diameter) and a cutting length of 6 mm are dispersed in water at a
proportion by weight of 60:40 to form papermaking dispersion. A
140-mesh papermaking net for handmade paper is provided on the
bottom, and the dispersion is fed at a rate of 100 g/m.sup.2 by a
small paper machine (from KUMAGAI RIKI KOGYO Co., Ltd.) with a size
of 25 cm.times.25 cm and a height of 40 cm. The other processing
conditions are the same as Example 7. Finally, diaphragm cloth for
a water electrolyzer with a volume density of 0.96 and an average
pore size of 4 .mu.m is obtained, wherein pores with a pore size of
0.2-10 .mu.m take up 90% of all pores, and the breaking strength of
the diaphragm cloth is 204 N/5 cm and 198 N/5 cm in warp and weft
directions, respectively.
[0072] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the
polytetrafluoroethylene fiber surface of the diaphragm cloth
contains oxygen-containing hydrophilic groups, and the content of
oxygen element is 25 wt %. The oxygen-containing hydrophilic groups
include carbonyl groups (C.dbd.O) and hydroxyl groups (--OH), and
the total content of the oxygen-containing hydrophilic groups takes
up 48% of the total content of surface groups of the fabric. The
physical properties of the diaphragm cloth for a water electrolyzer
in Example 8 are shown in Table 1.
Comparative Example 1
[0073] Warps and wefts are both woven with 20 s/6 polyphenylene
sulfide yarns to obtain plain cloth with a warp density of 36
yarns/inch and a weft density of 22 yarns/inch. After weaving, the
plain cloth is refined, dried and shaped to finally obtain
diaphragm cloth for a water electrolyzer with a cover factor of
2441.17 and an average pore size of 12 .mu.m, wherein the breaking
strength of the diaphragm cloth is 3800 N/5 cm and 2120 N/5 cm in
warp and weft directions, respectively.
[0074] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the content of
oxygen element on the polyphenylene sulfide fiber surface is 2 wt
%. The physical properties of this diaphragm cloth for a water
electrolyzer are shown in Table 1.
Comparative Example 2
[0075] Warps and wefts are both woven with 20 s/4 polyphenylene
sulfide yarns to obtain plain cloth with a warp density of 42
yarns/inch and a weft density of 24 yarns/inch. After weaving, the
plain cloth is refined, dried and shaped to finally obtain
diaphragm cloth for a water electrolyzer with a cover factor of
2268.13 and an average pore size of 15 .mu.m, wherein the breaking
strength of the diaphragm cloth is 2100 N/5 cm and 1980 N/5 cm in
warp and weft directions, respectively.
[0076] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the content of
oxygen element in the polyphenylene sulfide fiber surface is 4 wt
%. The physical properties of this diaphragm cloth for a water
electrolyzer are shown in Table 1.
Comparative Example 3
[0077] Polyphenylene sulfide fiber with a fineness of 2.2 dtex and
a length of 51 mm are successively subjected to opening, mixing,
carding, web-forming and needle-punched to form non-woven cloth,
and then the non-woven cloth is sulfonated in 98% H.sub.2SO.sub.4
at 80.degree. C. for 30 min and then treated with 30% KOH solution.
Finally, diaphragm cloth for a water electrolyzer with an average
pore size of 13 .mu.m is obtained, wherein the breaking strength of
the diaphragm cloth is 1180 N/5 cm and 1500 N/5 cm in warp and weft
directions, respectively.
[0078] The prepared diaphragm cloth is tested by an X-ray
photoelectron spectroscopy. It is measured that the
polytetrafluoroethylene fiber surface of the diaphragm cloth
contains oxygen-containing hydrophilic groups, and the content of
oxygen element on the polytetrafluoroethylene fiber surface is 12
wt %. The physical properties of the water electrolyzer are shown
in Table 1.
TABLE-US-00001 TABLE 1 Item Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Content of modified 0 0 20 50 80 0
cross-section fiber (%) Type of modified -- -- Crossed Hexagonal
Hexagonal -- cross-section fiber Form of fabric Woven Woven Woven
Knitted Woven Woven Fabric fabric fabric fabric fabric fabric
Thickness (mm) 1.0 0.8 0.8 1.2 1.4 0.5 Weight (g/m.sup.2) 568 426
455 400 1130 275 Density Warp 39 47 39 89 56 76 direction (yarns/
inch) Weft 27 32 28 63 40 62 direction (yarns/ inch) Cover factor
2777.89 2705.82 2658.70 1.3 -- 2895 (volume density) (g/cm.sup.3)
-- -- -- -- -- -- Average pore sizes (.mu.m) 3 4 5 7 8 5
Gas-tightness (mmH.sub.2O) 300 370 380 240 320 350 Venting quality
0.68 0.79 1.06 1.59 1.89 1.05 (L/cm.sup.2/min) Stiffness Warp 27.3
5.6 5.0 3.3 38.6 2.2 direction (N) Weft 14.3 7.0 5.6 3.0 42.3 1.3
direction (N) Water absorption 101.8 114 91 143.9 152 45 before
treatment (%) Water absorption 120.5 132.6 115.1 163.9 186 88 after
treatment (%) Water absorption 16 6 42 100 4 300 rate before
treatment (%) Water absorption <1 <1 <1 <1 <1 2 rate
after treatment (%) Operability of No No No Wrinkling, No Much a
diaphragm during wrinkling, wrinkling, wrinkling, no influence
wrinkling, wrinkling, mounting convenient convenient convenient on
cutting convenient inconvenient for cutting for cutting for cutting
and for cutting for cutting and and and mounting and and mounting
mounting mounting mounting mounting Stability of Not easy Not easy
Not easy Certain Not easy Easy to an electrolyzer to cause to cause
to cause deformation, to cause cause during deformation,
deformation, deformation, but stable deformation, deformation,
operation and stable and stable and stable system and stable and
system system system operation system poor long- operation
operation operation operation term operation stability Comparative
Comparative Comparative Item Example 7 Example 8 Example 1 Example
2 Example 3 Content of modified -- -- 0 0 0 cross-section fiber (%)
Type of modified -- -- -- -- -- cross-section fiber Form of fabric
Non- Non- Woven Woven Non- woven woven fabric fabric woven cloth
cloth cloth Thickness (mm) 0.09 0.11 0.9 0.8 1.5 Weight (g/m.sup.2)
83 106 498 419 500 Density Warp -- -- 36 42 -- direction (yarns/
inch) Weft -- -- 22 24 -- direction (yarns/ inch) Cover factor --
-- 2441.17 2268.13 -- (volume density) (g/cm.sup.3) 0.94 0.96 -- --
0.33 Average pore sizes (.mu.m) 8 4 12 15 13 Gas-tightness
(mmH.sub.2O) 370 480 200 130 180 Venting quality 0.82 0.33 2.68
2.98 2.43 (L/cm.sup.2/min) Stiffness Warp 2.6 3.4 24.5 4.8 21.5
direction (N) Weft 3.2 3.8 11.8 5.3 28.6 direction (N) Water
absorption 117 123 101.8 114.8 300 before treatment (%) Water
absorption 139 147 -- -- 318 after treatment (%) Water absorption
143 150 17 6 300 rate before treatment (%) Water absorption 4 6 --
-- 5 rate after treatment (%) Operability of Much Wrinkling, No No
No a diaphragm during wrinkling, no influence wrinkling, wrinkling,
wrinkling, mounting inconvenient on cutting convenient convenient
convenient for cutting and for cutting for cutting for cutting and
mounting and and and mounting mounting mounting mounting Stability
of Easy to Deformed, Unqualified Unqualified Unqualified an
electrolyzer cause but stable gas- gas- gas- during deformation,
system tightness, tightness, tightness, operation and operation and
can and can and can poor long- not be used not be used not be used
term operation stability
* * * * *