AU2021363108B2 - Wool cortex cell /PVA composite porous material and preparation method thereof - Google Patents
Wool cortex cell /PVA composite porous material and preparation method thereof Download PDFInfo
- Publication number
- AU2021363108B2 AU2021363108B2 AU2021363108A AU2021363108A AU2021363108B2 AU 2021363108 B2 AU2021363108 B2 AU 2021363108B2 AU 2021363108 A AU2021363108 A AU 2021363108A AU 2021363108 A AU2021363108 A AU 2021363108A AU 2021363108 B2 AU2021363108 B2 AU 2021363108B2
- Authority
- AU
- Australia
- Prior art keywords
- wool
- pva
- solution
- porous material
- liquid nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 210000002268 wool Anatomy 0.000 title claims abstract description 91
- 239000011148 porous material Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000009413 insulation Methods 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 102000004142 Trypsin Human genes 0.000 claims description 13
- 108090000631 Trypsin Proteins 0.000 claims description 13
- 239000012588 trypsin Substances 0.000 claims description 13
- 239000004201 L-cysteine Substances 0.000 claims description 12
- 235000013878 L-cysteine Nutrition 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 230000002779 inactivation Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000008204 material by function Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 description 46
- 238000012360 testing method Methods 0.000 description 24
- 230000007613 environmental effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 102000011782 Keratins Human genes 0.000 description 3
- 108010076876 Keratins Proteins 0.000 description 3
- 238000001739 density measurement Methods 0.000 description 3
- 238000011978 dissolution method Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 241000283707 Capra Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Materials For Medical Uses (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention discloses a wool cortex cell/PVA composite porous material and a
preparation method thereof, and belongs to the field of functional materials. A method for preparing
wool cortex cell/PVA composite porous material in the present invention comprises the following
steps: adding cortex cells into a PVA solution and mixing evenly to obtain a mixed solution; and
then freeze-drying the mixed solution to obtain a wool cortex cell/PVA composite porous material,
wherein a mass ratio of PVA and wool cortex cells is (50-37.5): (50-62.5), and the concentration of
the PVA solution is 6-10%. The extraction rate of the cortex cells in the present invention is 32.8%,
which can effectively utilize waste wool, and the prepared porous material has impact strength of
1.173 KJ/m2 , thermal insulation rate of 43.42%, low thermal conductivity of 0.0370 W/(m-°C),
sound absorption coefficient of more than 0.98 at 2000 Hz, noise reduction coefficient NRC of
more than 0.52, water absorption rate of more than 341%, small density of less than 0.235 g/cm3
and light weight.
Description
Technical Field
The present invention relates to a wool cortex cell/PVA composite porous material and a
preparation method thereof, and belongs to the field of functional materials.
Background
In recent years, people pay more and more attention to environmental protection, and the
shortage of resources is a problem to be urgently solved by people. Therefore, the pursuit of new
environmentally friendly materials has gradually become a new trend. The use of degradable and
renewable natural polymer materials to prepare green environmental protection materials is
gradually becoming a new research direction. About 100,000 tons of wool are discarded in China
every year, which not only wastes resources, but also causes environmental pollution. Wool cortex
cells adhere to each other to form a cortex which is an important part of wool fiber. The cellular
protein contains a large number of hydrophilic groups such as carboxyl and amino, which are
cross-linked by a large number of disulfide bonds. Extraction of cortex cells from wool fiber by
using waste goat hair as raw material is not only the recycling of waste, but also gives full play to
the better performance of the wool fiber than other man-made fibers, which conforms with the new
concept of environmental protection and energy saving advocated today.
There are generally two ideas for the recycling of the waste wool. One is a physical recycling
mode that can be used for textiles through cleaning, opening, screening and textile processing. The
other is a physicochemical mode which washes and smashes the wool firstly, then extracts keratin
by a chemical biological reagent dissolution method, mixes with other materials with excellent
performance to obtain a spinning solution, and conducts recycled spinning and textile processing to
form textiles. Literature (Li Changwei and Lv Lihua. Preparation and properties of waste wool
sound absorption composite [J]. Journal of Textile Research, 2018, 39(10): 74-80.) uses the waste
wool as reinforcement material and uses EVA (ethylene-vinyl acetate copolymer) as a matrix
material to prepare the sound absorption composite by a hot pressing method. The method not only
solves the problem of recycling waste wool, but also develops high-quality materials with high
sound absorption coefficient and high bandwidth, which conforms with the green industrialization
concept of sustainable development in China. However, the waste wool is only mixed with EVA, which does not really utilize the active ingredients.
The key to separate the cortex cells is to destroy the adhesion between the cortex cell
membrane and the intercellular substance. At present, the separation methods mainly include the
physical mechanical methods and the chemical dissolution methods. The physical mechanical
methods include the hot pressing method (which is difficult to grasp the degree of damage to the
intermolecular disulfide bonds of keratin, is extremely low in separation efficiency, and even
destroys the structure of the cortex cells, and thus is difficult to put into industrial application) and a
flash explosion separation method (which is uncertain to the damage to the internal structure of
wool, and is difficult to obtain pure cortex cells). The chemical dissolution methods include the
reduction method (which has instability to the cleavage of disulfide bonds and low decomposition
efficiency of the cortex cells), the biological enzymatic method (which has mild effect and high
efficiency and is in line with the current concept of green environmental protection, but has low
extraction rate) and the acid alkaline method (which is not easy to control the degree of damage to
keratin by acid-base reagents, may further damage the cortex cells, and easily pollutes the
environment, and thus is not in line with the current concept of green environmental protection).
At present, literature discloses the preparation of porous materials by compounding wool and
other substances, but the internal porosity of the material will have a great impact on the strength of
the materials. Therefore, such materials often do not have low strength, or are not reported,
especially no impact strength is reported, thereby limiting the application range. Therefore, it is of
great significance to prepare strong porous materials.
In engineering, a noise reduction coefficient NRC is generally used to roughly measure the
ability of a sample to absorb sound in a speech frequency range. This value is the arithmetic mean
of the sound absorption coefficient of the material measured at 250 Hz, 500 Hz, 1000 Hz and 2000
Hz. The frequencies usually used for sound absorption materials are 250, 500, 1000 and 2000 Hz.
Generally, materials whose average absorption coefficient for the above frequencies is greater than
0.2 are called sound absorption materials. Porous sound absorption materials have many tiny gaps
and continuous air bubbles, and thus have certain air permeability. When a sound wave is incident
on the surface of a porous material, two mechanisms mainly cause the attenuation of the sound
wave: Firstly, the vibration generated by the sound wave causes the air movement in the small hole
or the gap, causing friction with the hole wall. The air close to the hole wall and the fiber surface is
not easy to move due to the influence of the hole wall. Due to the effects of friction and viscous forces, a considerable part of the sound energy is converted into heat energy, so that the sound wave is attenuated and the reflected sound is weakened to achieve the purpose of sound absorption.
Secondly, the heat loss caused by the heat exchange of air in the small hole as well as the hole wall
and the fiber also attenuates the sound energy. In addition, high-frequency sound waves can
accelerate the vibration speed of air particles in the voids, and the heat exchange between the air
and the hole wall is also accelerated, which makes the porous material have good high-frequency
sound absorption performance, but the low-frequency sound absorption coefficient is low.
Therefore, how to prepare a sound absorption material which has good strength and excellent
thermal insulation performance, and has high sound absorption coefficient at 2000 Hz,
environmental protection and simple operation is a technical problem that needs to be solved
urgently.
Summary
It would be advantageous if at least preferred embodiments of the present invention provide a
wool cortex cell/PVA (Polyvinyl alcohol, vinyl alcohol polymer) composite porous material which
has high cortex cell extraction rate (more than 32.8%), environmental protection, reduction of use
amount of chemical reagents, impact strength of 1.173 KJ/m2 , thermal insulation rate of 43.42%,
low thermal conductivity of 0.0370 W/(m-°C), sound absorption coefficient of more than 0.98 at
2000 Hz and noise reduction coefficient NRC of more than 0.52.
The first purpose of the present invention is to provide a method for preparing wool cortex
cell/PVA composite porous material, comprising the following steps:
adding wool cortex cells into a PVA solution and mixing evenly to obtain a mixed solution;
and then freeze-drying the mixed solution to obtain the wool cortex cell/PVA composite porous
material, wherein the concentration of PVA in the PVA solution is 6- 1 0 % (% represents mass
percentage), and further preferably 6%, and wherein a mass ratio of PVA to the wool cortex cells is
(50-37.5): (50-62.5) (the sum is 100), and further preferably 37.5:62.5, and
wherein the extraction method of the wool cortex cells comprises the following steps:
cutting waste wool into 0.5-1 cm with scissors; then crushing the wool by a liquid nitrogen
freezing and crushing method; obtaining precipitates under the action of L-cysteine solution and
trypsin; and conducting freeze-drying to obtain wool cortex cells,
wherein the obtaining of the precipitates under the action of L-cysteine solution and trypsin
comprises the following steps:
(1) preparing 0.16-0.17 mol/L L-cysteine solution; then adding 8-15% (mass ratio) of trypsin
into the L-cysteine solution; adding dropwise sodium hydroxide solution to adjust pH as 7.0-8.0 to
obtain a mixed solution; putting the crushed wool into the mixed solution with a solid-liquid ratio of
1:(20-30) to obtain a mixture; then treating the mixture at 35-38 °C for 20-25 h; treating at 55-65 °C
for 0.5-1 h; inactivating the trypsin to ensure that the trypsin has no effect on subsequent processes;
and obtaining a mixture after the inactivation treatment;
(2) dropwise adding dilute hydrochloric acid into the mixture after inactivation treatment
obtained in step (1) to adjust the pH of the solution to 4.5-5.5, and then performing ultrasonic
treatment to obtain a mixture after ultrasonic treatment; wherein the temperature of ultrasonic
treatment is 20-25°C, the power of ultrasonic waves is 300-500 W, and the interval of ultrasonic
waves is 1-3 s;
(3) filtering, washing and centrifuging the mixture obtained after ultrasonic treatment in step (2)
to obtain a precipitate,
wherein the liquid nitrogen freezing and crushing method is used for crushing the wool, which
comprises the following steps: before turning on a pulverizer, firstly connecting a liquid nitrogen
pump with a liquid nitrogen tank; after confirming that an interface is well sealed, aligning a liquid
nitrogen outflow pipe with a wool feeding inlet of the pulverizer; starting the pulverizer; start using
the pump after 1-3s to flow in liquid nitrogen; after the liquid nitrogen flows into the pulverizer for
8-15s, starting to slowly scatter the waste wool which is cut from the previous step at a speed of
-15 g/min into the feeding inlet; after stopping scattering the wool, waiting for 20-40s; then
turning off the pulverizer and the pump that controls the inflow of liquid nitrogen; removing a
liquid nitrogen storage tank and placing in a safe place; and then taking out a clean beaker to collect
the crushed wool.
In one embodiment of the present invention, the uniform mixing is specifically:
at 90-100°C, stirring is conducted at rotation speed of 500-1000 rpm for 10-30 min, and then
standing is conducted for 5-10 min.
In one embodiment of the present invention, the mixed solution is prepared, and then sealed
and freeze-dried; and the sealing is conducted with a plastic wrap.
In one embodiment of the present invention, the freeze-drying means freezing at -70 to -90 °C
for 1-4 h, and then the solution is put into a freeze dryer for drying and freezing for 40-50 h.
In one embodiment of the present invention, the preparation method of the PVA solution is specifically as follows: adding PVA into water and mixing at 90-100°C for 0.5-1.5 h to obtain a PVA solution.
The second purpose of the present invention is the wool cortex cell/PVA composite porous
material prepared by the method of the present invention.
The third purpose of the present invention is an application of the wool cortex cell/PVA
composite porous material of the present invention in the field of sound absorption, thermal
insulation or adsorption.
The fourth purpose of the present invention is a sound absorption material for medium and low
frequency sound. The main component of the sound absorption material is the wool cortex
cell/PVA composite porous material of the present invention.
Beneficial effects of preferred embodiments of the present invention:
(1) In the preparation method of the wool cortex cell/PVA composite porous material of the
present invention, the extraction rate of the cortex cells is 32.8%, which can effectively utilize the
waste wool, and at the same time, the use of L-cysteine/trypsin solution system reduces the use of
the chemical reagents, alleviates the pressure of waste liquid treatment and is in line with the
current green industrial concept of sustainable development.
(2) The wool cortex cell/PVA composite porous material of the present invention can achieve a
thermal insulation rate of more than 43.42%, a thermal conductivity of less than 0.0493 W/(m-°C),
and a cro value of more than 0.46.
(3) The impact strength of the wool cortex cell/PVA composite porous material of the present
invention reaches more than 0.756KJ/m2, and can be as high as 1.173KJ/m 2
(4) The sound absorption coefficient of the wool cortex cell/PVA composite porous material of
the present invention can reach more than 0.98 in the medium and low frequency 2000HZ, and the
noise reduction coefficient NRC is more than 0.52.
(5) The water absorption rate of the wool cortex cell/PVA composite porous material of the
present invention can reach more than 341%.
(6) The wool cortex cell/PVA composite porous material of the present invention has low
density of below 0.235 g/cm 3 , and is light in weight.
Description of Drawings
Fig. 1 shows the morphological structure of cortex cells; (a) shows the wool cortex cells
observed under an optical microscope at a magnification of 400 times, and (b) shows the wool cortex cells observed under a scanning electron microscope at a magnification of 500 times.
Fig. 2 is a sectional SEM images of the composite porous materials with different ratios of
wool cortex cells/PVA; and the proportions of wool cortex cells in (a)-(f) are 0, 53%, 55%, 58.5%,
% and 62.5%, respectively.
Detailed Description
Preferred embodiments of the present invention will be described below, and it should be
understood that the embodiments are used to better explain the present invention and are not
intended to limit the present invention.
Test method:
1. Scanning Electron Microscope (SEM) observation: the composite porous materials with
different ratios of wool cortex cells/PVA are put into a container; a certain amount of liquid nitrogen
is poured and soaked for 2 min; and heat insulation gloves are worn to take out the materials and
break them quickly. A double-sided conductive tape is adhered to an aluminum tube, and a sample
is adhered on the other side to expose the surface to be observed. A 20 nm-thick gold layer is
sputtered in dilute argon gas; the surface morphology of the material is analyzed using a HITACHI
SU1510 scanning electron microscope under the condition of a scanning voltage of 5 KV; and the
magnification is gradually increased to observe the void and cytocompatibility of the porous
materials.
2. Thermal insulation performance test: YG606 flat thermal insulation instrument is used in the
test, which is suitable for measuring the thermal insulation performance of various fabrics and
materials. The instrument is controlled by a microcomputer to process data, directly calculate the
performance of each sample, and output the test results (thermal insulation rate, thermal
conductivity and cro value). The temperature adjustment range of a heating plate of the tester is
-50°C; the setting range of preheating time is 20-99.9 min; the size of the samples is 300 mm x
300 mm; and the test is performed under the conditions of 220 V and 200 W.
During the test, the prepared sample A, which is spliced into a size of 300 mm x 300 mm, is
covered on a sample plate. The sample plate, a bottom plate and surrounding protective plates are
all controlled by the electrothermal mode to be stable. A temperature sensor is used as a medium to
report data to the microcomputer in real time to maintain a constant temperature, so that the heat of
the sample plate can only be dissipated in the direction of the sample. The heating time required for
a test plate to maintain a certain temperature within a certain period of time is determined by the computer, and the system automatically calculates the thermal insulation rate, thermal conductivity and cro value.
3. Sound absorption coefficient test: the test uses a JTZB sound absorption system test system,
that is, a standing wave tube test. Standing wave is a characteristic of acoustic wave propagation.
The principle is that the incident sinusoidal plane wave and the plane wave reflected from the
sample are superimposed under normal incidence conditions to generate the standing wave. In order
to intuitively use a unified standard to study the ability of materials to absorb sound, the concept of
the sound absorption coefficient is proposed, that is, the ratio of the sound energy absorbed by the
materials to the total sound energy incident on the materials. Specific test steps are as follows:
(1) Before the test, confirming that each part is powered off, then assembling the system, and
preparing for the test; during the test, removing a sample, cylinder, pushing a piston into an equal
distance according to the thickness of the sample, and using Vaseline or other sealing media to seal
a gap between the piston and the pipe wall; installing a test piece; preferably applying sealing oil on
the outer circumference of the test piece and pushing in the sample cylinder; tightly fitting the
sample and the piston without leaving any gap; then evenly applying the sealing oil on the end
surface of the sample cylinder; and installing and locking the sample cylinder.
(2) During the test, adjusting the power to the minimum; opening the software; adjusting a
center frequency to 200Hz; selecting serial port 6, and clicking "OK"-"Start"; moving a trolley to
the maximum value of the measured frequency (e.g.: moving from 200Hz to 200M); adjusting a
power amplifier to the maximum; adjusting left and right; recording the maximum value; moving
the trolley to the current frequency minimum value (e.g.: moving from 200Hz to 200m); adjusting
left and right; recording the minimum value; adjusting the power amplifier to the minimum;
clicking "Stop" to end the 200Hz data test; repeating the above operation; and recording the test
data of the trolley from 200Hz to 2000Hz in sequence.
(3) After the test, clicking "Calculate" to obtain the sound absorption coefficient.
4. Water absorption performance test: soaking the samples in deionized water for 24 h, taking
out the samples, and absorbing the samples with absorbent paper until the surface does not drip;
weighing and recording the mass of the sample after immersion in water with an electronic balance,
and calculating a water absorption rate, wherein the water absorption rate refers to the weight
percentage increased by soaking the substance in water for a certain time at a certain temperature.
5. Density measurement: measuring and recording the weight of the sample; wrapping the sample tightly with a plastic wrap, putting the sample into a beaker full of deionized water, recording the volume of the overflowing deionized water, which is the volume of the sample, and calculating the density of the sample, wherein the density of the sample is a ratio of the mass to the volume.
6. Measurement of impact strength: GB-T 1043.1-2008 Plastics - Determination of charpy
impact properties - Part 1: Non - instrumented impact test is used for measurement.
Embodiment 1 (extraction of cortex cells)
A method for extracting cortex cells comprises the following steps:
(1) cutting the waste wool directly with scissors into a length of about 1 cm, and putting the
waste wool into a 500 mL beaker for use;
(2) crushing the wool by a liquid nitrogen freezing and crushing method;
before turning on a pulverizer, firstly connecting a liquid nitrogen pump with a liquid nitrogen
tank; after confirming that an interface is well sealed, aligning a liquid nitrogen outflow pipe with a
wool feeding inlet of the pulverizer; after stopping scattering the wool, waiting for about half a
minute; then turning off the pulverizer and the pump that controls the inflow of liquid nitrogen;
removing a liquid nitrogen storage tank and placing in a safe place; and then taking out a clean
beaker to collect the crushed wool.
(3) Effect of L-cysteine solution and trypsin
(1) preparing 0.165 mol/L L-cysteine solution; then adding 10% (mass ratio) of trypsin into the
L-cysteine solution; adding dropwise sodium hydroxide solution to adjust pH as 8.0 to obtain a
mixed solution; putting the crushed wool into the mixed solution with a solid-liquid ratio of 1:25 to
obtain a mixture; then treating the mixture in an oscillating water bath at reaction temperature of
37 °C for 24 h; then adjusting the temperature of the water bath as 60°C and treating for 0.5 h;
inactivating and removing the trypsin to ensure that the trypsin has no effect on subsequent
processes; and obtaining a mixture after the inactivation;
dropwise adding dilute hydrochloric acid into the mixture after inactivation to adjust the pH to
5.0; putting the mixture into an ultrasonic microwave combined system, at reaction temperature of
°C, ultrasonic power of 400 W and ultrasonic interval of 2 s; conducting the treatment for 30 min
at the interval of 2s; using an ultrasonic horn with a diameter of 15 mm; and submerging the horn at
about 1 cm below a liquid surface to obtain a mixture after ultrasonic treatment;
filtering the mixture after ultrasonic treatment by a 200-mesh sample screen, and cleaning the remaining wool fragments with a little deionized water; collecting the filtered washing solution and the filtrate on the screen; then, at room temperature, conducting high-speed centrifugation at 10,000 rpm for 20 min; collecting and observing the obtained precipitate; collecting the screen filtrate and the precipitate into a petri dish; then freeze-drying in a vacuum freeze dryer for 12 h; and taking out to obtain a sample, that is, the wool cortex cells. Through the test, the extraction rate of the wool cortex cells is 32.4%. The specific morphology is shown in Fig. 1. Reference example 1 The liquid nitrogen in step (2) of embodiment 1 is removed by a freezing treatment method, and the waste wool is directly treated to extract cortex cells. Through the test, the extraction rate of the wool cortex cells is only 12.3%. Embodiment 2 (Preparation of cortex cell/PVA composite porous material) A method for preparing wool cortex cell/PVA composite porous material comprises the following steps: (1) adding 6 g of PVA into 94 g of water, and stirring at 500 rpm for 1 h at 95°C to obtain a PVA solution, wherein the concentration of the PVA solution is 6%; (2) mixing 10 g of the wool cortex cells obtained in embodiment 1 with the PVA solution prepared in step (1), wherein the mass ratio of the PVA and the wool cortex cells is 37.5:62.5, the temperature is 95°C, and the rotational speed is 500 rpm; stirring for 15 min, and then standing for 5 min to obtain a mixed solution; (3) sealing the mixed solution obtained in step (2) with plastic wrap, freezing at -80°C for 2 h, and then putting the mixed solution into a freeze dryer to dry and freeze for 48 h to obtain the wool cortex cell/PVA composite porous material. Embodiment 3 The concentration of PVA in embodiment 2 is adjusted as shown in Table 1, and other parameters are unchanged to obtain the wool cortex cell/PVA composite porous material. The surface morphology is shown in Fig. 2. From Fig. 2, it can be seen that there are many voids in the image a without wool cortex cells, and a network structure skeleton is formed. After the wool cortex cells are added, the wool cortex cells can be clamped by PVA to form more voids.
Performance test:
The wool cortex cell/PVA composite porous materials obtained in embodiments 2 and 3 are
tested for performance, and the test results are as follows:
(1) Test of impact strength Table 1 Impact strength test results of different PVA concentrations
PVA Embodiment 2 Embodiment 3 concentration (%) 6.0 6.7 7.1 8.2 8.9 15.0 5.0 Mass ratio of PVA and wool 37.5: 62.5 40: 60 41.5: 58.5 45: 55 47: 53 60: 40 35: 75 cortex cells Impactsength 1.173 1.170 0.936 0.873 0.756 1.078
Note: "-" means that the cortex cells cannot be uniformly dispersed and cannot form porous
material at all.
(2) Thermal insulation performance test Table 2 Thermal insulation performance of porous materials with different PVA concentrations
PVA concentration Embodiment 2 Embodiment 3 (0) 6.0 6.7 7.1 8.2 8.9 15.0 Thermal insulation 49.88 47.52 45.87 43.91 43.42 35.42 rate (%) Thermal conductivity 0.0370 0.0439 0.0466 0.0491 0.0493 0.0658
[W/(m-°C)] CLO value 0.64 0.52 0.49 0.47 0.46 0.33
Note: Thermal conductivity refers to the heat transferred through 1 square meter area within a
certain period of time by a material with a thickness of 1 m and a temperature difference of 1 degree
(K, °C) on surfaces of both sides under stable heat transfer conditions, with the unit W/(m-K) (K
can be replaced by °C). Generally, the materials with thermal conductivity less than 0.2 W/(m-K)
are called thermal insulation materials. The thermal conductivity of fiber materials such as wool is
generally 0.05-0.07 W/(m-K). K can also be °C. The thickness of the porous material prepared in
the embodiments is 0.035 mm.
(3) Sound absorption performance test
Table 3 Sound absorption performance of porous materials with different PVA concentrations PVA Embodiment 2 Embodiment 3 concentration (%) 6.0 6.7 7.1 8.2 8.9 5.0 15.0 Sound absorption 0.46 0.47 0.46 0.46 0.46 0.32 coefficient at 250 Hz Sound The cortex absorption 0.50 0.42 0.45 0.38 0.36 cells cannot 0.24 coefficient at b 500Hz b Sound uniformly Sortn dispersed absorption 0.37 0.36 0.35 0.30 0.28 and cannot 0.20 coefficient at form 1000 Hz porous Sound material at absorption 0.99 0.99 0.98 0.98 0.98 all. 0.78 coefficient at 2000 Hz Noise reduction coefficient 0.58 0.56 0.56 0.53 0.52 0.39 (NRC) (4) Water absorption performance test Table 4 Water absorption performances of porous materials with different PVA concentrations
PVA concentration Embodiment 2 Embodiment 3 (0) 6.0 6.7 7.1 8.2 8.9 15.0
Dry mass (g) 4.76 4.82 5.22 5.61 5.63 5.81
Mass after soaking 21.47 21.55 23.28 24.89 24.81 25.08 for 24h (g) Water absorption 351 347 346 344 341 331 rate(%o) (5) Density measurement Table 5 Density measurement of porous materials with different PVA concentrations
PVAconcentration Embodiment 2 Embodiment 3
(%) 6.0 6.7 7.1 8.2 8.9 15.0
Mass (g) 4.76 4.82 5.22 5.61 5.45 5.51
Volume (cm 3) 21.44 21.43 23.11 24.73 23.19 22.95
Density (g/cm 3) 0.222 0.224 0.225 0.226 0.235 0.240
Although the present invention is disclosed above with preferred embodiments, the embodiments are not intended to limit the present invention. Any of those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims. It is to be understood that any prior art publication referred to herein does not constitute an admission that the publication forms part of the common general knowledge in the art. In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
Claims (8)
1. A method for preparing wool cortex cell/PVA composite porous material, comprising the
following steps:
adding wool cortex cells into a PVA solution and mixing evenly to obtain a mixed solution;
and then freeze-drying the mixed solution to obtain the wool cortex cell/PVA composite porous
material, wherein the concentration of PVA in the PVA solution is 6-10%, and % represents mass
percentage,
wherein a mass ratio of PVA to the wool cortex cells is (50-37.5): (50-62.5), and
wherein an extraction method of the wool cortex cells comprises the following steps:
cutting waste wool into 0.5-1 cm with scissors; then crushing the wool by a liquid nitrogen
freezing and crushing method; obtaining precipitates under an action of L-cysteine solution and
trypsin; and conducting freeze-drying to obtain wool cortex cells,
wherein obtaining of the precipitates under the action of L-cysteine solution and trypsin
comprises the following steps:
(1) preparing 0.16-0.17 mol/L L-cysteine solution; then adding 8-15% of trypsin into the
L-cysteine solution; adding dropwise sodium hydroxide solution to adjust pH as 7.0-8.0 to
obtain a mixed solution; putting the crushed wool into the mixed solution with a solid-liquid
ratio of 1:(20-30) to obtain a mixture; then treating the mixture at 35-38 °C for 20-25 h; and
treating at 55-65 °C for 0.5-1 h to obtain a mixture after the inactivation treatment;
(2) dropwise adding dilute hydrochloric acid into the mixture after inactivation treatment
obtained in step (1) to adjust the pH of the solution to 4.5-5.5, and then performing ultrasonic
treatment to obtain a mixture after ultrasonic treatment; wherein the temperature of ultrasonic
treatment is 20-25°C, the power of ultrasonic waves is 300-500 W, and the interval of
ultrasonic waves is 1-3 s;
(3) filtering, washing and centrifuging the mixture obtained after ultrasonic treatment in
step (2) to obtain a precipitate,
wherein the liquid nitrogen freezing and crushing method is used for crushing the wool,
which comprises the following steps: before turning on a pulverizer, firstly connecting a liquid
nitrogen pump with a liquid nitrogen tank; after confirming that an interface is well sealed,
aligning a liquid nitrogen outflow pipe with a wool feeding inlet of the pulverizer; starting the pulverizer; start using the pump after 1-3s to flow in liquid nitrogen; after the liquid nitrogen flows into the pulverizer for 8-15s, starting to slowly scatter the waste wool which is cut from the previous step at a speed of 5-15 g/min into the feeding inlet; after stopping scattering the wool, waiting for 20-40s; then turning off the pulverizer and the pump that controls the inflow of liquid nitrogen; removing a liquid nitrogen storage tank and placing in a safe place; and then taking out a clean beaker to collect the crushed wool.
2. The method according to claim 1, wherein the uniform mixing is specifically:
at 90-100°C, stirring is conducted at rotation speed of 500-1000 rpm for 10-30 min, and then
standing is conducted for 5-10 min.
3. The method according to claim 1, wherein the freeze-drying means freezing at -70 to -90 °C
for 1-4 h, and then the solution is put into a freeze dryer for drying and freezing for 40-50 h.
4. The method according to claim 1, wherein the mixed solution is prepared, and then sealed
and freeze-dried; and the sealing is conducted with a plastic wrap.
5. The method according to claim 1, wherein the preparation method of the PVA solution
comprises the following steps:
adding PVA into water and mixing at 90-100°C for 0.5-1.5 h to obtain a PVA solution.
6. A wool cortex cell/PVA composite porous material prepared by the method of any one of
claims 1-5.
7. An application of the wool cortex cell/PVA composite porous material of claim 6 in the
field of sound absorption, thermal insulation or adsorption.
8. A sound absorption material for medium and low frequency sound, comprising the main
component of the wool cortex cell/PVA composite porous material of claim 6.
(a) (b 510 5.00kV 13 8mm x500 SE Oum
Fig. 1 Fig. 1
（a） (a) （b）
0% 53% 10 0.0um SU1510 5 .00kV 13 4mm x5.00k SE SU1510 5 00kV 5 5mm x500 SE 100um
（c） Cc （d）
55% 58.5% SU1510 5.00kV 10. 7mm x500 SE 100um SU1510 5.00kV 10.6mm.x500 SE 100um
（e） （f） (f)
60% 62.5% 015105 OOKV 15 6mm x500 SE 100um SU1510 5.00kV 16.7mm x500 SE 100um
Fig. 2 Fig.
1/1 1/1
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011482481.6A CN112608510B (en) | 2020-12-15 | 2020-12-15 | Sheep skin cytoplasmic cell/PVA composite porous material and preparation method thereof |
| CN202011482481.6 | 2020-12-15 | ||
| PCT/CN2021/115938 WO2022127198A1 (en) | 2020-12-15 | 2021-09-01 | Wool cortical cell/pva composite porous material and manufacturing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2021363108A1 AU2021363108A1 (en) | 2022-06-30 |
| AU2021363108B2 true AU2021363108B2 (en) | 2023-11-02 |
Family
ID=75239622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2021363108A Active AU2021363108B2 (en) | 2020-12-15 | 2021-09-01 | Wool cortex cell /PVA composite porous material and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN112608510B (en) |
| AU (1) | AU2021363108B2 (en) |
| WO (1) | WO2022127198A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608510B (en) * | 2020-12-15 | 2021-08-20 | 江南大学 | Sheep skin cytoplasmic cell/PVA composite porous material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144760A (en) * | 2019-05-21 | 2019-08-20 | 江南大学 | A kind of preparation method of low cost heat-insulating sound-insulating waste wool/PVA extrusion coating paper |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1088861B (en) * | 1976-10-28 | 1985-06-10 | Asahi Chemical Ind | ABSORBENT MATERIAL FOR PROTEINS |
| CN106832866B (en) * | 2016-12-11 | 2019-02-26 | 河北伟成毛毡有限公司 | A method of absorbing material is prepared using wool fiber |
| CN108610590B (en) * | 2018-03-16 | 2020-08-18 | 西安理工大学 | Microwave absorbing material and preparation method thereof |
| CN109096528B (en) * | 2018-08-23 | 2020-04-07 | 江南大学 | Method for preparing porous material based on wool keratin cortical cells |
| CN109232932B (en) * | 2018-08-23 | 2020-04-07 | 江南大学 | Method for preparing reinforced and toughened L-polylactic acid composite membrane based on wool keratin cortical cells |
| CN109082403B (en) * | 2018-08-23 | 2020-04-07 | 江南大学 | Preparation method of wool keratin cortical cells |
| CN112608510B (en) * | 2020-12-15 | 2021-08-20 | 江南大学 | Sheep skin cytoplasmic cell/PVA composite porous material and preparation method thereof |
-
2020
- 2020-12-15 CN CN202011482481.6A patent/CN112608510B/en active Active
-
2021
- 2021-09-01 AU AU2021363108A patent/AU2021363108B2/en active Active
- 2021-09-01 WO PCT/CN2021/115938 patent/WO2022127198A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144760A (en) * | 2019-05-21 | 2019-08-20 | 江南大学 | A kind of preparation method of low cost heat-insulating sound-insulating waste wool/PVA extrusion coating paper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112608510B (en) | 2021-08-20 |
| CN112608510A (en) | 2021-04-06 |
| AU2021363108A1 (en) | 2022-06-30 |
| WO2022127198A1 (en) | 2022-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108281592B (en) | High-temperature-resistant composite battery diaphragm and preparation method thereof | |
| AU2021363108B2 (en) | Wool cortex cell /PVA composite porous material and preparation method thereof | |
| CN104511045B (en) | A kind of preparation method of the polyvinyl alcohol containing nano silver/chitosan nano fiber membrane dressing | |
| CN108305972B (en) | Ceramic coating diaphragm and preparation method and application thereof | |
| CN105720224B (en) | A kind of lithium ion battery separator and preparation method thereof of nano-cellulose improvement | |
| CN104037375B (en) | Diaphragm for lithium ion power batteries and making method thereof | |
| WO2021017353A1 (en) | Flexible photothermal conversion material, preparation method therefor, and use in sea water desalination | |
| CN106299213B (en) | A kind of bacteria cellulose-base microporous compound film and its preparation method and application | |
| CN105463606A (en) | Nano-crystalline cellulose fiber high in carboxyl group content and preparation and application thereof | |
| CN103855346A (en) | Storage battery AGM separator, preparation method thereof and storage battery | |
| MX2013007712A (en) | Microporous membrane and manufacturing method therefor. | |
| CN108258171A (en) | A kind of high-temperaure coating composite diaphragm and its preparation method and application | |
| JP5995239B2 (en) | Biosensor for quartz crystal microbalance and manufacturing method thereof | |
| CN110409224A (en) | A kind of preparation method of cellulose coating lithium ion battery diaphragm | |
| CN107546391A (en) | poly-dopamine and graphene composite coating | |
| CN113549228A (en) | Solar energy evaporation body based on controllable closed-pore hydrogel and preparation method thereof | |
| CA2823163A1 (en) | Porous membrane and process for preparing the same | |
| CN115275514A (en) | Battery diaphragm, preparation method thereof and battery | |
| CN108448028B (en) | Lithium ion battery diaphragm and preparation method thereof | |
| CN113981677B (en) | Porous fiber composite sound-absorbing material and preparation method and application thereof | |
| CN108539096A (en) | A kind of lithium ion battery separator and preparation method thereof for new-energy automobile | |
| CA2823168A1 (en) | Porous membrane and process for preparing the same | |
| CN108305973B (en) | Composite diaphragm with coating, preparation method and application | |
| CN108735952A (en) | A kind of heat-resisting preparation method for protecting liquid type lithium battery diaphragm | |
| CN102694204B (en) | Graphite oxide-modified P(AN-MMA) porous polymer electrolyte membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) |