CN103785305A - Multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane and preparation method thereof - Google Patents
Multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN103785305A CN103785305A CN201410025348.6A CN201410025348A CN103785305A CN 103785305 A CN103785305 A CN 103785305A CN 201410025348 A CN201410025348 A CN 201410025348A CN 103785305 A CN103785305 A CN 103785305A
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Abstract
The invention provides a multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane and a preparation method thereof. The multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane is prepared from polyvinylidene fluoride, N-N-dimethylacetamide and multi-walled carbon nanotubes. According to the conductive ultrafiltration membrane, the insulated polyvinylidene fluoride serves as a film-forming matrix, the carboxylated multi-walled carbon nanotubes serve as a nano conductive filler, the multi-walled carbon nanotubes are uniformly dispersed in the matrix by adopting an ultrasonic dispersion method, and the multi-walled composite conductive carbon nanotube-polyvinylidene fluoride ultrafiltration membrane is prepared by adopting a wet-phase inversion method. Because the carbon nanotubes have the extremely high conductivity, the conductive performance of the composite membrane is well improved due to the addition of the carbon nanotubes, and the strength and the hydrophilicity of the membrane are enhanced. Therefore, the membrane can be effectively prevented from being polluted during water treatment, and the service life of the membrane is prolonged. The preparation method and a process flow are simple, the operation is convenient, the cost is low, equipment is not required to be transformed, and the operability is high.
Description
Technical field
The present invention not only belongs to diffusion barrier modification technology field, but also belongs to polymer base conductive composite material technical field, particularly relates to a kind of multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter and preparation method thereof.
Technical background
Kynoar (PVDF) is a kind of macromolecular material of the function admirable being widely used, its outstanding advantage is: have excellent dielectricity, piezoelectricity, pyroelectricity, chemical stability is high, corrosion resistance, oxidative resistance, wearability and pliability is good and raw material is cheap, this makes it in the development of film separation field rapidly, but because PVDF self surface energy is low and hydrophobicity is extremely strong, so cause it easily contaminated, this has just limited PVDF microfiltration membranes and the application of milipore filter in aqueous based systems.In addition, PVDF is insulator, and its electrical conductivity is 10
-14～10
-15s/cm, this has also limited its development in some field and application.
CNT (CNTs) is a kind of monodimension nanometer material, and draw ratio is large, lightweight, becomes one of optimal conductive filler and reinforcement owing to having excellent electric conductivity and mechanical property and intensity.In polymer, add CNT can make polyalcohol group compound film show more excellent performance at aspects such as electrochemistry, optics, mechanics.In addition, CNT add the hydrophilicity that can also improve composite membrane, the chemical property of this performance and composite membrane combines can sterilization and effectively prevent that film from polluting, thereby this film has very wide application prospect aspect water treatment.
Patent 201110187394.2 discloses a kind of preparation method of carbon nano-tube/composite conducting polymer material, the preparation of this composite is that CNT is mixed with Kynoar, then inserts in the blender that rotating speed is 23000rpm and carries out mechanical mixture; Mixed powder is placed in and framedly under 200 ℃, the pressure of 10MPa, is molded, and then air cooling is to room temperature.Owing to making adding of CNT this material have very low percolation threshold and very high electric conductivity, but this material is through hot press moulding moulding, complicated process of preparation, and can not be applied to the problem such as water treatment that solves diffusion barrier.Still there is no at present a kind of composite conducting milipore filter, the hydrophily of electric conductivity and diffusion barrier can well can be combined, better solve the membrane pollution problem in the time processing aqueous based systems.
Summary of the invention
In order to address the above problem, to the invention provides a kind of electric conductivity and hydrophily that can effectively improve composite membrane, and improve film contamination resistance, the simple multi-walled carbon nano-tubes-Kynoar of operating procedure composite conducting milipore filter and preparation method thereof.
To achieve these goals, the present invention has used the carbon nano-tube material with satisfactory electrical conductivity, SWCN is more than multi-walled carbon nano-tubes costliness, consider this problem of cost, so the present invention chooses multi-walled carbon nano-tubes as conductive filler, prepare a kind of multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter, in parts by weight, made by following component:
Kynoar 5-7
N-N dimethylacetylamide 40-60
Multi-walled carbon nano-tubes (MWCNTs) 0.1-0.5
The molecular weight of described Kynoar is between 40-90 ten thousand, in composite membrane of the present invention as host material.
Preferably, the multi-walled carbon nano-tubes that described multi-walled carbon nano-tubes is carboxylated, draw ratio is 500-3000: 1.
The film hole diameter size of described Kynoar is between 0.5～1 μ m.
The pore size of the compound fenestra of multi-walled carbon nano-tubes-Kynoar prepared by the present invention, between 0.2～0.8 μ m, changes along with the size of content of carbon nanotubes, is applicable to micro-filtration, ultrafiltration and nanofiltration process.
Preferably, multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is Flat Membrane.
The present invention also provides a kind of preparation method of described multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter, do not need to add any dispersant, because adding all of any dispersant can be coated CNT, thereby it is unfavorable to the formation of conductive network to affect CNT contact each other, comprises the steps:
(1) multi-walled carbon nano-tubes is joined in organic solvent N-N dimethylacetylamide, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 1-2 hour, then put into the ultrasonic dispersion liquid that disperses to obtain half an hour carbon pipe dispersion homogeneous of cell pulverization machine.
(2) in this dispersion liquid, add Kynoar again, be placed in the thermostat water bath magnetic agitation of 50-60 ℃ after 4-5 hour through the ultrasonic dispersion of ultrasonic washing instrument 1-2 hour, put into again the ultrasonic dispersion of cell pulverization machine 1-2 hour, to obtain the uniform casting solution of carbon nanotube dispersed.
(3) by above-mentioned casting solution standing and defoaming 2-4 hour in the vacuum drying chamber of 25-35 ℃;
(4) casting solution after above-mentioned (3) deaeration is scraped to the film of making thickness homogeneous with knifing rod under room temperature on glass plate;
(5) casting solution after knifing is left standstill in air to volatilization 20-50s, immerse afterwards film forming in coagulating bath (deionized water);
(6) film is taken out from coagulating bath, at least soak 48 hours with putting into new deionized water after deionized water rinsing, take out again film, film is put into absolute ethyl alcohol and soak 48 hours above rear taking-ups, repeatedly rinse well by deionized water again, can obtain multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter.
This method, take Kynoar as matrix, take CNT as additive, has been prepared the Kynoar composite hyperfiltration membrane of the CNT that adulterated by wet method phase inversion.The surface of having improved Kynoar that adds of multi-walled carbon nano-tubes can make the hydrophily of film be improved, and because CNT has formed network structure in membrane matrix, being formed with of this structure is beneficial to the electric conductivity that improves composite membrane, the comprehensive function of these two performances has improved the contamination resistance of film, greatly extend the service life of film, widened the range of application of composite membrane at aqueous based systems.The preparation of the prepared composite membrane of the present invention is to use wet method forming film with phase transformation method by solution blending, preparation process condition is simple, prepared film, fenestra size is applicable to microfiltration process, be mainly used in water treatment, potential germicidal etc., preparation method and technological process are simple, easy to operate, cost is low, need not change existing equipment.
Accompanying drawing explanation
Fig. 1 is the ESEM picture surface topography map that amplifies the pure polyvinylidene fluoride film of 2000 times.
Fig. 2 is the ESEM picture surface topography map that amplifies the pure polyvinylidene fluoride film of 50000 times.
Fig. 3 is the ESEM picture surface topography map that amplifies multi-walled carbon nano-tubes-polyvinylidene fluoride film that 2000 times of the present invention make.
Fig. 4 is the ESEM picture surface topography map that amplifies multi-walled carbon nano-tubes-polyvinylidene fluoride film that 100000 times of the present invention make.
The specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1:
By the multi-walled carbon nano-tubes of 0.18g carboxylated, (draw ratio is 500-3000: 1) join in 42gN-N dimethylacetylamide by the ultrasonic dispersion of ultrasonic washing instrument 1 hour, then put into the ultrasonic dispersion of cell pulverization machine half an hour, and then add 6g Kynoar, in the thermostat water bath of 60 ℃ magnetic agitation after 5 hours through the ultrasonic dispersion of ultrasonic washing instrument 2 hours, put into again the ultrasonic dispersion of cell pulverization machine 1 hour, finally be placed in the vacuum drying chamber of 35 ℃ standing and defoaming after 2 hours, under room temperature, on glass plate, scrape with knifing rod the film of making thickness homogeneous, to after film prevapourising 20s, immerse in deionized water to its freezing film, after repeatedly rinsing by deionized water, putting into new deionized water soaks 48 hours, film is put into absolute ethyl alcohol to be soaked after 48 hours and takes out, repeatedly rinse well by deionized water again, finally the film of wash clean is dried in rear at the vacuum drying chamber of 40 ℃, can carry out test and the sign of film properties, and compare with pure polyvinylidene fluoride film.Test result shows, the electrical conductivity of pure polyvinylidene fluoride film is 10
-14～10
-15s/cm, and in this example, measured composite membrane surface resistance is 10
6Ω/m
2, electrical conductivity is 10
-6s/cm.In this example, the membrane aperture magnitude range of prepared multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is between 0.2-0.4 μ m.
Embodiment 2:
By the multi-walled carbon nano-tubes of 0.35g carboxylated, (draw ratio is 500-3000: 1) join in 40gN-N dimethylacetylamide by the ultrasonic dispersion of ultrasonic washing instrument 1 hour, then put into the ultrasonic dispersion of cell pulverization machine half an hour, and then add 7g Kynoar, in the thermostat water bath of 60 ℃ magnetic agitation after 5 hours through the ultrasonic dispersion of ultrasonic washing instrument 2 hours, put into again the ultrasonic dispersion of cell pulverization machine 1 hour, finally be placed in the vacuum drying chamber of 35 ℃ standing and defoaming after 2 hours, under room temperature, on glass plate, scrape with knifing rod the film of making thickness homogeneous, to after film prevapourising 20s, immerse in deionized water to its freezing film, after repeatedly rinsing by deionized water, putting into new deionized water soaks 48 hours, film is put into absolute ethyl alcohol to be soaked after 48 hours and takes out, repeatedly rinse well by deionized water again, finally by the film of wash clean after the vacuum drying chamber of 40 ℃ is dried, can carry out test and the sign of film properties, and compare with pure polyvinylidene fluoride film.Test result shows, the electrical conductivity of pure polyvinylidene fluoride film is 10
-14～10
-15s/cm, and in this example, measured composite membrane surface resistance is 10
4Ω/m
2, electrical conductivity is 10
-4s/cm.In this example, the membrane aperture magnitude range of prepared multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is between 0.3-0.6 μ m.
Embodiment 3:
By 0.5g, (draw ratio is 500-3000: 1) multi-walled carbon nano-tubes of carboxylated joins in 60gN-N dimethylacetylamide by the ultrasonic dispersion of ultrasonic washing instrument 1 hour, then put into the ultrasonic dispersion of cell pulverization machine half an hour, and then add 5g Kynoar, in the thermostat water bath of 60 ℃ magnetic agitation after 5 hours through the ultrasonic dispersion of ultrasonic washing instrument 2 hours, put into again the ultrasonic dispersion of cell pulverization machine 1 hour, finally be placed in the vacuum drying chamber of 35 ℃ standing and defoaming after 2 hours, under room temperature, on glass plate, scrape with knifing rod the film of making thickness homogeneous, to after film prevapourising 20s, immerse in deionized water to its freezing film, after repeatedly rinsing by deionized water, putting into new deionized water soaks 48 hours, film is put into absolute ethyl alcohol to be soaked after 48 hours and takes out, repeatedly rinse well by deionized water again, finally by the film of wash clean after the vacuum drying chamber of 40 ℃ is dried, can carry out test and the sign of film properties, and compare with pure polyvinylidene fluoride film.Test result shows, the electrical conductivity of pure polyvinylidene fluoride film is 10
-14～10
-15s/cm, and in this example, measured composite membrane surface resistance is 10
4Ω/m
2, electrical conductivity is 10
-4s/cm.In this example, the membrane aperture magnitude range of prepared multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is between 0.7-0.9 μ m.
Above preferred embodiments of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variation and improvement etc. of doing according to the present patent application scope, within all should belonging to patent covering scope of the present invention.
Claims (5)
1. multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter, is characterized in that: meter by weight, and multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is made up of following component:
Kynoar 5-7
N-N dimethylacetylamide 40-60
Multi-walled carbon nano-tubes 0.1-0.5.
2. a kind of multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter according to claim 1, it is characterized in that: the multi-walled carbon nano-tubes that described multi-walled carbon nano-tubes is carboxylated, the draw ratio of the multi-walled carbon nano-tubes of carboxylated is 500-3000: 1, and the fenestra pore size of prepared multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is between 0.2～1 μ m.
3. a kind of multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter according to claim 1 and 2, is characterized in that: described multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter is Flat Membrane.
4. a preparation method for the multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter described in claim 1-3 any one, is characterized in that: comprise the steps:
(1) multi-walled carbon nano-tubes is joined in organic solvent N-N dimethylacetylamide, solution is placed in to the ultrasonic dispersion of ultrasonic washing instrument 1-2 hour, then put into the ultrasonic dispersion liquid that disperses to obtain half an hour carbon pipe dispersion homogeneous of cell pulverization machine;
(2) in this dispersion liquid, add Kynoar again, be placed in the thermostat water bath magnetic agitation of 50-60 ℃ after 4-5 hour through the ultrasonic dispersion of ultrasonic washing instrument 1-2 hour, put into again the ultrasonic dispersion of cell pulverization machine 1-2 hour, to obtain the uniform casting solution of carbon nanotube dispersed;
(3) by above-mentioned casting solution standing and defoaming 2-4 hour in the vacuum drying chamber of 25-35 ℃;
(4) casting solution after above-mentioned (3) deaeration is scraped to the film of making thickness homogeneous with knifing rod under room temperature on glass plate;
(5) casting solution after knifing is left standstill in air to volatilization 20-50s, immerse afterwards film forming in coagulating bath;
(6) film is taken out from coagulating bath, at least soak 48 hours with putting into new deionized water after deionized water rinsing, take out again film, film is put into absolute ethyl alcohol and soak 48 hours above rear taking-ups, repeatedly rinse well by deionized water again, can obtain multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter.
5. the application of the multi-walled carbon nano-tubes-Kynoar composite conducting milipore filter described in claim 1-3 any one in micro-filtration, ultrafiltration and nanofiltration process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209015A (en) * | 2014-07-30 | 2014-12-17 | 昆明理工大学 | Electric-filtering membrane, preparation method and application thereof |
| CN104437109A (en) * | 2014-11-18 | 2015-03-25 | 华南理工大学 | Polyvinyl chloride-carbon nano tube composite ultrafiltration membrane as well as preparation method and application of polyvinyl chloride-carbon nano tube composite ultrafiltration membrane |
| CN104530614A (en) * | 2014-12-25 | 2015-04-22 | 武汉工程大学 | Porous polyvinylidene fluoride-carbon nanotube composite material and preparation method thereof |
| CN104587841A (en) * | 2015-01-27 | 2015-05-06 | 昆明纳太能源科技有限公司 | Conductive filter membrane and preparation method and application thereof |
| CN104826503A (en) * | 2015-05-27 | 2015-08-12 | 天津工业大学 | Production formula and method of PVDF (polyvinylidene fluoride)/carbon nano-tube super-hydrophobic film |
| CN104941466A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water |
| CN105327624A (en) * | 2015-11-30 | 2016-02-17 | 上海应用技术学院 | Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane |
| CN105478018A (en) * | 2015-12-25 | 2016-04-13 | 西南石油大学 | Preparation method of functionalized multiwalled carbon nanotube blended ultrafiltration membrane |
| CN106607012A (en) * | 2015-10-23 | 2017-05-03 | 中国人民大学 | Polyvinylidene fluoride nanocomposite material and its preparation method and application |
| CN106693726A (en) * | 2015-11-18 | 2017-05-24 | 天津工业大学 | Formula for preparing polyvinylidene fluoride and carbon nanotube composite film and preparation method of formula |
| CN106914149A (en) * | 2017-04-05 | 2017-07-04 | 天津工业大学 | A kind of method that new hydrophobically modified system is etched to carboxylated MWCNT/PVDF blend films surface plasma |
| CN107433141A (en) * | 2017-06-27 | 2017-12-05 | 上海师范大学 | A kind of multi-walled carbon nanotube hybrid membranes for possessing antipollution automatically cleaning, anti-microbial property |
| CN108097223A (en) * | 2017-10-30 | 2018-06-01 | 天津工业大学 | A kind of ultrasonic wave added phase inversion prepares multi-walled carbon nanotube/polyvinylidene fluoride porous film MATERIALS METHODS |
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| CN109833783A (en) * | 2017-11-28 | 2019-06-04 | 天津工业大学 | The preparation of carbon nanomaterial/conducting polymer hybridized film and fouling membrane monitoring technology |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614784A (en) * | 2012-04-05 | 2012-08-01 | 天津工业大学 | Polyvinylidene fluoride-carbon nano tube composite separation film and preparation method thereof |
| CN103349921A (en) * | 2013-06-27 | 2013-10-16 | 北京市理化分析测试中心 | Multiwalled carbon nanotubes-polyether sulfone composite filter membrane as well as preparation method and application thereof |
-
2014
- 2014-01-15 CN CN201410025348.6A patent/CN103785305A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614784A (en) * | 2012-04-05 | 2012-08-01 | 天津工业大学 | Polyvinylidene fluoride-carbon nano tube composite separation film and preparation method thereof |
| CN103349921A (en) * | 2013-06-27 | 2013-10-16 | 北京市理化分析测试中心 | Multiwalled carbon nanotubes-polyether sulfone composite filter membrane as well as preparation method and application thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209015A (en) * | 2014-07-30 | 2014-12-17 | 昆明理工大学 | Electric-filtering membrane, preparation method and application thereof |
| CN104437109A (en) * | 2014-11-18 | 2015-03-25 | 华南理工大学 | Polyvinyl chloride-carbon nano tube composite ultrafiltration membrane as well as preparation method and application of polyvinyl chloride-carbon nano tube composite ultrafiltration membrane |
| CN104530614A (en) * | 2014-12-25 | 2015-04-22 | 武汉工程大学 | Porous polyvinylidene fluoride-carbon nanotube composite material and preparation method thereof |
| CN104587841A (en) * | 2015-01-27 | 2015-05-06 | 昆明纳太能源科技有限公司 | Conductive filter membrane and preparation method and application thereof |
| CN104826503A (en) * | 2015-05-27 | 2015-08-12 | 天津工业大学 | Production formula and method of PVDF (polyvinylidene fluoride)/carbon nano-tube super-hydrophobic film |
| CN104941466A (en) * | 2015-06-09 | 2015-09-30 | 同济大学 | Preparation method of mesoporous carbon organic composite film for removing macromolecular hepatotoxins in water |
| CN104941466B (en) * | 2015-06-09 | 2017-07-11 | 同济大学 | A kind of preparation method for being used to remove the hepatotoxic mesoporous carbon organic hybrid films of macromolecular in water removal |
| CN106607012B (en) * | 2015-10-23 | 2019-12-13 | 北京中科艾加科技有限公司 | Polyvinylidene fluoride nano composite material and preparation method and application thereof |
| CN106607012A (en) * | 2015-10-23 | 2017-05-03 | 中国人民大学 | Polyvinylidene fluoride nanocomposite material and its preparation method and application |
| CN106693726A (en) * | 2015-11-18 | 2017-05-24 | 天津工业大学 | Formula for preparing polyvinylidene fluoride and carbon nanotube composite film and preparation method of formula |
| CN105327624A (en) * | 2015-11-30 | 2016-02-17 | 上海应用技术学院 | Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane |
| CN105478018A (en) * | 2015-12-25 | 2016-04-13 | 西南石油大学 | Preparation method of functionalized multiwalled carbon nanotube blended ultrafiltration membrane |
| CN106914149A (en) * | 2017-04-05 | 2017-07-04 | 天津工业大学 | A kind of method that new hydrophobically modified system is etched to carboxylated MWCNT/PVDF blend films surface plasma |
| CN107433141A (en) * | 2017-06-27 | 2017-12-05 | 上海师范大学 | A kind of multi-walled carbon nanotube hybrid membranes for possessing antipollution automatically cleaning, anti-microbial property |
| CN108097223A (en) * | 2017-10-30 | 2018-06-01 | 天津工业大学 | A kind of ultrasonic wave added phase inversion prepares multi-walled carbon nanotube/polyvinylidene fluoride porous film MATERIALS METHODS |
| CN109833783A (en) * | 2017-11-28 | 2019-06-04 | 天津工业大学 | The preparation of carbon nanomaterial/conducting polymer hybridized film and fouling membrane monitoring technology |
| CN109621756A (en) * | 2019-01-28 | 2019-04-16 | 沈阳建筑大学 | The preparation method of high-throughput resistant to pollution PVDF ultrafiltration membrane |
| CN112316558A (en) * | 2020-10-28 | 2021-02-05 | 鄂尔多斯市清科紫荆技术开发有限公司 | High-efficiency integrated water purification equipment polymer and CNTs (carbon nanotubes) composite filter material for sewage treatment and preparation method thereof |
| CN114618327A (en) * | 2022-03-21 | 2022-06-14 | 南昌航空大学 | Preparation method and application of adsorptive ultrafiltration composite membrane doped with carboxylated multi-walled carbon nanotubes |
| CN114618327B (en) * | 2022-03-21 | 2023-11-24 | 南昌航空大学 | Preparation method and application of carboxylated multiwall carbon nanotube doped adsorptive ultrafiltration composite membrane |
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Application publication date: 20140514 |
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