CN105839228B - A kind of preparation method of polyacrylonitrile-radical conductive fiber material - Google Patents
A kind of preparation method of polyacrylonitrile-radical conductive fiber material Download PDFInfo
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- CN105839228B CN105839228B CN201610382926.0A CN201610382926A CN105839228B CN 105839228 B CN105839228 B CN 105839228B CN 201610382926 A CN201610382926 A CN 201610382926A CN 105839228 B CN105839228 B CN 105839228B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention provides a kind of polyacrylonitrile-radical conductive fiber materials and preparation method thereof, the conductive fiber material is using polyacrylonitrile as template, anion surface active activating agent is emulsifier and dopant, using the method for matrix polymerization, by conducting polymer directly in polyacrylonitrile fibre surface aggregate, conducting polymer can form fine and close clad in fiber surface, and it is conductive can, prepare conducting polypropylene nitrile fibrous material.This can make polyacrylonitrile have certain conductivity, have the effect of polyacrylonitrile conductive or antistatic, in order to further widen application range, we have carried out high temperature cabonization processing to polyaniline-coated polyacrylonitrile fibre membrane obtained, a kind of new carbon fibre material is obtained, the material has preferable super capacitor performance, can be used as electrode material for super capacitor.
Description
Technical field
The present invention relates to a kind of conductive fibers and preparation method thereof, and in particular to arrives a kind of polyacrylonitrile-radical conductive fiber material
The preparation method of material.
Background technique
Intrinsic conducting polymer is due to special structure and excellent physicochemical characteristics, making it aobvious in electrochromism
Show device, rechargeable battery and fuel cell, the electrode material of supercapacitor, electromagnetic shielding material, microwave absorption stealth material,
Electroluminescent device anode decorative material, sensor, transparent conducting coating, conductive fiber, polymer photovoltaic cell material and again
Adsorption of metal ions etc. has extensive and tempting application prospect.Intrinsic conducting polymer is often a kind of indissoluble infusibility
Polymer is limited its application there are certain difficulty in processing.Therefore, Recent study person with different fibers and knit
Object is that matrix prepares conducting polymer conductive fiber composite material.Conducting polymer is deposited on fiber table using matrix polymerization method
Face obtains electric conductivity while keeping matrix some strength.For example, Zhang Huiqin etc., " a kind of polyacrylonitrile/polyaniline is multiple
Close the preparation method of micro-nano conductive fiber " (Chinese patent CN103255634A) by electrostatic spinning to be prepared for polyacrylonitrile micro-
Then nanofiber wraps up a strata aniline in fiber surface by template in situ, it is compound to obtain conductive polymer micro-nano rice
Fiber.Hydrochloric acid acid doped polyaniline is aggregated in method of electrostatic spinning by template and fibrillated polytetrafluoroethylene is made by Hui Zhou etc.
Tie up film surface, prepare polyaniline/polytetrafluoroethylcomposite composite film, the tunica fibrosa have preferable electric conductivity, absorption heavy metal from
Sub- aspect has excellent performance (Hui Zhou, Zhiquan Shi, Yun Lu.Conducting polyaniline/poly
(tetrafluoroethylene)composite films with tunable surface morphology and
Hydrophilicity [J] .Synthetic Metals, 2010,160:1925-1930.).Nanofiber has specific surface area
Greatly, the features such as porosity is high, and micro/nano fibrous membrane material has small-size effect, skin effect etc..Common nanofiber
Preparation method has method of electrostatic spinning, centrifugal spinning, template drawing-off etc..Currently, (Zhuan Xupin, " one kind is poly- for solution jet spinning method
Close object and receive the preparation method of microfiber nonwoven cloth " (Chinese patent CN102071542A)) as a kind of nanofiber for preparing
Novel method is paid close attention to, and this method has many advantages, such as that high-efficient, low energy consumption, simple process.Herein by matrix polymerization method
Conducting polymer is deposited on to the polyacrylonitrile fibre membrane surface of solution jet spinning method preparation, has been made with stable, lasting
The composite cellulosic membrane of electric conductivity, the composite material can be used for conductive spinning product, solar battery, energy storage material, sensor,
With water process etc..
In order to further expand the application range of prepared composite cellulosic membrane, carbonization treatment has been carried out to it herein to answer
For in terms of supercapacitor.Supercapacitor as a kind of novel electrochemical energy storage device there is electrode material to enrich, fill
The features such as velocity of discharge is fast, environmental-friendly, the extensive concern by whole world scientist and government department.Supercapacitor can be with
Apply in some products for needing quick charge, such as electric vehicle, flashlight etc., in addition to this it can also be used as it is static with
The backup power supply of the Weak currents such as machine memory, data transmission system power supply.With widening for its application field, the market demand
It is stepping up, therefore quality-high and inexpensive electrode material how is made to become the key of research.Fiber-like carbon material is widely answered
For electrode material for super capacitor, the present invention is by by polyaniline/polyacrylonitrile core-skin composite fiber film high-temp. carbonization treatment
A kind of new carbon fibre material is obtained, which can be used as electrode material for super capacitor.
Summary of the invention
The present invention provides a kind of conducting polypropylene nitrile fibrous materials and preparation method thereof, and the conductive fiber material is with solution
The polyacrylonitrile fibre membrane of jet spinning method preparation is template, and anionic surfactant had not only been emulsifier but also had been dopant, was adopted
With the method for matrix polymerization, conducting polypropylene nitrile fibrous material is prepared.This makes polyacrylonitrile fibre have certain conductivity,
There is the performance of absorption heavy metal ion simultaneously, expand the application range of polyacrylonitrile.High temperature cabonization further is carried out to it
Processing, is made a kind of carbon material with preferable super capacitor performance, can be used as electrode material for super capacitor use.
1. the present invention prepares a kind of conducting polypropylene nitrile fibrous material, specific step is as follows:
(1) preparation of spinning solution: polyacrylonitrile is dissolved in solvent, and forming mass concentration is 4~30% uniform
Spinning solution；
(2) polyacrylonitrile is prepared using solution jet spinning method in the polyacrylonitrile solution for obtaining step (1)
Micro/nano-fibre film；
(3) a certain amount of demulsifier and deionized water are mixed in a certain ratio uniformly, it is living that a certain amount of anionic surface is added
Property agent is made into 0.05~1mol/L mixed solution；
(4) nano fibrous membrane that will be made in step (2) takes in a certain amount of mixed solution that step (3) are added and is sufficiently impregnated 5
~30min.Then monomer is added, 0.5~2mol/L of monomer concentration stirs 10~60min at room temperature；
(5) oxidant is added into step (4) system, oxidant concentration is 0.3~4mol/L, is carried out at 0~30 DEG C
Chemical oxidising polymerisation stirs 6~8h, and mixing speed control is then allowed to stand 10~for 24 hours in 1~1000rpm.After reaction, will
Reactant filtering, successively sufficiently being washed with organic solvent, deionized water to filtrate is colourless, 50~120 DEG C of 10~48h of drying,
Obtain conducting polypropylene nitrile fibrous material；
(6) the conducting polypropylene nitrile fibrous material that step (5) obtains pre-oxidation treatment: is subjected to pre- oxygen in air atmosphere
Change obtains pre-oxidized fibers, and Pre oxidation is 160~300 DEG C, and preoxidation time is 2~3h；
(7) carbonization treatment: the pre-oxidized fibers that step (6) obtains are subjected to carbonization treatment in nitrogen or argon atmosphere and are obtained
To carbon fiber, carburizing temperature is 600~1300 DEG C, and carbonization time is 0.5~3h.
2. wherein polyacrylonitrile is polyacrylonitrile homopolymer or copolymer in step (1), viscosity average molecular weigh is 8~300,000,
Wherein propylene nitrile segments account for 85% or more, remaining is methyl acrylate, acrylic acid, acrylamide, itaconic acid, sodium styrene sulfonate
Or sodium allylsulfonate.
3. solvent described in step (1) is n,N-Dimethylformamide, in n,N-dimethylacetamide, dimethyl sulfoxide
One or two kinds of or more mixtures, solution temperature range are room temperature to 100 DEG C.
During 4. polyacrylonitrile micro/nano-fibre felt is prepared in solution jet spinning method described in step (2), shadow
The technological parameter for ringing the diameter of fiber is viscosity 1000-10000mPas, the fltting speed 0.5-50ml/h of high polymeric solution,
Orifice diameter is 0.05-1.25mm, and air-flow slit is 0.02-0.75mm, and air inlet stream amount is 300-1200m3/ h, exhaust
Oral air flow is 1600-3200m3/ h, the size 0.01-0.8MPa of spinning air pressure, 20-380 DEG C of the temperature of air-flow receive distance
The factors such as 0.4-10m.
5. demulsifier described in step (3) is one or both of methanol, ethyl alcohol, acetone and butanone or more.With go
The ratio of ionized water is 1: 1~5.
6. anionic surfactant described in step (3) is lauryl sodium sulfate, sodium hexadecyl sulfate, dodecane
Base benzene sulfonic acid and its salt, cetyl benzenesulfonic acid and its salt, ethyoxyl sodium alkyl sulfate, ethyoxyl alkyl ammonium sulfate, polypropylene
Acid and its salt, dodecyl polyoxyethylene ether sodium sulphate, sodium soap, dodecyl polyoxyethylene ether carboxylic acid sodium, di-2-ethylhexylphosphine oxide
One or both of sodium naphthalene sulfonate or more.Anionic surfactant is not only used as emulsifier, but also the doping as polyaniline
Agent.Solution concentration is 0.05~1mol/L.
7. monomer described in step (4) be pyrroles, aniline, thiophene, one or both of 3,4-ethylene dioxythiophene and
More than.Monomer concentration is 0.5~2mol/L.
8. oxidant described in step (5) is ferric trichloride, hydrogen peroxide, ammonium persulfate, alchlor, potassium permanganate, weight
Potassium chromate, Potassiumiodate, one or both of manganese dioxide or more.Oxidant concentration is 0.1~4mol/L.
9. preparation method as described in claim 1, the polyaniline/polyacrylonitrile composite conductive fibre that is prepared can
Applied to solar battery, energy storage material, sensor and heavy metal ion adsorbed etc..
10. preparation method as described in claim 1, the silicon carbide/polypropylene itrile group conductive fiber application is lithium ion
The fields such as secondary cell anode material, electrical double layer capacitor electrodes, high-efficiency adsorbent, Heat Conduction Material, field electron emission materials.
Detailed description of the invention
Fig. 1 is that 1 solution gunite of embodiment prepares polyacrylonitrile fibre membrane figure (scanning electron micrographs).
Fig. 2 is that 1 solution gunite of embodiment prepares polyacrylonitrile fibre membrane figure.
Fig. 3 is 1 polyaniline-coated conducting polypropylene nitrile tunica fibrosa figure (scanning electron micrographs) of embodiment.
Fig. 4 is polyaniline-coated conducting polypropylene nitrile tunica fibrosa figure obtained by embodiment 1.
Fig. 5 is the composite cellulosic membrane figure after 1 high temperature cabonization of embodiment.(scanning electron micrographs).
Specific embodiment
It is used to further illustrate the method that the present invention describes below by way of specific embodiment, it is not intended that of the invention
It is confined to these embodiments.
Embodiment 1:
A kind of polyacrylonitrile-radical conductive fiber material preparation method, includes the following steps:
(1) preparation of spinning solution: being dissolved in N for the polyacrylonitrile of viscosity average molecular weigh 90,000 with the ratio of mass fraction 12%,
In dinethylformamide, spinning solution is made to being uniformly mixed in stirring；
(2) solution jet spinning method prepares polyacrylonitrile fibre material: spinning solution is supplied to spinneret through metering pump
Die head makes spinning solution be extruded into spinning solution thread from the spinneret orifice of spinneret die；It is blown simultaneously with high speed jet-stream wind
To extruding spinning solution thread, high-speed flow stretches solution thread and solvent volatilization is promoted to be allowed to form polyacrylonitrile micro-/ nano
Fiber.Related process parameters are as follows: the apparent viscosity of solution is 8058mPas, and gas flow temperature is 80 DEG C, fltting speed 5ml/
H, orifice diameter 0.3mm, air-flow slit are 0.2mm, air inlet stream amount 700m3/ h, the throughput 1800m of exhaust outlet3/
H, spinning air pressure are 0.15MPa, and receiving distance is 80cm；
(3) a certain amount of ethyl alcohol is uniformly mixed with deionized water volume ratio 1: 5, a certain amount of dodecyl benzene sulfonic acid is added and matches
At 0.3mol/L mixed solution；
(4) polyacrylonitrile fibre membrane that will be made in step (2) takes in a certain amount of mixed solution that step (3) are added and fills
Sub-dip stain 10min.Then aniline monomer is added, monomer concentration 0.5mol/L stirs 30min at room temperature；
(5) ammonium persulfate is added into step (4) system as oxidant, oxidant concentration 0.5mol/L, at 0 DEG C
Chemical oxidising polymerisation is carried out, 6h is stirred, mixing speed is controlled in 800rpm, is then allowed to stand 12h.After reaction, by reactant
Filtering, it is colourless for successively sufficiently being washed with ethyl alcohol, deionized water to filtrate, and 50 DEG C of drying for 24 hours, obtain conducting polypropylene nitrile fiber
Material；
(6) the conducting polypropylene nitrile fibrous material that step (5) obtains pre-oxidation treatment: is subjected to pre- oxygen in air atmosphere
Change obtains pre-oxidized fibers, and Pre oxidation is 280 DEG C, preoxidation time 2h；
(7) carbonization treatment: the pre-oxidized fibers that step (6) obtains are subjected to carbonization treatment in nitrogen atmosphere and obtain carbon fiber
Dimension, 5 DEG C/min of heating rate, carburizing temperature are 700 DEG C, carbonization time 2h.
Conducting polypropylene nitrile fibrous material obtained by preparing, Fig. 1 are the polyacrylonitrile fibre of solution gunite preparation, Fig. 3
It is the composite fibre scanning electron microscope (SEM) photograph that polyaniline-coated polyacrylonitrile fibre material obtains, polyaniline is in fiber as seen from the figure
Surface forms fine and close clad.Conductivity is up to 1.24x10-2S/cm.Fig. 5 is polyaniline/polyacrylonitrile composite fiber pyrocarbon
Scanning electron microscope (SEM) photograph after change.
Embodiment 2:
The present embodiment unlike the first embodiment, step (4) then be added pyrrole monomer, monomer concentration 0.5mol/L,
It is same as Example 1.
Embodiment 3:
The present embodiment unlike the first embodiment, step (4) then be added thiophene monomer, monomer concentration 0.5mol/L,
It is same as Example 1.
Embodiment 4:
A kind of conducting polypropylene nitrile fibrous material preparation method, includes the following steps:
(1) preparation of spinning solution: being dissolved in N for the polyacrylonitrile of viscosity average molecular weigh 90,000 with the ratio of mass fraction 12%,
In dinethylformamide, spinning solution is made to being uniformly mixed in stirring；
(2) solution jet spinning method prepares polyacrylonitrile fibre material: spinning solution is supplied to spinneret through metering pump
Die head makes spinning solution be extruded into spinning solution thread from the spinneret orifice of spinneret die；It is blown simultaneously with high speed jet-stream wind
To extruding spinning solution thread, high-speed flow stretches solution thread and solvent volatilization is promoted to be allowed to form polyacrylonitrile micro-/ nano
Fiber.Related process parameters are as follows: the apparent viscosity of solution is 8058mPas, and gas flow temperature is 80 DEG C, fltting speed 5ml/
H, orifice diameter 0.3mm, air-flow slit are 0.2mm, air inlet stream amount 700m3/ h, the throughput 1800m of exhaust outlet3/
H, spinning air pressure are 0.15MPa, and receiving distance is 80cm；
(3) a certain amount of ethyl alcohol is uniformly mixed with deionized water volume ratio 2: 5, a certain amount of dodecyl benzene sulfonic acid is added and matches
At 0.3mol/L mixed solution；
(4) polyacrylonitrile fibre membrane that will be made in step (2) takes in a certain amount of mixed solution that step (3) are added sufficiently
Impregnate 10min.Then aniline monomer is added, monomer concentration 0.5mol/L stirs 30min at room temperature；
(5) ammonium persulfate is added into step (4) system as oxidant, oxidant concentration 0.5mol/L, at 0 DEG C
Chemical oxidising polymerisation is carried out, 6h is stirred, mixing speed is controlled in 800rpm, is then allowed to stand 12h.After reaction, by reactant
Filtering, it is colourless for successively sufficiently being washed with ethyl alcohol, deionized water to filtrate, and 50 DEG C of drying for 24 hours, obtain conducting polypropylene nitrile fiber
Material；
(6) the conducting polypropylene nitrile fibrous material that step (5) obtains pre-oxidation treatment: is subjected to pre- oxygen in air atmosphere
Change obtains pre-oxidized fibers, and Pre oxidation is 280 DEG C, preoxidation time 2h；
(7) carbonization treatment: the pre-oxidized fibers that step (6) obtains are subjected to carbonization treatment in nitrogen atmosphere and obtain carbon fiber
Dimension, 5 DEG C/min of heating rate, carburizing temperature are 800 DEG C, carbonization time 2h.
Claims (7)
1. a kind of preparation method of polyacrylonitrile-radical conductive fiber material comprising following steps:
(1) preparation of spinning solution: polyacrylonitrile is dissolved in solvent, and forming mass concentration is 4~30% uniform spinning
Solution；
(2) polyacrylonitrile nanofiber is prepared using solution jet spinning method in the spinning solution for obtaining step (1)
Film；
(3) a certain amount of demulsifier and deionized water are mixed in a certain ratio uniformly, the demulsifier is methanol, ethyl alcohol, acetone
One or more of with butanone；Ratio with deionized water is 1: 1~5；A certain amount of anionic surfactant is added
It is made into 0.05~1mol/L mixed solution；The anionic surfactant is one of dodecyl benzene sulfonic acid and its salt；
Anionic surfactant is not only used as emulsifier, but also the dopant as polyaniline；
(4) by nano fibrous membrane obtained in step (2), take and be sufficiently impregnated 5 in a certain amount of mixed solution that step (3) are added~
30min；Then monomer aniline is added, 0.5~2mol/L of monomer concentration stirs 10~60min at room temperature；
(5) oxidant is added into step (4) system, oxidant concentration is 0.3~4mol/L, and chemistry is carried out at 0~30 DEG C
6~8h is stirred in oxidation polymerization, and mixing speed control is then allowed to stand 10~for 24 hours in 1~1000rpm；After reaction, it will react
Object filtering, it is colourless for successively sufficiently being washed with organic solvent, deionized water to filtrate, and 50~120 DEG C of 10~48h of drying are obtained
Conducting polypropylene nitrile fibrous material；
(6) pre-oxidation treatment: the conducting polypropylene nitrile fibrous material that step (5) obtains is carried out pre-oxidizing in air atmosphere
To pre-oxidized fibers, Pre oxidation is 160~300 DEG C, and preoxidation time is 2~3h；
(7) carbonization treatment: the pre-oxidized fibers that step (6) obtains are subjected to carbonization treatment in nitrogen or argon atmosphere and obtain carbon
Fiber, carburizing temperature are 600~1300 DEG C, and carbonization time is 0.5~3h.
2. preparation method as described in claim 1, polyacrylonitrile is polyacrylonitrile homopolymer or copolymer in step (1), is glued
Average molecular weight be 8~300,000, wherein propylene nitrile segments account for 85% or more, remaining for methyl acrylate, acrylic acid, acrylamide,
Itaconic acid, sodium styrene sulfonate or sodium allylsulfonate.
3. preparation method as described in claim 1, solvent described in step (1) is n,N-Dimethylformamide, N, N- diformazan
The mixture of one or both of yl acetamide, dimethyl sulfoxide or more, solution temperature range are room temperature to 100 DEG C.
4. preparation method as described in claim 1, polyacrylonitrile nanofiber film is prepared in the solution jet spinning method
During, the technological parameter of the diameter of the influence fiber used pushes away for the viscosity 1000-10000mPas of high polymeric solution
Into speed 0.5-50ml/h, orifice diameter 0.05-1.25mm, air-flow slit is 0.02-0.75mm, and air inlet stream amount is
300-1200m3/ h, exhaust oral air flow are 1600-3200m3/ h, the size 0.01-0.8MPa of spinning air pressure, the temperature of air-flow
20-380 DEG C, receive distance 0.4-10m.
5. preparation method as described in claim 1, oxidant described in step (5) is ferric trichloride, hydrogen peroxide, persulfuric acid
Ammonium, alchlor, potassium permanganate, potassium bichromate, Potassiumiodate, one or both of manganese dioxide or more；Oxidant concentration
For 0.1~4mol/L.
6. preparation method as described in claim 1, the polyacrylonitrile-radical conductive fiber material being prepared is applied to too
Positive energy battery, energy storage material, sensor and heavy metal ion adsorbed aspect.
7. preparation method as described in claim 1, the polyacrylonitrile-radical conductive fiber material is applied to lithium ion secondary electricity
Pond anode material, electrical double layer capacitor electrodes, high-efficiency adsorbent, Heat Conduction Material, field electron emission materials field.
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| CN106868714A (en) * | 2017-02-20 | 2017-06-20 | 南通市中和化纤有限公司 | PAN micro nanometer fiber films are spun in heavy metal ion adsorbed liquid spray |
| JP7074054B2 (en) * | 2017-03-27 | 2022-05-24 | 東レ株式会社 | Fiber manufacturing method and carbon fiber manufacturing method |
| CN109913971A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of porous composite nano fiber and its preparation method and application |
| CN108486690A (en) * | 2018-03-15 | 2018-09-04 | 上海应用技术大学 | A kind of nitrogen-doped carbon nano-fiber electrode material and preparation method thereof |
| CN109267347A (en) * | 2018-09-27 | 2019-01-25 | 天津工业大学 | A kind of preparation method of polypyrrole/oxidization fiber felt flexible electromagnetic shielding material |
| CN109763338B (en) * | 2018-12-29 | 2020-11-27 | 厦门大学 | Polyacrylonitrile-based carbon fiber/polyaniline composite conductive fiber with core-sheath structure and preparation method thereof |
| CN110184683B (en) * | 2019-05-07 | 2020-06-19 | 清华大学 | Anisotropic layered carbon fiber-based aerogel material and preparation method thereof |
| CN114486861B (en) * | 2022-01-25 | 2024-01-02 | 东南大学 | Electrochemiluminescence molecular imprinting sensor and preparation method and application thereof |
| CN115323784A (en) * | 2022-01-27 | 2022-11-11 | 青岛大学 | Polypyrrole conductive flexible fiber membrane material and preparation method thereof |
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