CN115584038B - Flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film and preparation method and application thereof - Google Patents
Flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film and preparation method and application thereof Download PDFInfo
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C08K9/02—Ingredients treated with inorganic substances
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Abstract
The invention belongs to the technical field of thermal interface materials, and particularly relates to a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film, a preparation method and application thereof, and a preparation method of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film, which comprises the following steps: mixing an aramid nanofiber solution with a filler MXene solution, and performing ultrasonic treatment to obtain a mixed solution; pouring the mixed solution into a mould, immersing in water, and obtaining a hydrogel film after complete crosslinking, and air-drying and hot-pressing to obtain the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film. Through the synergistic construction of the aramid nanofiber and the MXene nanosheet filler, a cross-linked heat conduction path is formed, so that the heat resistance is reduced, the heat conduction performance is improved, and the mechanical property is excellent. The preparation method is simple, the base body and the heat conducting filler are fully crosslinked, the thermal resistance of a hot surface is reduced, the phenomena of dry solidification and pulverization and the like are effectively overcome, and the reliability of the product is improved.
Description
Technical Field
The invention belongs to the technical field of thermal interface materials, and particularly relates to a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film, and a preparation method and application thereof.
Background
With the rise of 5G communication technology, microelectronic devices are rapidly developing toward high frequency, integration and miniaturization. The device works under continuous high frequency and high power, heat accumulation is rapid, and the working efficiency, reliability and service life of the device and the equipment are seriously affected. To ensure safe and reliable operation of electronic devices, efficient and safe thermal management must be achieved using highly thermally conductive and flame retardant materials.
The aramid nanofibers (Aramid nanofibers, ANF for short) have excellent mechanical properties, impressive chemical and thermal properties, and thus have great application value in the field of thermal interface materials. At present, the heat conducting particles can be introduced to greatly improve the heat conducting property, which is verified by a plurality of researches. However, the uneven dispersion of a large amount of fillers directly affects the improvement of the heat conduction performance of the aramid nanofiber and also leads to the reduction of the mechanical performance.
The conventional aramid nano heat-conducting composite film is a composite material prepared by directly mixing common heat-conducting fillers such as reduced graphene oxide, boron nitride, nitrogen carbide and the like with aramid nano fibers. Due to the addition of a large amount of heat conducting filler, the cost and the weight of the composite material are increased, and the interface compatibility between the filler and the aramid nanofiber is poor, so that certain interface thermal resistance is generated, and the heat conducting property is limited to a certain extent. In addition, the conventional process for preparing the heat conductive film includes exposing to high temperature for a long time, inevitably generating internal cracks, affecting the working performance and reducing the service life thereof. In addition, the flexible high-heat-conductivity material obtained by the common preparation process is single in shape, narrow in application range and harsh in processing process, and the flame-retardant safety of the flexible high-heat-conductivity material is not effectively considered.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film.
The invention further aims to provide the flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film prepared by the method.
The invention also aims to provide application of the flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
Mixing the aramid nanofiber solution with the two-dimensional filler MXen solution, and performing ultrasonic treatment to obtain a mixed solution;
pouring the mixed solution into a mould, immersing in water, and obtaining a hydrogel film after complete crosslinking, and air-drying and hot-pressing to obtain the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film.
Preferably, the mass ratio of the MXene to the aramid nanofiber in the mixed solution is 1:20 to 6:20, more preferably 6:20.
Preferably, the concentration of the aramid nanofiber solution is 20-30 mg/ml, more preferably 20mg/ml; the concentration of the MXene solution is 20-30 mg/ml, more preferably 20mg/ml.
Preferably, the aramid nanofiber solution is an aramid nanofiber/dimethyl sulfoxide solution, and is prepared by the following steps:
and dissolving the poly-p-phenylene terephthalamide and potassium hydroxide in a dimethyl sulfoxide solution, and stirring until the poly-p-phenylene terephthalamide and the potassium hydroxide are completely dissolved to obtain an aramid nanofiber/dimethyl sulfoxide solution.
Preferably, the MXene solution is MXene/dimethyl sulfoxide solution, and is prepared by the following steps:
Adding lithium fluoride into a dilute hydrochloric acid solution, stirring and carrying out ultrasonic treatment until the lithium fluoride is completely dissolved to prepare etching solution; adding Ti3AlC2 into the etching solution, stirring at 42-50 ℃ for 24-36 h, repeatedly centrifuging and washing the mixed acid solution with deionized water until the pH is 6-7, removing supernatant to obtain multi-layer MXene precipitate, adding deionized water, performing ultrasonic treatment and centrifuging, collecting supernatant to obtain single-layer or less-layer MXene solution, drying, dissolving in dimethyl sulfoxide solution, and stirring at room temperature for 24-36 h to obtain MXene/dimethyl sulfoxide solution.
Preferably, the MXene material is Ti 3C2Tx, wherein T x is at least one of an-OH functional group and an-F functional group.
Preferably, the water is deionized water.
The aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film prepared by the method.
Preferably, the thickness of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film is 20-100 mu m.
The aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film is applied to microelectronic elements and electronic equipment.
Compared with the prior art, the invention has the following advantages:
(1) The preparation reaction provided by the invention does not involve a high-temperature process, the process is safe and simple, and the prepared product has excellent performance.
(2) The flexible composite film prepared by the invention has high thermal conductivity and good flame retardance, the thermal conductivity of the highest plane direction is more than or equal to 15.5 W.m -1·K-1, the lowest total heat release value is 8.2kJg -1, and meanwhile, the phenomena of dry solidification pulverization and the like are effectively overcome, and the reliability of the product is improved.
(3) The flexible composite film prepared by the invention has excellent mechanical property, the tensile strength is 52.7MPa, and the tensile strain is 1.2%.
(4) The preparation method provided by the invention can be applied to the preparation of the thin film with controllable shape and size.
Drawings
FIG. 1 is a transmission electron microscope image of an aramid nanofiber prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the MXene nanoplatelets prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the composite film prepared in example 6 of the present invention;
FIG. 4 shows a dolphin-shaped composite film prepared in example 6 of the present invention;
FIG. 5 is a square composite film produced in example 6 of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects of the invention more apparent, the invention is further described in detail below with reference to the following examples. The specific embodiments described herein are to be considered in an illustrative sense and are not to be construed as limiting the invention.
Example 1
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
(1) Preparing an aramid nanofiber/dimethyl sulfoxide solution: 5g of poly (p-phenylene terephthalamide) (PPTA for short) and 5g of potassium hydroxide are dissolved in 245ml of dimethyl sulfoxide solution, stirred at room temperature for 1 week until the solution is completely dissolved, and the solution is observed to be completely changed into dark red, so as to obtain an aramid nanofiber/dimethyl sulfoxide solution, wherein the concentration of the aramid nanofiber/dimethyl sulfoxide solution is 20mg/ml;
(2) Preparation of MXene/dimethyl sulfoxide solution: adding 5g of lithium fluoride into 100ml of dilute hydrochloric acid solution, stirring and carrying out ultrasonic treatment for five minutes until the lithium fluoride is completely dissolved, so as to prepare etching solution; adding 5g of Ti 3AlC2 into the etching solution, stirring at 42 ℃ for 24 hours, repeatedly centrifuging and washing the mixed acid solution with deionized water, wherein the centrifugation speed is 3500rpm until the pH=6-7, removing the supernatant to obtain multi-layer MXene precipitate, dispersing the multi-layer MXene precipitate into 200ml of deionized water, carrying out ultrasonic treatment and centrifugation for 30 minutes, collecting the supernatant to obtain single-layer or less-layer MXene aqueous solution, drying in a baking oven at 60 ℃, dissolving the dried MXene in dimethyl sulfoxide solution, and stirring at room temperature for 24 hours; the concentration of the MXene/dimethyl sulfoxide solution is 20mg/ml;
(3) Preparing an aramid nanofiber/MXene composite film: mixing and stirring 20mg/ml of aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of MXene/dimethyl sulfoxide solution for 6 hours, and carrying out ultrasonic treatment for 30 minutes to obtain the aramid nanofiber with the mass ratio of MXene to aramid nanofiber of 1: 20; pouring the mixed solution into a mould, immersing the mixed solution into a container containing deionized water by a solvent replacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing the hydrogel film at 60 ℃ to form a film, thereby obtaining the aramid nanofiber/MXene composite film with the thickness of 26 mu m (see figure 3).
As shown in fig. 1, the deprotonation of PPTA by an alkaline solvent system illustrates the successful preparation of aramid nanofibers having an average length in the range of 2-3 μm; as shown in FIG. 2, the removal of the Al element layer in the system by selective etching and ultrasonic treatment, demonstrated the successful production of MXene nanoplatelets having an average size of 0.3-0.5 μm; as shown in fig. 3, it can be clearly seen that the MXene nanoplatelets and the aramid nanofibers form a good crosslinked structure after the crosslinking reaction, and there is no blocking phenomenon.
Example 2
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
Referring to example 1, 20mg/ml of an aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of an MXene/dimethyl sulfoxide solution were prepared, respectively, and the prepared 20mg/ml of the aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of the MXene/dimethyl sulfoxide solution were mixed and stirred for 6 hours, and then sonicated for 30 minutes, so that the mass ratio of the MXene to the aramid nanofiber was 1: 10; pouring the mixed solution into a mould, immersing the mixed solution into a container containing deionized water by a solvent replacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing the hydrogel film at 60 ℃ to form a film, thereby obtaining the aramid nanofiber/MXene composite film with the thickness of 24 mu m.
Example 3
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
Referring to example 1, 20mg/ml of an aramid nanofiber/dimethyl sulfoxide solution and 20 mg/mlMXene/dimethyl sulfoxide solution were prepared, respectively, and the prepared 20mg/ml of the aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of an MXene/dimethyl sulfoxide solution were mixed and stirred for 6 hours, and then sonicated for 30 minutes, so that the mass ratio of the MXene to the aramid nanofiber was 3: 20; pouring the mixed solution into a mould, immersing the mixed solution into a container containing deionized water by a solvent replacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing the hydrogel film at 60 ℃ to form a film, thereby obtaining the aramid nanofiber/MXene composite film with the thickness of 24 mu m.
Example 4
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
Referring to example 1, 20mg/ml of an aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of an MXene/dimethyl sulfoxide solution were prepared, respectively, and the prepared 20mg/ml of the aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of the MXene/dimethyl sulfoxide solution were mixed and stirred for 6 hours, and then sonicated for 30 minutes, so that the mass ratio of the MXene to the aramid nanofiber was 1: 5; pouring the mixed solution into a mould, immersing the mixed solution into a container containing deionized water by a solvent replacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing the hydrogel film at 60 ℃ to form a film, thereby obtaining the aramid nanofiber/MXene composite film with the thickness of 24 mu m.
Example 5
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
Referring to example 1, 20mg/ml of an aramid nanofiber/dimethyl sulfoxide solution and 20 mg/mlMXene/dimethyl sulfoxide solution were prepared, respectively, and the prepared 20mg/ml of the aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of an MXene/dimethyl sulfoxide solution were mixed and stirred for 6 hours, and then sonicated for 30 minutes, so that the mass ratio of the MXene to the aramid nanofiber was 1: 4; pouring the mixed solution into a mould, immersing the mixed solution into a container containing deionized water by a solvent replacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing the hydrogel film at 60 ℃ to form a film, thereby obtaining the aramid nanofiber/MXene composite film with the thickness of 25 mu m.
Example 6
A preparation method of a flexible aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film comprises the following steps:
referring to example 1, 20mg/ml of an aramid nanofiber/dimethyl sulfoxide solution and 20 mg/mlMXene/dimethyl sulfoxide solution were prepared, respectively, and the prepared 20mg/ml of the aramid nanofiber/dimethyl sulfoxide solution and 20mg/ml of an MXene/dimethyl sulfoxide solution were mixed and stirred for 6 hours, and then sonicated for 30 minutes, so that the mass ratio of the MXene to the aramid nanofiber was 3: 10; pouring the mixed solution into a mould (wherein the dolphin mould has the size of 6 multiplied by 3cm, the square mould has the size of 6 multiplied by 6 cm), immersing the mould into a container containing deionized water by a solvent displacement method, after the cross-linking is completed, air-drying the obtained hydrogel film, and further hot-pressing at 60 ℃ to form a film to obtain the aramid nanofiber/MXene composite film with the thickness of 24 mu m, wherein the composite films with different shapes and sizes are shown in figures 4-5, and the composite film prepared in the embodiment 6 is uniform and is not limited by the shape and the size.
Comparative example 1
A preparation method of a flexible aramid nanofiber film comprises the following steps:
Referring to example 1, a 20mg/ml aramid nanofiber/dimethyl sulfoxide solution was prepared, sonicated for 30min, poured into a mold, immersed in a container containing deionized water by a solvent displacement method, and after crosslinking was completed, the resulting hydrogel film was air-dried, and further hot-pressed at 60 ℃ to form a film of 25 μm thick aramid nanofiber.
Test example 1 thermal conductivity test
The heat conductive films prepared in examples 1 to 6 and comparative example 1 were subjected to heat conductive property test in the following manner, respectively:
(1) The heat conductive films prepared in examples 1 to 6 and comparative example 1 were each subjected to a thermal diffusivity test using LFA467 laser heat conductive instrument from Netzsch corporation, germany;
(2) The heat conductive films prepared in examples 1 to 6 and comparative example 1 were each tested for specific heat capacity using a DSC1 low temperature differential scanning calorimeter of Metler-toli-Toril multi METLER company;
The test results of the above test are shown in table 1:
TABLE 1
| Coefficient of thermal diffusivity (mm 2s-1) | Specific heat capacity (Jg -1K-1) | Heat conductivity coefficient (W m -1K-1) | |
| Example 1 | 8.5 | 0.82 | 4.8 |
| Example 2 | 7.4 | 0.96 | 6.0 |
| Example 3 | 10.6 | 0.97 | 7.7 |
| Example 4 | 13.2 | 1.17 | 11.0 |
| Example 5 | 13.0 | 0.98 | 13.9 |
| Example 6 | 11.5 | 1.27 | 15.5 |
| Comparative example 1 | 3.4 | 1.26 | 4.7 |
As shown in the test results of Table 1, according to the embodiment of the invention, the heat conduction coefficient of the heat conduction film can reach 15.5 W.m -1·K-1 by adjusting the amount of the MXene nano-sheets, so that the heat conduction function can be more effectively realized, and the electronic element is protected. The heat conductive film obtained in comparative example 1 had a heat conductivity of 4.7W.m -1·K-1. The thermal conductivity of example 1 was increased by 765.96% compared to comparative example 1. Therefore, the heat conduction film prepared by compounding the MXene nano-sheets can effectively improve the heat conduction performance.
Test example 2 mechanical Property test
The heat conductive composite films prepared in examples 1 to 6 and comparative example 1 were subjected to mechanical properties test in the following manner:
Examples 1-6, and comparative example 1 were cut into 6X 30mm strips, and tensile tested using a universal materials tester (CMT 4503, MTS) at a tensile speed of 1mm min -1 and 5 times each;
the test results of the above test are shown in table 2:
TABLE 2
| Tensile Strength (MPa) | Tensile Strain (%) | |
| Example 1 | 74.9 | 3.1 |
| Example 2 | 62.5 | 3.6 |
| Example 3 | 63.1 | 4.5 |
| Example 4 | 56.6 | 2.1 |
| Example 5 | 54.4 | 1.2 |
| Example 6 | 52.7 | 1.2 |
| Comparative example 1 | 100.5 | 2.1 |
As can be seen from Table 2, in the above examples 1 to 6, as the content of the MXene nano-sheets increases, the tensile strength of the prepared aramid nanofiber heat-conducting composite film gradually decreases as compared with that of comparative example 1, but the tensile strength of the prepared aramid nanofiber heat-conducting composite film still can reach the commercial application standard, and the aramid nanofiber/MXene composite film prepared by the preparation method provided by the invention has good mechanical properties. This is due to the strong intermolecular hydrogen bonding between the MXene nanoplatelets and the aramid nanofibers that tightly cross-link the two together.
Test example 3 Combustion Performance test
The heat conductive composite films prepared in the above example 6 and comparative example 1 were subjected to micro combustion calorimeter test, respectively, in the following manner:
example 6, as well as comparative example 1, was tested with a microcombustion calorimeter (MCC-2, GOVMARK) under an atmosphere of 80% nitrogen and 20% oxygen at a temperature rise rate of 1℃m -1 at 80-750℃and analyzed for combustion behavior;
the test results of the above test are shown in table 3:
TABLE 3 Table 3
| Total heat release (kJg -1) | |
| Example 6 | 8.2 |
| Comparative example 1 | 9.8 |
As is clear from Table 3, the total heat release amount of the heat conductive composite film obtained in example 6 was 8.2kJg -1, which was lower than that of comparative example 1, compared with comparative example 1. Total heat release refers to the sum of the heat released by the material from ignition to flame extinction at a preset incident heat flow intensity. The larger the total heat release amount, the more heat is fed back to the surface of the material by combustion, and as a result, the pyrolysis speed of the material is increased and the generation amount of volatile combustibles is increased, so that the propagation of flame is accelerated. In the invention, the heat resistance of the composite film is improved due to the addition of the MXene nano-sheets with heat stability, which shows that the aramid fiber/MXene composite film with excellent flame resistance is prepared.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (3)
1. The preparation method of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film is characterized by comprising the following steps of:
mixing an aramid nanofiber solution with a two-dimensional filler MXene solution, and performing ultrasonic treatment to obtain a mixed solution;
Pouring the mixed solution into a mold, immersing in water, and obtaining a hydrogel film after complete crosslinking, and air-drying and hot-pressing to obtain the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film;
The mass ratio of the MXene to the aramid nanofiber in the mixed solution is 1:20 to 6:20, a step of;
The concentration of the aramid nanofiber solution is 20-30 mg/ml, and the concentration of the MXene solution is 20-30 mg/ml;
the aramid nanofiber solution is an aramid nanofiber/dimethyl sulfoxide solution and is prepared through the following steps:
Dissolving poly-p-phenylene terephthalamide and potassium hydroxide in dimethyl sulfoxide solution, and stirring until the poly-p-phenylene terephthalamide and the potassium hydroxide are completely dissolved to obtain aramid nanofiber/dimethyl sulfoxide solution;
the MXene solution is MXene/dimethyl sulfoxide solution and is prepared through the following steps:
Adding lithium fluoride into a dilute hydrochloric acid solution, stirring and carrying out ultrasonic treatment until the lithium fluoride is completely dissolved to prepare etching solution; adding Ti 3AlC2 into the etching solution, stirring at 42-50 ℃ for 24-36 h, repeatedly centrifuging and washing the mixed acid solution with deionized water until the pH value is 6-7, removing supernatant to obtain multi-layer MXene precipitate, adding deionized water, performing ultrasonic treatment and centrifuging, collecting supernatant to obtain single-layer or less-layer MXene solution, drying, dissolving in dimethyl sulfoxide solution, and stirring at room temperature for 24-36 h to obtain MXene/dimethyl sulfoxide solution;
the thickness of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film is 24-26 mu m.
2. The aramid nanofiber/MXene high-thermal-conductivity flame-retardant composite film according to claim 1, wherein the MXene material is Ti 3C2Tx, wherein T x is at least one of-OH functional group, -F functional group.
3. The application of the aramid nanofiber/MXene high-heat-conductivity flame-retardant composite film in microelectronic elements and electronic equipment.
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