CN109762221B - Graphene oxide-loaded halloysite modified styrene butadiene rubber and preparation method thereof - Google Patents
Graphene oxide-loaded halloysite modified styrene butadiene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified styrene butadiene rubber with graphene oxide loaded with halloysite and a preparation method thereof, wherein modified filler graphene oxide loaded with halloysite is added into styrene butadiene rubber for improving the mechanical property of the styrene butadiene rubber; graphene oxide-loaded halloysite is prepared by taking graphene oxide as a carrier, and a one-dimensional halloysite nano material is tightly attached to the graphene oxide. According to the invention, the styrene butadiene rubber is modified by the graphene oxide loaded halloysite, the one-dimensional halloysite and the two-dimensional graphene oxide are cooperated with each other, the agglomeration problem of a single nano material in the rubber is avoided, and the strong interaction force between the two materials enables the mutual promotion and dispersion effect to be more remarkable, a filler network structure is formed in a matrix, and the mechanical property of the styrene butadiene rubber is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of composite material science, and particularly relates to graphene oxide loaded halloysite modified styrene butadiene rubber and a preparation method thereof.
Background
The styrene butadiene rubber is the most common synthetic rubber variety in the world, has very similar physical properties, processing properties and use properties to natural rubber, is low in price and good in toughness, but has very low electric conductivity, wear resistance and strength. Therefore, exploring a suitable modification method to improve the performance of styrene butadiene rubber is a key to expanding the application of styrene butadiene rubber.
The nano material has the characteristics of small particle size, large specific surface area and the like, so that the nano material has a larger contact area with a matrix when a polymer is modified, the improvement of interface bonding strength is facilitated, and the polymer can be effectively enhanced. However, since the surface energy of the nanomaterial is large and is usually in a thermodynamically unstable state, modification of a polymer with the nanomaterial tends to have the following problems. First, the nanomaterial is prone to agglomeration after incorporation into the polymer, resulting in a loss of the small size advantage. When the composite material is stressed, the positions of the agglomerates are usually firstly broken due to stress concentration, so that the reinforcing effect of the filler is not obvious, and the strength of the composite material is even lower than that before modification when the agglomerates are serious. Second, the nanomaterial interacts poorly with the polymer interface. The existence of the interface can prevent the crack from expanding and slow down the stress concentration, so that the filler and the matrix form a whole and transfer the stress. If the wettability between the matrix and the filler is poor, the interface bonding strength is low, and the performance of the polymer composite material is directly influenced. At present, the main method for improving the dispersibility of the nano material in the polymer and improving the interaction force of the interface is surface chemical modification. Through modification, the functional groups on the surface of the nano material increase the moving resistance of the nano material in the polymer, and the nano material is prevented from being agglomerated. However, the means for improving compatibility by chemical modification has the following problems: 1) a large amount of organic solvent is generally consumed in the chemical modification process, so that the cost is high and the environment is not protected; 2) modified molecules are difficult to uniformly cover the surface of the nano material, the interaction between the nano material which is not covered by the modified groups and the interface of the polymer matrix is weak, and the defects usually appear firstly when the nano material is stressed; 3) the introduction of organic functional groups can weaken the properties of the nano material and reduce the due modification effect of the nano material. For example, Wang et al added silanized graphene oxide into an epoxy resin matrix, and found that modified graphene oxide was coated with a flexible interfacial layer, which decreased the stress transfer efficiency of the filler and polymer interface; therefore, the method for exploring a brand-new method for promoting the uniform dispersion of the nano-components in the polymer, improving the interface combination and simultaneously not sacrificing the intrinsic performance of the nano-material has important research value.
The research of the invention finds that: in order to reduce the dependence of the nano unit on surface modification, the key point is to fully utilize the characteristics of the nano unit, and the characteristics of the nano unit mainly comprise the difference of functional groups and dimensions contained in the surface. Firstly, different nano-materialsThe surface of the material contains different types of functional groups, and the abundant surface functional groups provide possibility for the nano material to have better compatibility with a target polymer matrix without modification. Secondly, the modification effect is different after the nanometer units with different dimensions are compounded with the polymer, and the performance is different when the nanometer units are agglomerated. The one-dimensional nano material has large length-diameter ratio and few defects, can increase the impact strength of the polymer, and is mainly agglomerated in the axial direction when the compatibility with a matrix is poor; the two-dimensional nano material has higher modulus along the surface direction, can improve the mechanical strength and the barrier property of the material, and is agglomerated into a curled shape in the surface when the compatibility with a matrix is poor; the three-dimensional nano-particles are usually isotropic and can improve the strength and toughness of the polymer at the same time, but when the three-dimensional nano-particles are poor in compatibility with a matrix, the three-dimensional nano-particles can be agglomerated to form micron-sized or larger particles, and stress concentration is caused. The agglomeration modes of the nano materials with different dimensions have differences, and if the nano materials are assembled into a specific structure, the differences can be utilized to mutually inhibit the agglomeration of the nano materials from occurring. For example, the one-dimensional nano materials are uniformly attached to the surface of the two-dimensional material, the one-dimensional material with higher rigidity can inhibit the curling of the two-dimensional material, the close interaction between the two-dimensional material and the one-dimensional material can avoid the axial mass kinetic analysis of the one-dimensional material, the distance between the same materials is effectively increased by assembling different nano materials together, the probability of mutual contact between the same nano materials is reduced, and the agglomeration of the nano materials is prevented. When the interaction force exists among the different nano materials, the effect of mutually promoting dispersion is more remarkable, and even a filler network structure can be formed in a matrix to generate a synergistic effect. From thermodynamic analysis, the interaction between different nano materials is lower than that between the same nano materials, so the agglomeration difficulty between different nano materials is higher. After the nano materials with different dimensions are compounded, the spatial distance of the same nano material is increased, the interaction between different nano materials is greatly stronger than the mixing among particles, the possibility of forming aggregates by mutual contact is reduced, the uniform dispersion of the nano materials in a polymer matrix is effectively promoted, and the polymer chain is coated on the surface of the multidimensional nano particles to generate more winding, thereby being more beneficial to the matrix and the filler particlesThe stress transfer between the subunits provides possibility for the preparation of high-performance polymer materials. However, since the nano materials have various kinds and different properties, how to effectively select the nano materials to prepare the nano composite needs to be reasonably screened and designed. During assembly, a nano material is required to play a role of a carrier, and the material serving as the carrier is required to have the following characteristics: enough nano materials can be loaded, and receptor materials can be fully dispersed; the surface needs to contain more functional groups, so that the surface has stronger interaction with a receptor material and has good compatibility with a polymer matrix. Structurally, two-dimensional materials facilitate the spreading of receptor materials and are best suited as carriers, of which graphene is an important member among many two-dimensional nanomaterials. The graphene is formed by the SP of carbon atoms2The layered material formed by hybrid connection is the material with the highest known mechanical strength at present. Graphene oxide is an oxide of graphene, and the surface of graphene oxide prepared by a chemical method contains abundant carboxyl, hydroxyl and epoxy groups, so that the graphene oxide can be dispersed in various polymer matrixes at a nanometer level and can form strong interaction with other nanometer materials. Therefore, the graphene is used as a carrier, and after a proper nano material is screened and compounded, the graphene has great research value when being used for modifying the styrene butadiene rubber material.
Disclosure of Invention
The invention discloses graphene oxide loaded halloysite modified styrene butadiene rubber and a preparation method thereof, and aims to solve the problems of agglomeration and low bonding strength when used alone through mutual cooperation of graphene oxide and halloysite so as to improve the mechanical property of styrene butadiene rubber to the maximum extent.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention firstly discloses graphene oxide loaded halloysite modified styrene butadiene rubber which is characterized in that: the modified styrene-butadiene rubber is prepared by adding modified filler graphene oxide loaded halloysite into styrene-butadiene rubber and is used for improving the mechanical property of the styrene-butadiene rubber;
the graphene oxide-loaded halloysite is prepared by taking graphene oxide as a carrier and closely attaching a one-dimensional halloysite nano material to the graphene oxide.
Further, the one-dimensional halloysite nanometer material is a KH550 silane coupling agent modified one-dimensional halloysite nanometer material.
Further, the graphene oxide-loaded halloysite is obtained by uniformly mixing graphene oxide and a one-dimensional halloysite nano material in the form of aqueous dispersion, washing with water, and freeze-drying, wherein the mass ratio of the graphene oxide to the one-dimensional halloysite nano material is 1: 1-9, and most preferably 1: 9.
Further, the addition amount of the graphene oxide loaded halloysite accounts for 1-8% of the mass of the styrene butadiene rubber.
The invention also discloses a preparation method of the graphene oxide loaded halloysite modified styrene butadiene rubber, which comprises the following steps:
Respectively dispersing graphene oxide and HNTs-KH550 in water, then ultrasonically mixing water dispersions of the graphene oxide and the HNTs-KH550 according to the mass ratio of 1: 1-9, standing for 15-24h, washing and freeze-drying the obtained precipitate to obtain graphene oxide loaded halloysite, which is marked as GO-HNTs;
Mixing styrene butadiene rubber, GO-HNTs, a vulcanizing agent N, N' -m-phenylene bismaleimide PDM, stearic acid, an accelerator CZ, zinc oxide and elemental sulfur uniformly in a double-roll mill, and then discharging; and then, vulcanizing and pressing the plate by a plate vulcanizing machine to obtain the graphene oxide loaded halloysite modified styrene butadiene rubber.
Further, in the step 3, the raw materials comprise the following components in parts by weight: 100 parts of styrene butadiene rubber, 1-8 parts of GO-HNTs, 0.5 part of PDM, 2 parts of stearic acid, 1.5 parts of accelerator CZ, 5 parts of zinc oxide and 1.5 parts of elemental sulfur.
Further, the vulcanization temperature of the vulcanization press plate in the step 3 is 160 ℃, and the vulcanization time is 40 min.
The invention has the beneficial effects that:
1. according to the invention, the styrene butadiene rubber is modified by the graphene oxide loaded halloysite, the one-dimensional halloysite and the two-dimensional graphene oxide are cooperated with each other, the agglomeration problem of a single nano material in the rubber is avoided, and the strong interaction force between the two materials enables the mutual promotion and dispersion effect to be more remarkable, a filler network structure is formed in a matrix, and the mechanical property of the styrene butadiene rubber is remarkably improved.
2. According to the preparation method, the lamellar graphene oxide is prepared by an improved Hummers method, the damage degree of the traditional graphene oxide preparation method to a graphite structure is large, the oxidation degree is low, a high-temperature oxidation stage at 95 ℃ is omitted, and the reaction time of a medium-temperature reaction stage at 35 ℃ is increased, so that the oxidation of graphite is more sufficient, the oxidation degree of the graphene oxide is higher, and the structural damage degree of the graphene oxide is smaller.
Drawings
FIG. 1 shows an infrared spectrum of a graphene oxide sheet (GO), a one-dimensional halloysite nanomaterial HNTs, a KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550, and each graphene oxide-loaded halloysite sample prepared according to the present invention;
FIGS. 2(a) - (c) are SEM images of a lamellar Graphene Oxide (GO) prepared by the method, a KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550 and a graphene oxide-loaded halloysite sample GO-HNTs (1:9) in sequence;
FIG. 3 is an XRD spectrum of a sample prepared from lamellar Graphene Oxide (GO), a KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550, and each graphene oxide loaded halloysite;
fig. 4 is a raman spectrum of a sample of lamellar Graphene Oxide (GO) and graphene oxide-supported halloysite (GO-HNTs 1:9) prepared by the present invention.
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The one-dimensional halloysite nanomaterials used in the examples below are commercially available.
The preparation method of the graphene sheet oxide used in the following examples is as follows: 2g of graphite powder and 1g of NaNO3Adding the powder into a three-neck flask, and adding 50mL of concentrated H with the mass concentration of 98%2SO4Magnetic stirring in ice-water bath, adding 6g KMnO4Adding the solid particles into a three-neck flask in batches at the temperature of 5 ℃, heating to 35 ℃ after adding, and stirring for reacting for 24 hours; after the reaction is finished, adding 100mL of deionized water into the reaction solution, stirring and mixing uniformly, then adding 250mL of deionized water, then dropwise adding 15mL of 30 wt% hydrogen peroxide into the reaction solution, then adding 200mL of 1mol/L HCl solution, stirring and mixing uniformly, then centrifuging at the rotating speed of 4500r/min, removing the supernatant, washing with water and centrifuging the precipitate until the pH is close to neutral; transferring the centrifuged precipitate to a 500mL big beaker, adding 300mL deionized water, performing ultrasonic treatment for more than 2h, centrifuging the solution for 20min at the rotating speed of 4500r/min, collecting the liquid on the upper part of the centrifuge tube, namely the brown graphene oxide solution, dialyzing for one week by a dialysis bag with the molecular weight cutoff of 12000-14000, and then performing freeze drying for 24h at-50 ℃ to obtain the lamellar graphene oxide.
Preparation of graphene oxide loaded halloysite
The graphene oxide-supported halloysite used in the following examples was prepared as follows:
Respectively dispersing graphene oxide and HNTs-KH550 in water, then respectively ultrasonically mixing water dispersions of the graphene oxide and the HNTs-KH550 according to the mass ratio of 5:5, 3:7, 2:8 and 1:9, standing for 24h, washing and freeze-drying the obtained precipitate to obtain graphene oxide-loaded halloysite which is respectively marked as GO-HNTs (5:5), GO-HNTs (3:7), GO-HNTs (2:8) and GO-HNTs (1: 9).
Fig. 1 shows an infrared spectrum of a lamellar Graphene Oxide (GO), a one-dimensional halloysite nanomaterial HNTs, a KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550, and each graphene oxide-loaded halloysite sample prepared by the present invention. As can be seen from FIG. 1, the main infrared absorption peak of HNTs is 3759-3456cm-1And 1631cm-1Corresponding to stretching vibration of hydroxyl groups in the coordinated water inside HNTs and stretching vibration of Si-O bonds, respectively. Compared with HNTs, the modified HNTs-KH550 is 2978cm-1A new infrared peak appears, which is a stretching vibration peak of C-H bonds on KH550 chains grafted on the surface of HNTs, and the successful modification of the HNTs is proved. GO and GO-HNTS of three different chemical examples are at 1797cm-1There is a distinct infrared peak, which is the stretching vibration of C ═ O bonds in the GO surface.
FIGS. 2(a) - (c) are SEM images of the lamellar Graphene Oxide (GO), the KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550 and the GO-HNTs (1:9) prepared by the method in sequence. As can be seen from fig. 2: GO is in a folded lamellar structure; HNTs presents a one-dimensional rod-like nano structure and is randomly distributed, so that a large amount of aggregates are generated; in GO-HNTs (1:9), one-dimensional HNTs are closely attached to the surface of a GO sheet layer, the accumulation among HNTs is obviously weakened, and the dispersion-assisting effect of GO is shown. By characterization, in the GO-HNTs (1:9) samples, the HNTs were most uniformly dispersed on GO sheets compared to other GO-HNTs samples.
FIG. 3 is an XRD spectrum of a graphene oxide sheet (GO), a KH550 modified one-dimensional halloysite nanomaterial HNTs-KH550 prepared by the method, and each graphene oxide-supported halloysite sample. As can be seen from fig. 3: the HNTs-KH550 has diffraction peaks at 2 θ of 12.34 °, 15.55 °, 18.07 °, and 19.96 °, corresponding to the (100), (010), (110), and (-101) crystal planes thereof, respectively. And GO has a strong diffraction peak at the position of 10.48 degrees at 2 theta, which corresponds to the (002) crystal plane parallel to the GO lamella, and the lamella spacing of GO is calculated to be 0.84nm by the Bragg equation. In the GO-NHTs 1:9 sample, the characteristic peak of GO almost disappeared, since the insertion of NHTs during sonication allowed the GO lamellae to be fully exfoliated. With the increase of the content of GO in GO-NHTs, the position of a diffraction peak of the NHTs is unchanged, and the intensity of the diffraction peak from GO is gradually increased and the position is shifted. Diffraction peaks of GO in GO-NHTs (1:9), GO-NHTs (2:8), GO-NHTs (3:7) and GO-NHTs (5:5) are respectively 10.05 °, 10.24 °, 10.57 ° and 10.69 °, and the interlayer distances are calculated to be 0.87nm, 0.86nm, 0.83nm and 0.82nm, which indicates that as GO content increases, relative content decrease of NHTs leads to weakening of intercalation, so that the interlayer distance of GO gradually decreases.
FIG. 4 shows Raman spectra of graphene oxide platelets (GO) and graphene oxide loaded halloysite samples (GO-HNTs (1:9)) prepared according to the present invention. As can be seen from the figure: two obvious characteristic peaks are found at 1351cm-1 and 1600cm-1, which are respectively a D peak reflecting the structural defect and disorder degree of the carbon plane and a G peak reflecting the order degree of the carbon plane. After the GO is compounded with HNTs, the strength of a Raman D peak and the G peak of GO is reduced, while the width is increased, which probably results from the inhibition effect of the HNTs. The ratio ID/IG of the D peak and the G peak can be used to evaluate the structural defect degree of the carbon material as a whole. In this example, the ID/IG value of GO is 0.75, while the ID/IG value of GO-HNTs (1:9) is 0.74, which are not significantly changed, indicating that the carbon structure of GO is not changed by the attachment of HNTs, because the function between HNTs and GO is non-covalent electrostatic bonding.
Modification of styrene butadiene rubber material by graphene oxide loaded halloysite
Comparative example 1
The styrene-butadiene rubber material is prepared by the following steps:
adding 100 parts of styrene butadiene rubber, 0.5 part of vulcanizing agent N, N' -m-phenylene bismaleimide PDM, 2 parts of stearic acid, 1.5 parts of accelerant CZ, 5 parts of zinc oxide and 1.5 parts of elemental sulfur into a double-roll open mill for mixing for 5min, rolling for 5 times, wrapping for 5 times, mixing uniformly, and then discharging; and then a flat vulcanizing machine is used for vulcanizing and pressing the plate, the vulcanizing temperature is set to be 160 ℃, and the vulcanizing time is 40min, so that the unmodified styrene-butadiene rubber is obtained.
Example 1
In this embodiment, a graphene oxide-loaded halloysite-modified styrene-butadiene rubber is prepared by the following steps:
adding 100 parts of styrene butadiene rubber, 1 part of GO-HNTs (1:9), 0.5 part of vulcanizing agent N, N' -m-phenylene bismaleimide PDM, 2 parts of stearic acid, 1.5 parts of accelerant CZ, 5 parts of zinc oxide and 1.5 parts of elemental sulfur into a double-roll mill, mixing for 5min, rolling for 5 times, wrapping for 5 times by a triangular bag, and discharging after mixing uniformly; and then, vulcanizing and pressing the plate by a plate vulcanizing machine, wherein the vulcanizing temperature is set to 160 ℃, and the vulcanizing time is 40min, so that the graphene oxide loaded halloysite modified styrene-butadiene rubber (the content of GO-HNTs is 1%) is obtained.
Example 2
In this example, graphene oxide-loaded halloysite modified styrene-butadiene rubber was prepared according to the same method steps as in example 1, except that the amount of GO-HNTs (1:9) was 2 parts, to obtain graphene oxide-loaded halloysite modified styrene-butadiene rubber (GO-HNTs content was 2%).
Example 3
In this example, graphene oxide-loaded halloysite modified styrene-butadiene rubber was prepared according to the same method steps as in example 1, except that the amount of GO-HNTs (1:9) was 4 parts, to obtain graphene oxide-loaded halloysite modified styrene-butadiene rubber (GO-HNTs content was 4%).
Example 4
In this example, graphene oxide-loaded halloysite modified styrene-butadiene rubber was prepared according to the same method steps as in example 1, except that 6 parts of GO-HNTs (1:9) was used, to obtain graphene oxide-loaded halloysite modified styrene-butadiene rubber (GO-HNTs content: 6%).
Example 5
In this example, graphene oxide-loaded halloysite modified styrene-butadiene rubber was prepared according to the same method steps as in example 1, except that the amount of GO-HNTs (1:9) was 8 parts, to obtain graphene oxide-loaded halloysite modified styrene-butadiene rubber (GO-HNTs content was 8%).
Example 6
In this example, graphene oxide-loaded halloysite modified styrene-butadiene rubber was prepared according to the same method steps as in example 4, except that 6 parts of GO-HNTs (1:9) were replaced with 6 parts of HNTs-KH 550.
The mechanical properties (tensile strength and elongation at break) of the rubber samples obtained in the above examples are shown in Table 1.
TABLE 1
From Table 1, the styrene butadiene rubber added with the modified filler has obviously improved mechanical properties, and the properties are optimal when the addition amount of GO-HNTs is 6%. Compared with HNTs-KH550, the performance of the styrene-butadiene rubber is improved greatly when GO-HNTs are used as a filler, and the mutual synergistic effect of the graphene oxide and the halloysite is proved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. The graphene oxide-loaded halloysite modified styrene butadiene rubber is characterized in that: the modified styrene-butadiene rubber is prepared by adding modified filler graphene oxide loaded halloysite into styrene-butadiene rubber and is used for improving the mechanical property of the styrene-butadiene rubber; the graphene oxide-loaded halloysite is prepared by taking graphene oxide as a carrier and closely attaching a one-dimensional halloysite nano material to the graphene oxide;
the one-dimensional halloysite nano material is a KH550 silane coupling agent modified one-dimensional halloysite nano material;
the graphene oxide-loaded halloysite is obtained by uniformly mixing graphene oxide and a one-dimensional halloysite nano material in the form of aqueous dispersion, washing with water and freeze-drying, wherein the mass ratio of the graphene oxide to the one-dimensional halloysite nano material is 1: 9;
the addition amount of the graphene oxide loaded halloysite accounts for 6% of the mass of the styrene butadiene rubber.
2. The preparation method of the graphene oxide-supported halloysite-modified styrene-butadiene rubber according to claim 1, which is characterized by comprising the following steps:
step 1, adding 8-12 g of one-dimensional halloysite nano material into 300mL of ethanol, then dropwise adding 4-6 g of KH550 silane coupling agent, carrying out condensation reflux reaction at 80 ℃ for 5h, and continuously stirring in the reaction process; centrifuging and washing the obtained product, and then freeze-drying to obtain a KH550 modified one-dimensional halloysite nano material which is marked as HNTs-KH 550;
step 2, respectively dispersing graphene oxide and HNTs-KH550 in water, then ultrasonically mixing the water dispersions of the graphene oxide and the HNTs-KH550 according to the mass ratio of 1: 1-9, standing for 15-24h, washing and freeze-drying the obtained precipitate to obtain graphene oxide loaded halloysite, which is marked as GO-HNTs;
step 3, mixing styrene butadiene rubber, GO-HNTs, a vulcanizing agent N, N' -m-phenylene bismaleimide PDM, stearic acid, an accelerator CZ, zinc oxide and elemental sulfur uniformly in a double-roll mill, and then discharging; and then, vulcanizing and pressing the plate by a plate vulcanizing machine to obtain the graphene oxide loaded halloysite modified styrene butadiene rubber.
3. The preparation method of the graphene oxide-supported halloysite-modified styrene-butadiene rubber according to claim 2, wherein the graphene oxide-supported halloysite-modified styrene-butadiene rubber in the step 3 comprises the following raw materials in parts by weight:
100 parts of styrene butadiene rubber, 1-8 parts of GO-HNTs, 0.5 part of PDM, 2 parts of stearic acid, 1.5 parts of accelerator CZ, 5 parts of zinc oxide and 1.5 parts of elemental sulfur.
4. The preparation method of the graphene oxide-supported halloysite-modified styrene-butadiene rubber according to claim 2, wherein the preparation method comprises the following steps: and 3, the vulcanization temperature of the vulcanization press plate in the step 3 is 160 ℃, and the vulcanization time is 40 min.
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