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Open AccessOpen Access JUSTC Research Reviews: Chemistry

Preparation of hollow silica microsphere and its effect on the thermal conductivity of polymer composites

  • 1.

    CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China

  • 2.

    CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China

Cite this:
https://doi.org/10.52396/JUST-2021-0072
  • Received Date: 13 March 2021
  • Rev Recd Date: 09 April 2021
  • Publish Date: 30 June 2021
    Abstract

  • Abstract

    The thermal conductivity of polymer composites filled with hollow microspheres is closely related to the content and structure of hollow microspheres. In this paper, micron-sized monodisperse polystyrene (PS) microspheres are synthesized as the sacrificial template to prepare a series of hollow SiO2 (H-SiO2) microspheres with different inner and outer radius ratios (r/R).The r/R value is controlled by the relative content of PS microspheres and tetraethyl orthosilicate (TEOS). The chemical composition and morphology of H-SiO2 microspheres are characterized by infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Further, H-SiO2 microspheres are blended with polydimethylsiloxane (PDMS) at a certain content to obtain H-SiO2/PDMS composite rubbers. The effect of the content and the r/R value of H-SiO2 microspheres on the thermal conductivity of the composite rubber are investigated.Combined with the theoretical model calculation on the thermal conductivity of the silicone rubber,it can be concluded that the addition of H-SiO2 microspheres with a complete hollow structure and an r/R value higher than 0.963 can reduce the thermal conductivity of H-SiO2/PDMS composite rubbers.The more the H-SiO2 microspheres, the smaller the thermal conductivity of the composite rubber.At the same time, when the mass fraction of H-SiO2 microspheres is no more than 5%, the mechanical properties of the H-SiO2/PDMS composite rubber are also enhanced with the increase of the weight content of H-SiO2 microspheres. This work provides theoretical and experimental guidance for the design and preparation of high-performance hollow microspheres filled with polymer thermal insulation materials.

    Abstract

    The thermal conductivity of polymer composites filled with hollow microspheres is closely related to the content and structure of hollow microspheres. In this paper, micron-sized monodisperse polystyrene (PS) microspheres are synthesized as the sacrificial template to prepare a series of hollow SiO2 (H-SiO2) microspheres with different inner and outer radius ratios (r/R).The r/R value is controlled by the relative content of PS microspheres and tetraethyl orthosilicate (TEOS). The chemical composition and morphology of H-SiO2 microspheres are characterized by infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Further, H-SiO2 microspheres are blended with polydimethylsiloxane (PDMS) at a certain content to obtain H-SiO2/PDMS composite rubbers. The effect of the content and the r/R value of H-SiO2 microspheres on the thermal conductivity of the composite rubber are investigated.Combined with the theoretical model calculation on the thermal conductivity of the silicone rubber,it can be concluded that the addition of H-SiO2 microspheres with a complete hollow structure and an r/R value higher than 0.963 can reduce the thermal conductivity of H-SiO2/PDMS composite rubbers.The more the H-SiO2 microspheres, the smaller the thermal conductivity of the composite rubber.At the same time, when the mass fraction of H-SiO2 microspheres is no more than 5%, the mechanical properties of the H-SiO2/PDMS composite rubber are also enhanced with the increase of the weight content of H-SiO2 microspheres. This work provides theoretical and experimental guidance for the design and preparation of high-performance hollow microspheres filled with polymer thermal insulation materials.
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    • References(47)
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    Apostolopoulou K V, Munier P, Bergström L.Thermally insulating nanocellulose-based materials. Advanced Materials, 2020: 2001839; doi: 10.1002/adma.202001839.
    [2]
    Rajaei S, Shoaei P, Shariati M, et al. Rubberized alkali-activated slag mortar reinforced with polypropylene fibres for application in lightweight thermal insulating materials.Construction and Building Materials, 2021, 270: 121430.
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    Jelle B P. Traditional, state-of-the-art and future thermal building insulation materials and solutions: Properties, requirements and possibilities.Energy and Buildings, 2011, 43(10): 2549-2563.
    [4]
    Berardi U, Naldi M. The impact of the temperature dependent thermal conductivity of insulating materials on the effective building envelope performance.Energy and Buildings, 2017, 144: 262-275.
    [5]
    Kourtides D A. Thermal performance of composite flexible blanket insulations for hypersonic aerospace vehicles. Composites Engineering, 1993, 3(7): 805-813.
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    Sun Z Q, Lu C, Fan J M, et al. Porous silica ceramics with closed-cell structure prepared by inactive hollow spheres for heat insulation.Journal of Alloys and Compounds,2016, 662: 157-164.
    [7]
    Ji X F, Zhang H, Bai Z, et al. Self-assembled multifunctional bulk hollow microspheres: Thermal insulation, sound absorption and fire resistance. Energy and Buildings, 2019, 205: 109533.
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    Zhang C L, Zhang C Y, Huang R, et al. Effects of hollow microspheres on the thermal insulation of polysiloxane foam. Journal of Applied Polymer Science, 2017, 134(18):46025.
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    Wicklein B, Kocjan A,German S A, et al. Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide. Nature Nanotechnology, 2015, 10(3): 277-283.
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    Zhao S, Malfait W J, GuerreroA N, et al. Biopolymer aerogels and foams: Chemistry, properties, and applications.Angewandte Chemie International Edition, 2018, 57(26): 7580-7608.
    [11]
    Hu F, Wu S Y, Sun Y G. Hollow-structured materials for thermal insulation. Advanced Materials, 2019, 31(38): 1801001.
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    Gao J, Wang J B, Xu H Y, et al. Preparation and properties of hollow glass bead filled silicone rubber foams with low thermal conductivity. Materials & Design, 2013, 46: 491-496.
    [13]
    Zhang X Z, Wang Y M, Ma L Y, et al. Ultra-light, heat-resistant, flexible and thermal insulation graphene-fluororubber foam prepared by using N2 as a blowing agent. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 604: 125310.
    [14]
    Zhang X Z, Wang C, Wang S, et al. A lightweight, thermal insulation and excellent weatherability foam crosslinked by electron beam irradiation. Radiation Physics and Chemistry, 2020, 173: 108890.
    [15]
    Zhang C Y, Qu L J, Wang Y N, et al. Thermal insulation and stability of polysiloxane foams containing hydroxyl-terminated polydimethylsiloxanes. RSC Advances, 2018, 8(18): 9901-9909.
    [16]
    Phiri M M, Sibeko M A, Phiri M J, et al. Effect of free foaming and pre-curing on the thermal, morphological and physical properties of reclaimed tyre rubber foam composites.Journal of Cleaner Production, 2019, 218: 665-672.
    [17]
    Kim C B, You N H, Goh M. Hollow polymer microcapsule embedded transparent and heat-insulating film.RSC Advances, 2018, 8(17): 9480-9486.
    [18]
    Zhao X W, Zang C G, Sun Y L, et al. Effect of hybrid hollow microspheres on thermal insulation performance and mechanical properties of silicone rubber composites. Journal of Applied Polymer Science, 2018, 135(11): 46025.
    [19]
    Ernawati L, Ogi T, Balgis R, et al. Hollow silica as an optically transparent and thermally insulating polymer additive. Langmuir, 2016, 32(1): 338-345.
    [20]
    Fiedler T, Öchsner A. On the thermal conductivity of adhesively bonded and sintered hollow sphere structures (HSS). Materials Science Forum, 2007, 553: 39-44.
    [21]
    Ng S, Jelle B P, Sandberg L I, et al. Hollow silica nanospheres as thermal insulation materials for construction: Impact of their morphologies as a function of synthesis pathways and starting materials.Construction and Building Materials, 2018, 166: 72-80.
    [22]
    Bao Y, Guo R Y, Ma J Z. Hierarchical flower-like hollow SiO2@TiO2spheres with enhanced thermal insulation and ultraviolet resistance performances for building coating. ACS Applied Materials & Interfaces, 2020, 12(21): 24250-24261.
    [23]
    Sharma J, Polizos G. Hollow silica particles: Recent progress and future perspectives.Nanomaterials, 2020, 10(8): 1599.
    [24]
    Bao Y, Kang Q L, Ma J Z. Structural regulation of hollow spherical TiO2 by varying titanium source amount and their thermal insulation property. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 537: 69-75.
    [25]
    Gao T, Jelle B P, Sandberg L I C, et al. Monodisperse hollow silica nanospheres for nano insulation materials: Synthesis, characterization, and life cycle assessment.ACS Applied Materials & Interfaces, 2013, 5(3): 761-767.
    [26]
    Grandcolas M, Jasinski E, Gao T, et al. Preparation of low density organosilica monoliths containing hollow silica nanospheres as thermal insulation materials.Materials Letters, 2019, 250: 151-154.
    [27]
    Yang W X, Xu G Q, Shu J J, et al. Preparation and adsorption property of novel inverse-opal hierarchicalporous N-doped carbon microspheres. Chinese Chemical Letters, 2021, 32(2): 866-869.
    [28]
    Bao Y, Shi C H, Wang T, et al. Recent progress in hollow silica: Template synthesis, morphologies and applications. Microporous and Mesoporous Materials, 2016, 227: 121-136.
    [29]
    Nandiyanto A B D, Akane Y, Ogi T, et al.Mesopore-free hollow silica particles with controllable diameter and shell thickness via additive-free synthesis. Langmuir, 2012, 28(23): 8616-8624.
    [30]
    Zhang Y, Hsu B Y W, Ren C, et al. Silica-based nanocapsules: Synthesis, structure control and biomedical applications.Chemical Society Reviews, 2015, 44(1): 315-335.
    [31]
    Jiang M, Shu J J, Jin H Q, et al. Radiation-grafting modification of hollow mesoporous silica microspheres and their application in anti-corrosive coatings. Journal of Radiation Research and Radiation Processing, 2019, 37(5): 050203.
    [32]
    Kim K H, Ong J L, Okuno O. The effect of filler loading and morphology on the mechanical properties of contemporary composites.The Journal of Prosthetic Dentistry, 2002, 87(6): 642-649.
    [33]
    Crosby A J, Lee J Y. Polymer nanocomposites: The “nano” effect on mechanical properties.Polymer Reviews, 2007, 47(2): 217-229.
    [34]
    Syabani M W, Amaliyana I, Hermiyati I, et al. Silica from geothermal waste as reinforcing filler in artificial leather.Key Engineering Materials, 2020, 849: 78-83.
    [35]
    Wang H, Murray V J, Qian M, et al. Resistance of nanoclay reinforced epoxy composites to hyperthermal atomic oxygen attack.Chinese Journal of Chemical Physics, 2019, 32(5): 543-552.
    [36]
    Du B X, Ma T T, Su J G, et al. Effects of temperature gradient on electrical tree growth and partial discharge in silicone rubber under AC voltage. IEEE Access, 2020, 8: 54009-54018.
    [37]
    Zhan X B, Cai X Q, Zhang J Y. A novel crosslinking agent of polymethyl(ketoxime)siloxane for room temperature vulcanized silicone rubbers: Synthesis, properties and thermal stability. RSC Advances, 2018, 8(23): 12517-12525.
    [38]
    Yang K Q, Tang M. Three-dimensional phase evolution and stress-induced non-uniform Li intercalation behavior in lithium iron phosphate. Journal of Materials Chemistry A, 2020, 8(6): 3060-3070.
    [39]
    Wang Z G, Zhang X H, Wang F Q, et al. Chemical characterization and research on the silicone rubber material used for outdoor current transformer insulation. Phosphorus, Sulfur, and Silicon and the Related Elements, 2017, 192(1): 109-112.
    [40]
    Kim E S, Kim E J, Shim J H, et al. Thermal stability and ablation properties of silicone rubber composites.Journal of Applied Polymer Science, 2008, 110(2): 1263-1270.
    [41]
    Chen M, Wu L M, Zhou S X, et al. A method for the fabrication of monodisperse hollow silica spheres. Advanced Materials, 2006, 18(6): 801-806.
    [42]
    Zhang Q, Ge J P, Goebl J, et al. Rattle-type silica colloidal particles prepared by a surface-protected etching process. Nano Research, 2009, 2(7): 583-591.
    [43]
    Tao C Y, Yan H W, Yuan X D, et al. Sol-gel based antireflective coatings with superhydrophobicity and exceptionally low refractive indices built from trimethylsilanized hollow silica nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016, 509: 307-313.
    [44]
    Duan G W, Xie L Z, Zhao C, et al. Influence of the surface electrical property of polymer template microspheres on the morphology of hollow silica microspheres. Acta Polymerica Sinica, 2017(5): 785-792.
    [45]
    Hu Y, Mei R G, An Z G, et al. Silicon rubber/hollow glass microsphere composites: Influence of broken hollow glass microsphere on mechanical and thermal insulation property. Composites Science and Technology, 2013, 79: 64-69.
    [46]
    Liang J Z, Li F X. Theoretical model of heat transfer model for polymer/hollow micro-sphere composites. Jourmal of South China University Technology, 2005, 33(10): 34-37.
    [47]
    Liang J Z, Li F X. Experimental verification of theoretical heat-transfer model of polymer/hollow microsphere composite.Jourmal of South China University Technology, 2006, 34(1): 114-116.
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    [1]
    Apostolopoulou K V, Munier P, Bergström L.Thermally insulating nanocellulose-based materials. Advanced Materials, 2020: 2001839; doi: 10.1002/adma.202001839.
    [2]
    Rajaei S, Shoaei P, Shariati M, et al. Rubberized alkali-activated slag mortar reinforced with polypropylene fibres for application in lightweight thermal insulating materials.Construction and Building Materials, 2021, 270: 121430.
    [3]
    Jelle B P. Traditional, state-of-the-art and future thermal building insulation materials and solutions: Properties, requirements and possibilities.Energy and Buildings, 2011, 43(10): 2549-2563.
    [4]
    Berardi U, Naldi M. The impact of the temperature dependent thermal conductivity of insulating materials on the effective building envelope performance.Energy and Buildings, 2017, 144: 262-275.
    [5]
    Kourtides D A. Thermal performance of composite flexible blanket insulations for hypersonic aerospace vehicles. Composites Engineering, 1993, 3(7): 805-813.
    [6]
    Sun Z Q, Lu C, Fan J M, et al. Porous silica ceramics with closed-cell structure prepared by inactive hollow spheres for heat insulation.Journal of Alloys and Compounds,2016, 662: 157-164.
    [7]
    Ji X F, Zhang H, Bai Z, et al. Self-assembled multifunctional bulk hollow microspheres: Thermal insulation, sound absorption and fire resistance. Energy and Buildings, 2019, 205: 109533.
    [8]
    Zhang C L, Zhang C Y, Huang R, et al. Effects of hollow microspheres on the thermal insulation of polysiloxane foam. Journal of Applied Polymer Science, 2017, 134(18):46025.
    [9]
    Wicklein B, Kocjan A,German S A, et al. Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide. Nature Nanotechnology, 2015, 10(3): 277-283.
    [10]
    Zhao S, Malfait W J, GuerreroA N, et al. Biopolymer aerogels and foams: Chemistry, properties, and applications.Angewandte Chemie International Edition, 2018, 57(26): 7580-7608.
    [11]
    Hu F, Wu S Y, Sun Y G. Hollow-structured materials for thermal insulation. Advanced Materials, 2019, 31(38): 1801001.
    [12]
    Gao J, Wang J B, Xu H Y, et al. Preparation and properties of hollow glass bead filled silicone rubber foams with low thermal conductivity. Materials & Design, 2013, 46: 491-496.
    [13]
    Zhang X Z, Wang Y M, Ma L Y, et al. Ultra-light, heat-resistant, flexible and thermal insulation graphene-fluororubber foam prepared by using N2 as a blowing agent. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 604: 125310.
    [14]
    Zhang X Z, Wang C, Wang S, et al. A lightweight, thermal insulation and excellent weatherability foam crosslinked by electron beam irradiation. Radiation Physics and Chemistry, 2020, 173: 108890.
    [15]
    Zhang C Y, Qu L J, Wang Y N, et al. Thermal insulation and stability of polysiloxane foams containing hydroxyl-terminated polydimethylsiloxanes. RSC Advances, 2018, 8(18): 9901-9909.
    [16]
    Phiri M M, Sibeko M A, Phiri M J, et al. Effect of free foaming and pre-curing on the thermal, morphological and physical properties of reclaimed tyre rubber foam composites.Journal of Cleaner Production, 2019, 218: 665-672.
    [17]
    Kim C B, You N H, Goh M. Hollow polymer microcapsule embedded transparent and heat-insulating film.RSC Advances, 2018, 8(17): 9480-9486.
    [18]
    Zhao X W, Zang C G, Sun Y L, et al. Effect of hybrid hollow microspheres on thermal insulation performance and mechanical properties of silicone rubber composites. Journal of Applied Polymer Science, 2018, 135(11): 46025.
    [19]
    Ernawati L, Ogi T, Balgis R, et al. Hollow silica as an optically transparent and thermally insulating polymer additive. Langmuir, 2016, 32(1): 338-345.
    [20]
    Fiedler T, Öchsner A. On the thermal conductivity of adhesively bonded and sintered hollow sphere structures (HSS). Materials Science Forum, 2007, 553: 39-44.
    [21]
    Ng S, Jelle B P, Sandberg L I, et al. Hollow silica nanospheres as thermal insulation materials for construction: Impact of their morphologies as a function of synthesis pathways and starting materials.Construction and Building Materials, 2018, 166: 72-80.
    [22]
    Bao Y, Guo R Y, Ma J Z. Hierarchical flower-like hollow SiO2@TiO2spheres with enhanced thermal insulation and ultraviolet resistance performances for building coating. ACS Applied Materials & Interfaces, 2020, 12(21): 24250-24261.
    [23]
    Sharma J, Polizos G. Hollow silica particles: Recent progress and future perspectives.Nanomaterials, 2020, 10(8): 1599.
    [24]
    Bao Y, Kang Q L, Ma J Z. Structural regulation of hollow spherical TiO2 by varying titanium source amount and their thermal insulation property. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 537: 69-75.
    [25]
    Gao T, Jelle B P, Sandberg L I C, et al. Monodisperse hollow silica nanospheres for nano insulation materials: Synthesis, characterization, and life cycle assessment.ACS Applied Materials & Interfaces, 2013, 5(3): 761-767.
    [26]
    Grandcolas M, Jasinski E, Gao T, et al. Preparation of low density organosilica monoliths containing hollow silica nanospheres as thermal insulation materials.Materials Letters, 2019, 250: 151-154.
    [27]
    Yang W X, Xu G Q, Shu J J, et al. Preparation and adsorption property of novel inverse-opal hierarchicalporous N-doped carbon microspheres. Chinese Chemical Letters, 2021, 32(2): 866-869.
    [28]
    Bao Y, Shi C H, Wang T, et al. Recent progress in hollow silica: Template synthesis, morphologies and applications. Microporous and Mesoporous Materials, 2016, 227: 121-136.
    [29]
    Nandiyanto A B D, Akane Y, Ogi T, et al.Mesopore-free hollow silica particles with controllable diameter and shell thickness via additive-free synthesis. Langmuir, 2012, 28(23): 8616-8624.
    [30]
    Zhang Y, Hsu B Y W, Ren C, et al. Silica-based nanocapsules: Synthesis, structure control and biomedical applications.Chemical Society Reviews, 2015, 44(1): 315-335.
    [31]
    Jiang M, Shu J J, Jin H Q, et al. Radiation-grafting modification of hollow mesoporous silica microspheres and their application in anti-corrosive coatings. Journal of Radiation Research and Radiation Processing, 2019, 37(5): 050203.
    [32]
    Kim K H, Ong J L, Okuno O. The effect of filler loading and morphology on the mechanical properties of contemporary composites.The Journal of Prosthetic Dentistry, 2002, 87(6): 642-649.
    [33]
    Crosby A J, Lee J Y. Polymer nanocomposites: The “nano” effect on mechanical properties.Polymer Reviews, 2007, 47(2): 217-229.
    [34]
    Syabani M W, Amaliyana I, Hermiyati I, et al. Silica from geothermal waste as reinforcing filler in artificial leather.Key Engineering Materials, 2020, 849: 78-83.
    [35]
    Wang H, Murray V J, Qian M, et al. Resistance of nanoclay reinforced epoxy composites to hyperthermal atomic oxygen attack.Chinese Journal of Chemical Physics, 2019, 32(5): 543-552.
    [36]
    Du B X, Ma T T, Su J G, et al. Effects of temperature gradient on electrical tree growth and partial discharge in silicone rubber under AC voltage. IEEE Access, 2020, 8: 54009-54018.
    [37]
    Zhan X B, Cai X Q, Zhang J Y. A novel crosslinking agent of polymethyl(ketoxime)siloxane for room temperature vulcanized silicone rubbers: Synthesis, properties and thermal stability. RSC Advances, 2018, 8(23): 12517-12525.
    [38]
    Yang K Q, Tang M. Three-dimensional phase evolution and stress-induced non-uniform Li intercalation behavior in lithium iron phosphate. Journal of Materials Chemistry A, 2020, 8(6): 3060-3070.
    [39]
    Wang Z G, Zhang X H, Wang F Q, et al. Chemical characterization and research on the silicone rubber material used for outdoor current transformer insulation. Phosphorus, Sulfur, and Silicon and the Related Elements, 2017, 192(1): 109-112.
    [40]
    Kim E S, Kim E J, Shim J H, et al. Thermal stability and ablation properties of silicone rubber composites.Journal of Applied Polymer Science, 2008, 110(2): 1263-1270.
    [41]
    Chen M, Wu L M, Zhou S X, et al. A method for the fabrication of monodisperse hollow silica spheres. Advanced Materials, 2006, 18(6): 801-806.
    [42]
    Zhang Q, Ge J P, Goebl J, et al. Rattle-type silica colloidal particles prepared by a surface-protected etching process. Nano Research, 2009, 2(7): 583-591.
    [43]
    Tao C Y, Yan H W, Yuan X D, et al. Sol-gel based antireflective coatings with superhydrophobicity and exceptionally low refractive indices built from trimethylsilanized hollow silica nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016, 509: 307-313.
    [44]
    Duan G W, Xie L Z, Zhao C, et al. Influence of the surface electrical property of polymer template microspheres on the morphology of hollow silica microspheres. Acta Polymerica Sinica, 2017(5): 785-792.
    [45]
    Hu Y, Mei R G, An Z G, et al. Silicon rubber/hollow glass microsphere composites: Influence of broken hollow glass microsphere on mechanical and thermal insulation property. Composites Science and Technology, 2013, 79: 64-69.
    [46]
    Liang J Z, Li F X. Theoretical model of heat transfer model for polymer/hollow micro-sphere composites. Jourmal of South China University Technology, 2005, 33(10): 34-37.
    [47]
    Liang J Z, Li F X. Experimental verification of theoretical heat-transfer model of polymer/hollow microsphere composite.Jourmal of South China University Technology, 2006, 34(1): 114-116.
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