Skip to main content
Erschienen in: Journal of Materials Science 12/2016

08.03.2016 | Original Paper

Enhanced mechanical properties and thermal conductivity of styrene–butadiene rubber reinforced with polyvinylpyrrolidone-modified graphene oxide

verfasst von: Biao Yin, Jingyi Wang, Hongbing Jia, Junkuan He, Xumin Zhang, Zhaodong Xu

Erschienen in: Journal of Materials Science | Ausgabe 12/2016

Einloggen

Aktivieren Sie unsere intelligente Suche, um passende Fachinhalte oder Patente zu finden.

search-config
loading …

Abstract

A facile non-covalent surface treatment method is reported in this paper to modify graphene oxide (GO) sheets with the assistance of polyvinylpyrrolidone (PVP). The PVP-modified GO (PGO) was further adopted to fabricate PGO/styrene–butadiene rubber (SBR) nano-composites through the latex compounding method. The properties of PGO were carefully investigated and interaction between GO and PVP molecules was confirmed. The mechanical properties, dynamic mechanical properties, thermal stability, thermal conductivity as well as swelling properties of the PGO/SBR nano-composites were thoroughly studied. It was confirmed that PVP molecules could have strong interaction with GO via hydrogen bond; thus, the PGO significantly improved the strength of SBR matrix, e.g., 517 and 387 % increase in tensile strength and tear strength, respectively, with the presence of only 5 phr (parts per hundred rubber) PGO in the nano-composite. The presence of PGO had also greatly reduced the glass transition temperature (T g) and enhanced the storage modulus of SBR matrix in the nano-composites. Meanwhile, the maximum heat decomposition temperature (T max) was increased by 23.6 °C; equilibrium solvent uptake in toluene was reduced by 41 % and thermal conductivity was increased by 30 %. All the observations indicated that PVP modification of GO can achieve excellent exfoliation and dispersion of GO in the SBR matrix. These findings were further supported by X-ray diffraction and scanning electron microscopy measurements.

Sie haben noch keine Lizenz? Dann Informieren Sie sich jetzt über unsere Produkte:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

  • über 102.000 Bücher
  • über 537 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Finance + Banking
  • Management + Führung
  • Marketing + Vertrieb
  • Maschinenbau + Werkstoffe
  • Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

  • über 67.000 Bücher
  • über 390 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Maschinenbau + Werkstoffe




 

Jetzt Wissensvorsprung sichern!

Literatur
1.
Zurück zum Zitat Ariga K, Mori T, Hill JP (2012) Mechanical control of nanomaterials and nanosystems. Adv Mater 24:158–176CrossRef Ariga K, Mori T, Hill JP (2012) Mechanical control of nanomaterials and nanosystems. Adv Mater 24:158–176CrossRef
2.
Zurück zum Zitat Ariga K, Li J, Fei J, Ji Q, Hill JP (2016) Nanoarchitectonics for dynamic functional materials from atomic-/molecular-level manipulation to macroscopic action. Adv Mater 28:1251–1286CrossRef Ariga K, Li J, Fei J, Ji Q, Hill JP (2016) Nanoarchitectonics for dynamic functional materials from atomic-/molecular-level manipulation to macroscopic action. Adv Mater 28:1251–1286CrossRef
3.
Zurück zum Zitat Wang J, Jia H, Zhang J, Ding L, Huang Y, Sun D, Gong X (2014) Bacterial cellulose whisker as a reinforcing filler for carboxylated acrylonitrile-butadiene rubber. J Mater Sci 49:6093–6101. doi:10.1007/s10853-014-8336-7 CrossRef Wang J, Jia H, Zhang J, Ding L, Huang Y, Sun D, Gong X (2014) Bacterial cellulose whisker as a reinforcing filler for carboxylated acrylonitrile-butadiene rubber. J Mater Sci 49:6093–6101. doi:10.​1007/​s10853-014-8336-7 CrossRef
4.
Zurück zum Zitat Rahmat M, Hubert P (2011) Carbon nanotube–polymer interactions in nanocomposites: a review. Compos Sci Technol 72:72–84CrossRef Rahmat M, Hubert P (2011) Carbon nanotube–polymer interactions in nanocomposites: a review. Compos Sci Technol 72:72–84CrossRef
5.
Zurück zum Zitat Wang J, Jia H, Tang Y, Ji D, Sun Y, Gong X, Ding L (2013) Enhancements of the mechanical properties and thermal conductivity of carboxylated acrylonitrile butadiene rubber with the addition of graphene oxide. J Mater Sci 48:1571–1577. doi:10.1007/s10853-012-6913-1 CrossRef Wang J, Jia H, Tang Y, Ji D, Sun Y, Gong X, Ding L (2013) Enhancements of the mechanical properties and thermal conductivity of carboxylated acrylonitrile butadiene rubber with the addition of graphene oxide. J Mater Sci 48:1571–1577. doi:10.​1007/​s10853-012-6913-1 CrossRef
6.
Zurück zum Zitat Potts JR, Shankar O, Murali S, Du L, Ruoff RS (2013) Latex and two-roll mill processing of thermally-exfoliated graphite oxide/natural rubber nanocomposites. Compos Sci Technol 74:166–172CrossRef Potts JR, Shankar O, Murali S, Du L, Ruoff RS (2013) Latex and two-roll mill processing of thermally-exfoliated graphite oxide/natural rubber nanocomposites. Compos Sci Technol 74:166–172CrossRef
8.
Zurück zum Zitat Tang Z, Wu X, Guo B, Zhang L, Jia D (2012) Preparation of butadiene–styrene–vinyl pyridine rubber–graphene oxide hybrids through co-coagulation process and in situ interface tailoring. J Mater Chem 22:7492–7501CrossRef Tang Z, Wu X, Guo B, Zhang L, Jia D (2012) Preparation of butadiene–styrene–vinyl pyridine rubber–graphene oxide hybrids through co-coagulation process and in situ interface tailoring. J Mater Chem 22:7492–7501CrossRef
9.
Zurück zum Zitat Chouhan DK, Rath SK, Kumar A, Alegaonkar P, Kumar S, Harikrishnan G, Patro TU (2015) Structure-reinforcement correlation and chain dynamics in graphene oxide and laponite-filled epoxy nanocomposites. J Mater Sci 50:7458–7472. doi:10.1007/s10853-015-9305-5 CrossRef Chouhan DK, Rath SK, Kumar A, Alegaonkar P, Kumar S, Harikrishnan G, Patro TU (2015) Structure-reinforcement correlation and chain dynamics in graphene oxide and laponite-filled epoxy nanocomposites. J Mater Sci 50:7458–7472. doi:10.​1007/​s10853-015-9305-5 CrossRef
10.
11.
Zurück zum Zitat Kang H, Zuo K, Wang Z, Zhang L, Liu L, Guo B (2014) Using a green method to develop graphene oxide/elastomers nanocomposites with combination of high barrier and mechanical performance. Compos Sci Technol 92:1–8CrossRef Kang H, Zuo K, Wang Z, Zhang L, Liu L, Guo B (2014) Using a green method to develop graphene oxide/elastomers nanocomposites with combination of high barrier and mechanical performance. Compos Sci Technol 92:1–8CrossRef
12.
Zurück zum Zitat Wei J, Jacob S, Qiu J (2014) Graphene oxide-integrated high-temperature durable fluoroelastomer for petroleum oil sealing. Compos Sci Technol 92:126–133CrossRef Wei J, Jacob S, Qiu J (2014) Graphene oxide-integrated high-temperature durable fluoroelastomer for petroleum oil sealing. Compos Sci Technol 92:126–133CrossRef
13.
Zurück zum Zitat Liu X, Kuang W, Guo B (2015) Preparation of rubber/graphene oxide composites with in situ interfacial design. Polymer 56:553–562CrossRef Liu X, Kuang W, Guo B (2015) Preparation of rubber/graphene oxide composites with in situ interfacial design. Polymer 56:553–562CrossRef
14.
Zurück zum Zitat Kim H, Kobayashi S, AbdurRahim MA, Zhang MJ, Khusainova A, Hillmyer MA, Abdala AA, Macosko CW (2011) Graphene/polyethylene nanocomposites: effect of polyethylene functionalization and blending methods. Polymer 52:1837–1846CrossRef Kim H, Kobayashi S, AbdurRahim MA, Zhang MJ, Khusainova A, Hillmyer MA, Abdala AA, Macosko CW (2011) Graphene/polyethylene nanocomposites: effect of polyethylene functionalization and blending methods. Polymer 52:1837–1846CrossRef
15.
Zurück zum Zitat Wu J, Huang G, Li H, Wu S, Liu Y, Zheng J (2013) Enhanced mechanical and gas barrier properties of rubber nanocomposites with surface functionalized graphene oxide at low content. Polymer 54:1930–1937CrossRef Wu J, Huang G, Li H, Wu S, Liu Y, Zheng J (2013) Enhanced mechanical and gas barrier properties of rubber nanocomposites with surface functionalized graphene oxide at low content. Polymer 54:1930–1937CrossRef
16.
Zurück zum Zitat Mao Y, Zhang S, Zhang D, Chan TW, Liu L (2014) Enhancing graphene oxide reinforcing potential in composites by combined latex compounding and spray drying. Mater Res Express 1:025009CrossRef Mao Y, Zhang S, Zhang D, Chan TW, Liu L (2014) Enhancing graphene oxide reinforcing potential in composites by combined latex compounding and spray drying. Mater Res Express 1:025009CrossRef
17.
Zurück zum Zitat Zhao XW, Zang CG, Wen YQ, Jiao QJ (2015) Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide. J Appl Polym Sci 132:42582 Zhao XW, Zang CG, Wen YQ, Jiao QJ (2015) Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide. J Appl Polym Sci 132:42582
18.
Zurück zum Zitat Razak JA, Ahmad SH, Ratnam CT, Mahamood MA, Mohamad N (2015) Effects of poly (ethyleneimine) adsorption on graphene nanoplatelets to the properties of NR/EPDM rubber blend nanocomposites. J Mater Sci 50:6365–6381. doi:10.1007/s10853-015-9188-5 CrossRef Razak JA, Ahmad SH, Ratnam CT, Mahamood MA, Mohamad N (2015) Effects of poly (ethyleneimine) adsorption on graphene nanoplatelets to the properties of NR/EPDM rubber blend nanocomposites. J Mater Sci 50:6365–6381. doi:10.​1007/​s10853-015-9188-5 CrossRef
19.
Zurück zum Zitat Yang H, Li F, Shan C, Han D, Zhang Q, Niu L, Ivaska A (2009) Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement. J Mater Chem 19:4632–4638CrossRef Yang H, Li F, Shan C, Han D, Zhang Q, Niu L, Ivaska A (2009) Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement. J Mater Chem 19:4632–4638CrossRef
20.
Zurück zum Zitat Lian H, Li S, Liu K, Xu L, Wang K, Guo W (2011) Study on modified graphene/butyl rubber nanocomposites. I. Preparation and characterization. Polym Eng Sci 51:2254–2260CrossRef Lian H, Li S, Liu K, Xu L, Wang K, Guo W (2011) Study on modified graphene/butyl rubber nanocomposites. I. Preparation and characterization. Polym Eng Sci 51:2254–2260CrossRef
21.
Zurück zum Zitat Mao Y, Wen S, Chen Y, Zhang F, Panine P, Chan TW, Zhang L, Liang Y, Liu L (2013) High performance graphene oxide based rubber composites. Sci Rep 3:2508 Mao Y, Wen S, Chen Y, Zhang F, Panine P, Chan TW, Zhang L, Liang Y, Liu L (2013) High performance graphene oxide based rubber composites. Sci Rep 3:2508
22.
Zurück zum Zitat Chang X, Wang Z, Quan S, Xu Y, Jiang Z, Shao L (2014) Exploring the synergetic effects of graphene oxide (GO) and polyvinylpyrrodione (PVP) on poly (vinylylidenefluoride)(PVDF) ultrafiltration membrane performance. Appl Surf Sci 316:537–548CrossRef Chang X, Wang Z, Quan S, Xu Y, Jiang Z, Shao L (2014) Exploring the synergetic effects of graphene oxide (GO) and polyvinylpyrrodione (PVP) on poly (vinylylidenefluoride)(PVDF) ultrafiltration membrane performance. Appl Surf Sci 316:537–548CrossRef
23.
Zurück zum Zitat Zhang X, Zhang J (2005) Studies on the fundamental properties of butyl rubber. Petrochem Ind Technol 12:1–4 Zhang X, Zhang J (2005) Studies on the fundamental properties of butyl rubber. Petrochem Ind Technol 12:1–4
25.
Zurück zum Zitat Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRef Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRef
26.
Zurück zum Zitat Maria HJ, Lyczko N, Nzihou A, Mathew C, George SC, Joseph K, Thomas S (2013) Transport of organic solvents through natural rubber/nitrile rubber/organically modified montmorillonite nanocomposites. J Mater Sci 48:5373–5386. doi:10.1007/s10853-013-7332-7 CrossRef Maria HJ, Lyczko N, Nzihou A, Mathew C, George SC, Joseph K, Thomas S (2013) Transport of organic solvents through natural rubber/nitrile rubber/organically modified montmorillonite nanocomposites. J Mater Sci 48:5373–5386. doi:10.​1007/​s10853-013-7332-7 CrossRef
27.
Zurück zum Zitat Barkauskas J, Dakševič J, Juškėnas R, Mažeikienė R, Niaura G, Račiukaitis G, Selskis A, Stankevičienė I, Trusovas R (2012) Nanocomposite films and coatings produced by interaction between graphite oxide and Congo red. J Mater Sci 47:5852–5860. doi:10.1007/s10853-012-6485-0 CrossRef Barkauskas J, Dakševič J, Juškėnas R, Mažeikienė R, Niaura G, Račiukaitis G, Selskis A, Stankevičienė I, Trusovas R (2012) Nanocomposite films and coatings produced by interaction between graphite oxide and Congo red. J Mater Sci 47:5852–5860. doi:10.​1007/​s10853-012-6485-0 CrossRef
28.
Zurück zum Zitat Saroj A, Singh R, Chandra S (2013) Studies on polymer electrolyte poly (vinyl) pyrrolidone (PVP) complexed with ionic liquid: effect of complexation on thermal stability, conductivity and relaxation behaviour. Mater Sci Eng, B 178:231–238CrossRef Saroj A, Singh R, Chandra S (2013) Studies on polymer electrolyte poly (vinyl) pyrrolidone (PVP) complexed with ionic liquid: effect of complexation on thermal stability, conductivity and relaxation behaviour. Mater Sci Eng, B 178:231–238CrossRef
29.
Zurück zum Zitat Bourlinos AB, Georgakilas V, Zboril R, Steriotis TA, Stubos AK, Trapalis C (2009) Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes. Solid State Commun 149:2172–2176CrossRef Bourlinos AB, Georgakilas V, Zboril R, Steriotis TA, Stubos AK, Trapalis C (2009) Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes. Solid State Commun 149:2172–2176CrossRef
30.
Zurück zum Zitat Abdelghany A, Mekhail MS, Abdelrazek E, Aboud M (2015) Combined DFT/FTIR structural studies of monodispersed PVP/Gold and silver nano particles. J Alloys Compd 646:326–332CrossRef Abdelghany A, Mekhail MS, Abdelrazek E, Aboud M (2015) Combined DFT/FTIR structural studies of monodispersed PVP/Gold and silver nano particles. J Alloys Compd 646:326–332CrossRef
31.
Zurück zum Zitat Xing W, Tang M, Wu J, Huang G, Li H, Lei Z, Fu X, Li H (2014) Multifunctional properties of graphene/rubber nanocomposites fabricated by a modified latex compounding method. Compos Sci Technol 99:67–74CrossRef Xing W, Tang M, Wu J, Huang G, Li H, Lei Z, Fu X, Li H (2014) Multifunctional properties of graphene/rubber nanocomposites fabricated by a modified latex compounding method. Compos Sci Technol 99:67–74CrossRef
32.
Zurück zum Zitat Mehrdad A, Niknam Z (2015) Spectroscopic and viscometric studies on the interaction of ionic liquid, 1-butyl-3-methylimidazolium bromide with polyvinyl pyrrolidone. Fluid Phase Equilib 391:72–77CrossRef Mehrdad A, Niknam Z (2015) Spectroscopic and viscometric studies on the interaction of ionic liquid, 1-butyl-3-methylimidazolium bromide with polyvinyl pyrrolidone. Fluid Phase Equilib 391:72–77CrossRef
33.
Zurück zum Zitat Zhao C, Xu X, Chen J, Yang F (2014) Optimization of preparation conditions of poly (vinylidene fluoride)/graphene oxide microfiltration membranes by the Taguchi experimental design. Desalination 334:17–22CrossRef Zhao C, Xu X, Chen J, Yang F (2014) Optimization of preparation conditions of poly (vinylidene fluoride)/graphene oxide microfiltration membranes by the Taguchi experimental design. Desalination 334:17–22CrossRef
34.
Zurück zum Zitat Fan X, Peng W, Li Y, Li X, Wang S, Zhang G, Zhang F (2008) Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation. Adv Mater 20:4490–4493CrossRef Fan X, Peng W, Li Y, Li X, Wang S, Zhang G, Zhang F (2008) Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation. Adv Mater 20:4490–4493CrossRef
35.
Zurück zum Zitat Oh T-J, Nam J-H, Jung YM (2009) Molecular miscible blend of poly (2-cyano-1, 4-phenyleneterephthalamide) and polyvinylpyrrolidone characterized by two-dimensional correlation FTIR and solid state 13 C NMR spectroscopy. Vib Spectrosc 51:15–21CrossRef Oh T-J, Nam J-H, Jung YM (2009) Molecular miscible blend of poly (2-cyano-1, 4-phenyleneterephthalamide) and polyvinylpyrrolidone characterized by two-dimensional correlation FTIR and solid state 13 C NMR spectroscopy. Vib Spectrosc 51:15–21CrossRef
36.
Zurück zum Zitat Liu X, Pan X, Shen W, Ren P, Han X, Bao X (2012) NMR study of preferential endohedral adsorption of methanol in multiwalled carbon nanotubes. J Phys Chem C 116:7803–7809CrossRef Liu X, Pan X, Shen W, Ren P, Han X, Bao X (2012) NMR study of preferential endohedral adsorption of methanol in multiwalled carbon nanotubes. J Phys Chem C 116:7803–7809CrossRef
37.
Zurück zum Zitat Fini A, Cavallari C, Ospitali F (2008) Raman and thermal analysis of indomethacin/PVP solid dispersion enteric microparticles. Eur J Pharm Biopharm 70:409–420CrossRef Fini A, Cavallari C, Ospitali F (2008) Raman and thermal analysis of indomethacin/PVP solid dispersion enteric microparticles. Eur J Pharm Biopharm 70:409–420CrossRef
38.
Zurück zum Zitat Li X, Deng H, Li Z, Xiu H, Qi X, Zhang Q, Wang K, Chen F, Fu Q (2015) Graphene/thermoplastic polyurethane nanocomposites: surface modification of graphene through oxidation, polyvinyl pyrrolidone coating and reduction. Compos Part A 68:264–275CrossRef Li X, Deng H, Li Z, Xiu H, Qi X, Zhang Q, Wang K, Chen F, Fu Q (2015) Graphene/thermoplastic polyurethane nanocomposites: surface modification of graphene through oxidation, polyvinyl pyrrolidone coating and reduction. Compos Part A 68:264–275CrossRef
39.
Zurück zum Zitat Das A, Kasaliwal GR, Jurk R, Boldt R, Fischer D, Stöckelhuber KW, Heinrich G (2012) Rubber composites based on graphene nanoplatelets, expanded graphite, carbon nanotubes and their combination: a comparative study. Compos Sci Technol 72:1961–1967CrossRef Das A, Kasaliwal GR, Jurk R, Boldt R, Fischer D, Stöckelhuber KW, Heinrich G (2012) Rubber composites based on graphene nanoplatelets, expanded graphite, carbon nanotubes and their combination: a comparative study. Compos Sci Technol 72:1961–1967CrossRef
40.
Zurück zum Zitat Matos CF, Galembeck F, Zarbin AJ (2014) Multifunctional and environmentally friendly nanocomposites between natural rubber and graphene or graphene oxide. Carbon 78:469–479CrossRef Matos CF, Galembeck F, Zarbin AJ (2014) Multifunctional and environmentally friendly nanocomposites between natural rubber and graphene or graphene oxide. Carbon 78:469–479CrossRef
41.
Zurück zum Zitat Zheng D, Tang G, Zhang H-B, Yu Z-Z, Yavari F, Koratkar N, Lim S-H, Lee M-W (2012) In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites. Compos Sci Technol 72:284–289CrossRef Zheng D, Tang G, Zhang H-B, Yu Z-Z, Yavari F, Koratkar N, Lim S-H, Lee M-W (2012) In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites. Compos Sci Technol 72:284–289CrossRef
42.
Zurück zum Zitat Potts JR, Dreyer DR, Bielawski CW, Ruoff RS (2011) Graphene-based polymer nanocomposites. Polymer 52:5–25CrossRef Potts JR, Dreyer DR, Bielawski CW, Ruoff RS (2011) Graphene-based polymer nanocomposites. Polymer 52:5–25CrossRef
43.
Zurück zum Zitat Hu Y, Shen J, Li N, Ma H, Shi M, Yan B, Huang W, Wang W, Ye M (2010) Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials. Compos Sci Technol 70:2176–2182CrossRef Hu Y, Shen J, Li N, Ma H, Shi M, Yan B, Huang W, Wang W, Ye M (2010) Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials. Compos Sci Technol 70:2176–2182CrossRef
44.
Zurück zum Zitat Kim H, Abdala AA, Macosko CW (2010) Graphene/polymer nanocomposites. Macromolecules 43:6515–6530CrossRef Kim H, Abdala AA, Macosko CW (2010) Graphene/polymer nanocomposites. Macromolecules 43:6515–6530CrossRef
Metadaten
Titel
Enhanced mechanical properties and thermal conductivity of styrene–butadiene rubber reinforced with polyvinylpyrrolidone-modified graphene oxide
verfasst von
Biao Yin
Jingyi Wang
Hongbing Jia
Junkuan He
Xumin Zhang
Zhaodong Xu
Publikationsdatum
08.03.2016
Verlag
Springer US
Erschienen in
Journal of Materials Science / Ausgabe 12/2016
Print ISSN: 0022-2461
Elektronische ISSN: 1573-4803
DOI
https://doi.org/10.1007/s10853-016-9874-y

Weitere Artikel der Ausgabe 12/2016

Journal of Materials Science 12/2016 Zur Ausgabe

    Marktübersichten

    Die im Laufe eines Jahres in der „adhäsion“ veröffentlichten Marktübersichten helfen Anwendern verschiedenster Branchen, sich einen gezielten Überblick über Lieferantenangebote zu verschaffen.