Export file:


  • RIS(for EndNote,Reference Manager,ProCite)
  • BibTex
  • Text


  • Citation Only
  • Citation and Abstract

Morphology orientation of comb-like polymers with rigid backbones under the influence of shear fields

1 Fraunhofer Institut für Mikrostruktur von Werkstoffen und Systemen IMWS, Walter-Hülse-Straße 1, D-06120 Halle (Saale), Germany
2 Naturwissenschaftliche Fakultät II, Martin-Luther-Universität Halle-Wittenberg, Heinrich-Damerow-Str. 4, D-06120 Halle (Saale), Germany

Special Issue: Hierarchically structured Polymeric Materials for Advanced Applications

The influence of shear fields on the packing behavior and morphology orientation arestudied for two comb-like polymers viz. poly(1,4-phenylene-2,5-didecyloxy terephthalate) (PPDOT)and poly(2,5-didecyloxy-1,4-phenylenevinylene) (DOPPV) with different rigid backbones having C =10 alkyl carbons per side chain. Crystallographic analysis based on X-ray diffractometry measurementsshows that both PPDOT and DOPPV exhibit a long-range ordered layered structure with alternatingmain chains and alkyl nanodomains and can be characterized by an orthorhombic and monoclinic unitcell respectively. No measurable influence of processing on the unit cell of the individual polymersis observed comparing diffraction data on isotropic (powder) samples and extruded fibers. The maindifference between the PPDOT and DOPPV is in the molecular orientation of the backbones in shearaligned fibers as observed from the 2D diffraction patterns. While, for PPDOT the polymer backbonesalign along the direction of extrusion (fiber axis), for DOPPV the backbones align perpendicular to theextrusion direction. A possible relation between differences in backbone orientation under influence ofshear fields for DOPPV and PPDOT and differences in the packing state of the side chains, which arein a crystalline state for DOPPV but in a disordered state for PPDOT, is considered.
  Article Metrics

Keywords X-ray scattering; crystal structure; oriented fibers; side chain packing; alkyl nanodomains

Citation: Gaurav Gupta, Varun Danke, Tamoor Babur, Mario Beiner. Morphology orientation of comb-like polymers with rigid backbones under the influence of shear fields. AIMS Materials Science, 2017, 4(4): 970-981. doi: 10.3934/matersci.2017.4.970


  • 1. Heeger AJ (2001) Semiconducting and metallic polymers: The fourth generation of polymeric materials. J Phys Chem B 105: 8475–8491.    
  • 2. Ong BS, Wu YL, Liu P, et al. (2004) High-performance semiconducting polythiophenes for organic thin-film transistors. J Am Chem Soc 126: 3378–3379.    
  • 3. Blom PWM, Vissenberg MCJM (2000) Charge transport in poly(p-phenylene vinylene) lightemitting diodes. Mater Sci Eng R 27: 53–94.    
  • 4. Gallot B (1996) Comb like and block liquid crystalline polymers for biological applications. Prog Polym Sci 21: 1035–1088.    
  • 5. Jianquan T, Weiqu L, Honglei W, et al. (2016) Preparation and properties of UV-curable waterborne comb-like(meth)acrylate copolymers with long fluorinated side chains. Prog Org Coat 94: 62–72.    
  • 6. Jackson WJ (1980) Liquid crystal polymers. IV. Liquid crystalline aromatic polyesters. Brit Poly J 12: 154–162.
  • 7. Ballauf M (1989) Stiff-chain polymers-Structure, phase-behavior, and properties. Angew Chem Int Ed Engl 28: 253–267.    
  • 8. Shi H, Zhao Y, Dong X (2013) Frustrated crystallization and hierarchical self-assembly behavior of comb-like polymers. Chem Soc Rev 42: 2075–2099.    
  • 9. Beiner M, Huth H (2003) Nanophase separation and hindered glass transition in side-chain polymers. Nat Mater 2: 595–599.    
  • 10. Pankaj S, Beiner M (2010) Confined dynamics and crystallization in self-assembled alkyl nanodomains. J Phys Chem B 114: 15459–15465.    
  • 11. Zheng W, Levon K, Laakso J, et al. (1994) Characterization and solid-state properties of processable N-alkylated polyanilines in the neutral state. Macromolecules 27: 7754–7768.    
  • 12. Watanabe J, Ono H, Uematsu I, et al. (1985) Thermotropic polypeptides. 2. Molecular packing and thermotropic behavior of poly(L-glutamates) with long n-alkyl side chain. Macromolecules 18: 2141–2148.
  • 13. Gupta G, Danke V, Babur T, et al. (2017) Interrelations between side chain and main chain packing in different crystal modifications of alkoxylated polyesters. J Phys Chem B 121: 4583–4591.    
  • 14. Sirringhaus H, Brown PJ, Friend RH, et al. (1999) Two-dimensional charge transport in selforganized, high-mobility conjugated polymers. Nature 401: 685–688.    
  • 15. Gargi D, Kline RJ, DeLongchamp DM, et al. (2013) Charge transport in highly face-on poly(3-hexylthiophene) films. J Phys Chem C 117: 17421–17428.    
  • 16. Koynov K, Bahtiar A, Ahn T, et al. (2006) Molecular weight dependence of chain orientation and optical constants of thin films of the conjugated polymer MEH-PPV. Macromolecules 39: 8692–8698.    
  • 17. Hamaguchi M, Yoshino K (1995) Rubbing-induced molecular orientation and polarized electroluminescence in conjugated polymer. Jpn J Appl Phys 34: 712–715.    
  • 18. Okuzaki H, Hirata Y, Kunugi T (1999) Mechanical properties and structure of zone-drawn poly(pphenylene vinylene) films. Polymer 40: 2625–2629.    
  • 19. Lin NT, Satyanarayana K, Chen CH, et al. (2014) Controlling the orientation of pendants in twodimensional comb-like polymers by varying stiffness of polymeric backbones. Macromolecules 47: 6166–6172.    
  • 20. Jeng U, Hsu CH, Sheu HS, et al. (2005) Morphology and charge transport in poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) films. Macromolecules 38: 6566–6574.    
  • 21. Singh CR, Gupta G, Lohwasser R, et al. (2013) Correlation of charge transport with structural order in highly ordered melt crystallized P3HT films. J Polym Sci Part B Polym Phys 51: 943–951.    
  • 22. Brinkmann M, Contal C, Kayunkid N, et al. (2010) Highly oriented and nanotextured films of regioregular poly(3-hexylthiophene) grown by epitaxy on the nanostructured surface of an aromatic substrate. Macromolecules 43: 7604–7610.    
  • 23. Kim JS, Park Y, Lee DY, et al. (2010) Poly(3-hexylthiophene) nanorods with aligned chain orientation for organic photovoltaics. Adv Funct Mater 20: 540–545.    
  • 24. Fischer FSU, Tremel K, Sommer M, et al. (2012) Directed crystallization of poly(3-hexylthiophene) in micrometre channels under confinement and in electric fields. Nanoscale 4: 2138–2144.    
  • 25. Ebert F, Thurn-Albrecht T (2003) Controlling the orientation of semicrystalline polymers by crystallization in magnetic fields. Macromolecules 36: 8685–8694.    
  • 26. Freidzon YAS, Talroze RV, Boiko NI, et al. (1988) Thermotropic liquid-crystalline polymers XXIII. Peculiarities of uniaxial orientation of comb-like liquid-crystalline polymers under mechanical stress. Liq Cryst 3: 127–132.
  • 27. Nagamatsu S, Takashima W, Kaneto K (2003) Backbone arrangement in friction-transferred regioregular poly(3-alkylthiophene)s. Macromolecules 36: 5252–5257.    
  • 28. Hamidi-Sakr A, Biniek L, Fall S, et al. (2016) Precise control of lamellar thickness in highly oriented regioregular poly(3-hexylthiophene) thin films prepared by high-temperature rubbing: Correlations with optical properties and charge transport. Adv Funct Mater 26: 408–420.    
  • 29. Rim YS, Bae SH, Chen HJ, et al. (2016) Recent progress in materials and devices toward Printable and flexible sensors. Adv Mater 28: 4415–4440.    
  • 30. Reinspach JA, Diao Y, Giri G, et al. (2016) Tuning the morphology of solution-sheared P3HT:PCBM films. ACS Appl Mater Interfaces 8: 1742–1751.    
  • 31. Rauwendaal C (2001) Polymer Extrusion, Carl Hanser Verlag Munich.
  • 32. Damman SB, Vroege GJ (1993) Liquid-crystalline main-chain polymers with a poly(p-phenylene terephthalate) backbone. X-ray-diffraction of the polyester with dodecyloxy side-chains. Polymer 34: 2732–2739.
  • 33. Babur T, Balko J, Budde H, et al. (2014) Confined relaxation dynamics in long range ordered polyesters with comb-like architecture. Polymer 55: 6844–6852.    
  • 34. Babur T (2017) Structure and relaxation dynamics of comb-like polymers with rigid backbone [PhD Dissertation]. Martin Luther University Halle-Wittenberg.
  • 35. Babur T, Gupta G, Beiner M (2016) About different packing states of alkyl groups in comb-like polymers with rigid backbones. Soft Matter 12: 8093–8097.    
  • 36. Nagamatsu S, Misaki M, Chikamatsu M, et al. (2007) Crystal structure of friction transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene). J Phys Chem B 111: 4349–4354.    
  • 37. Balsara NP, Dai HJ (1996) A transition from shear-induced order to shear-induced disorder in block copolymers. J Chem Phys 105: 2942–2945.    
  • 38. Vigild ME, Chu C, SugiyamaM(2001) Influence of shear on the alignment of a lamellae-forming pentablock Copolymer. Macromolecules 34: 951–964.
  • 39. Damman SB, Mercx FPM (1993) About di erent packing states of alkyl groups in comb-like polymers with rigid backbones. J Polym Sci Part B Polym Phys 31: 1759–1767.
  • 40. Falk U, Westermark B, Boeffel C, et al. (1987) NMR of stiff macromolecules with flexible side chains. Mol Cryst Liq Cryst 153: 199–206.


Reader Comments

your name: *   your email: *  

Copyright Info: © 2017, Mario Beiner, et al., licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution Licese (http://creativecommons.org/licenses/by/4.0)

Download full text in PDF

Export Citation

Copyright © AIMS Press All Rights Reserved