, Volume 25, Issue 12, pp 7167–7188 | Cite as

Microstructural development and mechanical performance of PLA/TPU blends containing geometrically different cellulose nanocrystals

  • Zahra Shakouri
  • Hossein NazockdastEmail author
Original Paper


Microstructural development and mechanical performance of poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) (80/20) blends containing single but geometrically different cellulose nanocrystals (CNCs) were investigated. The CNCs used in this study include cylindrical CNCs (ultrasonic treated), spherical CNCs (chemical treated) and rod-like CNCs (commercial), all characterized by particle size analyzer, atomic force microscopy (AFM) and X-ray diffraction. The melt viscoelastic results obtained for the melt compounded CNCs with PLA/TPU blend have implied a fine dispersion of both spherical and cylindrical CNCs which are preferentially localized in the PLA matrix and/or interface, while poorly dispersed rod-like CNCs were mostly accumulated in the TPU phase. These results were supported by AFM micrographs. More evidence was provided by scanning electron microscope micrographs which showed a decrease in TPU particle size in the blends filled with spherical and cylindrical CNCs, as a result of the nanoparticles’ localization in the PLA matrix and/or interface. The results of dynamic mechanical thermal analysis have revealed that the addition of spherical and cylindrical CNCs into the blends not only has compensated the reducing effect of TPU on the storage modulus but also has enhanced the modulus up to values even higher than that of PLA matrix. In contrast, the rod-like CNCs did not enhance the storage modulus of the blend significantly. More interestingly, the blend nanocomposite containing 3 wt% spherical CNCs exhibited a highly enhanced yield stress as well as significant elongation at break. This behavior could be explained by the induction of an interconnected type microstructure of spherical CNCs in which the nanoparticles are localized in PLA matrix, allowing the overlapping of stress counters around TPU particles and facilitating the stress transformation throughout the loaded sample. A similar enhancing effect but to a lesser extent, was obtained for those blend nanocomposites filled with cylindrical CNCs. In contrast to the other two types of CNCs, rod-like CNCs have weakened the mechanical performance of the blends. The results of fracture toughness obtained from single edge notch bending experiments have shown almost similar enhancing effect of the three types of CNCs on toughening. However, the sensitivity of the fracture test was not high enough to distinguish the effect of different CNCs on mechanical behavior of CNCs-filled blend nanocomposites.

Graphical abstract


PLA Cellulose nanocrystals Morphology Rheology Toughening Blend nanocomposites 



The authors acknowledge the financial support provided by the Iranian National Nanotechnology network. The authors are also grateful to FPInnovations for providing the rod-like CNCs.


  1. Arias A, Heuzey MC, Huneault M, Ausias G, Bendahou A (2015) Enhanced dispersion of cellulose nanocrystals in melt-processed polylactide-based nanocomposites. Cellulose 22:483–498. CrossRefGoogle Scholar
  2. Arrieta MP, Fortunati E, Dominici F, Rayón E, López J, Kenny JM (2014) Multifunctional PLA–PHB/cellulose nanocrystal films: processing, structural and thermal properties. Carbohydr Polym 107:16–24. CrossRefPubMedGoogle Scholar
  3. Baek C, Hanif Z, Cho SW, Kim DI, Um SH (2013) Shape control of cellulose nanocrystals via compositional acid hydrolysis. J Biomed Nanotechnol 9:1293–1298. CrossRefPubMedGoogle Scholar
  4. Bagheriasl D, Carreau PJ, Dubois C, Riedl B (2015) Properties of polypropylene and polypropylene/poly(ethylene-co-vinyl alcohol) blend/CNC nanocomposites. Compos Sci Technol 117:357–363. CrossRefGoogle Scholar
  5. Bagheriasl D, Riedl Carreau PJ, Riedl B, Dubois C, Hamad WY (2016) Shear rheology of polylactide (PLA)–cellulose nanocrystal (CNC) nanocomposites. Cellulose 23:1885–1897. CrossRefGoogle Scholar
  6. Battegazzore D, Bocchini S, Frache A (2011) Crystallization kinetics of poly (lactic acid)-talc composites. Express Polym Lett 5:849–858. CrossRefGoogle Scholar
  7. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditionson the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054. CrossRefPubMedGoogle Scholar
  8. Bitinis N, Verdejo R, Maya EM, Espuche E, Cassagnau P, Lopez-Manchado MA (2012) Physicochemical properties of organoclay filled polylactic acid/natural rubber blend bionanocomposites. Compos Sci Technol 72:305–313. CrossRefGoogle Scholar
  9. Bitinis N, Verdejo R, Bras J, Fortunati E, Kenny JM, Torre L, López-Manchado MA (2013) Poly(lactic acid)/natural rubber/cellulose nanocrystal bionanocomposites Part I. Processing and morphology. Carbohydr Polym 96:611–620. CrossRefPubMedGoogle Scholar
  10. Bondeson D, Oksman K (2007) Polylactic acid/cellulose whisker nanocomposites modified by polyvinyl alcohol. Compos Part A Appl Sci Manuf 38:2486–2492. CrossRefGoogle Scholar
  11. Bousmina M (1999) Rheology of polymer blends: linear model for viscoelastic emulsions. Rheol Acta 38:73–83. CrossRefGoogle Scholar
  12. Brinkmann A, Chen M, Couillard M, Jakubek ZJ, Leng T, Johnston LJ (2016) Correlating cellulose nanocrystal particle size and surface area. Langmuir 32:6105–6114. CrossRefPubMedGoogle Scholar
  13. Chen JJ, Liu HY, Zhang GZ, Qu JP (2013) Mechanical properties and thermal behavior of thermoplastic polyurethane toughening polylactide prepared by vane extruder. Appl Mech Mater 431:110–115. CrossRefGoogle Scholar
  14. Chen Y, Yuan D, Xu Ch (2014) Dynamically vulcanized biobased polylactide/natural rubber blend material with continuous cross-linked rubber phase. ACS Appl Mater Interfaces 6:3811–3816. CrossRefPubMedGoogle Scholar
  15. Ching YC, Ershad Ali Md, Abdullah LC, Choo KW, Kuan YC, Julaihi SJ, Chuah CH, Liou NS (2016) Rheological properties of cellulose nanocrystal-embedded polymer composites: a review. Cellulose 23:1011–1030. CrossRefGoogle Scholar
  16. Dankovich TA, Gray DG (2011) Contact angle measurements on smooth nanocrystalline cellulose (I) thin films. J Adhes Sci Technol 25:699–708. CrossRefGoogle Scholar
  17. Di YW, Iannace S, Di Maio E, Nicolais L (2005) Poly(lactic acid)/organoclay nanocomposites: thermal, rheological properties and foam processing. J Polym Sci Part B: Polym Phys 43:689–698. CrossRefGoogle Scholar
  18. Du L, Wang J, Zhang Y, Qi C, Wolcott MP, Yu Z (2017) Preparation and characterization of cellulose nanocrystals from the bio-ethanol residuals. Nanomaterials 7:51. CrossRefPubMedCentralGoogle Scholar
  19. Fengel D (1993) Influence of water on the OH valency range in deconvoluted FTIR spectra of cellulose. Holzforsch Int J Biol Chem Phys Technol Wood 47:103–108. CrossRefGoogle Scholar
  20. Fortunati E, Armentano I, Zhou Q, Iannoni A, Saino E, Visai L, Berglund LA, Kenny JM (2012) Multifunctional bionanocomposite films of poly (lactic acid), cellulose nanocrystals and silver nanoparticles. Carbohydr Polym 87:1596–1605. CrossRefGoogle Scholar
  21. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. CrossRefGoogle Scholar
  22. French AD, Santiago Cintron M (2013) Cellulose polymorphy, crystallite size, and the Segal crystallinity index. Cellulose 20:583–588. CrossRefGoogle Scholar
  23. Goffin AL, Raquez JM, Duquesne E, Siqueira G, Habibi Y, Dufresne A, Dubois P (2011) From interfacial ring-opening polymerization to melt processing of cellulose nanowhisker-filled polylactide-based nanocomposites. Biomacromolecules 12:2456–2465. CrossRefPubMedGoogle Scholar
  24. Graebling D, Muller R, Palierne JF (1993) Linear viscoelastic behavior of some incompatible polymer blends in the melt Interpretation of data with a model of emulsion of viscoelastic liquids. Macromolecules 26:320–329. CrossRefGoogle Scholar
  25. Grellmann W, Seidler S (2001) Deformation and fracture behavior of polymers. Springer, BerlinCrossRefGoogle Scholar
  26. Guo J, Guo X, Wang S, Yin Y (2016) Effects of ultrasonic treatment during acid hydrolysis on the yield, particle size and structure of cellulose nanocrystals. Carbohydr Polym 135:248–255. CrossRefPubMedGoogle Scholar
  27. Haji Abdolrasouli M, Nazockdast H, Mir Mohamad Sadeghi G, Kaschta J (2015) Morphology development, melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites. J Appl Polym Sci. CrossRefGoogle Scholar
  28. Heshmati V, Kamal MR, Favis BD (2018a) Tuning the localization of finely dispersed cellulose nanocrystal in poly (lactic acid)/bio-polyamide11 blends. J Polym Sci, Part B: Polym Phys 56:576–587. CrossRefGoogle Scholar
  29. Heshmati V, Kamal MR, Favis BD (2018b) Cellulose nanocrystal in poly(lactic acid)/polyamide11 blends: preparation, morphology and co-continuity. Eur Polym J 98:11–20. CrossRefGoogle Scholar
  30. Isayev A (2016) Encyclopedia of polymer blends: volume 3: structure. Wiley-VCH, Weinheim, pp 401–482CrossRefGoogle Scholar
  31. Ishida S, Nagasaki R, Chino K, Dong T, Inoue Y (2009) Toughening of poly(l-lactide) by melt blending with rubbers. J Appl Polym Sci 113:558–566. CrossRefGoogle Scholar
  32. Jiang L, Morelius E, Zhang J, Wolcott M, Holbery J (2008) Study of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhisker composites prepared by solution casting and melt processing. J Compos Mater 42:2629–2645. CrossRefGoogle Scholar
  33. Jonoobi M, Oladi R, Davoudpour Y, Oksman K, Dufresne A, Hamzeh Y, Davoodi R (2015) Different preparation methods and properties of nanostructured cellulose from various natural resources and residues: a review. Cellulose 22:935–969. CrossRefGoogle Scholar
  34. Kamal MR, Khoshkava V (2015) Effect of cellulose nanocrystals (CNC) on rheological and mechanical properties and crystallization behavior of pla/cnc nanocomposites. Carbohydr Polym 123:105–114. CrossRefPubMedGoogle Scholar
  35. Karimi K, Taherzadeh M (2016) A critical review of analytical methods in pretreatment of lignocelluloses: composition, imaging, and crystallinity. Biores Technol 200:1008–1018. CrossRefGoogle Scholar
  36. Khoshkava V, Kamal MR (2013) Effect of surface energy on dispersion and mechanical properties of polymer/nanocrystalline cellulose nanocomposites. Biomacromolecules 14:3155–3163. CrossRefPubMedGoogle Scholar
  37. Koutsianitis D, Mitani C, Giagli K, Tsalagkas D, Halsz K, Kolonics O, Gallis C, Csoka L (2015) Properties of ultrasound extracted bicomponent lignocellulose thin films. Ultrason Sonochem 23:148–155. CrossRefPubMedGoogle Scholar
  38. Li Q, Renneckar S (2011) Supramolecular structure characterization of molecularly thin cellulose I nanoparticles. Biomacromolecules 12:650–659. CrossRefPubMedGoogle Scholar
  39. Li Y, Shimizu H (2007) Toughening of polylactide by melt blending with a biodegradable poly (ether)urethane elastomer. Macromol Biosci 7:921–928. CrossRefPubMedGoogle Scholar
  40. Li J, Wei X, Wang Q, Chen J, Chang G, Kong L, Su J, Liu Y (2012a) Homogeneousisolation of nanocellulose from sugarcane bagasse by high pressure homogenization. Carbohydr Polym 90:1609–1613. CrossRefPubMedGoogle Scholar
  41. Li W, Yue J, Li S (2012b) Preparation of nanocrystalline cellulose via ultrasoundand its reinforcement capability for poly(vinyl alcohol) composites. Ultrason Sonochem 19:479–485. CrossRefPubMedGoogle Scholar
  42. Lin N, Dufresne A (2014) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees. Nanoscale 6:5384–5393. CrossRefPubMedGoogle Scholar
  43. Lin N, Huang J, Chang PR, Feng J, Yu J (2011) Surface acetylation of cellulose nanocrystal and its reinforcing function in poly(lactic acid). Carbohydr Polym 83:1834–1842. CrossRefGoogle Scholar
  44. Liu ZW, Chou HC, Chen SH, Tsao CT, Chuang CN, Cheng LC, Yang CH, Wang CK, Hsieh KH (2014a) Mechanical and thermal properties of thermoplastic polyurethane-toughened polylactide-based nanocomposites. Polym Compos 35:1744–1757. CrossRefGoogle Scholar
  45. Liu Y, Wang H, Yu G, Yu Q, Li B, Mu X (2014b) A novel approach for the preparation of nanocrystalline cellulose by using phosphotungstic acid. Carbohydr Polym 110:415–422. CrossRefPubMedGoogle Scholar
  46. Lu Q, Tang L, Lin F, Wang S, Chen Y, Chen X, Huang B (2014) Preparation and characterization of cellulose nanocrystals via ultrasonication-assisted FeCl3-catalyzed hydrolysis. Cellulose 21:3497–3506. CrossRefGoogle Scholar
  47. Nagarajan V, Mohanty AK, Misra M (2016) Perspective on polylactic acid (PLA) based sustainable materials for durable applications: focus on toughness and heat resistance. ACS Sustain Chem Eng 4:2899–2916. CrossRefGoogle Scholar
  48. Nam JY, Ray SS, Okamoto M (2003) Crystallization behavior and morphology of biodegradable polylactide/layered silicate nanocomposite. Macromolecules 36:7126–7131. CrossRefGoogle Scholar
  49. Nam S, French AD, Condon BD, Concha M (2016) Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose Iβ and cellulose II. Carbohydr Polym 135:1–9. CrossRefPubMedGoogle Scholar
  50. Ng HM, Sin LT, Bee ST, Tee TT, Rahmat AR (2017) Review of nanocellulose polymer composite characteristics and challenges. Polym Plast Technol Eng 56:687–731. CrossRefGoogle Scholar
  51. Pei AH, Zhou Q, Berglund LA (2010) Functionalized cellulose nanocrystals as biobased nucleation agents in poly(l-lactide) (PLLA)—crystallization and mechanical property effects. Compos Sci Technol 70:815–821. CrossRefGoogle Scholar
  52. Pracella M, Minhaz-Ul Haque Md, Puglia D (2014) Morphology and properties tuning of PLA/cellulose nanocrystals bionanocomposites by means of reactive functionalization and blending with PVAc. Polymer 55:3720–3728. CrossRefGoogle Scholar
  53. Raquez JM, Habibi Y, Murariu M, Dubois Ph (2013) Polylactide (PLA)-based nanocomposites. Prog Polym Sci 38:1504–1542. CrossRefGoogle Scholar
  54. Robertson ML, Chang K, Gramlich WM, Hillmyer MA (2010) Toughening of polylactide with polymerized soybean oil. Macromolecules 43:1807–1814. CrossRefGoogle Scholar
  55. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. CrossRefGoogle Scholar
  56. Shi YY, Zhang WB, Yang JH, Huang T, Zhang N, Wang Y, Yuan GP, Zhang CL (2013) Super toughening of the poly(l-lactide)/thermoplastic polyurethane blends by carbon nanotubes. RSC Adv 3:26271–26282. CrossRefGoogle Scholar
  57. Siqueira G, Tapin-Lingua S, Bras J, Perez DS, Dufresne A (2011) Mechanical properties of natural rubber nanocomposites reinforced with cellulosic nanoparticles obtained from combined mechanical shearing, and enzymatic and acid hydrolysis of sisal fibers. Cellulose 18:57–65. CrossRefGoogle Scholar
  58. Suryanegara L, Nakagaito AN, Yano H (2010) Thermo-mechanical properties of microfibrillated cellulose-reinforced partially crystallized PLA composites. Cellulose 17:771–778. CrossRefGoogle Scholar
  59. Tabi T, Sajo IE, Szabo F, Luyt AS, Kovacs JG (2010) Crystalline structure of annealed polylactic acid and its relation to processing. Express Polym Lett 4:659–668. CrossRefGoogle Scholar
  60. Ten E, Jiang L, Wolcott MP (2013) Preparation and properties of aligned poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhiskers composites. Carbohydr Polym 92:206–213. CrossRefPubMedGoogle Scholar
  61. Turner JF, Riga A, O’Connor A, Zhang J, Collis J (2004) Characterization of drawn and undrawn poly-l-lactide films by differential scanning calorimetry. J Therm Anal Calorim 75:257–268. CrossRefGoogle Scholar
  62. Tzetzis D, Mansour G (2016) Nanoindentation, compression and fractural characterization of highly dispersed epoxy silica nanocomposites. J Reinf Plast Compos 35:541–555. CrossRefGoogle Scholar
  63. Tzhayik O, Pulidindi IN, Gedanken A (2014) Forming nanospherical cellulose containers. Ind Eng Chem Res 53:13871–13880. CrossRefGoogle Scholar
  64. Vilay V, Todo M, Jaafar M, Ahmad Z, Pasomsouk K (2010) Characterization of microstructure and mechanical properties of biodegradable polymer blends of poly(l-lactic acid) and poly(butylene succinate-co-e-caprolactone) with lysine triisocyanate. Polym Eng Sci 50:1485–1491. CrossRefGoogle Scholar
  65. Wang N, Ding E, Cheng R (2008) Preparation and liquid crystalline properties of spherical cellulose nanocrystals. Langmuir 24:5–8. CrossRefPubMedGoogle Scholar
  66. Xiao HW, Yang L, Ren XM, Jiang T, Yeh JT (2010) Kinetics and crystal structure of poly(lactic acid) crystallized nonisothermally: effect of plasticizer and nucleating agent. Polym Compos 31:2057–2068. CrossRefGoogle Scholar
  67. Xiu H, Bai HW, Huang CM, Xu CL, Li XY, Fu Q (2013) Selective localization of titanium dioxide nanoparticles at the interface and its effect on the impact toughness of poly (l-lactide)/poly(ether)urethane blends. Express Polym Lett 7:261–271. CrossRefGoogle Scholar
  68. Xiu H, Huang C, Bai H, Jiang J, Chen F, Deng H, Wang K, Zhang Q, Fu Q (2014) Improving impact toughness of polylactide/poly(ether)urethane blends via designing the phase morphology assisted by hydrophilic silica nanoparticles. Polymer 55:1593–1600. CrossRefGoogle Scholar
  69. Yang H, Zhang X, Qu Ch, Fu Q (2007) Largely improved toughness of PP/EPDM blends by adding nano-SiO2 particles. Polymer 48:860–869. CrossRefGoogle Scholar
  70. Yasuniwa M, Sakamo K, Ono Y, Kawahara W (2008) (Melting behavior of poly(l-lactic acid): X-ray and DSC analyses of the melting process. Polymer 49:1943–1951. CrossRefGoogle Scholar
  71. Yu F, Huang HX (2015) Simultaneously toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane blend via enhancing interfacial adhesion by hydrophobic silica nanoparticles. Polym Test 45:107–113. CrossRefGoogle Scholar
  72. Yuan DS, Chen KL, Xu CH, Chen ZH, Chen YK (2014) Crosslinked bicontinuous biobased PLA/NR blends via dynamic vulcanization using different curing systems. Carbohydr Polym 113:438–445. CrossRefPubMedGoogle Scholar
  73. Zhang C, Wang W, Huang Y, Pan Y, Jiang L, Dan Y, Luo Y, Peng Z (2013) Thermal, mechanical and rheological properties of polylactide toughened by expoxidized natural rubber. Mater Des 45:198–205. CrossRefGoogle Scholar
  74. Zhou YM, Fu SY, Zheng LM, Zhan HY (2012) Effect of nanocellulose isolation techniques on the formation of reinforced poly (vinyl alcohol) nanocomposite films. Express Polym Lett 6:794–804. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of Polymer EngineeringAmirkabir University of Technology-Mahshahr CampusBandar-e MahshahrIran
  2. 2.Department of Polymer Engineering and Color TechnologyAmirkabir University of TechnologyTehranIran

Personalised recommendations