Journal of Polymers and the Environment

, Volume 24, Issue 3, pp 241–254 | Cite as

Assessment of Ball Milling as a Compounding Technique to Develop Nanocomposites of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) and Bacterial Cellulose Nanowhiskers

  • Jesús Ambrosio-Martin
  • María José Fabra
  • Amparo López-Rubio
  • Giuliana Gorrasi
  • Andrea Sorrentino
  • Jose M. LagaronEmail author
Original Paper


The aim of this study was the assessment of high energy ball milling technique to develop poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanocomposites containing bacterial cellulose nanowhiskers (BCNW). Crystallization behaviour of PHBV/BCNW nanocomposites was studied under non-isothermal and isothermal conditions using differential scanning calorimetry. The changes in PHBV crystalline structure were also studied using X-ray diffraction. The results confirmed that BCNW acted as nucleating agents and, hence, favored the crystallization of the PHBV. The oxygen permeability of the nanocomposites was reduced by ~22 % when compared to that of the neat PHBV. This work provides a new insight into the development of polyhydroxyalkanoate composites by means of the high energy ball milling technique.


Polyhydroxyalkanoates Bacterial cellulose nanowhiskers Bacterial cellulose nanocrystals Oxygen barrier Ball milling 



J. Ambrosio-Martín would like to thank the Spanish Ministry of Economy and Competitiveness for the FPI grant BES-2010-038203. M. J. Fabra is recipient of a “Juan de la Cierva” contract from the Spanish Ministry of Economy and Competitiveness. The authors acknowledge financial support from the MINECO (MAT2012-38947-C02-01 project) and from the FP7 ECOBIOCAP project.


  1. 1.
    Gonzalez-Lopez J, Pozo C, Martinez-Toledo MV, Rodelas B, Salmeron V (1996) Int Biodeterior Biodegrad 38:271CrossRefGoogle Scholar
  2. 2.
    Lai M, Li J, Yang J, Liu J, Tong X, Cheng H (2004) Polym Int 53:1479CrossRefGoogle Scholar
  3. 3.
    Chen GX, Hao GJ, Guo TY, Song MD, Zhang BH (2004) J Appl Polym Sci 93:655CrossRefGoogle Scholar
  4. 4.
    Ublekov F, Baldrian J, Nedkov E (2009) J Polym Sci Part B Polym Phys 47:751CrossRefGoogle Scholar
  5. 5.
    Sanchez-Garcia MD, Lagaron JM (2010) J Appl Polym Sci 118:188CrossRefGoogle Scholar
  6. 6.
    Martínez-Sanz M, Vicente AA, Gontard N, Lopez-Rubio A, Lagaron JM (2014) Cellulose 22:535CrossRefGoogle Scholar
  7. 7.
    Kvien I, Sugiyama J, Votrubec M, Oksman K (2007) J Mater Sci 42:8163CrossRefGoogle Scholar
  8. 8.
    Petersson L, Kvien I, Oksman K (2007) Compos Sci Technol 67:2535CrossRefGoogle Scholar
  9. 9.
    Ten E, Turtle J, Bahr D, Jiang L, Wolcott M (2010) Polymer 51:2652CrossRefGoogle Scholar
  10. 10.
    Jiang L, Morelius E, Zhang J, Wolcott M, Holbery J (2008) J Compos Mater 42:2629CrossRefGoogle Scholar
  11. 11.
    Yu HY, Qin ZY, Liu L, Yang XG, Zhou Y, Yao JM (2013) Compos Sci Technol 87:22CrossRefGoogle Scholar
  12. 12.
    Ten E, Jiang L, Wolcott MP (2012) Carbohydr Polym 90:541CrossRefGoogle Scholar
  13. 13.
    Martínez-Sanz M, Lopez-Rubio A, Lagaron JM (2012) Biomacromolecules 13:3887CrossRefGoogle Scholar
  14. 14.
    Martínez-Sanz M, Villano M, Oliveira C, Albuquerque MGE, Majone M, Reis M, Lopez-Rubio A, Lagaron JM (2014) New Biotechnol 31:364CrossRefGoogle Scholar
  15. 15.
    Yu HY, Qin ZY, Yan CF, Yao JM (2014) ACS Sustain Chem Eng 2:875CrossRefGoogle Scholar
  16. 16.
    Yu H, Yan C, Yao J (2014) RSC Adv 4:59792CrossRefGoogle Scholar
  17. 17.
    Arias A, Heuzey MC, Huneault MA, Ausias G, Bendahou A (2014) Cellulose 22:483CrossRefGoogle Scholar
  18. 18.
    Martínez-Sanz M, Lopez-Rubio A, Lagaron JM (2013) J Appl Polym Sci 128:2666CrossRefGoogle Scholar
  19. 19.
    Ambrosio-Martín J, Fabra MJ, Lopez-Rubio A, Lagaron JM (2015) Cellulose 22:1201CrossRefGoogle Scholar
  20. 20.
    Goffin AL, Raquez JM, Duquesne E, Siqueira G, Habibi Y, Dufresne A, Dubois P (2011) Biomacromolecules 12:2456CrossRefGoogle Scholar
  21. 21.
    Herrera N, Mathew AP, Oksman K (2015) Compos Sci Technol 106:149CrossRefGoogle Scholar
  22. 22.
    Martínez-Sanz M, Olsson RT, Lopez-Rubio A, Lagaron JM (2011) Cellulose 18:335CrossRefGoogle Scholar
  23. 23.
    Srithep Y, Ellingham T, Peng J, Sabo R, Clemons C, Turng LS, Pilla S (2013) Polym Degrad Stab 98:1439CrossRefGoogle Scholar
  24. 24.
    Vertuccio L, Gorrasi G, Sorrentino A, Vittoria V (2009) Carbohydr Polym 75:172CrossRefGoogle Scholar
  25. 25.
    Perrin-Sarazin F, Sepehr M, Bouaricha S, Denault J (2009) Polym Eng Sci 49:651CrossRefGoogle Scholar
  26. 26.
    Bugatti V, Gorrasi G, Montanari F, Nocchetti M, Tammaro L, Vittoria V (2011) Appl Clay Sci 52:34CrossRefGoogle Scholar
  27. 27.
    Tammaro L, Vittoria V, Bugatti V (2014) Eur Polym J 52:172CrossRefGoogle Scholar
  28. 28.
    Gorrasi G, Bugatti V, Vittoria V (2012) Carbohydr Polym 89:132CrossRefGoogle Scholar
  29. 29.
    Gorrasi G, Sarno M, Di Bartolomeo A, Sannino D, Ciambelli P, Vittoria V (2007) J Polym Sci Part B Polym Phys 45:597CrossRefGoogle Scholar
  30. 30.
    Gorrasi G, Piperopoulos E, Lanza M, Milone C (2013) J Phys Chem Solids 74:1CrossRefGoogle Scholar
  31. 31.
    Gorrasi G, Di Lieto R, Patimo G, De Pasquale S, Sorrentino A (2011) Polymer 52:1124CrossRefGoogle Scholar
  32. 32.
    Wu H, Zhao W, Chen G (2012) J Appl Polym Sci 125:3899CrossRefGoogle Scholar
  33. 33.
    Moreira FKV, Marconcini JM, Mattoso LHC (2012) Cellulose 19:2049CrossRefGoogle Scholar
  34. 34.
    Ambrosio-Martín J, Lopez-Rubio A, Fabra MJ, Gorrasi G, Pantani R, Lagaron JM (2014) J Appl Polym Sci 132:41605Google Scholar
  35. 35.
    Martínez-Sanz M, Lopez-Rubio A, Lagaron JM (2011) Carbohydr Polym 85:228CrossRefGoogle Scholar
  36. 36.
    Buzarovska A, Bogoeva-Gaceva G, Grozdanov A, Avella M, Gentile G, Errico M (2007) J Mater Sci 42:6501CrossRefGoogle Scholar
  37. 37.
    Scandola M, Focarete ML, Adamus G, Sikorska W, Baranowska I, Świerczek S, Gnatowski M, Kowalczuk M, Jedliński Z (1997) Macromolecules 30:2568CrossRefGoogle Scholar
  38. 38.
    Chen G, Dufresne A, Huang J, Chang PR (2009) Macromol Mater Eng 294:59CrossRefGoogle Scholar
  39. 39.
    Yu HY, Qin ZY, Liu YN, Chen L, Liu N, Zhou Z (2012) Carbohydr Polym 89:971CrossRefGoogle Scholar
  40. 40.
    Yu HY, Yao JM, Qin ZY, Liu L, Yang XG (2013) J Appl Polym Sci 130:4299Google Scholar
  41. 41.
    Fei B, Chen C, Wu H, Peng S, Wang X, Dong L (2003) Eur Polym J 39:1939CrossRefGoogle Scholar
  42. 42.
    Sanchez-Garcia MD, Gimenez E, Lagaron JM (2008) Carbohydr Polym 71:235CrossRefGoogle Scholar
  43. 43.
    Gunaratne LMWK, Shanks RA (2005) Eur Polym J 41:2980CrossRefGoogle Scholar
  44. 44.
    Jiang L, Wolcott MP, Zhang J (2006) Biomacromolecules 7:199CrossRefGoogle Scholar
  45. 45.
    Owen AJ, Heinzel J, Škrbić Ž, Divjaković V (1992) Polymer 33:1563CrossRefGoogle Scholar
  46. 46.
    Wang S, Song C, Chen G, Guo T, Liu J, Zhang B, Takeuchi S (2005) Polym Degrad Stab 87:69CrossRefGoogle Scholar
  47. 47.
    Yu H, Qin Z, Liang B, Liu N, Zhoub Z, Chen L (2013) J Mater Chem A 1:3938CrossRefGoogle Scholar
  48. 48.
    Cimmino S, Iodice P, Silvestre C, Karasz FE (2000) J Appl Polym Sci 75:746CrossRefGoogle Scholar
  49. 49.
    Vidhate S, Innocentini-Mei L, D’Souza NA (2012) Polym Eng Sci 52:1367CrossRefGoogle Scholar
  50. 50.
    Sridhar V, Lee I, Chun HH, Park H (2013) Exp Polym Lett 7:320CrossRefGoogle Scholar
  51. 51.
    Kunioka M, Tamaki A, Doi Y (1989) Macromolecules 22:694CrossRefGoogle Scholar
  52. 52.
    Avrami M (1939) J Chem Phys 7:1103CrossRefGoogle Scholar
  53. 53.
    Avrami M (1940) J Chem Phys 8:212CrossRefGoogle Scholar
  54. 54.
    Avrami M (1941) J Chem Phys 9:177CrossRefGoogle Scholar
  55. 55.
    De Santis F, Pantani R (2013) J Therm Anal Calorim 112:1481CrossRefGoogle Scholar
  56. 56.
    Iannace S, Nicolais L (1997) J Appl Polym Sci 64:911CrossRefGoogle Scholar
  57. 57.
    Fabra MJ, Lopez-Rubio A, Lagaron JM (2013) Food Hydrocoll 32:106CrossRefGoogle Scholar
  58. 58.
    Ambrosio-Martín J, Gorrasi G, Lopez-Rubio A, Fabra MJ, Cabedo L, Lopez-Manchado MA, Lagaron JM (2014) J Appl Polym Sci 132:42101Google Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Jesús Ambrosio-Martin
    • 1
  • María José Fabra
    • 1
  • Amparo López-Rubio
    • 1
  • Giuliana Gorrasi
    • 2
  • Andrea Sorrentino
    • 3
  • Jose M. Lagaron
    • 1
    Email author
  1. 1.Novel Materials and Nanotechnology GroupIATA-CSICPaternaSpain
  2. 2.Department of Industrial EngineeringUniversity of SalernoFiscianoItaly
  3. 3.Institute for Polymers, Composites and Biomaterials (IPCB)National Research Council (CNR)PorticiItaly

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