Journal of Materials Science

, Volume 54, Issue 10, pp 8034–8046 | Cite as

Sodium alginate solutions: correlation between rheological properties and spinnability

  • Andrea Dodero
  • Silvia Vicini
  • Marina Alloisio
  • Maila CastellanoEmail author


In the present work, different sodium alginates were used to prepare nanofibrous mats by means of electrospinning technique. Firstly, a molecular characterization of each sample was carried out: the molecular mass and the composition, i.e. mannuronic/guluronic acid ratio, were determined using the Mark–Houwink–Sakurada relation and FTIR spectroscopy, respectively. Afterwards, the polyelectrolyte nature and the characteristic concentration regimes of each alginate were studied through rheological tests. The results indicated that both the molecular mass and the composition strongly influence the properties of the polymer in solution; in particular, long chains and the predominance of guluronic moiety lead to a marked polyelectrolyte behaviour. Subsequently, in order to obtain a good spinnability, polyethylene oxide and Triton X-100 were added to alginate-based solutions. The resulting solutions were carefully characterized by a rheological point of view; the viscosity, viscoelasticity, thixotropy and thermal stability were investigated and correlated with their capability of being electrospun. Two different set-ups were used for electrospinning: one consisted in a dry collector and the other one in a wet collector (immersed in a collecting solution). The morphology of the membranes was characterized through scanning electron microscopy; moreover, thermogravimetric analysis was performed in order to study the final composition and the thermal degradation. The preliminary results indicated that the membrane obtained using guluronic-rich alginate and the wet-collector system is composed of only sodium alginate and characterized by thin fibres and a high porosity, which could make it suitable for pharmaceutical and biomedical applications.


Compliance with ethical standards

Conflict of interest

The authors declared that they have no conflict of interest.


  1. 1.
    Kloareg B, Quatrano RS (1988) Structure of the cell walls of marine algae and ecophysiological functions of the matrix polysaccharides. Oceanogr Mar Biol Ann Rev 26:259–315Google Scholar
  2. 2.
    Masuelli MA, Illanes CO (2014) Review of the characterization of sodium alginate by intrinsic viscosity measurements. Comparative analysis between conventional and single point methods. Int J BioMater Sci Eng 1(1):1–11Google Scholar
  3. 3.
    Campos-Vallette MM, Chandía NP, Clavijo E et al (2010) Characterization of sodium alginate and its block fractions by surface-enhanced Raman spectroscopy. J Raman Spectrosc 41:758–763. Google Scholar
  4. 4.
    Viswanathan S, Nallamuthu T (2007) Extraction of sodium alginate from selected seaweeds and their physiochemical and biochemical properties. Int J Innov Res Sci Eng Technol 3(4):10998–11003Google Scholar
  5. 5.
    Sellimi S, Younes I, Ayed HB et al (2015) Structural, physicochemical and antioxidant properties of sodium alginate isolated from a Tunisian brown seaweed. Int J Biol Macromol 72:1358–1367. CrossRefGoogle Scholar
  6. 6.
    Stephen AM, Phillips GO, Williams PA (2006) Food polysaccharides and their applications, 2nd edn. CRC/Taylor & Francis, Boca RatonGoogle Scholar
  7. 7.
    Thakur VK, Thakur MK (2015) Handbook of polymers for pharmaceutical technologies, vol 1. John Wiley & Sons, New YorkCrossRefGoogle Scholar
  8. 8.
    Fu S, Thacker A, Sperger DM et al (2011) Relevance of rheological properties of sodium alginate in solution to calcium alginate gel properties. AAPS PharmSciTech 12:453–460. CrossRefGoogle Scholar
  9. 9.
    Sachan NK (2009) Sodium alginate: the wonder polymer for controlled drug delivery. J Pharm Res 2(8):1191–1199Google Scholar
  10. 10.
    Dodero A, Williams R, Gagliardi S et al (2018) Characterization of hyaluronic acid by dynamic light scattering and rheological techniques. In: AIP conf proc, vol 1981, p 020184.
  11. 11.
    Arvidson SA, Rinehart BT, Gadala-Maria F (2006) Concentration regimes of solutions of levan polysaccharide from Bacillus sp. Carbohydr Polym 65:144–149. CrossRefGoogle Scholar
  12. 12.
    Graessley WW (1980) Polymer chain dimensions and the dependence of viscoelastic properties on concentration, molecular weight and solvent power. Polymer 21:258–262. CrossRefGoogle Scholar
  13. 13.
    Förster S, Schmidt M, Antonietti M (1990) Static and dynamic light scattering by aqueous polyelectrolyte solutions: effect of molecular weight, charge density and added salt. Polymer 31:781–792. CrossRefGoogle Scholar
  14. 14.
    Cheng R (1997) On the concentration regimes of a flexible-chain polymer solution. Macromol Symp 124:27–34. CrossRefGoogle Scholar
  15. 15.
    Rubinstein M, Colby RH, Dobrynin AV (1994) Dynamics of semidilute polyelectrolyte solutions. Phys Rev Lett 73:2776–2779. CrossRefGoogle Scholar
  16. 16.
    Dobrynin AV, Colby RH, Rubinstein M (1995) Scaling theory of polyelectrolyte solutions. Macromolecules 28:1859–1871. CrossRefGoogle Scholar
  17. 17.
    Higgins JS (1979) Polymer conformation and dynamics. Treatise Mater Sci Technol 15:381–422CrossRefGoogle Scholar
  18. 18.
    Nierlich M, Boue F, Lapp A, Oberthür R (1985) Characteristic lengths and the structure of salt free polyelectrolyte solutions. A small angle neutron scattering study. Colloid Polym Sci 263:955–964. CrossRefGoogle Scholar
  19. 19.
    Graessley WW (1974) The entanglement concept in polymer rheology. Springer, BerlinCrossRefGoogle Scholar
  20. 20.
    Graessley WW, Raju VR (1984) Some rheological properties of solutions and blends of hydrogenated polybutadiene. J Polym Sci Polym Symp 71:77–93. CrossRefGoogle Scholar
  21. 21.
    Xue J, Xie J, Liu W, Xia Y (2017) Electrospun nanofibers: new concepts, materials, and applications. Acc Chem Res 50:1976–1987. CrossRefGoogle Scholar
  22. 22.
    Vicini S, Mauri M, Vita S, Castellano M (2018) Alginate and alginate/hyaluronic acid membranes generated by electrospinning in wet conditions: relationship between solution viscosity and spinnability. J Appl Polym Sci 135(25):46390. CrossRefGoogle Scholar
  23. 23.
    Go D (2003) Rheology of aqueous solutions of food additives: effect of concentration, temperature and blending. J Food Eng 56:387–392CrossRefGoogle Scholar
  24. 24.
    Rinaudo M, Graebling D (1986) On the viscosity of sodium alginates in the presence of external salt. Polym Bull 15:253–256. CrossRefGoogle Scholar
  25. 25.
    Brummer R, Griebenow M, Hetzel F et al (2000) Rheological swing test to predict the temperature stability of cosmetic emulsions. In: Conf proc XXIst IFSCC international congress, Berlin, pp 476–484Google Scholar
  26. 26.
    Chandia NP, Matsuhiro B, Vasquez AE (2001) Alginic acids in Lessonia trabeculata: characterization by formic acid hydrolysis and FT-IR spectroscopy. Carbohydr Polym 46:81–87. CrossRefGoogle Scholar
  27. 27.
    Chandía NP, Matsuhiro B, Mejías E, Moenne A (2004) Alginic acids in Lessonia vadosa: partial hydrolysis and elicitor properties of the polymannuronic acid fraction. J Appl Phycol 16:127–133. CrossRefGoogle Scholar
  28. 28.
    Lima AMF, Soldi V, Borsali R (2009) Dynamic light scattering and viscosimetry of aqueous solutions of pectin, sodium alginate and their mixtures: effects of added salt, concentration, counterions, temperature and chelating agent. J Braz Chem Soc 20:1705–1714. CrossRefGoogle Scholar
  29. 29.
    Masuelli MA (2014) Mark–Houwink parameters for aqueous-soluble polymers and biopolymers at various temperatures. J Polym Biopolym Phys Chem 2(2):37–43Google Scholar
  30. 30.
    Mancini M, Moresi M, Sappino F (1996) Rheological behaviour of aqueous dispersions of algal sodium alginates. J Food Eng 28:283–295. CrossRefGoogle Scholar
  31. 31.
    Pamies R, Schmidt RR, del Martínez MCL, de la Torre JG (2010) The influence of mono and divalent cations on dilute and non-dilute aqueous solutions of sodium alginates. Carbohydr Polym 80:248–253. CrossRefGoogle Scholar
  32. 32.
    McCrackin FL (1987) Relationship of intrinsic viscosity of polymer solutions to molecular weight. Polymer 28:1847–1850. CrossRefGoogle Scholar
  33. 33.
    Abdel-Azim A-AA, Atta AM, Farahat MS, Boutros WY (1998) Determination of intrinsic viscosity of polymeric compounds through a single specific viscosity measurement. Polymer 39:6827–6833. CrossRefGoogle Scholar
  34. 34.
    Kirkwood JG, Riseman J (1948) The intrinsic viscosities and diffusion constants of flexible macromolecules in solution. J Chem Phys 16:565–573. CrossRefGoogle Scholar
  35. 35.
    Clementi F, Mancini M, Moresi M (1998) Rheology of alginate from Azotobacter vinelandii in aqueous dispersions. J Food Eng 36:51–62. CrossRefGoogle Scholar
  36. 36.
    Hecht H, Srebnik S (2016) Structural characterization of sodium alginate and calcium alginate. Biomacromolecules 17:2160–2167. CrossRefGoogle Scholar
  37. 37.
    McKee MG, Hunley MT, Layman JM, Long TE (2006) Solution rheological behavior and electrospinning of cationic polyelectrolytes. Macromolecules 39:575–583. CrossRefGoogle Scholar
  38. 38.
    Colby RH (2010) Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions. Rheol Acta 49:425–442. CrossRefGoogle Scholar
  39. 39.
    Kitano T, Taguchi A, Noda I, Nagasawa M (1980) Conformation of polyelectrolyte in aqueous solution. Macromolecules 13:57–63. CrossRefGoogle Scholar
  40. 40.
    Gennes PGD, Pincus P, Velasco RM, Brochard F (1976) Remarks on polyelectrolyte conformation. J Phys 37:1461–1473. CrossRefGoogle Scholar
  41. 41.
    Morris ER, Cutler AN, Ross-Murphy SB et al (1981) Concentration and shear rate dependence of viscosity in random coil polysaccharide solutions. Carbohydr Polym 1:5–21. CrossRefGoogle Scholar
  42. 42.
    Morris ER, Rees DA, Welsh EJ (1980) Conformation and dynamic interactions in hyaluronate solutions. J Mol Biol 138:383–400. CrossRefGoogle Scholar
  43. 43.
    Cheung MS, Klimov D, Thirumalai D (2005) Molecular crowding enhances native state stability and refolding rates of globular proteins. Proc Natl Acad Sci 102:4753–4758. CrossRefGoogle Scholar
  44. 44.
    Ferry JD (1983) Introduction to polymer viscoelasticity, John J. Aklonis and William J. MacKnight. Wiley, New YorkGoogle Scholar
  45. 45.
    Tiwari SK, Venkatraman SS (2012) Importance of viscosity parameters in electrospinning: of monolithic and core–shell fibers. Mater Sci Eng C 32:1037–1042. CrossRefGoogle Scholar
  46. 46.
    Nezarati RM, Eifert MB, Cosgriff-Hernandez E (2013) Effects of humidity and solution viscosity on electrospun fiber morphology. Tissue Eng Part C Methods 19:810–819. CrossRefGoogle Scholar
  47. 47.
    Drew C, Wang X, Samuelson LA, Kumar J (2003) The effect of viscosity and filler on electrospun fiber morphology. J Macromol Sci Part A 40:1415–1422. CrossRefGoogle Scholar
  48. 48.
    Ma J, Lin Y, Chen X et al (2014) Flow behavior, thixotropy and dynamical viscoelasticity of sodium alginate aqueous solutions. Food Hydrocoll 38:119–128. CrossRefGoogle Scholar
  49. 49.
    de Gennes PG (1971) Reptation of a polymer chain in the presence of fixed obstacles. J Chem Phys 55:572–579. CrossRefGoogle Scholar
  50. 50.
    Feldman D (1986) The theory of polymer dynamics, by M. Doi and S. F. Edwards. The Clarendon Press, Oxford University Press, New YorkGoogle Scholar
  51. 51.
    Mewis J, Wagner NJ (2009) Thixotropy. Adv Colloid Interface Sci 147–148:214–227. CrossRefGoogle Scholar
  52. 52.
    Benchabane A, Bekkour K (2008) Rheological properties of carboxymethyl cellulose (CMC) solutions. Colloid Polym Sci 286:1173. CrossRefGoogle Scholar
  53. 53.
    Kasaai MR, Charlet G, Arul J (2000) Master curve for concentration dependence of semi-dilute solution viscosity of chitosan homologues: the Martin equation. Food Res Int 33:63–67. CrossRefGoogle Scholar
  54. 54.
    Ferry JD (1980) Viscoelastic properties of polymers, 3rd edn. John Wiley & Sons, New YorkGoogle Scholar
  55. 55.
    André V, Willenbacher N, Debus H et al (2003) Prediction of emulsion stability: facts and myth. In: Cosmetics and toiletries manufacture worldwide. Aston Publishing Group, Auckland, pp 102–109Google Scholar
  56. 56.
    Lee YJ, Shin DS, Kwon OW et al (2007) Preparation of atactic poly(vinyl alcohol)/sodium alginate blend nanowebs by electrospinning. J Appl Polym Sci 106:1337–1342. CrossRefGoogle Scholar
  57. 57.
    Fang D, Liu Y, Jiang S et al (2011) Effect of intermolecular interaction on electrospinning of sodium alginate. Carbohydr Polym 85:276–279. CrossRefGoogle Scholar
  58. 58.
    Alborzi S, Lim L-T, Kakuda Y (2010) Electrospinning of sodium alginate-pectin ultrafine fibers. J Food Sci 75:C100–C107. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Dipartimento di Chimica e Chimica IndustrialeUniversità degli Studi di GenovaGenoaItaly

Personalised recommendations