Utilization of freeze thaw process for polyvinyl alcohol/sodium alginate (PVA/SA) hydrogel composite


  • Rapeepan MUANGSRI Department of Materials and Textile Technology, Faculty of Science and Technology, Thammasat University, Pathumtani, Thailand
  • Piyachat CHUYSINUAN Laboratory of Organic Synthesis, Chulabhorn Research Institute, Bangkok, Thailand
  • Thanyaluck THANYACHAROEN Laboratory of Organic Synthesis, Chulabhorn Research Institute, Bangkok, Thailand
  • Supanna TECHASAKUL Laboratory of Organic Synthesis, Chulabhorn Research Institute, Bangkok, Thailand
  • Pongpat SUKHAVATTANAKUL Department of Materials and Textile Technology, Faculty of Science and Technology, Thammasat University, Pathumtani, Thailand
  • Sarute UMMARTYOTIN Department of Materials and Textile Technology, Faculty of Science and Technology, Thammasat University, Pathumtani, Thailand




Hydrogel, Composite, Polyvinyl alcohol, Sodium alginate, Freeze thaw


Polyvinyl alcohol/sodium alginate (PVA/SA) hydrogel was successfully prepared by freeze thaw process. Without crosslinking agent, hydrogel was formed by using 3, 5 and 7 consecutive cycles of freeze thaw. Hydrogel can be formed by hydrogen bonding formation between OH-group of sodium alginate and polyvinyl alcohol throughout network. Scanning electron microscope reported that microstructure of hydrogel was well packed. The interconnect porosity was also observed. Differential scanning calorimetry exhibited that two exothermic peaks at temperature of 110℃ and 225℃ were observed due to evaporation of water molecule and melting temperature of hydrogel, respectively. The swelling behavior was rapidly increased within initial stage and then it was dimensionally stable. With low sodium alginate content, tensile strength was slightly superior, whereas low in vitro degradation behavior was observed. It was remarkable to note that polyvinyl alcohol/sodium alginate (PVA/SA) hydrogel exhibited outstanding properties for being as a medical material.


Download data is not yet available.


L. Wang, X. Guo, J. Chen, Z. Zhen, B. Cao, W. Wan, Y. Dou, H. Pan, F. Xu, Z. Zhang, J. Wang, D. Li, Q. Guo, Q. Jiang, Y. Du, J. Yu, B.C. Heng, Q. Han, and Z. Ge, "Key considerations on the development of biodegradable biomaterials for clinical translation of medical devices: With cartilage repair products as an example," Bioactive Materials, 2021.

S. Zhang, D. Han, Z. Ding, X. Wang, D. Zhao, Y. Hu, and X. Xiao, "Fabrication and characterization of one interpenetrating network hydrogel based on sodium alginate and polyvinyl alcohol," Journal of Wuhan University of Technology, vol. 34, no. 3, pp. 744-751, 2019.

S. Jiang, S. Liu, and W. Feng, "PVA hydrogel properties for biomedical application," Journal of the Mechanical Behavior of Biomedical Materials, vol. 4, no. 7, pp. 1228-1233, 2011.

X. Huang, J. Li, J. Luo, Q. Gao, A. Mao, and J. Li, "Research progress on double-network hydrogels," Materials Today Communications, vol. 29, p. 102757, 2021.

W. Wu, L. Sheng, F. Tang, A. Zhang, and J. Liu, "A system dynamics model of green innovation and policy simulation with an application in Chinese manufacturing industry," Sustainable Production and Consumption, vol. 28, pp. 987-1005, 2021.

G. Granco, M. Caldas, J. Bergtold, J.L. Heier Stamm, M. Mather, M. Sanderson, M. Daniels, A. Sheshukov, D. Haukos, and S. Ramsey, "Local environment and individuals’ beliefs: The dynamics shaping public support for sustainability policy in an agricultural landscape," Journal of Environmental Management, vol. 301, p.113776, 2022.

M. Afshar, G. Dini, S. Vaezifar, M. Mehdikhani, and B. Movahedi, "Preparation and characterization of sodium alginate/ polyvinyl alcohol hydrogel containing drug-loaded chitosan nanoparticles as a drug delivery system," Journal of Drug Delivery Science and Technology, vol. 56, p. 101530, 2020.

C. C. DeMerlis, and D. R. Schoneker, "Review of the oral toxicity of polyvinyl alcohol (PVA)," Food and Chemical Toxicology, vol 41, no. 3, pp. 319-326, 2003.

R.V. Kulkarni, V. Sreedhar, S. Mutalik, and C.M. Setty, B. Sa, "Interpenetrating network hydrogel membranes of sodium alginate and poly(vinyl alcohol) for controlled release of prazosin hydrochloride through skin," International Journal of Biological Macromolecules, vol. 47, no. 4, pp. 520-527, 2020.

V. S. Ghorpade, R. J. Dias, K. K. Mali, and S. I. Mulla, "Citric acid crosslinked carboxymethylcellulose-polyvinyl alcohol hydrogel films for extended release of water soluble basic drugs," Journal of Drug Delivery Science and Technology, vol. 52, p. 421-430, 2019.

X. Jiang, N. Xiang, H. Zhang, Y. Sun, Z. Lin, and L. Hou, "Preparation and characterization of poly(vinyl alcohol)/ sodium alginate hydrogel with high toughness and electric conductivity," Carbohydrate Polymers, vol. 186, pp. 377-383, 2018.

F. Kong, C. Fan, Y. Yang, B. H. Lee, and K. Wei, "5-hydroxy-methylfurfural-embedded poly (vinyl alcohol)/sodium alginate hybrid hydrogels accelerate wound healing," International Journal of Biological Macromolecules, vol. 138, pp. 933-949, 2019.

K. Bialik-Wąs, K. Pluta, D. Malina, M. Barczewski, K. Malarz, and A. Mrozek-Wilczkiewicz, "Advanced SA/PVA-based hydrogel matrices with prolonged release of Aloe vera as promising wound dressings," Materials Science and Engineering: C, vol. 120, p. 111667, 2021.

R. Ricciardi, F. Auriemma, C. De Rosa, and F. Lauprêtre, X-ray diffraction analysis of poly(vinyl alcohol) hydrogels, obtained by freezing and thawing techniques," Macromolecules, vol. 37, no. 5, pp. 1921-1927, 2004.

S. Hua, H. Ma, X. Li, H. and Yang, A. Wang, "pH-sensitive sodium alginate/poly(vinyl alcohol) hydrogel beads prepared by combined Ca2+ crosslinking and freeze-thawing cycles for controlled release of diclofenac sodium," International Journal of Biological Macromolecules, vol. 46, no. 5, pp. 517-523, 2010.

A. Timofejeva, M. D'Este, and D. Loca, "Calcium phosphate/ polyvinyl alcohol composite hydrogels: A review on the freeze- thawing synthesis approach and applications in regenerative medicine," European Polymer Journal, vol, 95, pp. 547-565, 2017.

L. Ding, S. Song, L. Chen, J. Shi, B. Zhao, G. Teng, and J. Zhang, "A freeze-thawing method applied to the fabrication of 3-d curdlan/polyvinyl alcohol hydrogels as scaffolds for cell culture," International Journal of Biological Macromolecules, vol. 174, pp. 101-109, 2021.

J. M. Flórez-Castillo, J. L. Ropero-Vega, M. Perullini, and M. Jobbágy," Biopolymeric pellets of polyvinyl alcohol and alginate for the encapsulation of Ib-M6 peptide and its antimicrobial activity against E. coli," Heliyon, vol. 5, no. 6 p. e01872, 2019.

J. O. Kim, J. K. Park, J. H. Kim, S. G. Jin, C. S. Yong, D. X. Li, J. Y. Choi, J. S. Woo, B. K. Yoo, W. S. Lyoo, J. -A. Kim, and H. -G. Choi, "Development of polyvinyl alcohol–sodium alginate gel-matrix-based wound dressing system containing nitrofurazone," International Journal of Pharmaceutics vol. 359, no. 1, pp. 79-86, 2008.

R. Ma, Y. Wang, H. Qi, C. Shi, G. Wei, L. Xiao, Z. Huang, S. Liu, H. Yu, C. Teng, H. Liu, V. Murugadoss, J. Zhang, Y. Wang, and Z. Guo, Nanocomposite sponges of sodium alginate/ graphene oxide/polyvinyl alcohol as potential wound dressing: In vitro and in vivo evaluation," Composites Part B: Engineering, vol. 167, pp. 396-405, 2019.

E. A. Kamoun, E. -R. S. Kenawy, T. M. Tamer, M. A. El-Meligy, and M. S. Mohy Eldin," Poly (vinyl alcohol)-alginate physically crosslinked hydrogel membranes for wound dressing applications: Characterization and bio-evaluation," Arabian Journal of Chemistry, vol. 8, no. 1, pp. 38-47, 2015.

A. Roy, J. Bajpai, and A. K. Bajpai, Dynamics of controlled release of chlorpyrifos from swelling and eroding biopolymeric microspheres of calcium alginate and starch," Carbohydrate Polymers, vol. 76, no. 2, pp. 222-231, 2009.

A. Chhatri, J. Bajpai, A. K. Bajpai, S. S. Sandhu, N. Jain, and J. Biswas, Cryogenic fabrication of savlon loaded macroporous blends of alginate and polyvinyl alcohol (PVA). Swelling, deswelling and antibacterial behaviors," Carbohydrate Polymers, vol. 83, no. 2, pp. 876-882, 2011.

F. Boran, "The influence of freeze-thawing conditions on swelling and long-term stability properties of poly(vinyl alcohol) hydrogels for controlled drug release," Polymer Bulletin, vol. 78, no. 12, pp. 7369-7387, 2021.

M. Zhang, G. Wang, D. Wang, Y. Zheng, Y. Li, W. Meng, X. Zhang, F. Du, and S. Lee," Ag@MOF-loaded chitosan nano-particle and polyvinyl alcohol/sodium alginate/chitosan bilayer dressing for wound healing applications," International Journal of Biological Macromolecules, vol. 175, pp. 481-494, 2021.

R. Wang, Q. Wang, and L. Li, Evaporation behaviour of water and its plasticizing effect in modified poly(vinyl alcohol) systems," Polymer International, vol. 52, no. 12, pp. 1820-1826, 2003.

Z. Lutfi, Q. Kalim, A. Shahid, and A. Nawab, "Water chestnut, rice, corn starches and sodium alginate. A comparative study on the physicochemical, thermal and morphological characteristics of starches after dry heating," International Journal of Biological Macromolecules, vol. 184, pp. 476-482, 2021.

Z. Yu, J. Liu, H. He, S. Ma, and J. Yao, Flame-retardant PNIPAAm/sodium alginate/polyvinyl alcohol hydrogels used for fire-fighting application: Preparation and characteristic evaluations," Carbohydrate Polymers, vol. 255, p. 117485, 2021.

X. Gao, C. Guo, J. Hao, Z. Zhao, H. Long, M. Li, "Adsorption of heavy metal ions by sodium alginate based adsorbent-a review and new perspectives," International Journal of Biological Macromolecules, vol. 164, pp. 4423-4434, 2020.

S. Ahmad, K. Manzoor, R. Purwar, and S. Ikram, "Morphological and swelling potential evaluation of moringa oleifera gum/ poly(vinyl alcohol) hydrogels as a superabsorbent," ACS Omega, vol. 5, no. 29, pp. 17955-17961, 2020.

O. Hu, G. Chen, J. Gu, J. Lu, J. Zhang, X. Zhang, L. Hou, and X. Jiang, "A facile preparation method for anti-freezing, tough, transparent, conductive and thermoplastic poly(vinyl alcohol)/ sodium alginate/glycerol organohydrogel electrolyte," International Journal of Biological Macromolecules, vol. 164, pp. 2512-2523, 2020.

M. Mousa, and Y. Dong, "The role of nanoparticle shapes and structures in material characterisation of polyvinyl alcohol (PVA) bionanocomposite films," Polymers 12(2) (2020) 264.

S. Kouser, S. Sheik, A. Prabhu, G. K. Nagaraja, K. Prashantha, J. N. D'Souza, M. K. Navada, and D. J. Manasa, "Effects of reinforcement of sodium alginate functionalized halloysite clay nanotubes on thermo-mechanical properties and biocompatibility of poly(vinyl alcohol) nanocomposites," Journal of the Mechanical Behavior of Biomedical Materials, vol. 118, p. 104441, 2021.

X. Zhang, Y. Li, Z. Ma, D. He, and H. Li, Modulating degradation of sodium alginate/bioglass hydrogel for improving tissue infiltration and promoting wound healing," Bioactive Materials, vol. 6, no. 11, pp. 3692-3704, 2021.

D. H. Wardhani, H. N. Ulya, A. Rahmawati, T. V. K. Sugiarto, A. C. Kumoro, and N. Aryanti, "Preparation of degraded alginate as a pH-dependent release matrix for spray-dried iron and its encapsulation performances," Food Bioscience, vol. 41, p. 101002, 2021.

F. Cavalieri, F. Miano, P. D'Antona, and G. Paradossi, "Study of gelling behavior of poly(vinyl alcohol)-methacrylate for potential utilizations in tissue replacement and drug delivery," Biomacromolecules, vol. 5, no. 6, pp. 2439-2446, 2004.




How to Cite

R. MUANGSRI, P. CHUYSINUAN, T. THANYACHAROEN, S. TECHASAKUL, P. SUKHAVATTANAKUL, and S. UMMARTYOTIN, “Utilization of freeze thaw process for polyvinyl alcohol/sodium alginate (PVA/SA) hydrogel composite”, J Met Mater Miner, vol. 32, no. 2, pp. 34–41, Jun. 2022.



Original Research Articles

Most read articles by the same author(s)