The Effects of Pre-evaporation Time on the Structure and Performance of Na-Lignosulfonate/PVA Composite Films

Year 2025, Volume: 29 Issue: 5, 580 - 591, 27.10.2025

Emir Erişir

https://doi.org/10.16984/saufenbilder.1750450

Abstract

Lignin, an abundant renewable biopolymer in nature, contains specific structural limitations affecting its application strategies. So, a favoured strategy is to use it into the manufacturing of composite materials with other natural or synthetic polymers. This study examines the impact of controlled accelerated solvent removal (pre-evaporation), a subject that is still not thoroughly explored, on the structural, morphological, and thermal characteristics of Na-lignosulfonate (LS) and polyvinyl alcohol (PVA) composite films. Aqueous solutions containing LS, PVA, glycerol and urea were formulated for the casting of composite films. A pre-evaporation at 85-90 °C for 0 to 240 min was employed to solution enhancing its concentration prior to being poured into moulds. The 13C-NMR and FTIR used for structural characterisation validated the specific aromatic and aliphatic structure of LS. FTIR analysis identified interactions between LS and PVA in the films, indicating changes in the ether bond peaks (~1039 cm⁻¹). TGA demonstrated that LS enhanced the thermal stability of the composites and facilitated carbonisation above 450°C. Examination by SEM of the composite films indicated that the pre-evaporation duration significantly affected the morphology. A 5–14% decrease in film thickness and an increase in pore size and number, particularly on the exposed surface, were observed, but the change did not occur uniformly. LS/PVA films were effectively produced without internal stress during pre-evaporation durations of up to 150 min. At times exceeding 150 min, excessive solvent loss and increased solution viscosity resulted in significant morphological defects such as internal stresses, large pores, and structural integrity failure, leading film casting impossible at 240 min. The study determined that the 150 min pre-evaporation procedure is an essential limit for the production of composite films from these polymers. The results obtained are crucial for improving the processing parameters of lignin-based composites intended for packaging or carbon precursor applications.

Keywords

Sodium lignosulfonate , Lignin , Polyvinyl alcohol , Film , Solvent removal

References

• H. Chung, N. R. Washburn, “Extraction and types of lignin,” in Lignin in Polymer Composites, O. Faruk and M. Sain, Eds. Oxford, UK: Elsevier Inc., pp. 13-25, 2016.
• Y. Lei, A. H. Alshareef, W. Zhao, S. Inal, “Laser-scribed graphene electrodes derived from lignin for biochemical sensing,” ACS Applied Nano Materials, vol. 3, no. 2, pp. 1166-1174, 2020.
• Y. Lei, W. Zhao, Y. Zhu, U. Buttner, X. Dong, H. N. Alshareef, “Three-dimensional Ti3C2T x MXene-Prussian blue hybrid microsupercapacitors by water lift-off lithography,” ACS Nano, vol. 16, no. 2, pp. 1974-1985, 2022.
• C. Lee, S. Jeong, Y. Kwon, J. Lee, S. Cho, B. Shin, “Fabrication of laser-induced graphene-based multifunctional sensing platform for sweat ion and human motion monitoring,” Sensors and Actuators A: Physical, vol. 334, p. 113320, 2021.
• Y. Lin, Q. Zhang, Y. Deng, Q. Wu, X. P. Ye, S. Wang, G. Fang, “Fabricating graphene and nanodiamonds from lignin by femtosecond laser irradiation,” ACS Omega, vol. 6, no. 49, pp. 33995-34002, 2021.
• F. Mahmood, C. Zhang, Y. Xie, D. Stalla, J. Lin, C. Wan, “Transforming lignin into porous graphene via direct laser writing for solid-state supercapacitors,” RSC Advances, vol. 9, pp. 22713-22720, 2019.
• L. Meng, S. Chirtes, X. Liu, M. Eriksson, W. C. Mak, “A green route for lignin-derived graphene electrodes: A disposable platform for electrochemical biosensors,” Biosensors and Bioelectronics, vol. 218, p. 114742, 2022.
• K. Sinha, L. Meng, Q. Xu, X. Wang, “Laser induction of graphene onto lignin-upgraded flexible polymer matrix,” Materials Letters, vol. 286, p. 129268, 2021.
• A. Wen, C. Wang, J. Nong, C. Hu, “Rapid construction of robust and hydrophilic lignin-derived laser-induced graphene electrodes using PVA-free dopants,” Carbon, vol. 232, p. 119767, 2025.
• J. Du, J. Guo, Q. Zhu, J. Guo, J. Gu, Y. Wu, L. Ren, S. Yang, J. Jiang, “Enhancement of polyvinyl alcohol-based films by chemically modified lignocellulosic nanofibers derived from bamboo shoot shells,” Polymers, vol. 17, no. 11, p. 1571, 2025.
• S. G. Jin, “Production and application of biomaterials based on polyvinyl alcohol (PVA) as wound dressing,” Chemistry–An Asian Journal, vol. 17, no. 21, p. e202200595, 2022.
• R. Nagarkar, J. Patel, “Polyvinyl alcohol: A comprehensive study,” Acta Scientific Pharmaceutical Sciences, vol. 3, no. 4, pp. 34-44, 2019.
• R. El Hage, N. Brosse, L. Chrusciel, C. Sanchez, P. Sannigrahi, A. Ragauskas, “Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus,” Polymer Degradation and Stability, vol. 94, no. 10, pp. 1632-1638, 2009.
• I. Korbag, S. Mohamed Saleh, “Studies on the formation of intermolecular interactions and structural characterization of polyvinyl alcohol/lignin film,” International Journal of Environmental Studies, vol. 73, no. 2, pp. 226-235, 2016.
• L. Yang, D. Wang, D. Zhou, Y. Zhang, T. Yang, “Isolation and further structural characterization of lignins from the valonea of Quercus variabilis,” International Journal of Biological Macromolecules, vol. 97, pp. 164-172, 2017.
• Z. Xia, L. G. Akim, D. S. Argyropoulos, “Quantitative 13C NMR analysis of lignins with internal standards,” Journal of Agricultural and Food Chemistry, vol. 49, no. 8, pp. 3573-3578, 2001.
• P. Phansamarng, A. Bacchus, F. H. Pour, C. Kongvarhodom, P. Fatehi, “Cationic lignin incorporated polyvinyl alcohol films for packaging applications,” Industrial Crops and Products, vol. 221, p. 119217, 2024.
• S. M. Nasef, A. Sayed, G. A. Mahmoud, “Comparative study of lignin and sodium lignosulfonate extracted from irradiated and non-irradiated sawdust wastes,” Radiation Physics and Chemistry, vol. 214, p. 111302, 2024.
• O. Y. Abdelaziz, S. Meier, J. Prothmann, C. Turner, A. Riisager, C. P. Hulteberg, “Oxidative depolymerisation of lignosulphonate lignin into low-molecular-weight products with Cu–Mn/δ-Al2O3,” Topics in Catalysis, vol. 62, pp. 639-648, 2019.
• N. S. Abdelrahman, E. Galiwango, A. H. Al-Marzouqi, E. Mahmoud, “Sodium lignosulfonate: A renewable corrosion inhibitor extracted from lignocellulosic waste,” Biomass Conversion and Biorefinery, vol. 14, no. 6, pp. 7531-7541, 2024.
• J. Ou, J. Zhao, “Modification of sodium lignosulfonate and evaluation of its potential use as detergent builders,” Journal of Wood Chemistry and Technology, vol. 37, no. 2, pp. 99-109, 2017.
• E. S. Wibowo, B. D. Park, “Chemical and thermal characteristics of ion-exchanged lignosulfonate,” Molecules, vol. 28, no. 6, p. 2755, 2023.
• X. Li, Y. Liu, X. Ren, “Transparent and ultra-tough PVA/alkaline lignin films with UV shielding and antibacterial functions,” International Journal of Biological Macromolecules, vol. 216, pp. 86-94, 2022.
• E. Apaydın Varol, Ü. Mutlu, “TGA-FTIR analysis of biomass samples based on the thermal decomposition behavior of hemicellulose, cellulose, and lignin,” Energies, vol. 16, no. 9, p. 3674, 2023.
• H. E. Mahmud, A. Kassim, Z. Zainal, W. M. M. Yunus, “Fourier transform infrared study of polypyrrole–poly (vinyl alcohol) conducting polymer composite films: evidence of film formation and characterization,” Journal of Applied Polymer Science, vol. 100, no. 5, pp. 4107-4113, 2006.
• H. S. Mansur, R. L. Oréfice, A. A. Mansur, “Characterization of poly (vinyl alcohol)/poly (ethylene glycol) hydrogels and PVA-derived hybrids by small-angle X-ray scattering and FTIR spectroscopy,” Polymer, vol. 45, no. 21, pp. 7193-7202, 2004.
• L. Su, G. Fang, “Characterization of cross-linked alkaline lignin/poly (vinyl alcohol) film with a formaldehyde cross-linker,” BioResources, vol. 9, no. 3, pp. 4477-4488, 2014.
• P. B. Bhargav, V. M. Mohan, A. K. Sharma, V. N. Rao, “Structural, electrical and optical characterization of pure and doped poly (vinyl alcohol)(PVA) polymer electrolyte films,” International Journal of Polymeric Materials and Polymeric Biomaterials, vol. 56, no. 6, pp. 579-591, 2007.
• H. S. Mansur, C. M. Sadahira, A. N. Souza, A. A. Mansur, “FTIR spectroscopy characterization of poly (vinyl alcohol) hydrogel with different hydrolysis degree and chemically crosslinked with glutaraldehyde,” Materials Science and Engineering: C, vol. 28, no. 4, pp. 539-548, 2008.
• S. Akhter, K. Allan, D. Buchanan, J. A. Cook, A. Campion, J. M. White, “XPS and IR study of X-ray induced degradation of PVA polymer film,” Applied Surface Science, vol. 35, no. 2, pp. 241-258, 1988.
• L. Su, Z. Xing, D. Wang, G. Xu, S. Ren, G. Fang, “Mechanical properties research and structural characterization of alkali lignin/poly (vinyl alcohol) reaction films,” BioResources, vol. 8, no. 3, pp. 3532-3543, 2013.
• M. E. El Moustaqim, A. El Kaihal, M. El Marouani, S. Menlayakhaf, M. Taibi, S. Sebbahi, S. El Hajjaji, F. Kifani-Sahban, “Thermal and thermomechanical analyses of lignin,” Sustainable Chemistry and Pharmacy, vol. 9, pp. 63-68, 2018.
• M. T. Taghizadeh, N. Yeganeh, M. Rezaei, “The investigation of thermal decomposition pathway and products of poly (vinyl alcohol) by TG‐FTIR,” Journal of Applied Polymer Science, vol. 132, no. 25, p. 42117, 2015.
• Y. W. Chua, H. Wu, Y. Yu, “Interactions between low-and high-molecular-weight portions of lignin during fast pyrolysis at low temperatures,” Energy & Fuels, vol. 33, no. 11, pp. 11173-11180, 2019.
• J. Li, M. H. P. de Heer Kloots, G. van Ewijk, D. J. van Dijken, W. M. de Vos, J. van der Gucht, “Evaporation-induced polyelectrolyte complexation: The role of base volatility and cosolvents,” Langmuir, vol. 40, no. 5, pp. 2531-2542, 2024.
• S. Feng, D. Ma, Y. Qiu, L. Duan, “Deep insights into the viscosity of small molecular solutions for organic light-emitting diodes,” RSC Advances, vol. 8, no. 8, pp. 4153-4161, 2018.
• G. Xu, S. Ren, D. Wang, L. Su, G. Fang, “Fabrication and properties of alkaline lignin/poly (vinyl alcohol) blend membranes,” BioResources, vol. 8, no. 2, pp. 2510-2520, 2013.
• S. Kubo, J. F. Kadla, “The formation of strong intermolecular interactions in immiscible blends of poly(vinyl alcohol) (PVA) and lignin,” Biomacromolecules, vol. 4, no. 3, pp. 561-567, 2003.