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Pylypchuk, I. V., Tkachenko, O., Budnyak, T. & Sipponen, M. H. (2025). Beta-Radiation-Resistant Anticorrosion Coatings Based on Lignin. Small Science
Open this publication in new window or tab >>Beta-Radiation-Resistant Anticorrosion Coatings Based on Lignin
2025 (English)In: Small Science, ISSN 2688-4046Article in journal (Refereed) Epub ahead of print
Abstract [en]

As humanity ventures beyond Earth, developing radiation-stable coatings from non-fossil sources becomes essential. Beta radiation can significantly harm materials, making it essential to seek resilient, biobased alternatives to work in corrosive environments and high temperatures. Herein, a novel lignin-based coating demonstrating exceptional beta-radiation resistance and anticorrosion properties is presented. The coatings are applied to copper substrates and exposed to 500 kGy electron beam irradiation in air to evaluate their structural and functional stability under extreme conditions. Spectroscopic, microscopic, and thermogravimetric analyses confirm the structural integrity of the coatings post-irradiation. Anticorrosion efficiencies after irradiation are maintained at 99.6% (H2SO4) and 99.8% (NaCl) for 61 μm thick films, while thinner 9.5 μm films show 86.4% and 85.7% protection in the respective media, with a ≈4% performance drop post-irradiation. Adhesion strength improves from 0.28 to 0.49 MPa after irradiation, and the water contact angle decreases from 74° to 66°, indicating an increase in hydrophilicity. The superior performance is attributed to the aromatic structure of lignin and its thermally triggered cyclization, which renders it stable against chemical chain scission by oxygen radicals formed in atmospheric conditions under radiation exposure. The performance of thicker films in anticorrosion tests is attributed to a reduced penetration of corrosive agents, due to better morphological integrity. These findings demonstrate the viability of lignin-based coatings as radiation-stable and environmentally sustainable solutions for protecting metal surfaces in harsh environments.

Keywords
anticorrosion, beta-particles, coatings, copper, lignin, radiation
National Category
Physical Chemistry
Identifiers
urn:nbn:se:su:diva-246271 (URN)10.1002/smsc.202500007 (DOI)001519557500001 ()2-s2.0-105009442236 (Scopus ID)
Available from: 2025-09-02 Created: 2025-09-02 Last updated: 2025-09-02
Wan, X., Liu, L.-Y., Karaaslan, M. A., Hua, Q., Shen, F., Sipponen, M. H. & Renneckar, S. (2025). Circular poly(ethylene terephthalate) with lignin-based toughening additives. Chemical Engineering Journal, 504, Article ID 158255.
Open this publication in new window or tab >>Circular poly(ethylene terephthalate) with lignin-based toughening additives
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2025 (English)In: Chemical Engineering Journal, ISSN 1385-8947, E-ISSN 1873-3212, Vol. 504, article id 158255Article in journal (Refereed) Published
Abstract [en]

Creating sustainable plastics demands an efficient strategy to reduce the carbon footprint and enhance the circularity of widely used materials. Inspired by the structure of plant cell walls, renewable lignin macromolecules are modified with benzoate ethyl functional groups and combined with semi-crystalline poly(ethylene terephthalate) (PET) at a 10 % weight ratio. This process significantly improves the toughness (+97 %) and strength (+ 56 %) of PET while also reducing greenhouse gas emissions (−17 %) and promoting circularity, outperforming traditional toughening agents. Our in-depth analysis indicates that benzoate ethyl lignin derivatives exhibit improved thermal stability and controllable physical structure. The newly added benzoate ethyl groups are similar to the fundamental units in PET, facilitating the formation of micro-scale particles within the PET matrix and improving their crystallinity and mechanical performance. The resulting composite can be reprocessed at least three times, representing a significant breakthrough in mechanical processing of thermoplastics. Therefore, this study presents a promising approach to utilizing lignin biopolymer and waste PET for advanced materials with positive environmental footprints.

Keywords
Circularity, Lignin, Modification, Poly (ethylene terephthalate), Toughening additives
National Category
Polymer Technologies
Identifiers
urn:nbn:se:su:diva-240034 (URN)10.1016/j.cej.2024.158255 (DOI)001393956700001 ()2-s2.0-85212588274 (Scopus ID)
Available from: 2025-03-03 Created: 2025-03-03 Last updated: 2025-03-03Bibliographically approved
Andersson, M., Pylypchuk, I. V., Alexakis, A. E., Liu, L.-Y. & Sipponen, M. H. (2025). Esterified Lignin Nanoparticles for Targeted Chemical Delivery in Plant Protection. ACS Applied Materials and Interfaces, 17(1), 1931-1941
Open this publication in new window or tab >>Esterified Lignin Nanoparticles for Targeted Chemical Delivery in Plant Protection
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2025 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 17, no 1, p. 1931-1941Article in journal (Refereed) Published
Abstract [en]

There is a growing demand for biobased functional materials that can ensure targeted pesticide delivery and minimize active ingredient loss in the agricultural sector. In this work, we demonstrated the use of esterified lignin nanoparticles (ELNPs) as carriers and controlled-release agents of hydrophobic compounds. Curcumin was selected as a hydrophobic model compound and was incorporated during ELNP fabrication with entrapment efficiencies exceeding 95%. ELNPs presented a sustained release of curcumin over 60 days in an oil medium, with a tunable release rate dependent on the lignin-to-curcumin mass ratio. The ELNPs showed a strong adhesion interaction with the hydrophobic wax surface. Quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM) analysis suggested that the ELNPs permeated into the wax layer, potentially preventing pesticide loss due to runoff or rainwater leaching. Rapidly decreasing contact angles between a droplet containing an aqueous dispersion of the ELNPs and a fresh leaf surface provided further evidence of a favorable interaction between the two. Overall, our results portray ELNPs as promising biobased nanoparticulate systems for pesticide delivery to hydrophobic plant surfaces.

Keywords
entrapment, esterification, lignin, model system, wax interaction
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:su:diva-240059 (URN)10.1021/acsami.4c16912 (DOI)001381732200001 ()39708339 (PubMedID)2-s2.0-85212787051 (Scopus ID)
Available from: 2025-03-03 Created: 2025-03-03 Last updated: 2025-03-03Bibliographically approved
Hadi, S. E., Davoodi, S., Oliaei, E., Morsali, M., Åhl, A., Nocerino, E., . . . Lundell, F. (2025). High-Performance and Energy-Efficient Nanolignocellulose Foams for Sustainable Technologies. ACS Sustainable Chemistry and Engineering, 13(25), 9467-9480
Open this publication in new window or tab >>High-Performance and Energy-Efficient Nanolignocellulose Foams for Sustainable Technologies
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2025 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 13, no 25, p. 9467-9480Article in journal (Other (popular science, discussion, etc.)) Published
Abstract [en]

There has been a recent surge of interest in biobased foams for applications ranging from building sustainability (insulation) to biomedicine, pharmaceutics, and electronics (scaffolds), with nanocellulose-based foams being particularly promising due to their porous and low-density structure. This study compares the production energy, structure, and properties of foams made from TEMPO-oxidized lignocellulose nanofibers (FTOLCNF) derived from unbleached wood pulp, and TEMPO-oxidized cellulose nanofibers (FTOCNF) from bleached cellulose pulp. Additionally, the incorporation of tannic acid (TA) as a biobased additive is explored for its ability to enhance the mechanical strength of FTOLCNF, contributing to improved performance. This builds upon the inherent advantages of FTOLCNF, which not only demonstrate superior structural integrity and load-bearing capacity (specific Young’s modulus of 37.4 J g–1, compared to 16.4 J g–1 for TOCNF) but also exhibit a higher yield during production due to the minimal processing required for unbleached pulp. Furthermore, FTOLCNF production requires about 18% less cumulative energy than FTOCNF (27 vs 33 MJ kg–1), largely owing to the energy-efficient preparation of TOLCNF from unbleached wood pulp. FTOLCNF also have a significantly lower cumulative energy demand (CED) compared to fossil-based alternatives like expanded polystyrene (EPS) and polyurethane (PU), highlighting their reduced environmental impact. Despite their lightweight nature, FTOLCNF exhibit competitive compressive strength, making them viable candidates for eco-friendly applications across various industries. Overall, this study demonstrates that FTOLCNF are an attractive alternative to other bio- and fossil-based foams, offering a balance of energy efficiency, higher yield, mechanical performance, and sustainability.

Keywords
lignocellulose nanofibers, biobased foams, freeze casting, tannic acid, cumulative energy demand (CED), sustainable materials, mechanical properties, energy-efficient processing
National Category
Materials Chemistry Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:su:diva-226811 (URN)10.1021/acssuschemeng.5c00761 (DOI)001510214200001 ()2-s2.0-105008457588 (Scopus ID)
Available from: 2024-02-21 Created: 2024-02-21 Last updated: 2025-09-18Bibliographically approved
Thalakkale Veettil, U., Huertas Alonso, A. J., Plivelic, T. S. & Sipponen, M. H. (2025). High-yield production of lignin nanoparticle photonic glasses. Green Chemistry, 27(7), 2130-2137
Open this publication in new window or tab >>High-yield production of lignin nanoparticle photonic glasses
2025 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 27, no 7, p. 2130-2137Article in journal (Refereed) Published
Abstract [en]

Lignin has emerged as a sustainable alternative to fossil-based polymers in advanced materials such as photonics. However, current methods for preparing photonic lignin materials are limited by non-benign organic solvents and low production yields. In this work, we present a highly efficient process that enables the production of photonic glasses with yields ranging from 48% to 72%, depending on the size of the lignin nanoparticles obtained from herbaceous soda lignin, softwood kraft lignin, and hardwood organosolv lignin. The hydrodynamic diameter of lignin nanoparticles can be regulated by the rate of water addition to the lignin-ethanol solution. We demonstrate that this control over particle size allows for tailoring the color of the photonic glass across the visible spectrum.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-240155 (URN)10.1039/d4gc05797j (DOI)001403383200001 ()2-s2.0-85217105680 (Scopus ID)
Available from: 2025-03-04 Created: 2025-03-04 Last updated: 2025-03-04Bibliographically approved
Åhl, A., Jaworski, A., Nocerino, E., Andersson, M., Sipponen, M. H., Juranyi, F. & Bergström, L. (2025). Hydration- and Temperature-Dependent Rotational Dynamics and Water Diffusion in Nanocellulose. Small Structures
Open this publication in new window or tab >>Hydration- and Temperature-Dependent Rotational Dynamics and Water Diffusion in Nanocellulose
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2025 (English)In: Small Structures, E-ISSN 2688-4062Article in journal (Refereed) Epub ahead of print
Abstract [en]

Nanocellulose is a promising alternative to fossil-derived materials, but its development is hindered by a limited understanding of cellulose–water interactions. Herein, quasielastic neutron scattering (QENS) is used to investigate how hydration and temperature affect the localized rotations in cellulose nanocrystals (CNC) and the diffusion of mobile water. QENS reveals that the C6 hydrogens and the C6 OH in the surface regions of CNC exhibit an isotropic rotation. The extracted mean square displacement shows that hydration enhances the overall hydrogen mobility in the cellulose chains. The mobile water diffusion at 270 K is unaffected by cellulose and consistent with diffusion of supercooled bulk water. At 310 K, the diffusion slows compared to bulk water, consistent with water diffusing on the CNC surface. Decoupling of the translational and rotational motion provides insight into the local cellulose–water motions. The localized motions of the nondiffusing water are found to be coupled with cellulose at 310 K, indicating a more complex dynamics at higher temperature. These findings provide new insights into how hydration modulates hydrogen mobility in cellulose, highlighting the interplay between water diffusion and molecular motion.

Keywords
cellulose–water interactions, nanocellulose, quasielastic neutron scattering, water diffusion
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-241181 (URN)10.1002/sstr.202500229 (DOI)001531499700001 ()2-s2.0-105010968535 (Scopus ID)
Funder
Swedish Foundation for Strategic Research, GSn15-008Swedish Foundation for Strategic Research, SNP21-004Swedish Research Council Formas, 2021-01952Knut and Alice Wallenberg Foundation
Available from: 2025-03-24 Created: 2025-03-24 Last updated: 2025-09-02
Wang, F., Nithianandam, S., Pylypchuk, I. & Sipponen, M. H. (2025). Lignin gel emulsions for environmentally benign hair conditioning. Science Advances, 11(8), Article ID eadr8372.
Open this publication in new window or tab >>Lignin gel emulsions for environmentally benign hair conditioning
2025 (English)In: Science Advances, E-ISSN 2375-2548, Vol. 11, no 8, article id eadr8372Article in journal (Refereed) Published
Abstract [en]

Hair care products have complex surfactant and stabilizer compositions arising from oleochemicals, raising concerns over sustainability. Here, we show a fully biobased hair conditioner based on micellar lignin gels that stabilize emulsions with triglyceride oils. We demonstrate competitive emulsion stability, rheological properties, and performance relative to an off-the-shelf commercial product. Lignin gel emulsion with a 6% weight fraction of coconut oil effectively lubricates damaged hair, confirmed by a 13% reduction in wet combing force and validated through multiscale microscopy analysis. Notably, organic solvent-free production simplifies the ingredient list and offers an environmentally benign route for lignin utilization in hair care.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:su:diva-242051 (URN)10.1126/sciadv.adr8372 (DOI)001428018300008 ()39982999 (PubMedID)2-s2.0-85218972921 (Scopus ID)
Available from: 2025-04-15 Created: 2025-04-15 Last updated: 2025-04-15Bibliographically approved
Tran, V. C., Morsali, M., Khan, Z., Crispin, R., Sipponen, M. H. & Engquist, I. (2025). Lignin Nanoparticles as Biobased Redox Centers for Organic Battery Electrodes. ACS Sustainable Chemistry and Engineering, 13(24), 9053-9062
Open this publication in new window or tab >>Lignin Nanoparticles as Biobased Redox Centers for Organic Battery Electrodes
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2025 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 13, no 24, p. 9053-9062Article in journal (Refereed) Published
Abstract [en]

Lignin, a central renewable carbon resource in the biosphere, has recently emerged as a promising redox-active material for organic batteries. Currently, the main challenge lies in finding a form of lignin that combines water-based processability with good cyclic stability, as the two industrially common forms, kraft lignin and lignosulfonate, each offers only one of these advantages. In this work, we demonstrate that lignin nanoparticles (LNPs) act as redox-active centers that are insoluble but exhibit colloidal stability in aqueous media, allowing for straightforward processing into electrodes for zinc-ion batteries. Electrodes based on conductive composites of LNPs with poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) were shown electrochemically to achieve specific capacities reaching 42.5 mAh/g at a current density of 1 A/g. A zinc-ion battery prototype using this composite demonstrated a specific energy of 54 Wh/kg, outperforming previous lignin-based energy storage devices. This zinc-lignin battery exhibited excellent Coulombic efficiency of around 100%, with a specific capacity of 82.5 mAh/g at 0.05 A/g and a capacity retention of approximately 61% after 2000 charge/discharge cycles. Our results highlight the potential of LNPs in advancing eco-friendly, cost-effective, and high-performance lignin-based energy storage devices.

Keywords
catechol, energy storage, PEDOT:PSS, redox, zinc-lignin battery
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-245865 (URN)10.1021/acssuschemeng.5c01173 (DOI)001506459200001 ()2-s2.0-105007911732 (Scopus ID)
Available from: 2025-08-22 Created: 2025-08-22 Last updated: 2025-08-22Bibliographically approved
Yan, L., Huertas Alonso, A. J., Liu, H., Dai, L., Si, C. & Sipponen, M. H. (2025). Lignin polymerization: towards high-performance materials. Chemical Society Reviews, 54(14), 6634-6651
Open this publication in new window or tab >>Lignin polymerization: towards high-performance materials
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2025 (English)In: Chemical Society Reviews, ISSN 0306-0012, E-ISSN 1460-4744, Vol. 54, no 14, p. 6634-6651Article, review/survey (Refereed) Published
Abstract [en]

Lignocellulosic biomass is the only sufficiently available resource for the sustainable development of the bioeconomy. Among the main components of lignocellulose, lignin has a tremendous potential to serve as a natural aromatic polymer resource due to the vast amounts of lignin available from industrial processes. However, commercial application of lignin is still limited and represents only a minor fraction of the potential utilization of approximately 20 million tons that can readily be isolated from spent pulping liquors and obtained as a residue from lignocellulosic biorefineries. Industrial processes generally depolymerize lignin into heterogeneous mixtures of low molecular weight macromolecules with a high degree of condensation, which collectively makes it challenging to develop them into high-performance materials. Although often neglected, some of the major limitations of these so-called technical lignins are their low molar mass and high dispersity, which make these lignins have poor mechanical properties. The polymerization of small lignin fragments not only contributes to the development of high-performance and multifunctional advanced materials, but also helps to improve the fundamental theory of lignin polymer chemistry. In this review, the polymerization of lignin via physical (aggregation), chemical (chain extension, cross-linking, and grafting), and biological (enzymatic polymerization) routes is described, its applications are assessed, and prospects for the development of high-performance lignin polymer materials are discussed.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-245942 (URN)10.1039/d4cs01044b (DOI)001504818600001 ()40491312 (PubMedID)2-s2.0-105008038609 (Scopus ID)
Available from: 2025-08-28 Created: 2025-08-28 Last updated: 2025-10-06Bibliographically approved
Sipponen, M. H. & Liu, L. (2024). Advances in Preparation and Applications of Lignin Nanoparticles. In: Lignin Chemistry: Characterization, Isolation, and Valorization (pp. 369-400). John Wiley & Sons
Open this publication in new window or tab >>Advances in Preparation and Applications of Lignin Nanoparticles
2024 (English)In: Lignin Chemistry: Characterization, Isolation, and Valorization, John Wiley & Sons, 2024, p. 369-400Chapter in book (Refereed)
Place, publisher, year, edition, pages
John Wiley & Sons, 2024
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-239227 (URN)2-s2.0-85201484446 (Scopus ID)9783527839865 (ISBN)
Available from: 2025-02-10 Created: 2025-02-10 Last updated: 2025-02-10Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0001-7747-9310

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