Lignin Enabling Facile 3D Printing of Rubber for All-Weather Water Harvesting

Abstract

Soft materials, with high elasticity and low glass transition temperatures (T_gs), present significant challenges in fabricating finely structured components via 3D printing due to their inherent softness and slow curing kinetics. Current direct ink writing (DIW) methods for soft polymers typically rely on external stimuli (e.g., light and heat) or precious metal catalysts to ensure structural stability during printing, increasing process complexity and cost. Here, a simple DIW 3D printing strategy for rubber was developed by introducing modified lignin. By virtue of its rigid benzene ring structure and abundant reactive groups, the modified lignin forms covalently bonded crosslinked networks and intermolecular hydrogen bonds with rubber to enhance the viscoelasticity, and thixotropy of the ink. The addition of 30–50 wt% modified lignin increased the modulus of the ink by five orders of magnitude, which resulted in stable self-supported printing during the printing process. Water-collecting materials with a bionic cactus spine structure were fabricated utilizing 3D printing, which demonstrated superior capabilities for efficient fog capturing and photothermal evaporation, respectively. By combining these two water-harvesting methods, a daily cycle can ideally deliver an overall water yield approximately 22 L m⁻², which will providing a high-performance solution for all-weather fresh water access.

Keywords

3D printing / all-weather freshwater harvesting / lignin / rubber / self-supporting

References

[1] A. D. Valino, J. R. C. Dizon, A. H. Espera, Q. Chen, J. Messman, and R. C. Advincula, “Advances in 3D Printing of Thermoplastic Polymer Composites and Nanocomposites,” Progress in Polymer Science 98 (2019): 101162.

[2] C. Zhang, Y. Li, W. Kang, X. Liu, and Q. Wang, “Current Advances and Future Perspectives of Additive Manufacturing for Functional Polymeric Materials and Devices,” SusMat 1, no. 1 (2021): 127–147.

[3] M. Zarek, M. Layani, I. Cooperstein, E. Sachyani, D. Cohn, and S. Magdassi, “3D printing of Shape Memory Polymers for Flexible Electronic Devices,” Advanced Materials 28, no. 22 (2015): 4449–4454.

[4] H. W. Tan, Y. Y. Choong, C. N. Kuo, H. Y. Low, and C. K. Chua, “3D printed Electronics: Processes, Materials and Future Trends,” Progress in Materials Science 127 (2022): 100945.

[5] M. Wehner, R. L. Truby, D. J. Fitzgerald, et al., “An Integrated Design and Fabrication Strategy for Entirely Soft, Autonomous Robots,” Nature 536 (2016): 451–455.

[6] Y. Kim, H. Yuk, R. Zhao, S. Chester, and X. Zhao, “Printing Ferromagnetic Domains for Untethered Fast-Transforming Soft Materials,” Nature 558 (2018): 274–279.

[7] X. Zhao, J. Kim, C. A. Cezar, et al., “Active Scaffolds for On-Demand Drug and Cell Delivery,” Pnas 108, no. 1 (2010): 67–72.

[8] Z. Zhang, B. Wang, D. Hui, J. Qiu, and S. Wang, “3D Bioprinting of Soft Materials-Based Regenerative Vascular Structures and Tissues,” Composites Part B: Engineering 123 (2017): 279–291.

[9] S. Fusco, M. S. Sakar, S. Kennedy, et al., “An Integrated Microrobotic Platform for On-Demand, Targeted Therapeutic Interventions,” Advanced Materials 26, no. 6 (2013): 952–957.

[10] B. N. Peele, T. J. Wallin, H. Zhao, and R. F. Shepherd, “D Printing Antagonistic Systems of Artificial Muscle Using Projection Stereolithography,” Bioinspiration & Biomimetics 10 (2015): 055003.

[11] T. J. Wallin, L.-E. Simonsen, W. Pan, et al., “3D Printable Tough Silicone Double Networks,” Nature Communications 11 (2020): 4000.

[12] C. S. O'Bryan, T. Bhattacharjee, S. Hart, et al., “Self-Assembled Micro-Organogels for 3D Printing Silicone Structures,” Science Advances 3, no. 5 (2017): e1602800.

[13] C. Geng, Z. Ding, W. Qian, et al., “3D Printed Architectured Silicone Composites Containing a UV-Curable Rheological Modifier With Tailorable Structural Collapse,” Composites Part B: Engineering 280 (2024): 111490.

[14] M. A. S. R. Saadi, A. Maguire, N. T. Pottackal, et al., “Direct Ink Writing: A 3D Printing Technology for Diverse Materials,” Advanced Materials 34, no. 28 (2022): 2108855.

[15] M. Tang, Z. Zhong, and C. Ke, “Advanced Supramolecular Design for Direct Ink Writing of Soft Materials,” Chemical Society Reviews 52, no. 5 (2023): 1614–1649.

[16] B. E. Kelly, I. Bhattacharya, H. Heidari, M. Shusteff, C. Spadaccini, and H. Taylor, “Volumetric Additive Manufacturing via Tomographic Reconstruction,” Science 363, no. 6431 (2019): 1075–1079.

[17] J. Beach, S. Mann, C. Ault, et al., ““All-in-One” Thixotropic Polysiloxane Pastes for UV-Activated Room Temperature Hydrosilylation Cross-Linking in Additive Manufacturing,” Macromolecules 54, no. 4 (2021): 1715–1724.

[18] L.-Y. Zhou, Q. Gao, J.-Z. Fu, et al., “Multimaterial 3D Printing of Highly Stretchable Silicone Elastomers,” American Chemical Society Applied Materials & Interfaces 11, no. 26 (2019): 23573–23583.

[19] M. Schaffner, J. A. Faber, L. Pianegonda, P. Rühs, F. Coulter, and A. Studart, “3D Printing of Robotic Soft Actuators With Programmable Bioinspired Architectures,” Nature Communications 9 (2018): 878.

[20] X. Chu, Y. Wang, L. Cai, et al., “Boosting the Energy Density of Aqueous MXene-Based Supercapacitor by Integrating 3D Conducting Polymer Hydrogel Cathode,” SusMat 2, no. 3 (2022): 379–390.

[21] A. Negro, T. Cherbuin, and M. P. Lutolf, “3D Inkjet Printing of Complex, Cell-Laden Hydrogel Structures,” Scientific Reports 8 (2018): 17099.

[22] Z. Ji, X. Zhang, C. Yan, et al., “3D Printing of Photocuring Elastomers With Excellent Mechanical Strength and Resilience,” Macromolecular Rapid Communications 40 (2019): 1800873.

[23] P. Figueiredo, K. Lintinen, J. T. Hirvonen, M. Kostiainen, and H. Santos, “Properties and Chemical Modifications of Lignin: Towards Lignin-Based Nanomaterials for Biomedical Applications,” Progress in Materials Science 93 (2018): 233–269.

[24] A. Tribot, G. Amer, M. Abdou Alio, et al., “Wood-Lignin: Supply, Extraction Processes and Use as Bio-Based Material,” European Polymer Journal 112 (2019): 228–240.

[25] Y. Shi, O. Ilic, H. A. Atwater, and J. Greer, “All-Day Fresh Water Harvesting by Microstructured Hydrogel Membranes,” Nature Communications 12 (2021): 2797.

[26] J. Ju, H. Bai, Y. M. Zheng, T. Zhao, R. Fang, and L. Jiang, “A Multi-Structural and Multi-Functional Integrated Fog Collection System in Cactus,” Nature Communications 3 (2012): 1247.

[27] F. R. Gleuwitz, G. Sivasankarapillai, G. Siqueira, C. Friedrich, and M. Laborie, “Lignin in Bio-Based Liquid Crystalline Network Material With Potential for Direct Ink Writing,” ACS Applied Bio Materials 3, no. 9 (2020): 6049–6058.

[28] K. Xia, Q. Ouyang, Y. Chen, X. Wang, X. Qian, and L. Wang, “Preparation and Characterization of Lignosulfonate–Acrylonitrile Copolymer as a Novel Carbon Fiber Precursor,” American Chemical Society Sustainable Chemistry & Engineering 4, no. 1 (2015): 159–168.

[29] B. Jiang, C. Chen, Z. Liang, et al., “Lignin as a Wood-Inspired Binder Enabled Strong, Water Stable, and Biodegradable Paper for Plastic Replacement,” Advanced Functional Materials 30, no. 4 (2019): 1906307.

[30] Z. Dong, Y. Du, M. Geng, et al., “In Situ Formed Three-Dimensionally Conducting Polymer Electrolyte for Solid-State Lithium Metal Batteries with High-Cathode Loading,” Sus Mat 5 (2025): e7004.

[31] M. Li, L. Zhu, H. Xiao, et al., “Design of a Lignin-Based Versatile Bioreinforcement for High-Performance Natural Rubber Composites,” ACS Sustainable Chemistry & Engineering 10, no. 24 (2022): 8031–8042.

[32] E. Stefanis and C. Panayiotou, “Prediction of Hansen Solubility Parameters With a New Group-Contribution Method,” International Journal of Thermophysics 29 (2008): 568–585.

[33] C. D. Tran, J. Chen, J. K. Keum, and A. Naskar, “A New Class of Renewable Thermoplastics With Extraordinary Performance From Nanostructured Lignin-Elastomers,” Advanced Functional Materials 26, no. 16 (2016): 2677–2685.

[34] W. Thielemans and R. P. Wool, “Lignin Esters for Use in Unsaturated Thermosets: Lignin Modification and Solubility Modeling,” Biomacromolecules 6, no. 4 (2005): 1895–1905.

[35] D. Barana, M. Orlandi, L. Zoia, et al., “Lignin Based Functional Additives for Natural Rubber,” ACS Sustainable Chemistry & Engineering 6, no. 9 (2018): 11843–11852.

[36] S. Lee, S. Eom, J. Won, J. Bae, S. Park, and S. Lee, “Evaluation of Aging Behavior of Nitrile Butadiene Rubbers via Oxygen-Consumption Experiments,” Fibers and Polymers 22 (2021): 639–646.

[37] D. Kokkinis, M. Schaffner, and A. R. Studart, “Multimaterial Magnetically Assisted 3D Printing of Composite Materials,” Nature Communications 6 (2015): 8643.

[38] B. Jiang, Y. Yao, Z. Liang, et al., “Lignin-Based Direct Ink Printed Structural Scaffolds,” Small 16, no. 31 (2020): 1907212.

[39] B. Jiang, H. Huang, W. Gong, et al., “Wood-Inspired Binder Enabled Vertical 3D Printing of G-C₃N₄/CNT Arrays for Highly Efficient Photoelectrochemical Hydrogen Evolution,” Advanced Functional Materials 31, no. 45 (2021): 2105045.

[40] M. S. H. Thakur, C. Shi, L. T. Kearney, et al., “Three-Dimensional Printing of Wood,” Science Advances 10, no. 11 (2024): eadk3250.

[41] J. Li, W. Liu, X. Qiu, et al., “Lignin: A Sustainable Photothermal Block for Smart Elastomers,” Green Chemistry 24, no. 2 (2022): 823–836.

[42] Q. Shao, Y. Li, Z. Liang, et al., “Lignin: A Multifunctional and Sustainable Photothermal Material for Solar-Driven Thermoelectric Generation and Desalination,” Composites Part B: Engineering 284 (2024): 111694.

[43] X. Chen, Q. Ye, C. Shi, L. Zhang, P. Zhou, and M. Chen, “Understanding Solar Thermal Gradient to Improve Solar Evaporation Performance for Water Collection,” Nano Research Energy 4, no. 2 (2025): e9120152.

[44] M. Chen, S. Li, X. Chen, et al., “3D Bridge-Arch-Structured Dual-Side Evaporator for Practical, All-Weather Water Harvesting and Desalination,” Journal of Materials Chemistry A 12, no. 16 (2024): 9574–9583.

[45] X. Zhao, C. Huang, D. Xiao, et al., “Melanin-Inspired Design: Preparing Sustainable Photothermal Materials From Lignin for Energy Generation,” American Chemical Society Applied Materials & Interfaces 13, no. 6 (2021): 7600–7607.

[46] Z. Wei, C. Cai, Y. Huang, Y. Wang, and Y. Fu, “Biomimetic Surface Strategy of Spectrum-Tailored Liquid Metal via Blackbody Inspiration for Highly Efficient Solar Steam Generation, Desalination, and Electricity Generation,” Nano Energy 86 (2021): 106138.

[47] L. Hao, N. Liu, B. Zhang, R. Niu, J. Gong, and T. Tang, “Waste-to-Wealth: Sustainable Conversion of Polyester Waste Into Porous Carbons as Efficient Solar Steam Generators,” Journal of the Taiwan Institute of Chemical Engineers 115 (2020): 71–78.

[48] X. Lin, P. Wang, R. Hong, et al., “Fully Lignocellulosic Biomass-Based Double-Layered Porous Hydrogel for Efficient Solar Steam Generation,” Advanced Functional Materials 32, no. 51 (2022): 09262.

[49] W. Chao, Y. Li, X. Sun, G. Cao, C. Wang, and S. Ho, “Enhanced Wood-Derived Photothermal Evaporation System by In-Situ Incorporated Lignin Carbon Quantum Dots,” Chemical Engineering Journal 405 (2021): 126703.

[50] W. Li, G. Wang, T. Li, et al., “All-in-One Self-Cleaning Lignin-Derived Spherical Solar Evaporator for Continuous Desalination and Synergic Water Purification,” Water Research 282 (2025): 123932.

[51] Y. Gu, D. Wang, Y. Gao, et al., “Solar-Powered High-Performance Lignin-Wood Evaporator for Solar Steam Generation,” Advanced Functional Materials 33, no. 43 (2023): 06947.

[52] X. Lin, T. Shen, M. Li, et al., “Synthesis, Characterization, and Utilization of Poly-Amino Acid-Functionalized Lignin for Efficient and Selective Removal of Lead Ion From Aqueous Solution,” Journal of Cleaner Production 347 (2022): 131219.

[53] R. Hu, M. Li, T. Shen, et al., “A Sustainable Process to 100% Bio-Based Nylons Integrated Chemical and Biological Conversion of Lignocellulose,” Green Energy & Environment 9, no. 2 (2024): 390–402.

[54] X. Su, D. Hao, P. Li, et al., “Setaria viridis-Inspired Hydrogels With Multilevel Structures for Efficient All-Day Fresh Water Harvesting,” Journal of Materials Chemistry A 11, no. 14 (2023): 7702–7710.

[55] E. Lorenceau and D. Quéré, “Drops on a Conical Wire,” Journal of Fluid Mechanics 510, no. 510 (2004): 29–45.

[56] Z. Yu, T. Zhu, J. Zhang, M. Ge, S. Fu, and Y. Lai, “Fog Harvesting Devices Inspired From Single to Multiple Creatures: Current Progress and Future Perspective,” Advanced Functional Materials 32, no. 26 (2022): 2200359.

[57] C. Shi, B. W. Sheldon, and M. Chen, “Unveiling Passive Design to Enable Synergistic Water Harvesting and Irrigation,” Matter 7, no. 10 (2024): 3247–3250.

RIGHTS & PERMISSIONS

2025 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.