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Researchers at the Department of Energy's Oak Ridge National Laboratory have made a better thermoplastic by replacing styrene with lignin, a brittle and rigid polymer that forms the wood cell wall of plants together with cellulose. To this end, they invented a solvent-free production process that connects equal amounts of nano-sized lignin dispersed in a synthetic rubber matrix to each other to produce a meltable, plastic, and malleable material with a toughness of at least It is 10 times that of ABS. The resulting thermoplastic is called acrylonitrile-butadiene-lignin ABL; it is recyclable because it can be melted three times and still performs well. The results published in the "Advanced Functional Materials" magazine may lead to cleaner and cheaper raw materials for different manufacturers. "The new ORNL thermoplastic has better performance than commercial plastics such as ABS," said Amit Naskar, senior author of ORNL's Materials Science and Technology Department, who filed a patent application for the process of manufacturing the new material together with co-inventor Chau Tran. "We can call it a green product because 50% of its ingredients are renewable, and realizing its commercially developed technology will reduce the demand for petrochemical products. This technology can use rich sources from biorefineries, pulp and paper The biomass by-product stream of lignin. With the decline in natural gas and oil prices, renewable fuels cannot compete with fossil fuels, so bio-refineries are exploring options for developing other economically viable products. In cellulose, hemicellulose and wood Among lignin (the main structural component of plants), lignin is the most underutilized commercially. ORNL research aims to use it for production, focusing on commercialization, a renewable thermoplastic whose properties can be derived from current petroleum The alternatives are comparable. To produce an energy-saving method of synthesizing and extruding high-performance thermoplastics based on lignin elastomers, the ORNL team needs to answer several questions: whether changes in lignin feed can overcome difficulties in order to achieve superior performance Products? Can lignin be integrated into a soft polymer matrix? Can you understand the chemical and physical properties of lignin-derived polymers in order to better control their performance? Can the process of producing lignin-derived polymers be designed?" Lignin is a very brittle natural polymer, so it needs to be toughened,” explains Naskar, the head of ORNL’s Carbon and Composites Group. One of the main goals of the group is to produce strength and toughness that are strong enough to not break. An industrial polymer that deforms under circumstances. "We need to chemically combine soft matter with lignin. This soft matrix is ​​malleable and therefore malleable or stretchable. The very hard lignin fragments will provide resistance to deformation and thus stiffness. "All lignins are not the same in terms of thermal stability. In order to determine which type of thermoplastic raw material is the best, scientists evaluated the lignin in softwoods such as wheat straw, pine and hardwoods such as oak. They found hardwood wood. The thermal stability of lignin is the highest, and certain types of softwood lignin also have melt stability. Next, researchers need to combine lignin with soft substances. Chemists usually achieve this by synthesizing polymers in the presence of solvents. .Because lignin and synthetic rubber containing acrylonitrile and butadiene (called nitrile rubber) have chemical groups with uneven electronic distribution, they may interact with each other. Naskar and Chau Tran (melt mixed and characterized Experiment) Instead, they tried to put the two in the molten phase without solvent. In a heating chamber with two rotors, the researchers "kneaded" a molten mixture of equal parts of powdered lignin and nitrile rubber. During the mixing process In the process, the lignin agglomerates are broken down into 10 to 200 nanometer interpenetrating layers or sheets, which are well dispersed in the rubber and interact with the rubber. Without the proper selection of a soft matrix and mixing conditions, lignin agglomerates are at least 10 times larger than those obtained with the ORNL process. The resulting product has neither the properties of lignin nor rubber, but is somewhere in between, combining the stiffness of lignin and the elasticity of nitrile rubber. Through By changing the content of acrylonitrile in the soft matrix, the researchers hope to further improve the mechanical properties of the material. They tried 33%, 41% and 51% acrylonitrile, and found that 41% acrylonitrile reached the best between toughness and stiffness Balance. Next, researchers want to know whether controlling processing conditions can improve the properties of polymer alloys. For example, materials produced with 33% acrylonitrile content are elastic but not strong and behave more like rubber than plastic. At higher With the ratio of acrylonitrile, the researchers found that the material was enhanced by the effective interaction between the components. They also wanted to know at what temperature the components should be mixed to optimize the material properties. They found heating components between 140 and 160 degrees Celsius The required mixed phase was formed. Scientists used ORNL's resources, including the Nanophase Materials Science Center of the Office of Science User Facilities of the U.S. Department of Energy, to analyze the morphology of the mixture. A scanning electron microscope performed by Chau Tran explored the surface of the material. Jihua Chen and Tran used transmission electron microscopy to characterize the soft matter phase, placing a piece of material in the path of the electron beam, and revealing the structure through the contrast difference between the lignin and rubber phases. Jong Keum's small-angle X-ray scattering revealed certain domains or Layer-sized repeating clusters. Fourier Leaf transform infrared spectroscopy identified chemical functional groups and their interactions. Future research will explore the correlation between different raw materials, especially those from biorefineries, as well as processing conditions, material structure and properties. Investigations are also planned to study the performance of ORNL's new thermoplastics in carbon fiber reinforced composites. "In the future, more renewable materials may be used," Nazca said. "I am very happy that we can continue to work on renewable materials, not only for automotive applications, but even for commercial purposes."

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