From Biomass Fractionation to Final Biobased Polymer Nanocomposites in European Sustainable Biobased Nanomaterials Community (BIOMAC)

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Biomacromolecules, Biobased and Biodegradable Polymers".

Deadline for manuscript submissions: 29 November 2024 | Viewed by 8678

Special Issue Editors

Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR 54124 Thessaloniki, Greece
Interests: synthesis and characterization of polyesters; development of biobased polymers; biodegradable polymers; polymer composites and nanocomposites; synthesis and characterization of copolymers; polymer blends; recycling of polymers with various techniques; enzymatic hydrolysis studies; modification of natural polymers; polymer for wastewater treatment pollutant removal; polymers for tissue engineering and drug delivery applications; drug–polymer solid dispersions; drug targeting; drug nanoencapsulation and microencapsulation
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Laboratory of Chemical and Environmental Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR 54124 Thessaloniki, Greece
Interests: green chemistry; heterogeneous catalysis; synthesis and characterization of nanostructured materials; thermochemical and catalytic processes for biomass valorisation; biobased polymers and nanocomposites
Special Issues, Collections and Topics in MDPI journals
Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR 54124 Thessaloniki, Greece
Interests: polymers; composites; nanocomposites; biomaterials; polyesters; scaffolds; biobased polymers
Special Issues, Collections and Topics in MDPI journals
Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Interests: polymer chemistry; bioderived and biodegradable polymers; material engineering; polymer processing and engineering; material chemistry and characterization; nanotechnology; rheology; smart and stimuli-responsive polymers and composites; polymer and composite recycling; advanced manufacturing; solar light harvesting; managing and conversion; energy storage
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The global mass production of plastics started in the 1950s, with an estimated total number of 8.3 to 9.1 million metric tons (Mt) already manufactured up to the current day. From this, only 9% has been recycled and 12% incinerated, whereas the remaining 79% has now accumulated in landfills or in the environment. Their high stability and nondegradability cause serious environmental issues to living organisms with a problem called today “microplastics”. Research efforts have focused on producing environmentally friendly materials that could “disappear” after their use without leaving fragments or harmful products behind. Biodegradability is directly dependent on the chemical structure of polymers, with polysaccharides, peptides and aliphatic polyesters having hydrolysable bonds. Most of them can be found in biomass, a cheap energy and functional material source.

Biomass is produced in abundance from plants every year through photosynthesis, using only CO2 and water (approximately 954 Mt/year in EU countries). However, the chemical energy stored in biomass (4.500 EJ) in the form of glucose or sugars is lost during the annual cycle of seasons (animals–microorganisms). In recent years, apart from biofuels and energy, the production of biobased platform chemicals, monomers and polymers from biomass has received great attention. In this direction, there has been a high demand to valorise agricultural and forest residues, animal waste from farms, municipal solid waste and waste from industry and households. Different pretreatments (hydrothermal, steam explosion, mild acid/base hydrothermal, organosolv, enzymatic hydrolysis, pyrolysis, liquefaction, gasification, etc.) can be applied to convert lignocellulosic or other relevant biomass and isolate primary fractions (i.e., extractives, cellulose, hemicellulose, lignin, etc.), bio-oils, as well as sugars and phenolic compounds, to serve as platform chemicals and raw materials for further upgrading and utilization.

Based on all of the above, the worldwide demand for a sustainability and green economy has led research interest in the field of biorefining and polymer technology in three different directions:

  • To effectively valorise biomass using green processes to extract or synthesize functional nanoadditives and building blocks (biobased monomers, nanocellulose, nanolignin, biochar, etc.);
  • To produce novel, eco-friendly, compostable or mainly biodegradable polymers and composites based on these additives and monomers;
  • To replace the use of fossil-derived polymers and composites in various applications, for example, in the fields of food packaging, agriculture and construction, with eco-friendly biomaterials.

Developments in biobased nanomaterials are coupled with biotechnologies applied to biomass, converting renewable resources into high-added-value polymers. Although a lot of research has been conducted in this area in the last two decades, only a very limited number of products have been commercialized, reaching market end users. The major challenge in the area lays in the fact that novel product concepts are restricted from entering the market because end user applications remain at small lab-scale tests, therefore, having limited exploitation capacity for industrial deployment. This is the ‘valley of death’ which BIOMAC intends to overcome (https://www.biomac-oitb.eu). To accelerate the market entrance of nanoenabled biobased materials (NBMs), BIOMAC aims to establish an open innovation test bed (OITB) dedicated to upscaling processes incorporating major developments in this area based on two pillars: to generate knowledge and to capture business value. Starting from the utilization of biomass sources, followed by the production of biobased nanoparticles and different building blocks, the ecosystem community is currently developing biopolymers for the strategic sectors of food packaging, agriculture, construction, automotive and printed electronics, making up a large market share.

This Special Issue of the international open access journal Polymers aims to collect cutting-edge, state-of-the-art and original full-length research articles and critical or tutorial reviews on the topic of “nanoenabled biobased materials”, including, but not limited to:

  • Green techniques for biomass (pre)treatment and valorisation;
  • Ecofriendly processes to recover biobased additives and monomers from biomass;
  • Biomass (pre)treatment to produce biobased monomers and building blocks, such as lactic acid, succinic acid, adipic acid, azelaic acid, aminodecanoic acid, terephthalic acid, furan dicarboxylic acid, diol-like ethylene, propylene and butane diol and polyols, isosorbide, acetic acid, formic acid, diamines, etc., originating from the chemo/bio/electro/photocatalytic processing of biomass primary sugars and phenolics.
  • Production of nanocellulose, nanolignin, biochar and respective modified materials to serve as the functional nanoadditives of biobased polymers;
  • Synthesis and characterization of biobased and biodegradable macromolecules such as poly(lactic acid, poly(butylene succinate), polyhydroxyalkanoates, polycaprolactone, etc., with desired mechanical and biodegradable properties;
  • Synthesis of biobased copolymers using biomass precursors with enhanced performance and biodegradability;
  • Development of biobased composites and nanocomposites with enhanced properties;
  • Assessment and demonstration of specific advantages of biobased and/or biodegradable polymers and composites compared with fossil-derived polymers;
  • Properties of biomacromolecules and composites and their applications in relevant fields;
  • Production and study of biodegradable blends;
  • Biobased polymer recycling methods and depolymerization techniques.

This Special Issue is supported by BIOMAC, funded by the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement no. 952941.

Prof. Dr. Dimitrios Bikiaris
Prof. Dr. Konstantinos S. Triantafyllidis
Dr. Zoi Terzopoulou
Prof. Dr. Gianmarco Griffini
Guest Editors

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Keywords

  • biomass pretreatment
  • biomass fractionation
  • biobased platform chemicals
  • biobased monomers
  • biobased additives
  • nanocellulose
  • nanolignin
  • biochar
  • biomacromolecules
  • biobased polymers
  • biodegradable polymers
  • natural biobased polymers
  • synthetic biobased polymers
  • nanocomposites
  • enzymatically hydrolysable polymers
  • biodegradability
  • compostability
  • environmentally friendly polymers
  • biopolymer and composite applications

Published Papers (3 papers)

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17 pages, 2961 KiB  
Article
Poly(Lactic Acid) Composites with Lignin and Nanolignin Synthesized by In Situ Reactive Processing
Polymers 2023, 15(10), 2386; https://doi.org/10.3390/polym15102386 - 19 May 2023
Cited by 4 | Viewed by 2317
Abstract
Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized [...] Read more.
Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized rapidly using reactive processing that took under 20 min. When the catalyst amount was doubled, the reaction time was reduced to under 15 min. The dispersion, thermal transitions, mechanical properties, antioxidant activity, and optical properties of the resulting PLA-based composites were evaluated with SEM, DSC, nanoindentation, DPPH assay, and DRS spectroscopy. All reactive processing-prepared composites were characterized by means of SEM, GPC, and NMR to assess their morphology, molecular weight, and free lactide content. The benefits of the size reduction of lignin and the use of in situ ROP by reactive processing were demonstrated, as the reactive processing-produced nanolignin-containing composites had superior crystallization, mechanical, and antioxidant properties. These improvements were attributed to the participation of nanolignin in the ROP of lactide as a macroinitiator, resulting in PLA-grafted nanolignin particles that improved its dispersion. Full article
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25 pages, 6693 KiB  
Article
Non-Isothermal Crystallization Kinetics of PBSu/Biochar Composites Studied by Isoconversional and Model Fitting Methods
Polymers 2023, 15(7), 1603; https://doi.org/10.3390/polym15071603 - 23 Mar 2023
Cited by 2 | Viewed by 1456
Abstract
Non-isothermal crystallization of Poly(butylene succinate) (PBSu)/biochar composites was studied at various constant cooling rates using differential scanning calorimetry. The analysis of the kinetics data revealed that the overall crystallization rate and activation energy of the PBSu polymer were significantly influenced by the addition [...] Read more.
Non-isothermal crystallization of Poly(butylene succinate) (PBSu)/biochar composites was studied at various constant cooling rates using differential scanning calorimetry. The analysis of the kinetics data revealed that the overall crystallization rate and activation energy of the PBSu polymer were significantly influenced by the addition of biochar. Specifically, the PBSu/5% biochar composite with a higher filler content was more effective as a nucleation agent in the polymer matrix, as indicated by the nucleation activity (ψ) value of 0.45. The activation energy of the PBSu/5% biochar composite was found to be higher than that of the other compositions, while the nucleation activity of the PBSu/biochar composites decreased as the biochar content increased. The Avrami equation, which is commonly used to describe the kinetics of crystallization, was found to be limited in accurately predicting the non-isothermal crystallization behavior of PBSu and PBSu/biochar composites. Although the Nakamura/Hoffman–Lauritzen model performed well overall, it may not have accurately predicted the crystallization rate at the end of the process due to the possibility of secondary crystallization. Finally, the combination of the Šesták–Berggren model with the Hoffman–Lauritzen theory was found to accurately predict the crystallization behavior of the PBSu/biochar composites, indicating a complex crystallization mechanism involving both nucleation and growth. The Kg parameter of neat PBSu was found to be 0.7099 K2, while the melting temperature and glass transition temperature of neat PBSu were found to be 114.91 °C and 35 °C, respectively, very close to the measured values. The Avrami nucleation dimension n was found to 2.65 for PBSu/5% biochar composite indicating that the crystallization process is complex in the composites. Full article
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22 pages, 5101 KiB  
Article
Synthesis and Study of Fully Biodegradable Composites Based on Poly(butylene succinate) and Biochar
Polymers 2023, 15(4), 1049; https://doi.org/10.3390/polym15041049 - 20 Feb 2023
Cited by 6 | Viewed by 2340
Abstract
Biodegradable polymers offer a promising alternative to the global plastic problems and especially in the last decade, to the microplastics problems. For the first time, samples of poly(butylene succinate) (PBSu) biocomposites containing 1, 2.5, and 5 wt% biochar (BC) were prepared by in [...] Read more.
Biodegradable polymers offer a promising alternative to the global plastic problems and especially in the last decade, to the microplastics problems. For the first time, samples of poly(butylene succinate) (PBSu) biocomposites containing 1, 2.5, and 5 wt% biochar (BC) were prepared by in situ polymerization via the two-stage melt polycondensation procedure. BC was used as a filler for the PBSu to improve its mechanical properties, thermal transitions, and biodegradability. The structure of the synthesized polymers was examined by 1H and 13C nuclear magnetic resonance (NMR) and X-Ray diffraction (XRD) along with an estimation of the molecular weights, while differential scanning calorimetry (DSC) and light flash analysis (LFA) were also employed to record the thermal transitions and evaluate the thermal conductivity, respectively. It was found that the amount of BC does not affect the molecular weight of PBSu biocomposites. The fine dispersion of BC, as well as the increase in BC content in the polymeric matrix, significantly improves the tensile and impact strengths. The DSC analysis results showed that BC facilitates the crystallization of PBSu biocomposites. Due to the latter, a mild and systematic increase in thermal diffusivity and conductivity was recorded indicating that BC is a conductive material. The molecular mobility of PBSu, local and segmental, does not change significantly in the biocomposites, whereas the BC seems to cause an increase in the overall dielectric permittivity. Finally, it was found that the enzymatic hydrolysis degradation rate of biocomposites increased with the increasing BC content. Full article
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