The acetosolv extraction, allylation and subsequent cross-linking of wheat straw lignin to thermoset biomaterials is herein described. The extraction temperature proved to be of great importance for the quality of the resulting lignin, with moderate temperature being key for preservation of β-O-4’ linkages. The allylation of the acetosolv lignin was carried out using three different synthetic strategies, resulting in selective installation of either benzylic or phenolic allyl ethers, or unselective allylation of various hydroxyl groups via etherification and carboxyallylation. The different allylation protocols employed either allyl alcohol, allyl chloride, or diallylcarbonate as allyl precursors, with the latter resulting in the highest degree of functionalization. Selected allylated acetosolv lignins were cross-linked using a thiol-ene approach and the lignin with the highest density of allyl groups was found to form a cross-linked thermoset material with properties comparable to kraft lignin-based analogues.

An increasing demand for alternative electrolyte systems is emerging to address limitations associated with traditional liquid electrolytes in lithium-ion batteries (LIBs). Hybrid polymer-liquid electrolytes (HEs) combine the merits of solid polymers and liquid electrolytes in a heterogeneous phase-separated system where the polymer phase encapsulates the liquid ion-conducting phase. These electrolytes are synthesized through polymerization-induced phase separation (PIPS), resulting in the formation of a porous three-dimensional polymer network. Carbon black (CB) serves as conductive additive in LIBs electrodes, enhancing electric conductivity and thereby improving the battery performance and lifespan. How CB, already present in conventional electrodes, affects the PIPS process during the formation of HEs for LIBs, focusing on the material interactions and the formed microstructure properties, has been investigated. Addition of CB does not negatively affect the result of PIPS process, and it permits high conversion rate and compatibility with HE at all CB concentrations investigated. Morphological analysis in combination with nuclear magnetic resonance (NMR) and electrochemical impedance spectroscopy (EIS) reveals consistent macroporous and mesoporous structures, indicating the robustness of HEs to CB content variation. Understanding the interaction between CB and HEs during the manufacturing process and the impact of CB on the structural integrity and compatibility of the HE system, aids the integration of HEs with existing electrode materials in practical battery configurations.

Deterioration of steel infrastructures is oftencaused by corrosive substances. In harsh conditions, theprotection against corrosion is provided by high-performancecoatings. The major challenge in this field is tofind replacements for the fossil-based resins constitutinganticorrosive coatings, due to increasing needs tosynthesize new environmentally friendly materials. Inthis study, softwood Kraft lignin was epoxidized with theaim of obtaining a renewable resin for anticorrosivecoatings. The reaction resulted in the formation ofheterogeneous, solid, coarse agglomerates. Therefore,the synthetized lignin particles were mechanicallyground and sieved to break up the agglomerates andobtain a fine powder. To reduce the use of fossil fuelbasedepoxy novolac resins in commercial anticorrosivecoatings, a series of formulations were prepared andcured on steel panels varying the content of epoxidizedlignin resin. Epoxidized lignin-based coatings used inconjunction with conventional epoxy novolac resindemonstrated improved performance in terms of corrosionprotection and adhesion properties, as measuredby salt spray exposure and pull-off adhesion test,respectively. In addition, the importance of size fractionationfor the homogeneity of the final coatingformulations was highlighted. The findings from thisstudy suggest a promising route to develop highperforminglignin-based anticorrosive coatings.

In the development of polymer electrolytes, the understanding of the complex interplay of factors that affect ion transport is of importance. In this study, the strongly coordinating and flexible poly (ethylene oxide) (PEO) is compared to the weakly coordinating and stiff poly (trimethylene carbonate) (PTMC) as opposing model systems. The effect of molecular weight (Mn) and end group chemistry on the physical properties: glass transition temperature (Tg) and viscosity (η) and ion transport properties: transference number (T+), ion coordination strength and ionic conductivities were investigated. The cation transference number (T+) showed the opposite dependence on Mn for PEO and PTMC, decreasing at low Mn for PTMC and increasing for PEO. This was shown to be highly dependent on the ion coordination strength of the system regardless of whether the end group was OH or if the chains were end-capped. Although the coordination is mainly of the cations in the systems, the differences in T+ were due to differences in anion rather than cation conductivity, with a similar Li+ conductivity across the polymer series when accounting for the differences in segmental mobility.

Most products today have several functions, but these are achieved by integrating different monofunctional devices and/or materials in a system. Having several functions simultaneously in one single material has many potential advantages, such as a structural material that can also store energy, have self-sensing or self-healing capability or any other physical function. This would lead mass and resource savings, being more energy efficient and thus more sustainable. This paper presents a mini review on how carbon fibres can be used for integrating several functions simultaneously in a high-performance load carrying structural material using the electrical and electrochemical properties of carbon fibres. Through this carbon fibre composites can also store energy like a lithium-ion battery, be used as a strain sensor, have electrically controlled actuation and shape-morphing, and be used as an energy harvester.

Bio-based monomers are under investigation to replace fossil-based materials due to the concerns regarding climate change and depletion of fossil raw materials. Lignin, cellulose and hemicellulose represent the main interesting platform to use for developing new monomers due to their significant abundance. Ferulic acid is one of the moieties derived from lignin which can be suitable for many applications. In this study, the ferulic acid was epoxidated and it was investigated in cationic UV-curing. Due to the limited performance obtained during UV-curing, two alternative strategies were developed to overcome the initial problem of poor material properties. A thiol-ene epoxy system based on the ferulic epoxy derivative and a commercially available thiol as well as a thermally cured system based on pure cationic curing of ferulic acid diepoxy were chosen as alternative methods. The different curing processes were thoroughly investigated by means of FTIR (Fourier transform infrared spectroscopy) and photo-DSC (differential scanning calorimetry). The thermo-mechanical properties of the thermosets employing DMA- (dynamic mechanical analysis) and tensile analysis were deeply evaluated. Finally, the possibility to use the best cured system as an adhesive was raised investigating the shear strength of metallic and composite joined samples using the single lap offset (SLO) test under compression.

The scientific community is deeply investigating bio-based derivatives to reduce the consumption of fossil-based material and lessen the environmental impact. The development of bio-based plastic is one of the main challenges that needs to be overcome to achieve the goal of sustainability and green economy. In this view, we exploit the use of a bio-based monomer, isosorbide, for the production of bio-based resins which can be used in coating applications. The isosorbide was functionalized in a two-step reaction to introduce epoxy groups that subsequently were activated via UV radiation to trigger cross-linking to obtain dry films. The curing process was followed by means of real time analyses such as FT-IR, photo-DSC and photorheology. The bio-based resin showed the feasibility to be used in UV-cationic curing reaching conversion above 85 %. Furthermore, a bio-based filler from macadamia nutshell was selected as an additive to the formulation with the aim of increasing the surface hardness of the final coating. A significant increase in hardness was observed for coatings containing 30 wt% of macadamia nut shell powder (MAC). In this case, the hardness reached 72 Shore D, whereas the pristine bio-based epoxy resin achieved only 19 Shore D. Thermo-mechanical analysis of the final properties was carried out by means of DMTA, DSC and tensile test. Interestingly, the addition of MAC resulted in a noticeable increase of the Tg, from 24 °C for the pristine resin to 39 °C for the coating with 20 wt% of filler. Lastly, a morphology assessment was performed to investigate the size and shape of the filler and the interaction between the polymer matrix and the filler.

To provide protection against corrosion in harsh environments, high performance anticorrosive coatings are applied on steel structures at all scales. However, to also limit the use of fossil-based ingredients, there is a growing demand to incorporate renewable raw materials in the coating formulations. In this study, to replace pigments and fillers of an epoxy novolac coating, technical Kraft lignin particles were ground and size fractionated (i.e., sieved), and used for formulation work. The effects of sieved and unsieved Kraft lignin, as structure-reinforcing components, on the anticorrosive and mechanical performance of epoxy coatings were subsequently investigated using the following methods: size exclusion chromatography (SEC), phosphorous nuclear magnetic resonance spectroscopy (31P NMR), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), salt spray exposure, pull-off, König pendulum hardness, and chemical resistance tests. Compared to the unsieved-lignin reference (U-L EN), the coating based on lignin fines (S-L EN) showed about 31 % lower rust creep after 70 days of salt spray exposure. However, no surface defects or chemical degradation were observed for any of the coatings. For the S-L EN coating, excellent adhesion strength (23 MPa) and impact resistance (0.49 N), relative to reference values of 17 and 13 MPa and 0.41 and 0.07 N for commercial and lignin-based diglycidyl ether bisphenol F (L-DGEBF) coatings, respectively, were measured. The addition of lignin particles did not influence the chemical resistance, the hardness, and the glass transition temperature of the epoxy novolac coatings. In summary, chemically unmodified Kraft lignin particles, after grinding and sieving, can be incorporated in epoxy novolac coatings (up to 25 vol%), thereby providing a bio-based alternative to pigments and fillers in heavy duty coatings (primers in particular). 

In this study, the combination of sequential solvent fractionation of technical Kraft lignin was followed by allylation of most OH functionalities to give highly functional thermoset resins. All lignin fractions were highly functionalized on the phenolic (≥95%) and carboxylic acid OH (≥85%) and to a significant extent on the aliphatic OH moieties (between 43 and 75%). The resins were subsequently cross-linked using thiol-ene chemistry. The high amount of allyl functionalities resulted in a high cross-link density. Dynamic mechanical analysis measurements showed that the thioether content, directly related to the allyl content, strongly affects the performance of these thermosets with a glass transition temperature (Tg) between 81 and 95 °C and with a storage modulus between 1.9 and 3.8 GPa for all thermosets. The lignin fractions and lignin-based thermosets’ morphology, at the nanoscale, was studied by wide-angle X-ray scattering measurements. Two π-π stacking interactions were observed: sandwich (≈4.1-4.7 Å) and T-shaped (≈5.5-7.2 Å). The introduction of allyl functionalities weakens the T-shaped π-π stacking interactions. A new signal corresponding to a distance of ≈3.5 Å was observed in lignin-based thermosets, which was attributed to a thioether organized structure. At the same time, a lignin superstructure was observed with a distance/size corresponding to 7.9-17.5 Å in all samples.