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). 

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.

Lignin is the most abundant aromatic biopolymer, with a potential to serve as a building block of rigid and thermally stable bio-based materials. However, it is still underutilized because of the heterogeneous and not fully understood chemical structure. Here, technical softwood Kraft lignin is refined in to narrow-dispersity and relatively low molar mass fractions by microwave-assisted processing, followed by microwave-assisted allylation and further application in lignin-based thermosets. This microwave processing is carried out under non-catalyzed conditions using a low boiling point solvent and elevated pressure. The properties of the retrieved fractions are investigated by 31P-NMR, heteronuclear single quantum coherence spectroscopy-NMR, SEC, differential scanning calorimetry, and thermogravimetric analysis. The extraction yield of the selected lignin fraction is around 25%, with the number-average molar mass (Mn), weight-average molar mass (Mw), and dispersity (Đ) significantly reduced. The chemically modified lignin is characterized by 31P NMR and FTIR, which provides evidence of the introduction of the allyl moieties. The analyses demonstrate that 90 ± 3% of the hydroxyl groups in fractionated lignin are successfully allylated. Subsequently, the allylated lignin is cross-linked through thermally induced thiol-ene chemistry to produce lignin-based thermosets. The final thermosets exhibit a storage modulus of 4050 ± 60 MPa and a Tg of 105 ± 5°C.

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 where the latter gave the highest degree of functionality. The results also show that it is crucial to choose a functionalization protocol that is adapted to the functional groups present in the specific lignin used. 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.