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Chemically-resistant epoxy novolac coatings: Effects of size-fractionated technical Kraft lignin particles as a structure-reinforcing component
CoaST, Department of Chemical and Biochemical Engineering, Technical University of Denmark, DTU, Building 229, 2800 Kgs., Lyngby, Denmark.ORCID iD: 0000-0002-6736-4875
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0002-1184-1310
CoaST, Department of Chemical and Biochemical Engineering, Technical University of Denmark, DTU, Building 229, 2800 Kgs., Lyngby, Denmark.ORCID iD: 0000-0003-3802-0851
CoaST, Department of Chemical and Biochemical Engineering, Technical University of Denmark, DTU, Building 229, 2800 Kgs., Lyngby, Denmark.ORCID iD: 0000-0001-7178-4808
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2023 (English)In: Progress in organic coatings, ISSN 0300-9440, E-ISSN 1873-331X, Vol. 183, article id 107793Article in journal (Refereed) Published
Abstract [en]

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). 

Place, publisher, year, edition, pages
Elsevier, 2023. Vol. 183, article id 107793
Keywords [en]
Anticorrosive coatings, Bio-based, Sustainable, High performance, Organic polymers
National Category
Materials Engineering Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-332093DOI: 10.1016/j.porgcoat.2023.107793ISI: 001044190800001Scopus ID: 2-s2.0-85165192498OAI: oai:DiVA.org:kth-332093DiVA, id: diva2:1783175
Note

QC 20230719

Available from: 2023-07-19 Created: 2023-07-19 Last updated: 2024-09-23Bibliographically approved
In thesis
1. Lignin towards thermoset applications
Open this publication in new window or tab >>Lignin towards thermoset applications
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The global shift towards sustainable development requires the replacement of fossil-based materials with renewable alternatives. Lignin, a complex aromatic biopolymer derived from lignocellulosic biomass, represents one of the most abundant sources of renewable carbon. Retrieved as a byproduct from the pulp and paper industry, lignin has thus far been underutilized despite its potential. Its unique chemical structure, characterized by phenolic units linked through various interunit linkages, makes it a strong candidate for creating durable resistant materials. However, lignin's complex and heterogeneous structure, as well as its limited reactivity, present challenges for its use. In this work, lignin has been investigated for thermosetting applications through different methodologies, including extraction, fractionation, chemical modification, and direct utilization of unmodified lignin. This present research demonstrates different ways to develop materials with enhanced mechanical, thermal, and chemical properties, suitable for industrial applications. To achieve this, various methodologies and lignin sources were employed. Lignin was extracted through a mild extraction from wheat straw in order to valorize agricultural products. Microwave-assisted fractionation was employedin order to isolate lignin fractions with more tunable properties and increased reactivity. Chemical modifications, including epoxidation and allylation, were performed to enhance the reactivity of lignin and improve its compatibility in thermosetting formulations. These modified lignins were incorporated into epoxy-based coatings and thiol-ene systems, demonstrating their potential in producing durable and high-performance materials. In addition to modified lignin, unmodified lignin was directly utilized in coating formulations. This thesis demonstrates that both modified and unmodified lignin can be successfully integrated into thermosetting systems, furnishing materials that meet or exceed the performance of conventional fossil-based counterparts. The work emphasizes the advantages and limitations of each method, highlighting the importance of optimizing processing efficiency, material performance, and environmental sustainability.

Abstract [sv]

Den globala övergången till hållbar utveckling kräver att fossila material ersätts med förnybara alternativ. Lignin, en komplex aromatisk biopolymer som härrör från lignocellulosisk biomassa, representerar en av de mest rikliga källorna till förnybart kol. Lignin utvinns som en biprodukt från massa- och pappersindustrin och har trots sin potential varit underutnyttjad. Dess unika kemiska struktur, som kännetecknas av fenolenheter kopplade genom olika interenhetsbindningar, gör det till en stark kandidat för att skapa hållbara och resistenta material. Dock utgör lignins komplexa och heterogena struktur, samt dess begränsade reaktivitet, utmaningar för dess användning. I detta arbete har lignin undersökts för användning i härdplaster genom olikametoder som inkluderar extraktion, fraktionering, kemisk modifiering och direkt användning av modifierat lignin. Forskningen syftade till att utveckla material med förbättrade mekaniska, termiska och kemiska egenskaper, lämpade för industriella tillämpningar. För att uppnå detta användes olika metoder och ligninkällor. Lignin extraherades genom en mild extraktion från vetestrå för att valorisering jordbruksprodukter. Mikrovågsassisterad fraktionering användes för att isolera ligninfraktioner med mer anpassningsbara egenskaper och ökad reaktivitet. Kemiska modifieringar, inklusive epoxidering och allylering, genomfördes för att förbättra lignins reaktivitet och dess kompatibilitet i härdplastformuleringar. Dessa modifierade lignin integrerades i epoxibaserade beläggningar och thiolen-system, vilket visade deras potential att producera hållbara och högpresterande material. Förutom modifierat lignin användes även modifierat lignin direkt i beläggningsformuleringar. Denna avhandling visar att både modifierat och modifierat lignin framgångsrikt kan integreras i härdplastsystem och skapa material som uppfyller eller överträffar prestandan hos konventionella fossilbaserade motsvarigheter. Arbetet framhäver fördelar och begränsningar med varje metod och understryker vikten av att optimera processeffektivitet, materialprestanda och miljömässig hållbarhet.

Place, publisher, year, edition, pages
Stockholm, Sweden: KTH Royal Institute of Technology, 2024. p. 70
Series
TRITA-CBH-FOU ; 2024:43
Keywords
technical lignin, softwood, coatings, thiol-ene thermosets, epoxy-amine, fractionation
National Category
Polymer Technologies Materials Chemistry Organic Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-353722 (URN)978-91-8106-069-0 (ISBN)
Public defence
2024-10-18, F3, https://kth-se.zoom.us/j/65370649186, Lindstedtsvägen 26 & 28, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20240925

Available from: 2024-09-25 Created: 2024-09-23 Last updated: 2024-09-30Bibliographically approved

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Truncali, AlessioJohansson, Mats

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