Structural Analysis of Lignin-Based Furan Resin

The global “carbon emission peak” and “carbon neutrality” strategic goals promote us to replace current petroleum-based resin products with biomass-based resins. The use of technical lignins and hemicellulose-derived furfuryl alcohol in the production of biomass-based resins are among the most promising ways. Deep understanding of the resulting resin structure is a prerequisite for the optimization of biomass-based resins. Herein, a semiquantitative 2D HSQC NMR technique supplemented by the quantitative 31P NMR and methoxyl group wet chemistry analysis were employed for the structural elucidation of softwood kraft lignin-based furfuryl alcohol resin (LFA). The LFA was fractionated into water-insoluble (LFA-I) and soluble (LFA-S) parts. The analysis of methoxyl groups showed that the amount of lignin was 85 wt% and 44 wt% in LFA-I and LFA-S fractions, respectively. The HSQC spectra revealed the high diversity of linkages formed between lignin and poly FA (pFA). The HSQC and 31P results indicated the formation of new condensed structures, particularly at the 5-position of the aromatic ring. Esterification reactions between carboxyl groups of lignin and hydroxyl groups of pFA could also occur. Furthermore, it was suggested that lignin phenolic hydroxyl oxygen could attack an opened furan ring to form several aryl ethers structures. Therefore, the LFA resin was produced through crosslinking between lignin fragments and pFA chains.

Improved procedure for electro-spinning and carbonisation of neat solvent-fractionated softwood Kraft lignin

In general, the electro-spinning of lignin requires it to be functionalised and/or blended with synthetic or natural polymers. This paper reports on the use of solvent fractionated lignin-lignin blend to electro-spin BioChoice softwood Kraft lignin. The blend consisted of acetone-soluble and ethanol-soluble lignin in a binary solvent of acetone and DMSO. Solvent fractionation was used to purify lignin where the ash content was reduced in the soluble lignin fractions from 1.24 to ~ 0.1%. The corresponding value after conventional acid-washing in sulphuric acid was 0.34%. A custom-made electro-spinning apparatus was used to produce the nano-fibres. Heat treatment procedures were developed for drying the electro-spun fibres prior to oxidation and carbonisation; this was done to prevent fibre fusion. The lignin fibres were oxidised at 250 °C, carbonised at 1000 °C, 1200 °C and 1500 °C. The cross-section of the fibres was circular and they were observed to be void-free. The longitudinal sections showed that the fibres were not fused. Thus, this procedure demonstrated that solvent fractionated lignin can be electro-spun without using plasticisers or polymer blends using common laboratory solvents and subsequently carbonised to produce carbon fibres with a circular cross-section.

Molar mass determination of lignins and characterization of their polymeric structures by multi-detector gel permeation chromatography

Molar masses, Mark-Houwink-Sakurada (MHS) exponents, and refractive index increments (dn/dc) for three lignins were determined without derivatization by multi-detector gel permeation chromatography (GPC) in dimethylformamide (DMF) with 0.05 M lithium bromide (LiBr). The lack of effectiveness of fluorescence filters on molar mass determination by GPC-multi-angle laser light scattering (MALS) was confirmed for softwood kraft lignin (Indulin AT) and revealed for mixed hardwood organosolv lignin (Alcell) as well as soda straw/grass lignin (Protobind 1000). GPC with viscometry detection confirmed that these lignins were present as compact molecules. The MHS exponent α for Indulin AT and Alcell was in the order of 0.1. Additionally, the intrinsic viscosity of Protobind 1000 for a given molar mass was much lower than that of either Alcell or Indulin AT. This is the first report of dn/dc values for these three lignins in DMF with 0.05 M LiBr.

Understanding the local structure of disordered carbons from cellulose and lignin

An electron microscopy investigation was performed to understand the relationship between the microstructure and properties of carbonized cellulose and lignin (softwood kraft lignin) relative to the structure of the original biomass components. Structure details at micro- and molecular levels were investigated by scanning transmission electron microscopy. Atomic-resolution images revealed the presence of random disordered carbon in carbonized cellulose (C-CNC) and of large domains of well-ordered carbon with graphite sheet structure in carbonized lignin (C-Lignin). These structural differences explain why C-CNC exhibits higher surface area and porosity than C-Lignin. The presence of certain well-ordered carbon in carbonized lignin indicates some of the carbon in lignin are graphitized with heat treatment temperature up to 950 °C. This result is encouraging for future endeavors of attaining acceptable modulus of carbon fiber from lignin given suitable modifications to the chemistry and structure of lignin. The results of this research contribute to an improved understanding of the carbonization mechanism of the key cellulose and lignin components of biomass materials.

On the Feasibility of a pMDI-Reduced Production of Wood Fiber Insulation Boards by Means of Kraft Lignin and Ligneous Canola Hulls

The thermal insulation of buildings using wood fiber insulation boards (WFIBs) constitutes a positive contribution towards climate change. Thereby, the bonding of wood fibers using mainly petrochemical-based resins such as polymeric diphenylmethane diisocyanate (pMDI) is an important measure to meet required board properties. Still there is a need to reduce or partial substitute the amount of these kinds of resins in favor of a greener product. This study therefore focusses on the feasibility of reducing the amount of pMDI by 50% through the addition of 1% BioPiva 395 or Indulin as two types of softwood Kraft-Lignin and lignin rich canola hulls together with propylene carbonate as a diluent. A panel density of 160 kg/m3 and a thickness of 40 mm was aimed. The curing of these modified pMDI was investigated by using two types of techniques: hot-steam (HS) and innovative hot-air/hot-steam-process (HA/HS). The WFIBs were then tested on their physical-mechanical properties. The equilibrium moisture content (EMC) was determined at two different climates. An exemplary investigation of thermal conductivity was conducted as well. The WFIBs did undergo a further chemically based analysis towards extractives content and elemental (C, N) composition. The results show that it is feasible to produce WFIBs with lower quantities of pMDI resin and added lignin with enhanced physical-mechanical board properties, which were lacking no disadvantages towards thermal conductivity or behavior towards moisture, especially when cured via HA/HS-process.

Improved Procedure for Electro-Spinning and Carbonisation of Neat Solvent-Fractionated Softwood Kraft Lignin

In general, the electro-spinning of lignin requires it to be functionalised and/or blended with synthetic or natural polymers. This paper reports on the use of solvent fractionated lignin-lignin blend to electro-spin BioChoice® softwood Kraft lignin. The blend consisted of acetone-soluble and ethanol-soluble lignin in a binary solvent of acetone and DMSO. Solvent fractionation was used to purify lignin where the ash content was reduced in the soluble lignin fractions from 1.24% to ~0.1%. The corresponding value for conventional acid-washing in sulphuric acid was 0.34%. A custom-made electro-spinning apparatus was used to produce the nano-fibres. Heat treatment procedures were developed for drying the electro-spun fibres prior to oxidation and carbonisation; this was done to prevent fibre fusion. The lignin fibres were oxidised at 250⁰C, carbonised at 1000⁰C and 1500⁰C. The cross-section of the fibres was circular and they were observed to be void-free. The longitudinal sections showed that the fibres were not fused. Thus, this procedure demonstrated that solvent fractionated lignin can be electro-spun without using plasticisers or polymer blends using common laboratory solvents and subsequently carbonised to produce carbon fibres with a circular cross-section.