Högskolan i Skövde

A rapeseed straw biorefinery process was demonstrated with more than 50% of the straw recovered as products. Xylan with a weight-average molecular weight of 56 760 g/mol was extracted in an alkaline step. The straw residue was subjected to soda pulping, resulting in cellulose-rich fibers and a lignin-rich liquid fraction. The lignin contained syringyl and guaiacyl aromatic structural units in a 1/0.75 ratio. The cellulose pulp was bleached, resulting in a cellulose fraction of 85% purity and a crystallinity index (CI) of 83%. Two grades of nanocellulose, CNF and CNC, were isolated from the bleached pulp. The CNF was very heterogeneous in size with an average diameter of 4 nm and an average length of 1177 nm. The CNC had an average diameter of 6 nm and an average particle length of 193 nm. CNF and CNC had good thermal stability and an aspect ratio of 294 and 32, respectively.

This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating values, and thermal and adsorption properties of industrial hardwood and softwood kraft lignins. The aim of the research was to develop a simple approach for obtaining lignin fractions with tailored properties for applications in certain materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations, were found to be efficient for separating spruce and eucalyptus kraft lignins into fractions with low polydispersities. The ethanol fraction of spruce and the ethyl acetate fraction of eucalyptus afforded the highest yields. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material was characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and 31P NMR spectroscopy. The thermal properties of the lignin samples were studied using thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) was obtained through the direct measurement of weight changes in each experimental curve, and the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The adsorption properties of fractionated kraft lignins were studied using methylene blue dye. The correlations observed between molecular weight, composition and functionality and the thermal, radical scavenging and adsorption properties of the lignin fractions provides useful information for selecting the appropriate solvent combinations for specific applications of lignin raw materials (including their use as antioxidants, biofuels or sorbents in water treatment processes). © 2018

This study presents comparative assessments on hydrophilic and hydrophobic ZnO nanoparticles and their deposition methods on the surface hydrophobicity of silicone rubber (PDMS) and glass substrates. The influence on the surface hydrophobicity and wettability of all the variables regarding the deposition methodologies and the interaction of the nanoparticles with the substrates were within the scope of this study. The different surfaces created by spraying, dipping and drop-pipetting deposition methods were assessed by static contact angle measurements and contact angle hysteresis from advancing and receding angles, as well as by the calculation of the sliding angle and the surface energy parameters. An accurate methodology to determine the contact angle hysteresis was proposed to obtain repetitive and comparative results on all surfaces. All the measurements have been correlated with the morphology and topography of the different surfaces analysed by FE-SE microscopy. The spray-deposition of hydrophobic ZnO nanoparticles on PDMS resulted in super-hydrophobic surfaces, exhibiting hierarchical structures with micro-and nanometer features which, together with the low surface energy, promotes the Cassie-Baxter wetting behavior. This study provides the fundamental approach to select critically the most promising combination in terms of materials and deposition techniques to create silicone-based super-hydrophobic surfaces with potential to be applied in high voltage outdoor insulation applications.

Cellulose nanocrystals (CNCs) were isolated for the first time from pine cones (PC) by alkali and bleaching treatments and subsequent sulfuric acid hydrolysis (64%) at 45 degrees C. The influence of the hydrolytic reaction time (30, 45, and 90 min) on the yield, chemical composition and structure, and thermal stability of CNCs was evaluated. The removal of non-cellulosic constituents during the alkaline and bleaching treatment resulted in high pure cellulosic fibres. The isolation of CNCs from these cellulosic fibres at different reaction times was verified by the nano-dimensions of the individual crystals (< 3 and < 335 nm of average diameter and length, respectively). The highest yield (15%) and the optimum CNCs properties in terms of aspect ratio, thermal stability and crystallinity were obtained for an extraction time of 45 min. PC appeared to be a new promising source of cellulose fibres and CNCs with potential to be applied as reinforcement in composites and for food-packaging.

In this work, different loads (3, 5 and 7 wt%) of pine cone cellulose nanocrystals (CNCs) were added to films ofpoly(3-hydroxybutyrate)/poly(ε-caprolactone) (PHB/PCL) blends with a composition of 75 wt% PHB and 25 wt% PCL (PHB75/PCL25). The films were obtained after solvent casting followed by melt compounding in anextruder and finally subjected to a thermocompression process. The influence of different CNCs loadings on themechanical, thermal, optical, wettability and disintegration in controlled compost properties of the PHB75/PCL25blend was discussed. Field emission scanning electron microscopy (FESEM) revealed the best dispersion of CNCson the polymeric matrix was at a load of 3 wt%. Over this loading, CNCs aggregates were formed enhancing thefilms fragilization due to stress concentration phenomena. However, the addition of CNCs improved the opticalproperties of the PHB75/PCL25films by increasing their transparency and accelerated the film disintegration incontrolled soil conditions. In general, the blend with 3 wt% CNCs offers the best balanced properties in terms ofmechanical, thermal, optical and wettability

The potential of organosolv and kraft eucalyptus and spruce lignin as feedstock for polymeric materials and biofuel applications was assessed. Proximate analysis was used to predict the heating values and char formation. Chemical modification, based on the esterification reaction with methacryloyl chloride, was applied to introduce vinyl groups into the lignin macromolecules for enhanced reactivity. Kraft eucalyptus and spruce lignins had a more condensed structure than organosolv lignins, which resulted in greater thermal stability for these lignins. For different species within the same process, the thermal parameters showed a correlation with certain structural and compositional parameters (ash and sugars content, molecular weight and degree of condensation). Organosolv spruce lignin produced the highest heating value of 24. MJ/Kg, which is suitable for biofuel applications. The content of phenolic OH groups was higher for kraft lignins and especially higher for softwood lignins, both organosolv and kraft. The degree of methacrylation, estimated from the content of vinyl groups per C9 lignin unit, was significantly greater for organosolv lignins than for kraft lignins despite the higher OH-groups content in the latter.

In this study, new wood-inspired films were developed from microfibrillated cellulose and galactoglucomannan-lignin networks isolated from chemothermomechanical pulping side streams and cross-linked using laccase enzymes. To the best of our knowledge, this is the first time that cross-linked galactoglucomannan-lignin networks have been used for the potential development of composite films inspired by woody-cell wall formation. Their capability as polymeric matrices was assessed based on thermal, structural, mechanical and oxygen permeability analyses. The addition of different amounts of microfibrillated cellulose as a reinforcing agent and glycerol as a plasticizer on the film performances was evaluated. In general, an increase in microfibrillated cellulose resulted in a film with better thermal, mechanical and oxygen barrier performance. However, the presence of glycerol decreased the thermal stability, stiffness and oxygen barrier properties of the films but improved their elongation. Therefore, depending on the application, the film properties can be tailored by adjusting the amounts of reinforcing agent and plasticizer in the film formulation.

This study investigates for the first time the feasibility of extracting cellulose nanocrystals (CNCs) from softwood forestry logging residues (woody chips, branches and pine needles), with an obtained gravimetric yield of over 13%. Compared with the other residues, woody chips rendered a higher yield of bleached cellulosic fibers with higher hemicellulose, pectin and lignin content, longer diameter, and lower crystallinity and thermal stability. The isolation of CNCs from these bleached cellulosic fibers was verified by the removal of most of their amorphous components, the increase in the crystallinity index, and the nano-dimensions of the individual crystals. The differences in the physico-chemical properties of the fibers extracted from the three logging residues resulted in CNCs with specific physico-chemical properties. The potential of using the resulting CNCs as reinforcements in nanocomposites was discussed in terms of aspect ratio, crystallinity and thermal stability.

A biorefinery of forest resources should be able to convert all components of trees, including the bark and other types of forest residues, into value-added products. Here, non-cellulosic polysaccharides (NCPs) isolated from Norway spruce bark and cellulose nanocrystals (CNCs) isolated from the logging residues of Norway spruce were mixed to prepare nanocomposites with competitive thermo-mechanical properties. Polyepoxy acid (PEA) derived from a monomer of suberin in birch bark was used as a coating on the nanocomposites to develop functional materials entirely based on forest resources. All of the PEA-coated nanocomposites were hydrophobic. At 50% and 80% relative humidity, they showed high oxygen-barrier properties that were comparable to or even better than those of some renewable materials such as xylan-, galactoglucomannan- and nanofibrillated cellulose-based films and synthetic materials such as polyvinylidene chloride and polyamide.

The potential of seven kraft cook materials to become functional char materials and fuels is investigated. Thermogravimetric analysis was used to study the thermal properties while a model-free isoconversional method was used to derive kinetic rate expressions. Black liquor precipitates had lower thermal stability (20-60 K lower) than pulps and spruce wood and the precipitates decomposed in a wider temperature range, producing chars with similar or higher thermal stability than char from pulps, but lower than those from spruce wood. Samples suitable to produce char were identified based on char yield, devolatilization rate and charring temperature. The highest char yield (46%), achieved from a precipitate, was more than twice as high as that from spruce powder. Under the studied conditions none of the materials had a pyrolysis process that for the whole conversion range could be described with a single set of kinetic parameters. The apparent activation energy varied between 170-260 kJ/mol for the pulps and 50-650 kJ/mol for the precipitates. The derived kinetic parameters were validated by predicting the conversion at a heating rate outside the range used for its derivation and at quasi isothermal conditions. Both these tests gave satisfactory results in good agreement with experimental data.