Morphological and Thermochemical Changes upon Autohydrolysis and Microemulsion Treatments of Coir and Empty Fruit Bunch Residual Biomass to Isolate Lignin-Rich Micro- and Nanofibrillar Cellulose

Autohydrolysis and microemulsion treatments followed by microfluidization are employed to isolate micro- and nanofibrillar cellulose (MNFC) from coir fibers and palm tree empty fruit bunches (EFB) with residual lignin content of ∼24 and ∼31 wt %, respectively. The fibers and associated MNFC are characterized in each treatment for their chemical, structural, and thermal properties. The most significant findings include the fact that two MNFC populations are produced, with distinctive structural differences and characteristic lateral dimensions of 20–70 nm and 1–3 μm. The lignin distribution after possible recondensation occurred in the form of nanodroplets. Finally, a correlation between thermal degradation of MNFC with spatial arrangement of lignin is hypothesized and a defibrillation mechanism is proposed. The detailed structural and thermochemical analyses presented here are expected to facilitate further interest in the development of new materials from MNFC isolated from coir and EFB, two abundant bioresources that are most suitable for their valorization

Effect of Anisotropy of Cellulose Nanocrystal Suspensions on Stratification, Domain Structure Formation, and Structural Colors

Outstanding optical and mechanical properties can be obtained from hierarchical assemblies of nanoparticles. Herein, the formation of helically ordered, chiral nematic films obtained from aqueous suspensions of cellulose nanocrystals (CNCs) were studied as a function of the initial suspension state. Specifically, nanoparticle organization and the structural colors displayed by the resultant dry films were investigated as a function of the anisotropic volume fraction (AVF), which depended on the initial CNC concentration and equilibration time. The development of structural color and the extent of macroscopic stratification were studied by optical and scanning electron microscopy as well as UV–vis spectroscopy. Overall, suspensions above the critical threshold required for formation of liquid crystals resulted in CNC films assembled with longer ranged order, more homogeneous pitches along the cross sections, and narrower specific absorption bands. This effect was more pronounced for the suspensions that were closer to equilibrium prior to drying. Thus, we show that high AVF and more extensive phase separation in CNC suspensions resulted in large, long-range ordered chiral nematic domains in dried films. Additionally, the average CNC aspect ratio and size distribution in the two separated phases were measured and correlated to the formation of structured domains in the dried assemblies

High Axial Ratio Nanochitins for Ultrastrong and Shape-Recoverable Hydrogels and Cryogels <i>via</i> Ice Templating

High yield (>85%) and low-energy deconstruction of never-dried residual marine biomass is proposed following partial deacetylation and microfluidization. This process results in chitin nanofibrils (nanochitin, NCh) of ultrahigh axial size (aspect ratios of up to 500), one of the largest for bioderived nanomaterials. The nanochitins are colloidally stable in water (ζ-potential = +95 mV) and produce highly entangled networks upon pH shift. Viscoelastic and strong hydrogels are formed by ice templating upon freezing and thawing with simultaneous cross-linking. Slow supercooling and ice nucleation at −20 °C make ice crystals grow slowly and exclude nanochitin and cross-linkers, becoming spatially confined at the interface. At a nanochitin concentration as low as 0.4 wt %, highly viscoelastic hydrogels are formed, with a storage modulus of ∼16 kPa, at least an order of magnitude larger compared to those measured for the strongest chitin-derived hydrogels reported so far. Moreover, the water absorption capacity of the hydrogels reaches a value of 466 g g–1. Lyophilization is effective in producing cryogels with a density that can be tailored in a wide range of values, from 0.89 to 10.83 mg·cm–3, and corresponding porosity, between 99.24 and 99.94%. Nitrogen adsorption results indicate reversible adsorption and desorption cycles of macroporous structures. A fast shape recovery is registered from compressive stress–strain hysteresis loops. After 80% compressive strain, the cryogels recovered fast and completely upon load release. The extreme values in these and other physical properties have not been achieved before for neither chitin nor nanocellulosic cryogels. They are explained to be the result of (a) the ultrahigh axial ratio of the fibrils and strong covalent interactions; (b) the avoidance of drying before and during processing, a subtle but critical aspect in nanomanufacturing with biobased materials; and (c) ice templating, which makes the hydrogels and cryogels suitable for advanced biobased materials