Molecularly Engineered Lignin-Derived Additives Enable Fire-Retardant, UV-Shielding, and Mechanically Strong Polylactide Biocomposites.

From a perspective of sustainable development and practical applications, there has been a great need for the design of advanced polylactide (PLA) biocomposites that are flame-retardant, ultraviolet (UV)-resistant, and mechanically strong by using biomass-derived additives. Unfortunately, the achievement of a desirable performance portfolio remains unsatisfactory because of improper design strategies. Herein, we report the design of lignin-derived multifunctional bioadditives (TP-g-lignin) with tunable chemical compositions through graft polymerization of a phosphorus-/nitrogen-containing vinyl monomer (TP). Our results show that the incorporation of 5.0 wt % of TP-g-lignin (at a lignin-to-TP ratio of 1:4 by mass) enables PLA to achieve a desirable flame retardancy rating meeting the UL-94 V-0 industrial standard requirements. Meanwhile, the final PLA composite exhibits an exceptional UV-shielding capability. Moreover, with 5.0 wt % of the bio-derived additive, the elastic modulus of PLA is increased by ∼26%, while mechanical strength is fully retained due to engineered favorable interfaces. This work offers an innovative and sustainable strategy for creating bio-based multifunctional additives by using industrial lignin waste and further the application of PLA in the areas of packaging, fabrics, electronics, automobiles, etc.

Atomic Layer Deposition of Metal Oxide on Nanocellulose for Enabling Microscopic Characterization of Polymer Nanocomposites.

Analysis of cellulose nanocrystals (CNCs) at low volume fractions in polymer nanocomposites through conventional electron microscopy still remains a challenge due to insufficient contrast between CNCs and organic polymer matrices. Herein, a methodology for enhancing the contrast of CNC, through atomic layer deposition (ALD) of alumina (Al2 O3 ) on CNCs is demonstrated. The metal oxide coated CNC allows clear visualization by transmission electron microscopy, when they are dispersed in water and polyol. A coating of about 6 ± 1 nm thick alumina layer on the CNC is achieved after 50 ALD cycles. This also enables the characterization of CNC dispersion/orientation (at 0.2 wt% loading) in an amorphous cellular system rigid polyurethane foam (RPUF), using backscattered electron microscopy with energy-dispersive X-ray spectroscopy. Microscopic analysis of the RPUF with alumina-coated CNC confirms that the predominant alignment of CNC occurs in a direction parallel to the foam rise.

Dip-and-Drag Lateral Force Spectroscopy for Measuring Adhesive Forces between Nanofibers.

Adhesive interactions between nanofibers strongly influence the mechanical behavior of soft materials composed of fibrous networks. We use atomic force microscopy in lateral force mode to drag a cantilever tip through fibrous networks, and use the measured lateral force response to determine the adhesive forces between fibers of the order of 100 nm diameter. The peaks in lateral force curves are directly related to the detachment energy between two fibers; the data is analyzed using the Jarzynski equality to yield the average adhesion energy of the weakest links. The method is successfully used to measure adhesion forces arising from van der Waals interactions between electrospun polymer fibers in networks of varying density. This approach overcomes the need to isolate and handle individual fibers, and can be readily employed in the design and evaluation of advanced materials and biomaterials which, through inspiration from nature, are increasingly incorporating nanofibers. The data obtained with this technique may also be of critical importance in the development of network models capable of predicting the mechanics of fibrous materials.

Influence of Different Nanocellulose Additives on Processing and Performance of PAN-Based Carbon Fibers.

Nanocellulose, as a biobased versatile nanomaterial that can be derived with tailorable surface functionalities, dimensions, and morphologies, has considerable implications for modifying the rheology, mechanical reinforcement, and influencing the carbonization efficiency in the production of polyacrylonitrile (PAN)-based carbon fibers. Herein, we report the influence of three different nanocellulose types, varying in the derivatization method, source, and aspect ratio, on the mechanical properties and thermal transformations of solution-spun PAN/nanocellulose nanocomposite fibers into carbon fibers. The incorporation of 0.1 wt % nanocellulose into solution-spun PAN fibers led to a 7-19% increase in tensile modulus and 0-27% increase in tensile strength in the solution-spun fibers, compared to a control PAN fiber. These improvements varied depending on the nanocellulose type. After low-temperature carbonization at 1200 °C, improvements in the mechanical properties of the nanocellulose-reinforced carbon fibers, compared with a PAN fiber, were also observed. In contrast to the precursor fibers, the improvement % in the carbonized fibers was found to be dependent on the nanocellulose morphology and was linearly correlated with increasing aspect ratio of nanocellulose. For example, in carbon fibers with a cotton-derived low-aspect-ratio cellulose nanocrystal and spinifex-derived high-aspect-ratio CNC and nanofiber, up to 4, 87, and 172% improvements in tensile moduli were observed, respectively. Due to the processing methods used, the nanocellulose aspect ratio and crystallinity are inversely related, and as such, the increase in the carbon fiber mechanical properties was also related to a decrease in crystallinity of the nanocellulose reinforcers. Raman spectra and electron microscopy analysis suggest that mechanical improvement after carbonization is due to internal reinforcement by highly ordered regions surrounding the carbonized nanocellulose, within the turbostratic carbon fibers.

Reinforcement of natural rubber latex using lignocellulosic nanofibers isolated from spinifex grass.

Reinforcement of natural rubber (NR) using nanofillers often results in an enhancement of the tensile strength, but at the expense of elongation at break and toughness. In this study, with the objective of strengthening NR without compromising its compliance, we investigate the reinforcement efficiency of a series of cellulose nanofibers (CNF) with variations in residual hemicellulose, lignin and therefore surface chemistry. Different types of high aspect ratio CNF isolated from Triodia pungens (T. pungens), an Australian arid grass commonly known as spinifex, were added at 0.1-2 wt% loadings into a pre-vulcanized NR latex. CNF/NR nanocomposites then were benchmarked against NR nanocomposites incorporating a well-known wood-derived CNF. It was found that the presence of residual lignin and hemicellulose, and the pretreatment with a deep eutectic solvent, a mixture of choline chloride and urea (CCU), could increase the compatibility of CNF with the NR matrix, while still enabling stability and handling of the colloidal latex mixture. Incorporation of 0.5 and 0.1 wt% of the sodium hydroxide treated CNF and choline chloride/urea treated CNF into the NR latex showed respectively 11 and 17% enhancement in tensile stress, and importantly without compromising viscoelastic properties; while addition of 0.1 wt% wood-derived CNF resulted in 18% decrease in both tensile stress and strain coupled with more pronounced latex stiffening.

Water-responsive mechanically adaptive nanocomposites based on styrene-butadiene rubber and cellulose nanocrystals--processing matters.

Biomimetic, stimuli-responsive polymer nanocomposites based on a hydrophobic styrene-butadiene rubber (SBR) matrix and rigid, rod-like cellulose nanocrystals (CNCs) isolated from cotton were prepared by three different approaches, and their properties were studied and related to the composition, processing history, and exposure to water as a stimulus. The first processing approach involved mixing an aqueous SBR latex with aqueous CNC dispersions, and films were subsequently formed by solution-casting. The second method utilized the first protocol, but films were additionally compression-molded. The third method involved the formation of a CNC organogel via a solvent exchange with acetone, followed by infusing this gel, in which the CNCs form a percolating network with solutions of SBR in tetrahydrofuran. The thermomechanical properties of the materials were established by dynamic mechanical thermal analysis (DMTA). In the dry state, all nanocomposites show much higher tensile storage moduli, E', than the neat SBR or the SBR latex. E' increases with the CNC content and depends strongly on the processing method, which appears to influence the morphology of the SBR nanocomposites produced. The highest E' values were observed for the solution cast samples involving an SBR latex, where E' increased from 3 MPa for the neat SBR to ca. 740 MPa for the nanocomposite containing 20% v/v CNCs. Upon submersion in deionized water, a dramatic reduction of E' was observed, for example from 740 to 5 MPa for the solution-cast nanocomposite containing 20% v/v CNCs. This change is interpreted as a disengagement of the percolating CNC network, on account of modest aqueous swelling and competitive hydrogen bonding of water molecules with the CNCs. It is shown that the method of preparation also influenced the swelling behavior and kinetics of modulus switching, consistent with different arrangements of the CNCs, which serve as channels for water absorption and transport within the hydrophobic SBR matrix.