Anisotropic foams derived from textile-based cellulose nanocrystals and xanthan gum.

The upcycling of discarded garments can help to mitigate the environmental impact of the textile industry. Here, we fabricated hybrid anisotropic foams having cellulose nanocrystals (CNCs), which were isolated from discarded cotton textiles and had varied surface chemistries as structural components, in combination with xanthan gum (XG) as a physical crosslinker of the dispersion used for foam preparation. All CNCs had crystallinity indices above 85 %, zeta potential values below -40 mV at 1 mM NaCl, and true densities ranging from 1.61 to 1.67 g·cm-3. Quartz crystal microbalance with dissipation (QCM-D) measurements indicated weak interactions between CNC and XG, while rheology measurements showed that highly charged CNCs caused the XG chains to change from an extended to a helicoidal conformation, resulting in changes the in viscoelastic properties of the dispersions. The inclusion of XG significantly enhanced the compression mechanical properties of the freeze-casted foams without compromising their thermal properties, anisotropy, or degree of alignment. CNC-XG foams maintained structural integrity even after exposure to high humidity (91 %) and temperatures (100 °C) and displayed very low radial thermal conductivities. This research provides a viable avenue for upcycling cotton-based clothing waste into high-performance materials.

Visualizing Noncovalent Interactions and Property Prediction of Submicron-Sized Charge-Transfer Crystals from ab-initio Determined Structures.

The charge-transfer (CT) interactions between organic compounds are reflected in the (opto)electronic properties. Determining and visualizing crystal structures of CT complexes are essential for the design of functional materials with desirable properties. Complexes of pyranine (PYR), methyl viologen (MV), and their derivatives are the most studied water-based CT complexes. Nevertheless, very few crystal structures of CT complexes have been reported so far. In this study, the structures of two PYRs-MVs CT crystals and a map of the noncovalent interactions using 3D electron diffraction (3DED) are reported. Physical properties, e.g., band structure, conductivity, and electronic spectra of the CT complexes and their crystals are investigated and compared with a range of methods, including solid and liquid state spectroscopies and highly accurate quantum chemical calculations based on density functional theory (DFT). The combination of 3DED, spectroscopy, and DFT calculation can provide important insight into the structure-property relationship of crystalline CT materials, especially for submicrometer-sized crystals.

Thermally Insulating and Moisture-Resilient Foams Based on Upcycled Aramid Nanofibers and Nanocellulose.

Low-density foams and aerogels based on upcycled and bio-based nanofibers and additives are promising alternatives to fossil-based thermal insulation materials. Super-insulating foams are prepared from upcycled acid-treated aramid nanofibers (upANFA ) obtained from Kevlar yarn and tempo-oxidized cellulose nanofibers (CNF) from wood. The ice-templated hybrid upANFA /CNF-based foams with an upANFA content of up to 40 wt% display high thermal stability and a very low thermal conductivity of 18-23 mW m-1 K-1 perpendicular to the aligned nanofibrils over a wide relative humidity (RH) range of 20% to 80%. The thermal conductivity of the hybrid upANFA /CNF foams is found to decrease with increasing upANFA content (5-20 wt%). The super-insulating properties of the CNF-upANFA hybrid foams are related to the low density of the foams and the strong interfacial phonon scattering between the very thin and partially branched upANFA and CNF in the hybrid foam walls. Defibrillated nanofibers from textiles are not limited to Kevlar, and this study can hopefully inspire efforts to upcycle textile waste into high-performance products.

Highly magnetic hybrid foams based on aligned tannic acid-coated iron oxide nanoparticles and TEMPO-oxidized cellulose nanofibers.

Lightweight iron oxide nanoparticle (IONP)/TEMPO-oxidized cellulose nanofibril (TOCNF) hybrid foams with an anisotropic structure and a high IONP content were produced using magnetic field-enhanced unidirectional ice-templating. Coating the IONP with tannic acid (TA) improved the processability, the mechanical performance, and the thermal stability of the hybrid foams. Increasing the IONP content (and density) increased the Young's modulus and toughness probed in compression, and hybrid foams with the highest IONP content were relatively flexible and could recover 14% axial compression. Application of a magnetic field in the freezing direction resulted in the formation of IONP chains that decorated the foam walls and the foams displayed a higher magnetization saturation, remanence, and coercivity compared to the ice-templated hybrid foams. The hybrid foam with an IONP content of 87% displayed a saturation magnetization of 83.2 emu g-1, which is 95% of the value for bulk magnetite. Highly magnetic hybrid foams are of potential interest for environmental remediation, energy storage, and electromagnetic interference shielding.

Tunable Ordered Nanostructured Phases by Co-assembly of Amphiphilic Polyoxometalates and Pluronic Block Copolymers.

The assembly of polyoxometalate (POM) metal-oxygen clusters into ordered nanostructures is attracting a growing interest for catalytic and sensing applications. However, assembly of ordered nanostructured POMs from solution can be impaired by aggregation, and the structural diversity is poorly understood. Here, we present a time-resolved small-angle X-ray scattering (SAXS) study of the co-assembly in aqueous solutions of amphiphilic organo-functionalized Wells-Dawson-type POMs with a Pluronic block copolymer over a wide concentration range in levitating droplets. SAXS analysis revealed the formation and subsequent transformation with increasing concentration of large vesicles, a lamellar phase, a mixture of two cubic phases that evolved into one dominating cubic phase, and eventually a hexagonal phase formed at concentrations above 110 mM. The structural versatility of co-assembled amphiphilic POMs and Pluronic block copolymers was supported by dissipative particle dynamics simulations and cryo-TEM.

Shape-induced superstructure formation in concentrated ferrofluids under applied magnetic fields.

The field-induced ordering of concentrated ferrofluids based on spherical and cuboidal maghemite nanoparticles is studied using small-angle neutron scattering, revealing a qualitative effect of the faceted shape on the interparticle interactions as shown in the structure factor and correlation lengths. Whereas a spatially disordered hard-sphere interaction potential with a short correlation length is found for ∼9 nm spherical nanoparticles, nanocubes of a comparable particle size exhibit a more pronounced interparticle interaction and the formation of linear arrangements. Analysis of the anisotropic two-dimensional pair distance correlation function gives insight into the real-space arrangement of the nanoparticles. On the basis of the short interparticle distances found here, oriented attachment, i.e. a face-to-face arrangement of the nanocubes, is likely. The unusual field dependence of the interparticle correlations suggests a field-induced structural rearrangement.

Plant biomechanics and resilience to environmental changes are controlled by specific lignin chemistries in each vascular cell type and morphotype.

The biopolymer lignin is deposited in the cell walls of vascular cells and is essential for long-distance water conduction and structural support in plants. Different vascular cell types contain distinct and conserved lignin chemistries, each with specific aromatic and aliphatic substitutions. Yet, the biological role of this conserved and specific lignin chemistry in each cell type remains unclear. Here, we investigated the roles of this lignin biochemical specificity for cellular functions by producing single cell analyses for three cell morphotypes of tracheary elements, which all allow sap conduction but differ in their morphology. We determined that specific lignin chemistries accumulate in each cell type. Moreover, lignin accumulated dynamically, increasing in quantity and changing in composition, to alter the cell wall biomechanics during cell maturation. For similar aromatic substitutions, residues with alcohol aliphatic functions increased stiffness whereas aldehydes increased flexibility of the cell wall. Modifying this lignin biochemical specificity and the sequence of its formation impaired the cell wall biomechanics of each morphotype and consequently hindered sap conduction and drought recovery. Together, our results demonstrate that each sap-conducting vascular cell type distinctly controls their lignin biochemistry to adjust their biomechanics and hydraulic properties to face developmental and environmental constraints.

Time-Resolved SAXS Study of Polarity- and Surfactant-Controlled Superlattice Transformations of Oleate-Capped Nanocubes During Solvent Removal.

Structural transformations and lattice expansion of oleate-capped iron oxide nanocube superlattices are studied by time-resolved small-angle X-ray scattering (SAXS) during solvent removal. The combination of conductor-like screening model for real solvents (COSMO-RS) theory with computational fluid dynamics (CFD) modeling provides information on the solvent composition and polarity during droplet evaporation. Evaporation-driven poor-solvent enrichment in the presence of free oleic acid results in the formation of superlattices with a tilted face-centered cubic (fcc) structure when the polarity reaches its maximum. The tilted fcc lattice expands subsequently during the removal of the poor solvent and eventually transforms to a regular simple cubic (sc) lattice during the final evaporation stage when only free oleic acid remains. Comparative studies show that both the increase in polarity as the poor solvent is enriched and the presence of a sufficient amount of added oleic acid is required to promote the formation of structurally diverse superlattices with large domain sizes.

A Stiff, Tough, and Thermally Insulating Air- and Ice-Templated Plant-Based Foam.

By forming and directionally freezing an aqueous foam containing cellulose nanofibrils, methylcellulose, and tannic acid, we produced a stiff and tough anisotropic solid foam with low radial thermal conductivity. Along the ice-templating direction, the foam was as stiff as nanocellulose-clay composites, despite being primarily methylcellulose by mass. The foam was also stiff perpendicular to the direction of ice growth, while maintaining λr < 25 mW m-1 K-1 for a relative humidity (RH) up to 65% and <30 mW m-1 K-1 at 80% RH. This work introduces the tandem use of two practical techniques, foam formation and directional freezing, to generate a low-density anisotropic material, and this strategy could be applied to other aqueous systems where foam formation is possible.

Rheo-SAXS study of shear-induced orientation and relaxation of cellulose nanocrystal and montmorillonite nanoplatelet dispersions.

The development of robust production processes is essential for the introduction of advanced materials based on renewable and Earth-abundant resources. Cellulose nanomaterials have been combined with other highly available nanoparticles, in particular clays, to generate multifunctional films and foams. Here, the structure of dispersions of rod-like cellulose nanocrystals (CNC) and montmorillonite nanoplatelets (MNT) was probed using small-angle X-ray scattering within a rheological cell (Rheo-SAXS). Shear induced a high degree of particle orientation in both the CNC-only and CNC:MNT composite dispersions. Relaxation of the shear-induced orientation in the CNC-only dispersion decayed exponentially and reached a steady-state within 20 seconds, while the relaxation of the CNC:MNT composite dispersion was found to be strongly retarded and partially inhibited. Viscoelastic measurements and Guinier analysis of dispersions at the shear rate of 0.1 s-1 showed that the addition of MNT promotes gel formation of the CNC:MNT composite dispersions. A better understanding of shear-dependent assembly and orientation of multi-component nanoparticle dispersions can be used to process materials with improved mechanical and functional properties.

Effect of density, phonon scattering and nanoporosity on the thermal conductivity of anisotropic cellulose nanocrystal foams.

Anisotropic cellulose nanocrystal (CNC) foams with densities between 25 and 130 kg m-3 (CNC25 -CNC130) were prepared by directional ice-templating of aqueous dispersions. Estimates of the solid and gas conduction contributions to the thermal conductivity of the foams using a parallel resistor model showed that the relatively small increase of the radial thermal conductivity with increasing foam density can be attributed to interfacial phonon scattering. The foam wall nanoporosity and, to a lesser extent, the orientation of the CNC particles and alignment of the columnar macropores, also influence the insulation performance of the foams. The insight on the importance of phonon scattering for the thermal insulation properties of nanocellulose foams provides useful guidelines for tailoring nanofibrillar foams for super-insulating applications.

Unravelling the Hydration Barrier of Lignin Oleate Nanoparticles for Acid- and Base-Catalyzed Functionalization in Dispersion State.

Lignin nanoparticles (LNPs) are promising renewable nanomaterials with applications ranging from biomedicine to water purification. However, the instability of LNPs under acidic and basic conditions severely limits their functionalization for improved performance. Here, we show that controlling the degree of esterification can significantly improve the stability of lignin oleate nanoparticles (OLNPs) in acidic and basic aqueous dispersions. The high stability of OLNPs is attributed to the alkyl chains accumulated in the shell of the particle, which delays protonation/deprotonation of carboxylic acid and phenolic hydroxyl groups. Owing to the enhanced stability, acid- and base-catalyzed functionalization of OLNPs at pH 2.0 and pH 12.0 via oxirane ring-opening reactions were successfully performed. We also demonstrated these new functionalized particles as efficient pH-switchable dye adsorbents and anticorrosive particulate coatings.

Assembly of cellulose nanocrystals and clay nanoplatelets studied by time-resolved X-ray scattering.

Time-resolved small-angle X-ray scattering (SAXS) was used to probe the assembly of cellulose nanocrystals (CNC) and montmorillonite (MNT) over a wide concentration range in aqueous levitating droplets. Analysis of the SAXS curves of the one-component and mixed dispersions shows that co-assembly of rod-like CNC and MNT nanoplatelets is dominated by the interactions between the dispersed CNC particles and that MNT promotes gelation and assembly of CNC, which occurred at lower total volume fractions in the CNC:MNT than in the CNC-only dispersions. The CNC dispersions displayed a d ∝ φ-1/2 scaling and a low-q power-law exponent of 2.0-2.2 for volume fractions up to 35%, which indicates that liquid crystal assembly co-exists and competes with gelation.

Local Crystallinity in Twisted Cellulose Nanofibers.

Cellulose is crystallized by plants and other organisms into fibrous nanocrystals. The mechanical properties of these nanofibers and the formation of helical superstructures with energy dissipating and adaptive optical properties depend on the ordering of polysaccharide chains within these nanocrystals, which is typically measured in bulk average. Direct measurement of the local polysaccharide chain arrangement has been elusive. In this study, we use the emerging technique of scanning electron diffraction to probe the packing of polysaccharide chains across cellulose nanofibers and to reveal local ordering of the chains in twisting sections of the nanofibers. We then use atomic force microscopy to shed light on the size dependence of the inherent driving force for cellulose nanofiber twisting. The direct measurement of crystalline twisted regions in cellulose nanofibers has important implications for understanding single-cellulose-fibril properties that influence the interactions between cellulose nanocrystals in dense assemblies. This understanding may enable cellulose extraction and separation processes to be tailored and optimized.

Thermally Insulating Nanocellulose-Based Materials.

Thermally insulating materials based on renewable nanomaterials such as nanocellulose could reduce the energy consumption and the environmental impact of the building sector. Recent reports of superinsulating cellulose nanomaterial (CNM)-based aerogels and foams with significantly better heat transport properties than the commercially dominating materials, such as expanded polystyrene, polyurethane foams, and glass wool, have resulted in a rapidly increasing research activity. Herein, the fundamental basis of thermal conductivity of porous materials is described, and the anisotropic heat transfer properties of CNMs and films with aligned CNMs and the processing and structure of novel CNM-based aerogels and foams with low thermal conductivities are presented and discussed. The extraordinarily low thermal conductivity of anisotropic porous architectures and multicomponent approaches are highlighted and related to the contributions of the Knudsen effect and phonon scattering.

Sclerotization-Inspired Aminoquinone Cross-Linking of Thermally Insulating and Moisture-Resilient Biobased Foams.

Thermally insulating foams and aerogels based on cellulose nanofibrils (CNFs) are promising alternatives to fossil-based thermal insulation materials. We demonstrate a scalable route for moisture-resilient lightweight foams that relies on sclerotization-inspired Michael-type cross-linking of amine-modified CNFs by oxidized tannic acid. The solvent-exchanged, ice-templated, and quinone-tanned cross-linked anisotropic structures were mechanically stable and could withstand evaporative drying with minimal structural change. The low-density (7.7 kg m-3) cross-linked anisotropic foams were moisture-resilient and displayed a compressive modulus of 90 kPa at 98% relative humidity (RH) and thermal conductivity values close to that of air between 20 and 80% RH at room temperature. Sclerotization-inspired cross-linking of biobased foams offers an energy-efficient and scalable route to produce sustainable and moisture-resilient lightweight materials.

Two-Stage Assembly of Mesocrystal Fibers with Tunable Diameters in Weak Magnetic Fields.

Controlling the morphology and crystallographic coherence of assemblies of magnetic nanoparticles is a promising route to functional materials. Time-resolved small-angle X-ray scattering (SAXS) was combined with microscopy and scaling analysis to probe and analyze evaporation-induced assembly in levitating drops and thin films of superparamagnetic iron oxide nanocubes in weak magnetic fields. We show that assembly of micrometer-sized mesocrystals with a cubic shape preceded the formation of fibers with a high degree of crystallographic coherence and tunable diameters. The second-stage assembly of aligned cuboidal mesocrystals into fibers was driven by the magnetic field, but the first-stage assembly of the oleate-capped nanocubes was unaffected by weak magnetic fields. The transition from 3D growth of the primary mesocrystals to the second stage 1D assembly of the elongated fibers was related to the size and field dependence of isotropic van der Waals and directional dipolar interactions between the interacting mesocrystals.

Strong size selectivity in the self-assembly of rounded nanocubes into 3D mesocrystals.

The self-assembly of nanoparticles into highly ordered crystals is largely influenced by variations in the size and shape of the constituent particles, with crystallization generally not observed if their polydispersity is too large. Here, we report on size selectivity in the self-assembly of rounded cubic maghemite nanoparticles into three-dimensional mesocrystals. Different X-ray scattering techniques are used to study and compare a nanoparticle dispersion that is used later for self-assembly, an ensemble of mesocrystals grown on a substrate, as well as an individual mesocrystal. The individual µm-sized mesocrystal is isolated using a focused-ion-beam-based technique and investigated by the diffraction of a micro-focused X-ray beam. Structural analysis reveals that individual mesocrystals have a drastically smaller size dispersity of nanoparticles than that in the initial dispersion, implying very strong size selectivity during self-assembly. The small size dispersity of the nanoparticles within individual mesocrystals is accompanied by a very narrow lattice parameter distribution. In contrast, the lattice parameter distribution within all mesocrystals of an ensemble is about four times wider than that of individual mesocrystals, indicating significant size fractionalization between mesocrystals during self-assembly. The small size dispersity within each mesocrystal has important implications for their physical properties.

Best Practice for Reporting Wet Mechanical Properties of Nanocellulose-Based Materials.

Nanocellulose-based materials and nanocomposites show extraordinary mechanical properties with high stiffness, strength, and toughness. Although the last decade has witnessed great progress in understanding the mechanical properties of these materials, a crucial challenge is to identify pathways to introduce high wet strength, which is a critical parameter for commercial applications. Because of the waterborne fabrication methods, nanocellulose-based materials are prone to swelling by both adsorption of moist air or liquid water. Unfortunately, there is currently no best practice on how to take the swelling into account when reporting mechanical properties at different relative humidity or when measuring the mechanical properties of fully hydrated materials. This limits and in parts fully prevents comparisons between different studies. We review current approaches and propose a best practice for measuring and reporting mechanical properties of wet nanocellulose-based materials, highlighting the importance of swelling and the correlation between mechanical properties and volume expansion.