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The utilization of lignin, the most abundant aromatic biomass component, is at the forefront of sustainable engineering, energy, and environment research, where its abundance and low‐cost features enable widespread application. Constructing lignin into material parts with controlled and desired macro‐ and microstructures and properties via additive manufacturing has been recognized as a promising technology and paves the way to the practical application of lignin. Considering the rapid development and significant progress recently achieved in this field, a comprehensive and critical review and outlook on three‐dimensional (3D) printing of lignin is highly desirable. This article fulfils this demand with an overview on the structure of lignin and presents the state‐of‐the‐art of 3D printing of pristine lignin and lignin‐based composites, and highlights the key challenges. It is attempted to deliver better fundamental understanding of the impacts of morphology, microstructure, physical, chemical, and biological modifications, and composition/hybrids on the rheological behavior of lignin/polymer blends, as well as, on the mechanical, physical, and chemical performance of the 3D printed lignin‐based materials. The main points toward future developments involve hybrid manufacturing, in situ polymerization, and surface tension or energy driven molecular segregation are also elaborated and discussed to promote the high‐value utilization of lignin. [ABSTRACT FROM AUTHOR]

Lactobacillus fermentum MTCC 25067 produces a hetero-exopolysaccharide (HePS) when cultured which forms supramolecular networks in the culture medium, increasing the viscosity. In the present study, the viscosity of the bacterial culture reached its maximum at 48 hr of cultivation and then decreased during a stationary growth phase lasting for up to 144 hr. The monosaccharide composition did not change during the stationary growth phase, whereas degradation of HePS molecules was noticeable, leading to partial disintegration of their supramolecular networks. The viscosity values of the HePS purified from the culture and dissolved in a fresh medium indicated little contribution of medium components to the viscosity. Absence of the apparent network structure of the HePS in the surrounding area of bacterial cells was observed during the late growth phase, supporting the idea that the decreases in culture viscosity during the prolonged period of cultivation were caused mainly by reduced interactions between bacterial cells and the intact supramolecular networks as a consequence of decreasing bacterial cell wall integrity and partial degradation of HePS molecules. [ABSTRACT FROM AUTHOR]

• Semi-dilute EPS solutions showed high zero-shear viscosities and shear thinning. • Semi-dilute EPS solutions were predominantly elastic at relatively high frequencies. • The EPS dissolved in water remained to be network-like supramolecular assemblies. Rheological properties and supramolecular structure of the exopolysaccharide (EPS) secreted by Lactobacillus fermentum MTCC 25067 were investigated. The critical concentration representing the lower-limit of the semi-dilute regime was estimated to be 0.71 g/L from the concentration dependence of zero-shear specific viscosity. The storage modulus (G ′) of a 20 g/L EPS solution was greater than the loss modulus (G ″) at 0.1–25 Hz. Approximately linear increases in G ′ and G ″ determined at a frequency of 1 Hz and a strain of 0.01 during cooling from 80 to 25 °C were an indication that the EPS did not undergo thermally-induced cooperative conformational transitions typical of gelling polysaccharides. Atomic force microscopy images revealed that EPS molecules were not completely dissociated into individual molecules in an aqueous solution but remained to form three-dimensional networks. The gel-like dynamic viscoelasticity of the 20 g/L EPS solution was thus attributed to the existence of supramolecular assemblies resulting from significant degrees of intermolecular association of the EPS in the solution. [ABSTRACT FROM AUTHOR]

D-mannitol is a common polyol that is used as additive in pharmaceutical and personal care product formulations. We investigated its effect on the microstructure and rheology of novel non-aqueous Carbopol dispersions employing traditional and time-resolved rheological analysis. We considered two types of sample, (i) fresh (i.e., mannitol completely dissolved in solution) and aged (i.e., visible in crystalline form). The analysis of the intracycle rheological transitions that were observed for different samples revealed that, when completely dissolved in solution, mannitol does not alter the rheological behaviour of the Carbopol dispersions. This highlights that the chemical similarity of the additive with the molecules of the surrounding solvent allows preserving the swollen dimension and interparticle interactions of the Carbopol molecules. Conversely, when crystals are present, a hierarchical structure forms, consisting of a small dispersed phase (Carbopol) agglomerated around a big dispersed phase (crystals). In keeping with this microstructural picture, as the concentration of Carbopol reduces, the local dynamics of the crystals gradually start to control the integrity of the microstructure. Rheologically, this results in a higher elasticity of the suspensions at infinitesimal deformations, but a fragile yielding process at intermediate strains. [ABSTRACT FROM AUTHOR]

• Rheological properties of composite gels were functions of stoichiometry with calcium ions. • Mechanical results showed highly interconnected gel-like structure of alginate/guar gels. • Alginate/guar gels structure exhibited an ordered mesh-like structure by increasing Ca2+. • High elasticity and rigidity of binary gels confirm the ability to endure mechanical stresses. • Both binary composite gels formed stronger gels at lower calcium level. Structure-rheology relationship of binary composite gel (BCG) systems of alginate/guar gum and basil seed gum/guar gum at ratio 2:1 at different Ca2+ levels (2–10%) were evaluated. The highest value of structural strength was obtained at 2 % of Ca2+, which can be attributed to its stronger network as assessed by rheological experiments. Mechanical spectra of the alginate/guar gels explained pseudoplastic behavior with a highly interconnected elastic gel structure. The mechanical strength as well as other textural properties of the alginate and basil seed gum network was functions of its stoichiometry with calcium ions. Whereas alginate/guar gels showed an elongated globular denser structure as determined by SEM, the BSG/guar gels showed a rigid cubic as the pieces of a puzzle, presenting a softer and weaker gel structure. The alginate/guar gels showed less porosity without syneresis or shrinkage during storage as supported by its high elasticity and rigidity. [ABSTRACT FROM AUTHOR]

Understanding how microscopic rearrangements manifest in macroscopic flow responses is one of the central goals of nonlinear rheological studies. Using the sequence-of-physical-processes framework, we present a natural 3D structure–rheology space that temporally correlates the structural and nonlinear viscoelastic parameters. Exploiting the rheo-small-angle neutron scattering (rheo-SANS) techniques, we demonstrate the use of the framework with a model system of polymer-like micelles (PLMs), where we unveil a sequence of microscopic events that micelles experience under dynamic shearing across a range of frequencies. The least-aligned state of the PLMs is observed to migrate from the total strain extreme toward zero strain with increasing frequency. Our proposed 3D space is generic, and can be equally applied to other soft materials under any sort of deformation, such as startup shear or uniaxial extension. This work therefore provides a natural approach for researchers to study complex out-of-equilibrium structure–rheology relationships of soft materials. [ABSTRACT FROM AUTHOR]

Lactobacillus fermentum MTCC 25067 produces a hetero-exopolysaccharide (HePS) when cultured which forms supramolecular networks in the culture medium, increasing the viscosity. In the present study, the viscosity of the bacterial culture reached its maximum at 48 hr of cultivation and then decreased during a stationary growth phase lasting for up to 144 hr. The monosaccharide composition did not change during the stationary growth phase, whereas degradation of HePS molecules was noticeable, leading to partial disintegration of their supramolecular networks. The viscosity values of the HePS purified from the culture and dissolved in a fresh medium indicated little contribution of medium components to the viscosity. Absence of the apparent network structure of the HePS in the surrounding area of bacterial cells was observed during the late growth phase, supporting the idea that the decreases in culture viscosity during the prolonged period of cultivation were caused mainly by reduced interactions between bacterial cells and the intact supramolecular networks as a consequence of decreasing bacterial cell wall integrity and partial degradation of HePS molecules., (©2020 BMFH Press.)