Understanding the Effect of Conformational Rigidity on Rheological Behavior and Formation of Polysaccharide-Based Hybrid Hydrogels.

The importance of conformational rigidity on macroscopic rheological properties was revealed using two model polysaccharides, namely, xanthan gum and hyaluronic acid. Xanthan gum has a rigid tertiary conformation due to its ordered double-helical structure, and the interactions between the tertiary structures result in the formation of a network/quaternary structure. In comparison, hyaluronic acid possesses a relatively flexible tertiary conformation due to its secondary random coil structure. Xanthan gum exhibits a much stronger shear thinning and more solidlike behavior compared to hyaluronic acid, owing to its network/quaternary structure. The rigid tertiary structure and the presence of a network/quaternary structure also endow xanthan gum with better resistance against environmental changes (e.g., salt and/or urea addition, temperature change) compared to hyaluronic acid. The network/quaternary structure allows xanthan gum to form gels with chitosan via electrostatic interactions when using the vapor-induced gelation technique, which is not possible for hyaluronic acid due to its flexible tertiary conformation under similar conditions.

Morphological and Rheological Properties of PLA, PBAT, and PLA/PBAT Blend Nanocomposites Containing CNCs.

Morphological and rheological properties of poly(lactic acid), PLA (semicrystalline and amorphous), and poly(butylene adipate-co-terephthalate), PBAT, and their blends (75 wt%/25 wt%; PLA/PBAT) were investigated in the presence of cellulose nanocrystals (CNCs) prepared from solution casting followed by melt mixing. For the solution casting step, the CNCs were either incorporated into the matrix, the dispersed phase, or both. The dispersion and distribution of the CNCs in the neat polymers and localization in their blends were analyzed via scanning electron microscopy (SEM) and atomic force microscopy (AFM). The highly dispersed CNCs in the solution cast nanocomposites were agglomerated after melt mixing. In the blends with 1 wt% CNCs, the nanoparticles were mostly localized on the surface of the PBAT droplets irrespective of their initial localization. The rheological behavior of the single polymer matrix nanocomposites and their blends was determined in dynamic and transient shear flow in the molten state. Upon melt mixing the complex viscosity and storage modulus of the solution cast nanocomposites decreased markedly due to re-agglomeration of the CNCs. Under shearing at 0.1 s-1, a significant droplet coalescence was observed in the neat blends, but was prevented by the presence of the CNCs at the interface in the blend nanocomposites.

Towards the scalable isolation of cellulose nanocrystals from tunicates.

In order for sustainable nanomaterials such as cellulose nanocrystals (CNCs) to be utilized in industrial applications, a large-scale production capacity for CNCs must exist. Currently the only CNCs available commercially in kilogram scale are obtained from wood pulp (W-CNCs). Scaling the production capacity of W-CNCs isolation has led to their use in broader applications and captured the interest of researchers, industries and governments alike. Another source of CNCs with potential for commercial scale production are tunicates, a species of marine animal. Tunicate derived CNCs (T-CNCs) are a high aspect ratio CNC, which can complement commercially available W-CNCs in the growing global CNC market. Herein we report the isolation and characterization of T-CNCs from the tunicate Styela clava, an invasive species currently causing significant harm to local aquaculture communities. The reported procedure utilizes scalable CNC processing techniques and is based on our experiences from laboratory scale T-CNC isolation and pilot scale W-CNC isolation. To our best knowledge, this study represents the largest scale where T-CNCs have been isolated from any tunicate species, under any reaction conditions. Demonstrating a significant step towards commercial scale isolation of T-CNCs, and offering a potential solution to the numerous challenges which invasive tunicates pose to global aquaculture communities.

Orienting Cellulose Nanocrystal Functionalities Tunes the Wettability of Water-Cast Films.

Cellulose nanocrystal (CNC)-based materials display apparently erratic wetting behaviors with contact angle (CA) variations as large as 30° from sample to sample. This work hypothesizes that it is the orientation of CNC amphiphilic functionalities at the interface with air that causes the variability in CA. By exploiting relationships with the Hansen solubility parameter theory, a set of surface tension parameters is proposed for both the polar and the non-polar surfaces of cellulose Iß nanocrystals. These coefficients elucidate the wettability of CNC materials by establishing a correlation between the wetting properties of the air/sample interface and its chemical composition in terms of non-polar moieties. Advancing/receding CA experiments suggest that, while spin-coating CNC suspensions yield purely polar films, oven-casting them produces amphiphilic surfaces. We proposed a mechanism where the state of dispersion (individual or agglomerated) in which CNCs reach the air/water interface during casting is the determining factor: while individual nanocrystals find it more stable to orient their non-polar surfaces toward the interface, the aspect ratio of CNC agglomerates favors an orientation of their polar surfaces. This represents the first compelling evidence of CNC orientation at an interface and can be applied to Pickering emulsions and nanocomposites and to the production of CNC materials with tuned wettability.

Self-assembly behaviors of colloidal cellulose nanocrystals: A tale of stabilization mechanisms.

HYPOTHESIS: In solvent casting, colloidal nanocrystal self-assembly patterns are controlled by a mix of cohesive and repulsive interactions that promote destabilization-induced self-assembly (DISA) or evaporation-induced self-assembly (EISA). Tuning the strength and nature of the stabilization mechanisms may allow repulsive interactions to govern self-assembly during the casting of colloidal cellulose nanocrystal (CNC) suspensions. EXPERIMENTS: We propose a tool to classify the level of electrostatic and solvation-induced stabilizations based on two solvent parameters only: dielectric constant, ε, and chemical affinity for CNCs, in terms of Hansen Solubility Parameters, Ra. These criteria are applied to study CNC self-assembly in solvent casting experiments in various media and binary mixtures. FINDINGS: In solvent casting of suspensions stabilized through a combination of electrostatic and solvation effects, the primarily governing mechanism is EISA, which leads to the formation of chiral nematic domains and optically active thin films. In electrostatically-stabilized suspensions, EISA and DISA are in competition and casting may yield anything from a continuous film to a powder. In other suspensions, DISA prevails and evaporation yields a powder of CNC agglomerates. By classifying media according to their stabilization mechanisms, this work establishes that the behavior of CNC suspensions in solvent casting may be predicted from solvent parameters only.

The structural amphiphilicity of cellulose nanocrystals characterized from their cohesion parameters.

Cellulose nanocrystals (CNCs), usually considered as isotropically polar nanoparticles, are sheet-like crystalline assemblies of cellulose chains. Here, we link the anisotropy of the CNC structure to an amphiphilic behavior in suspension. The Hansen solubility parameters (HSP: δD;δP;δH) of wood-based H2SO4-hydrolyzed CNCs were measured from sedimentation tests in a wide set of 59 solvents and binary mixtures. Two sets of cohesion parameters corresponding to a polar surface (18.1; 20.4; 15.3) ±â€¯(0.5; 0.5; 0.4) MPa1/2 and to a mildly non-polar one (17.4; 4.8; 6.5) ±â€¯(0.3; 0.5; 0.6) MPa1/2 were determined, with respective solubility radii of 7.8 and 2.1 MPa1/2. The polar sphere is thought to correspond to the (110) & (11¯0) surfaces of cellulose Iß nanocrystals, while the smaller non-polar sphere is coherent with the exposure of (200) surfaces. The HSP graph provides new insights on the amphiphilic nature of CNCs and a mapping of their chemical affinity for solvents and polymer matrices.

Poly (lactic acid) blends: Processing, properties and applications.

Poly (lactic acid) or polylactide (PLA) is a commercial biobased, biodegradable, biocompatible, compostable and non-toxic polymer that has competitive material and processing costs and desirable mechanical properties. Thereby, it can be considered favorably for biomedical applications and as the most promising substitute for petroleum-based polymers in a wide range of commodity and engineering applications. However, PLA has some significant shortcomings such as low melt strength, slow crystallization rate, poor processability, high brittleness, low toughness, and low service temperature, which limit its applications. To overcome these limitations, blending PLA with other polymers is an inexpensive approach that could also tailor the final properties of PLA-based products. During the last two decades, researchers investigated the synthesis, processing, properties, and development of various PLA-based blend systems including miscible blends of poly l-lactide (PLLA) and poly d-lactide (PDLA), which generate stereocomplex crystals, binary immiscible/miscible blends of PLA with other thermoplastics, multifunctional ternary blends using a third polymer or fillers such as nanoparticles, as well as PLA-based blend foam systems. This article reviews all these investigations and compares the syntheses/processing-morphology-properties interrelationships in PLA-based blends developed so far for various applications.

Ultrasonication of spray- and freeze-dried cellulose nanocrystals in water.

The structural and rheological properties of aqueous suspensions of spray-dried cellulose nanocrystals (CNCs) were investigated and compared to those of freeze-dried. The cellulose nanocrystals were obtained from sulfuric acid hydrolysis of wood pulp. Ultrasonication was used to disperse cellulose nanocrystals in Milli-Q water and the power applied during ultrasonication was shown to be the controlling parameter for their dispersion, more than total energy. Dynamic light scattering measurements showed a decrease of the average hydrodynamic diameter down to the same limiting value, i.e. ∼75 nm, for both spray and freeze-dried cellulose nanocrystals. Since the same maximum dispersion state was reached for both CNC types, it indicated that the spray drying process did not limit dispersion, provided that sufficient ultrasonication was provided. Moreover, no desulfation occurred during ultrasonication at ambient temperature. Strong ultrasonication also caused a decrease of intrinsic viscosity, along with an increase in maximum packing concentration. These properties were correlated to agglomerates break-up, which released both ions and water in suspension. The ionic strength increase may lead to a thinner electrostatic double layer surrounding the cellulose nanocrystals, reducing their apparent concentration.

Surface morphology and properties of ternary polymer blends: effect of the migration of minor components.

In this work, the surface morphology and properties of ternary polymer blends and the migration of minor component molecules to the top surface layer of the films were studied. We used polystyrene (PS), poly(butylene adipate-co-terephthalate), polycaprolactone, poly(methyl methacrylate), and polylactide as second minor phases in a blend of polyethylene terephthalate-poly(ethylene glycol) (PET-PEG). The morphology of the ternary systems predicted using the spreading coefficient and relative interfacial energy concepts was confirmed by scanning electron microscopy images. The surface characterization results showed a higher rate of migration of PEG to the polymer-air interface in the systems with a nonwetting morphology and the highest in the PET-PS-PEG blend. Atomic force microscopy images suggested that the high surface hydrophilicity of the PET-PS-PEG blend is due to a dendritic pattern of PEG crystals on the film surface, which were not observed for the other samples.

Surface roughening of PET films through blend phase coarsening.

In this study, a novel method to increase the surface roughness of polyethylene terephthalate (PET) films is proposed. The mechanism of phase coarsening at the surface in extruded thin films of PET blended with low concentrations of polystyrene (PS) was investigated. A small amount of poly(hyroxyl ether) of bisphenol A (phenoxy resin, PKHH) was found to significantly increase the surface roughness due to its effect on the PS-PET interfacial tension. X-ray photoelectron spectroscopy (XPS) results indicated that in the presence of PKHH, PS droplets migrated spontaneously towards the surface of the polymer film. An increased local concentration of PS near the surface took the form of encapsulated droplets. Above the flow temperature of the blend, the local concentration of PS eventually reached a level where a co-continuous morphology occurred, resulting in the instabilities on the surface of the film. The adhesion properties of films with various roughnesses were determined using a pull-off test and found to be significantly increased, which suggested that co-continuous morphology and the coarsening process increased the adhesive properties of the film.

Hierarchical structure and physicochemical properties of plasticized chitosan.

Plasticized chitosan with hierarchical structure, including multiple length scale structural units, was prepared by a "melt"-based method, that is, thermomechanical mixing, as opposed to the usual casting-evaporation procedure. Chitosan was successfully plasticized by thermomechanical mixing in the presence of concentrated lactic acid and glycerol using a batch mixer. Different plasticization formulations were compared in this study, in which concentrated lactic acid was used as protonation agent as well as plasticizer. The microstructure of thermomechanically plasticized chitosan was investigated by X-ray diffraction, scanning electron microscopy, and optical microscopy. With increasing amount of additional plasticizers (glycerol or water), the crystallinity of the plasticized chitosan decreased from 63.7% for the original chitosan powder to almost zero for the sample plasticized with additional water. Salt linkage between lactic acid molecules and amino side chains of chitosan was confirmed by FTIR spectroscopy: the lactic acid molecules expanded the space between the chitosan molecules of the crystalline phase. In the presence of other plasticizers (glycerol and water), various levels of structural units including an amorphous phase, nanofibrils, nanofibril clusters, and microfibers were produced under mechanical shear and thermal energy and identified for the first time. The thermal and thermomechanical properties of the plasticized chitosan were measured by thermogravimetric analysis, differential scanning calorimetric, and DMA. These properties were correlated with the different levels of microstructure, including multiple structural units.

Physical gelation of chitosan in the presence of beta-glycerophosphate: the effect of temperature.

When adding beta-glycerophosphate (beta-GP), a weak base, to chitosan aqueous solutions, the polymer remains in solution at neutral pH and room temperature, while homogeneous gelation of this system can be triggered upon heating. It is therefore one of the rare true physical chitosan hydrogels. In this study, physicochemical and rheological properties of chitosan solutions in the presence of acetic acid and beta-GP were investigated as a function of temperature in order to gain a better understanding of the gelation mechanisms. The gel structure formed at high temperature was only partially thermoreversible upon cooling to 5 degrees C because of the existence of remaining associations, confirmed by the spontaneous recovery of the gel after breakup at low temperature. Increasing temperature had no effect on the pH values of this system, while conductivity (and calculated ionic strength) increased. Values from the pH measurements were used to estimate the degree of protonation of each species as a function of temperature. The decreasing ratio of -NH3+ in chitosan and -OPO(O-)2 in beta-GP suggested reduced chitosan solubility along with a diminution of ionic interactions such as ionic bridging with increasing temperature. On the other hand, the increased ionic strength as a function of temperature, in the presence of beta-GP, enhanced screening of electrostatic repulsion and increased hydrophobic effect, resulting in favorable conditions for gel formation. Therefore, our study suggests that hydrophobic interactions and reduced solubility are the main driving force for chitosan gelation at high temperature in the presence of beta-GP.