Rheological and Rheo-optical Behaviors of Nanocellulose Suspensions Containing Unfibrillated Fibers

Cellulose nanofibers (CNFs) produced by mechanical processing have a more uneven fiber shape, diameter, and length than those produced by chemical processing. Depending on the manufacturing conditions, CNFs containing insufficient fibrillated fibers may be produced. In order to find practical applications for CNFs containing unfibrillated fibers, it is important to understand how to control the rheological behavior of these systems. In this study, we investigated the relationship between the nanosized volume fraction and the rheological behaviors of CNF suspensions containing unfibrillated fibers prepared by a wet refining system (Water Jet System). The macroscopic structural changes in those suspensions under shear flow were also discussed based on rheo-optic measurements. According to the frequency sweeps of the CNF suspensions, it was found that they were elastic-dominated gels, and the elasticity was attributed to the nanofibers. The elastic moduli increased with the volume fraction of the nanofibers, suggesting that the entanglement of the nanofibers was enhanced. The pseudo-plateau modulus Gp' is proportional to the nanofiber volume fraction, with the constant α = 1.5, suggesting that the entropic elasticity is dominant. The viscosity curves of the CNF suspensions showed a shear thinning behavior, in which the viscosity linearly decreased with the increasing shear rate. From the Rheo-SALS measured at the same time, we found that the aggregates of the nanofibers elongated in the flow direction and deformed into an elliptical shape with the applied shearing. The shape change of the aggregates comprised of the nanofibers became more pronounced with the increased nanofiber volume fraction. However, the effect of the shape change of the aggregates was hardly observed on the viscosity curve. We speculate that this is due to the fact that the unnanosized fibers, which exhibit a Newtonian flow, play a significant role in the flow behavior of the CNF suspensions.

Volume fraction and width of ribbon-like crystallites control the rubbery modulus of segmented block copolymers

We discuss the origin of the plateau modulus enhancement (χ) in semi-crystalline segmented block copolymers by increasing the concentration in hard segments within the chains (XHS). The message we deliver is that the plateau modulus of these thermoplastic elastomers is greatly dominated by the volume fraction (Φ) and the width (W) of crystallites according to χ–1 ~ ΦW in agreement with a recent topological model we have developed. We start by a quick review of literature with the aim to extract χ(Φ) for different chemical structures. As we suspected, we find that most of the data falls onto a mastercurve, in line with our predictions, confirming that the reinforcement in such materials is mainly dominated by the crystallite’s content. This important result is then supported by the investigation of copolymer mixtures in which Φ is fixed, providing a similar reinforcement, while the chains compositions is significantly different. Finally, we show that the reinforcement can be enhanced at constant Φ by increasing W for a given class of block copolymers. This can be done by changing the process route and is again in good agreement with our expectations.

Preferential Control of Forward Reaction Kinetics in Hydrogels Crosslinked with Reversible Conjugate Additions

<p>Molecular substitutions were used to demonstrate preferential control over the kinetic rate constants in a poly(ethylene glycol)-based hydrogel with two different reversible thia-conjugate addition reactions. A strong electron withdrawing nitrile group on the conjugate acceptor showed a 20-fold increase in the forward rate constant over a neutral withdrawing group, while the reverse rate constant only increased 6-fold. Rheometry experiments demonstrated that the hydrogel plateau modulus was primarily dictated by reaction equilibrium, while the stress relaxation characteristics of the hydrogel were dominated by the reverse rate constant. Furthermore, the dynamic crosslinking allowed the hydrogel to rapidly and spontaneously self-heal. These results indicate that decoupling the kinetic rate constants of bond exchange allow systematic control over dynamic covalent hydrogel bulk properties, such as their adaptability, stress relaxation ability, and self-healing properties.</p>

Preferential Control of Forward Reaction Kinetics in Hydrogels Crosslinked with Reversible Conjugate Additions

<p>Molecular substitutions were used to demonstrate preferential control over the kinetic rate constants in a poly(ethylene glycol)-based hydrogel with two different reversible thia-conjugate addition reactions. A strong electron withdrawing nitrile group on the conjugate acceptor showed a 20-fold increase in the forward rate constant over a neutral withdrawing group, while the reverse rate constant only increased 6-fold. Rheometry experiments demonstrated that the hydrogel plateau modulus was primarily dictated by reaction equilibrium, while the stress relaxation characteristics of the hydrogel were dominated by the reverse rate constant. Furthermore, the dynamic crosslinking allowed the hydrogel to rapidly and spontaneously self-heal. These results indicate that decoupling the kinetic rate constants of bond exchange allow systematic control over dynamic covalent hydrogel bulk properties, such as their adaptability, stress relaxation ability, and self-healing properties.</p>

Small and Medium Amplitude Oscillatory Shear Rheology of Model Branched Polystyrene (PS) Melts

Linear and nonlinear rheological properties of model comb polystyrenes (PS) with loosely to densely grafted architectures were measured under small and medium amplitude oscillatory shear (SAOS and MAOS) flow. This comb PS set had the same length of backbone and branches but varied in the number of branches from 3 to 120 branches. Linear viscoelastic properties of the comb PS were compared with the hierarchical model predictions. The model underpredicted zero-shear viscosity and backbone plateau modulus of densely branched comb with 60 or 120 branches because the model does not include the effect of side chain crowding. First- and third-harmonic nonlinearities reflected the hierarchy in the relaxation motion of comb structures. Notably, the low-frequency plateau values of first-harmonic MAOS moduli scaled with M w − 2 (total molecular weight), reflecting dynamic tube dilution (DTD) by relaxed branches. Relative intrinsic nonlinearity Q0 exhibited the difference between comb and bottlebrush via no low-frequency Q0 peak of bottlebrush corresponding to backbone relaxation, which is probably related to the stretched backbone conformation in bottlebrush.

Linear and Nonlinear Dynamic Behavior of Polymer Micellar Assemblies Connected by Metallo-Supramolecular Interactions

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene-b-poly(tert-butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model. For strongly associated (Ni2+, Fe2+) and sufficiently concentrated systems (15 w/v%), any given ligand end-group has a virtually 100% probability of being located in an overlapping hairy region between two micelles. By assuming a 50% probability of intermicellar crosslinks being formed, an excellent prediction of the plateau modulus was achieved and compared with the experimental results. For strongly associated but somewhat more dilute systems (12 w/v%) that still have significant overlap between hairy regions, the experimental modulus was lower than the predicted value, as the effective number of crosslinkers was further reduced along with possible density heterogeneities. The reversible destruction of the network by shear forces can be observed from the strain dependence of the storage and loss moduli. The storage moduli of the Ni2+ and Zn2+ systems at a lower concentration (12 w/v%) showed a rarely observed feature (i.e., a peak at the transition from linear to nonlinear regime). This peak disappeared at a higher concentration (15 w/v%). This behavior can be rationalized based on concentration-dependent network stretchability.

Increasing valence pushes DNA nanostar networks to the isostatic point

The classic picture of soft material mechanics is that of rubber elasticity, in which material modulus is related to the entropic elasticity of flexible polymeric linkers. The rubber model, however, largely ignores the role of valence (i.e., the number of network chains emanating from a junction). Recent work predicts that valence, and particularly the Maxwell isostatic point, plays a key role in determining the mechanics of semiflexible polymer networks. Here, we report a series of experiments confirming the prominent role of valence in determining the mechanics of a model system. The system is based on DNA nanostars (DNAns): multiarmed, self-assembled nanostructures that form thermoreversible equilibrium gels through base pair-controlled cross-linking. We measure the linear and nonlinear elastic properties of these gels as a function of DNAns arm number, f, and concentration [DNAns]. We find that, as f increases from three to six, the gel’s high-frequency plateau modulus strongly increases, and its dependence on [DNAns] transitions from nonlinear to linear. Additionally, higher-valence gels exhibit less strain hardening, indicating that they have less configurational freedom. Minimal strain hardening and linear dependence of shear modulus on concentration at high f are consistent with predictions for isostatic systems. Evident strain hardening and nonlinear concentration dependence of shear modulus suggest that the low-f networks are subisostatic and have a transient, potentially fractal percolated structure. Overall, our observations indicate that network elasticity is sensitive both to entropic elasticity of network chains and to junction valence, with an apparent isostatic point 5<fc≤6 in agreement with the Maxwell prediction.

Peat Fibers and Finely Ground Peat Powder for Application in Asphalt

In this study, the feasibility of a natural peat fiber and finely ground peat powder as a modifier for bitumen was investigated. Initially, the as-received peat material was characterized in detail: the material was ground to various degrees, separated into fiber and powder fractions, and the gradation of the powder fraction as well as the size of the fibers were determined. A possible solubility in bitumen, the moisture content, and the density of both fractions were evaluated, and a limited chemical characterization of the fibers was conducted. Secondly, the rheological behavior of the powder and the fibers when blended with bitumen was evaluated. Additionally, a limited asphalt study was conducted. The rheological data showed the stiffening effects of the powder fraction and the presence of a fiber network, which were obvious as a plateau modulus towards lower frequencies. The fiber network was strain-dependent and showed elastic effects. This was further confirmed by the multiple stress creep recovery (MSCRT) tests. These tests also indicated that the fibers should improve the rutting resistance, although it was not possible to confirm this in asphalt rutting tests. Asphalt drainage tests demonstrated that adding dry peat, whether this is ground or not, is effective in reducing the binder drainage. However, the data also revealed that the amount of added peat fibers and powder should be limited to avoid difficulties in the compaction of these asphalt mixes.

Viscoelastic Properties of Thixotropic Semisolid Alloy Relating the Microstructure

The subject of this work is to investigate viscoelastic properties such as loss modulus (G ́ ́), storage modulus (G ́), complex shear modulus (G*), complex viscosity (η*) and loss angle () at different temperatures by means of a small-amplitude oscillatory test. These properties allow to provide information about materials structure. For this purpose, we employed a tin-lead alloy (Sn-15%Pb) which exhibits a similar microstructure to aluminum alloys and is the classic alloy for semisolid thixotropic studies. It is interesting to note that the Sn-15%Pb alloy exhibits a slightly decrease in storage modulus (G ́) over the entire frequency (0.01-10Hz) at high temperatures, showing its viscoelastic behavior. In addition, a detailed analysis of master curves (oscillatory tests) was made to relate the semisolid microstructure (solid fraction) with the plateau modulus (GN0) which is directly related with both molecular weight or percolation threshold in polymer and gels science respectively.