Rheo-NMR: A versatile hyphenated technique for capturing molecular dynamics and structure under flow

The general development of Rheo-NMR during the last four decades as well as selective hyphenated apparatuses is presented.Based on different magnet types,the current review is divided into two categories,namely low-field and high-field NMR,while the timedomain NMR is normally applied in the former case and the frequency-domain NMR is adopted in the latter one.Depending on different rheometer cells,it can be further divided into tensile and shear mode Rheo-NMR.The combination of various rheometer cells and NMR facility guarantees our acquisition of molecular level structure and dynamics information under flow conditions,which is crucial for our understanding of the molecular origin of complex fluids.A personal perspective is also presented at last to highlight possible development in this direction.

Effects of Temperature and Concentration on the Rheological Behavior of Polyacrylamide-Based Polymers

Polymers are high molecular weight molecules that provide high viscosity at low concentrations to the media they are inserted. In the oil industry, they are used for enhanced oil recovery and for drilling fluids, where its viscosity is an important factor for a greater efficiency. From all the polymers used by industry, the polyacrylamide and the biopolymer xantham gum are those, which appear significantly in those applications. Taking that into consideration, this work intends to study the effects of the physical, chemical and structural parameters of those polymers in their rheological behaviour, by varying their concentrations from 400 ppm to 2,000 ppm and their temperatures from 298 K to 328 K, which are values similar to those found in the field. For that, a Brookfield Viscometer-Brookfield Engineering Labs rheometer was used. The results acquired showed that the increase on the polyacrylamides ionicity generates and increase on the medium viscosity. For the temperature, its increase causes a reduction of viscosity for the low ionicity polyacrylamides, while increases the viscosity for the high ionicity ones. In the comparative study between xantham gum and polyacrylamides, it was possible to notice that, even though the biopolymer is more complex, its viscosity still is lower when compared to the polyacrylamides.

Rheological Behaviors of Polymers with Nanoparticles Tethered at Each End

The polymer with nanoparticles tethered at each end is a unique model for unraveling the effect of chain ends on the polymer dynamics. We investigated the rheological behavior of this kind of polymer by using nonequilibrium molecular dynamics simulation. The effect of polymer lengths and nanoparticle radii on the complex moduli and viscosity was examined. The dependence of complex moduli on the frequency becomes less pronounced as the polymer is short or the nanoparticle is large. The shear thinning behavior was revealed for these systems, and the scaling exponent of complex viscosity with respect to the frequency was found to change from-1/2 to-3/4 as the polymer shortens or the nanoparticle enlarges. The rheological behavior was further explained by analyzing the mean square distance of nanoparticles. The simulation results were compared with the existing experimental finding, showing an agreement. The work provides information for understanding the chain end effect on polymer rheology.

Linear Viscoelasticity of ABA-type Vitrimer Based on Dioxaborolane Metathesis

In this study,we synthesized a series of ABA-type vitrimers by crosslinking the short A moieties of precursors with a bifunctional crosslinker and evaporating the small molecular byproduct.The vitrimer samples thus prepared exhibit linear viscoelasticity dependent on the length of A moiety as well as the content of the crosslinks.When the average number of A monomers per end moiety m=1.1,the crosslinker can only extend the chain but not crosslink the chain.When m becomes 2.8 or higher,introducing a crosslinker first leads to the gelation,whereas excess in crosslinker molecules leads opening of the crosslinking sites and accordingly reentry into the sol regime.Surprisingly,a further increase in the length of the A moieties increases the relaxation time much weaker than the exponential increase seen for the physically crosslinked ABAtype ionomers.We attribute this difference to the distinct relaxation mechanisms:the relaxation of the vitrimer samples is based on relatively independent exchange reactions,which contrasts with the ABA-type ionomers that relax through the collective hopping of connected ionic groups from one ion aggregate to another.