ترغب بنشر مسار تعليمي؟ اضغط هنا

Shear Melting and Recovery of Crosslinkable Cellulose Nanocrystal-Polymer Gels

208   0   0.0 ( 0 )
 نشر من قبل Abhinav Rao
 تاريخ النشر 2019
  مجال البحث فيزياء
والبحث باللغة English




اسأل ChatGPT حول البحث

Cellulose nanocrystals (CNC) are naturally-derived nanostructures of growing importance for the production of composites having attractive mechanical properties, and offer improved sustainability over purely petroleum-based alternatives. Fabrication of CNC composites typically involves extrusion of CNC suspensions and gels in a variety of solvents, in the presence of additives such as polymers and curing agents. However, most studies so far have focused on aqueous CNC gels, yet the behavior of CNC-polymer gels in organic solvents is important to their wider processability. Here, we study the rheological behavior of composite polymer-CNC gels in dimethylformamide, which include additives for both UV and thermal crosslinking. Using rheometry coupled with in-situ infrared spectroscopy, we show that under external shear, CNC-polymer gels display progressive and irreversible failure of the hydrogen bond network that is responsible for their pronounced elastic properties. In the absence of cross-linking additives, the polymer-CNC gels show negligible recovery upon cessation of flow, while the presence of additives allows the gels to recover via van der Waals interactions. By exploring a broad range of shear history and CNC concentrations, we construct master curves for the temporal evolution of the viscoelastic properties of the polymer-CNC gels, illustrating universality of the observed dynamics with respect to gel composition and flow conditions. We therefore find that polymer-CNC composite gels display a number of the distinctive features of colloidal glasses and, strikingly, that their response to the flow conditions encountered during processing can be tuned by chemical additives. These findings have implications for processing of dense CNC-polymer composites in solvent casting, 3D printing, and other manufacturing techniques.



قيم البحث

اقرأ أيضاً

We sandwich a colloidal gel between two parallel plates and induce a radial flow by lifting the upper plate at a constant velocity. Two distinct scenarios result from such a tensile test: ($i$) stable flows during which the gel undergoes a tensile de formation without yielding, and ($ii$) unstable flows characterized by the radial growth of air fingers into the gel. We show that the unstable regime occurs beyond a critical energy input, independent of the gels macroscopic yield stress. This implies a local fluidization of the gel at the tip of the growing fingers and results in the most unstable wavelength of the patterns exhibiting the characteristic scalings of the classical viscous fingering instability. Our work provides a quantitative criterion for the onset of fingering in colloidal gels based on a local shear-induced yielding, in agreement with the delayed failure framework.
Soft materials may break irreversibly upon applying sufficiently large shear oscillations, a process which physical mechanism remains largely elusive. In this work, the rupture of protein gels made of sodium caseinate under an oscillatory stress is s hown to occur in an abrupt, brittle-like manner. Upon increasing the stress amplitude, the build-up of harmonic modes in the strain response can be rescaled for all gel concentrations. This rescaling yields an empirical criterion to predict the rupture point way before the samples are significantly damaged. Fatigue experiments under stress oscillations of constant amplitude can be mapped onto the former results, which indicates that rupture is independent of the temporal pathway in which strain and damage accumulate. Finally, using ultrasonic imaging, we measure the local mechanical properties of the gels before, during and after breakdown, showing that the strain field remains perfectly homogeneous up to rupture but suddenly gives way to a solid-fluid phase separation upon breakdown.
There is growing evidence that the flow of driven amorphous solids is not homogeneous, even if the macroscopic stress is constant across the system. Via event driven molecular dynamics simulations of a hard sphere glass, we provide the first direct e vidence for a correlation between the fluctuations of the local volume-fraction and the fluctuations of the local shear rate. Higher shear rates do preferentially occur at regions of lower density and vice versa. The temporal behavior of fluctuations is governed by a characteristic time scale, which, when measured in units of strain, is independent of shear rate in the investigated range. Interestingly, the correlation volume is also roughly constant for the same range of shear rates. A possible connection between these two observations is discussed.
Yield stress fluids (YSFs) display a dual nature highlighted by the existence of a yield stress such that YSFs are solid below the yield stress, whereas they flow like liquids above it. Under an applied shear rate $dotgamma$, the solid-to-liquid tran sition is associated with a complex spatiotemporal scenario. Still, the general phenomenology reported in the literature boils down to a simple sequence that can be divided into a short-time response characterized by the so-called stress overshoot, followed by stress relaxation towards a steady state. Such relaxation can be either long-lasting, which usually involves the growth of a shear band that can be only transient or that may persist at steady-state, or abrupt, in which case the solid-to-liquid transition resembles the failure of a brittle material, involving avalanches. Here we use a continuum model based on a spatially-resolved fluidity approach to rationalize the complete scenario associated with the shear-induced yielding of YSFs. Our model provides a scaling for the coordinates of the stress maximum as a function of $dotgamma$, which shows excellent agreement with experimental and numerical data extracted from the literature. Moreover, our approach shows that such a scaling is intimately linked to the growth dynamics of a fluidized boundary layer in the vicinity of the moving boundary. Yet, such scaling is independent of the fate of that layer, and of the long-term behavior of the YSF. Finally, when including the presence of long-range correlations, we show that our model displays a ductile to brittle transition, i.e., the stress overshoot reduces into a sharp stress drop associated with avalanches, which impacts the scaling of the stress maximum with $dotgamma$. Our work offers a unified picture of shear-induced yielding in YSFs, whose complex spatiotemporal dynamics are deeply connected to non-local effects.
Shear thickening denotes the rapid and reversible increase in viscosity of a suspension of rigid particles under external shear. This ubiquitous phenomenon has been documented in a broad variety of multiphase particulate systems, while its microscopi c origin has been successively attributed to hydrodynamic interactions and frictional contact between particles. The relative contribution of these two phenomena to the magnitude of shear thickening is still highly debated and we report here a discriminating experimental study using a model shear-thickening suspension that allows us to tune independently both the surface chemistry and the surface roughness of the particles. We show here that both properties matter when it comes to continuous shear thickening (CST) and that the presence of hydrogen bonds between the particles is essential to achieve discontinuous shear thickening (DST) by enhancing solid friction between closely contacting particles. Moreover, a simple argument allows us to predict the onset of CST, which for these highly-textured particles occurs at a critical volume fraction much lower than that previously reported in the literature. Finally, we demonstrate how mixtures of particles with opposing surface chemistry make it possible to finely tune the shear-thickening response of the suspension at a fixed volume fraction, paving the way for a fine control of shear-thickening transition in engineering applications.
التعليقات
جاري جلب التعليقات جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
mircosoft-partner

هل ترغب بارسال اشعارات عن اخر التحديثات في شمرا-اكاديميا