From paints to food products, solvent evaporation is ubiquitous and critically impacts product rheological properties. It affects Newtonian fluids by concentrating any non-volatile components and viscoelastic materials, which hardens up. In both of these cases, solvent evaporation leads to a change in the sample volume, which makes any rheological measurements particularly challenging with traditional shear geometries. Here we show that the rheological properties of a sample experiencing `slow' evaporation can be monitored in a time-resolved fashion by using a zero normal-force controlled protocol in a parallel-plate geometry. Solvent evaporation from the sample leads to a decrease of the normal force, which is compensated at all times by a decrease of the gap height between the plates. As a result, the sample maintains a constant contact area with the plates despite the significant decrease of its volume. We validate the method under both oscillatory and continuous shear by accurately monitoring the viscosity of water-glycerol mixtures experiencing evaporation and a relative volume decrease as large as 70%. Moreover, we apply this protocol to dehydrating suspensions. Specifically, we monitor a dispersion of charged silica nanoparticles undergoing a glass transition induced by evaporation. While the decrease in gap height provides a direct estimate of the increasing particle volume fraction, oscillatory and continuous shear measurements allow us to monitor the suspension's evolving viscoelastic properties in real-time. Overall, our study shows that a zero normal-force protocol provides a simple approach to bulk and time-resolved rheological characterization for systems experiencing slow volume variations.
A potential strategy for controlling stratification in a drying suspension of bidisperse particles is studied using molecular dynamics simulations. When the suspension is maintained at a constant temperature during fast drying, it can exhibit "small-on-top" stratification with an accumulation (depletion) of smaller (larger) particles in the top region of the drying film, consistent with the prediction of current theories based on diffusiophoresis. However, when only the region near the substrate is thermalized at a constant temperature, a negative temperature gradient develops in the suspensio…
Drying of bacterial suspensions is frequently encountered in a plethora of natural and engineering processes. However, the evaporation-driven mechanical instabilities of dense consolidating bacterial suspensions have not been explored heretofore. Here, we report the formation of two different crack patterns of drying suspensions of \textit{Escherichia coli} (\textit{E. coli}) with distinct motile behaviors. Circular cracks are observed for wild-type \textit{E. coli} with active swimming, whereas spiral-like cracks form for immotile bacteria. Using the elastic fracture mechanics and the poroela…
Cracking of suspensions during drying is a common problem. While additives, e.g. binders and surfactants, can mitigate this problem, some applications, such as printing conductive pastes or sintering green bodies, do not lend themselves to the use of additives. Capillary suspensions provide an alternative formulation without additives. In this work, we use simultaneous stress and weight measurements to investigate the influence of formulation and drying conditions. Capillary suspensions dry more homogeneously and with lower peak stresses, leading to an increased robustness against cracking com…
Dynamic density functional theory (DDFT) is a promising approach for predicting the structural evolution of a drying suspension containing one or more types of colloidal particles. The assumed free-energy functional is a key component of DDFT that dictates the thermodynamics of the model and, in turn, the density flux due to a concentration gradient. In this work, we compare several commonly used free-energy functionals for drying hard-sphere suspensions including local-density approximations based on the ideal-gas, virial, and Boublík-Mansoori-Carnahan-Starling-Leland (BMCSL) equations of sta…
Large scale molecular dynamics simulations are used to study drying suspensions of a binary mixture of large and small particles in explicit and implicit solvents. The solvent is first modeled explicitly and then mapped to a uniform viscous medium by matching the diffusion coefficients and the pair correlation functions of the particles. `Small-on-top' stratification of the particles, with an enrichment of the smaller ones at the receding liquid-vapor interface during drying, is observed in both models under the same drying conditions. With the implicit solvent model, we are able to model much…
From suspensions to porous multilayers: microstructure formation and particle packing in drying colloidal films
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（于利希研究中心埃尔朗根-纽伦堡亥姆霍兹可再生能源研究所（IET-2））；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
The ordering of particles in the drying process of a colloidal suspension is crucial in determining the properties of the resulting film. For example, microscopic inhomogeneities can lead to the formation of cracks and defects that can deteriorate the quality of the film considerably. This type of problem is inherently multiscale and here we study it numerically, using our recently developed method for the simulation of soft polymeric capsules in multicomponent fluids. We focus on the effect of the particle softness on the film microstructure during the drying phase and how it relates to the f…
The deposition of particles on a substrate by drying a colloidal suspension droplet is at the core of applications ranging from traditional printing on paper to printable electronics or photovoltaic devices. The self-pinning induced by the accumulation of particles at the contact line plays an important role in the formation of the deposition. In this paper, we investigate both numerically and theoretically, the effect of friction between the particles and the substrate on the deposition pattern. Without friction, the contact line shows a stick-slip behaviour and a dot-like deposit is left aft…
Hypothesis: Lateral accumulation and film defects during drying of hard particle coatings is a common problem, typically solved using polymeric additives and surface active ingredients, which require further processing of the dried film. Capillary suspensions with their tunable physical properties, devoid of polymers, offer new pathways in producing uniform and defect free particulate coatings. Experiments: We investigated the effect of small amounts of secondary liquid on the coating's drying behavior. Stress build-up and weight loss in a temperature and humidity controlled drying chamber wer…
Exploring the role of hydrodynamic interactions in spherically-confined drying colloidal suspensions
Auburn University（奥本大学）；Leibniz-Institut für Polymerforschung Dresden e.V.（德累斯顿莱布尼茨聚合物研究所）；Technische Universität Dresden（德累斯顿工业大学）；Johannes Gutenberg University Mainz（美因茨约翰内斯·古腾堡大学）
The flow of colloidal suspensions is ubiquitous in nature and industry. Colloidal suspensions exhibit a wide range of rheological behavior, which should be closely related to the microscopic structure of the systems. With in-situ small-angle neutron scattering complemented by rheological measurements, we investigated the deformation behavior of a charge-stabilized colloidal glass at particle level undergoing steady shear. A short-lived, localized elastic response at particle level, termed as transient elasticity zone (TEZ), was identified from the neutron spectra. The existence of the TEZ is a…
The process of colloidal drying gives way to particle self-assembly in numerous elds including photonics or biotechnology. Yet, the mechanisms and conditions driving the nal particle arrangement in dry colloidal layers remain elusive. Here, we examine how the drying rate selects the nanostructure of thick dried layers in four dierent suspensions of silica nanospheres. Depending on particle size and dispersity, either an amorphous arrangement, a crystalline arrangement, or a rate-dependent amorphous-to-crystalline transition occurs at the drying surface. Amorphous arrangements are observed in t…
Granular suspensions present a transition from a Newtonian rheology in the Stokes limit to a Bagnoldian rheology when inertia is increased. A custom rheometer which can be run in a pressure or a volume-imposed mode is used to examine this transition in the dense regime close to jamming. By varying systematically the interstitial fluid, shear rate, and packing fraction in volume-imposed measurements, we show that the transition takes place at a Stokes number of 10 independent of the packing fraction. Using pressure-imposed rheometry, we investigate whether the inertial and viscous regimes can b…
Competing time scales generate novelty. Here, we show that a coupling between the time scales imposed by instrument inertia and the formation of inter-particle frictional contacts in shear-thickening suspensions leads to highly asymmetric shear-rate oscillations. Experiments tuning the presence of oscillations by varying the two time-scales validate our model. The observed oscillations give access to a shear-jamming portion of the flow curve that is forbidden in conventional rheometry. Moreover, the oscillation frequency allows us to quantify an intrinsic relaxation time for particle contacts.…
The linear and nonlinear rheological behavior of two rod-like particle suspensions as a function of concentration is studied using small amplitude oscillatory shear, steady shear and capillary breakup extensional rheometry. The rod-like suspensions are composed of fd virus and its mutant fdY21M, which are perfectly monodisperse, with a length on the order of 900 nm. The particles are semi flexible yet differ in their persistence length. The effect of stiffness on the rheological behavior in both, shear and extensional flow, is investigated experimentally. The linear viscoelastic shear data is …
A method of simulating the drying process of a soft matter solution with an implicit solvent model by moving the liquid-vapor interface is applied to various solution films and droplets. For a solution of a polymer and nanoparticles, we observe "polymer-on-top" stratification, similar to that found previously with an explicit solvent model. Furthermore, "polymer-on-top" is found even when the nanoparticle size is smaller than the radius of gyration of the polymer chains. For a suspension droplet of a bidisperse mixture of nanoparticles, we show that core-shell clusters of nanoparticles can be …
Drying dynamics of a charged colloidal dispersion in a confined drop
我们进行了彻底的调查，在一个封闭的几何形状的带电胶体分散液滴的干燥动力学。我们开发了一种基于拉曼显微光谱的原始方法来测量液滴干燥过程中的空间分辨胶体浓度分布。这些测量导致，第一次，估计的集体扩散系数的分散在很宽的范围内的浓度。集体扩散系数是一个数量级高于斯托克斯-爱因斯坦估计的浓度梯度的松弛的静电相互作用的重要性。与此同时，我们还进行了荧光成像的示踪剂嵌入分散液中的干燥过程中的下降，这揭示了两个不同的制度。在早期阶段，沿液滴的浓度梯度导致浮力诱导的流动。引人注目的是，这些流动并不影响产生它们的胶体浓度梯度，因为质量传递仍然由扩散主导。在较长的时间尺度上，示踪剂的轨迹揭示了准均匀干燥的凝胶的形成。对于这样的凝胶，我们表明使用线性孔隙弹性模型，干燥动力学仍然是由相同的传输方程描述的液体分散体。然而，集体扩散系数遵循修改的广义斯托克斯-爱因斯坦关系，如Style等人在单向固结的上下文中所证明的那样[Crust formation in drying colloidal suspension，Style等人，程序R. A 467，174（2011）]。
Mud is a suspension of fine-grained particles (sand, silt, and clay) in water. The interaction of clay minerals in mud gives rise to complex rheological behaviors, such as yield stress, thixotropy and viscoelasticity. Here, we experimentally examine the flow behaviors of kaolinite clay suspensions, a model mud, using steady shear rheometry. The flow curves exhibit both yield stress and rheological hysteresis behaviors for various kaolinite volume fractions ($ϕ_k$). Further understanding of these behaviors requires fitting to existing constitutive models, which is challenging due to numerous fi…
Nanofluids hold promise for a wide range of areas of industry. However, understanding of wetting behavior and deposition formation in course of drying and spreading of nanofluids, particularly containing surfactants, is still poor. In this paper, the evaporation dynamics of quantum dot-based nanofluids and evaporation-driven self-assembly in nanocolloidal suspensions on hexamethyldisilazane-, polystyrene-, and polypropylene-coated hydrophobic surfaces have been studied experimentally. Moreover, for the very first time, we make a step to understanding of wetting dynamics of superspreader surfac…
Large scale molecular dynamics simulations for bidisperse nanoparticle suspensions with an explicit solvent are used to investigate the effects of evaporation rates and volume fractions on the nanoparticle distribution during drying. Our results show that ``small-on-top'' stratification can occur when ${\rm Pe}_sϕ_s \gtrsim c$ with $c\sim 1$, where ${\rm Pe}_s$ is the Péclet number and $ϕ_s$ is the volume fraction of the smaller particles. This threshold of ${\rm Pe}_sϕ_s$ for ``small-on-top'' is larger by a factor of $\simα^2$ than the prediction of the model treating solvent as an implicit v…
We develop a lattice gas model for the drying of droplets of a nanoparticle suspension on a planar surface, using dynamical density functional theory (DDFT) to describe the time evolution of the solvent and nanoparticle density profiles. The DDFT assumes a diffusive dynamics but does not include the advective hydrodynamics of the solvent, so the model is relevant to highly viscous or near to equilibrium systems. Nonetheless, we see an equivalent of the coffee-ring stain effect, but in the present model it occurs for thermodynamic rather the fluid-mechanical reasons. The model incorporates the …
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 r…
We present a detailed comparison of the rheological behaviour of sheared sediment beds in a pressure-driven, straight channel configuration based on data that was generated by means of fully coupled, grain-resolved direct numerical simulations and experimental measurements reviously published by Aussillous {\it et al.} (J. Fluid Mech., vol. 736, 2013, pp. 594-615). The highly-resolved simulation data allows to compute the stress balance of the suspension in the streamwise and vertical directions and the stress exchange between the fluid and particle phase, which is information needed to infer …
