Understanding particle drift in suspension flows is of the highest importance in numerous engineering applications where particles need to be separated and filtered out from the suspending fluid. Commonly known drift mechanisms such as the Magnus force, Saffman force and Segre-Silberberg effect all arise only due to inertia of the fluid, with similar effects on all non-spherical particle shapes. In this work, we present a new shape-selective lateral drift mechanism, arising from particle inertia rather than fluid inertia, for ellipsoidal particles in a parabolic velocity profile. We show that the new drift is caused by an intermittent tumbling rotational motion in the local shear flow together with translational inertia of the particle, while rotational inertia is negligible. We find that the drift is maximal when particle inertial forces are of approximately the same order of magnitude as viscous forces, and that both extremely light and extremely heavy particles have negligible drift. Furthermore, since tumbling motion is not a stable rotational state for inertial oblate spheroids (nor for spheres), this new drift only applies to prolate spheroids or tri-axial ellipsoids. Finally, the drift is compared with the effect of gravity acting in the directions parallel and normal to the flow. The new drift mechanism is stronger than gravitational effects as long as gravity is less than a critical value. The critical gravity is highest (i.e. the new drift mechanism dominates over gravitationally induced drift mechanisms) when gravity acts parallel to the flow and the particles are small.

As the quest for more sustainable and environmentally friendly materials has increased in the last decades, cellulose nanofibrils (CNFs), abundant in nature, have proven their capabilities as building blocks to create strong and stiff filaments. Experiments have been conducted to characterize CNFs with a rheo-optical flow-stop technique to study the Brownian dynamics through the CNFs’ birefringence decay after stop. This paper aims to predict the initial relaxation of birefringence using Principal Component Analysis (PCA) and Long Short-Term Memory (LSTM) networks. By reducing the dimensionality of the data frame features, we can plot the principal components (PCs) that retain most of the information and treat them as time series. We employ LSTM by training with the data before the flow stops and predicting the behavior afterward. Consequently, we reconstruct the data frames from the obtained predictions and compare them to the original data.

Cellulose nanofibrils (CNFs) can be used as building blocks for future sustainable materials including strong and stiff filaments. The goal of this paper is to introduce a data analysis of flow-induced birefringence experiments by means of unsupervised learning techniques. By reducing the dimensionality of the data with Principal Component Analysis (PCA) we are able to exploit information for the different cellulose materials at several concentrations and compare them to each other. Our approach aims at classifying the CNF materials at different concentrations by applying unsupervised machine learning algorithms, like k-means and Gaussian Mixture Models (GMMs). Finally, we analyze the autocorrelation function (ACF) and the partial autocorrelation function (PACF) of the first principal component, detecting seasonality in lower concentrations. The focus is given to the initial relaxation of birefringence after the flow is stopped to have a better understanding of the Brownian dynamics for the given materials and concentrations.

Our method can be used to distinguish the different materials at specific concentrations and could help to identify possible advantages and drawbacks of one material over the other. 

Dynamics of colloidal particles can be controlled by the application of electric fields at micrometer-nanometer length scales. Here, an electric field-coupled microfluidic flow-focusing device is designed for investigating the effect of an externally applied alternating current (AC) electric field on the hydrodynamic assembly of cellulose nanofibrils (CNFs). We first discuss how the nanofibrils align parallel to the direction of the applied field without flow. Then, we apply an electric field during hydrodynamic assembly in the microfluidic channel and observe the effects on the mechanical properties of the assembled nanostructures. We further discuss the nanoscale orientational dynamics of the polydisperse and entangled fibrillar suspension of CNFs in the channel. It is shown that electric fields induced with the electrodes locally increase the degree of orientation. However, hydrodynamic alignment is demonstrated to be much more efficient than the electric field for aligning CNFs. The results are useful for understanding the development of the nanostructure when designing high-performance materials with microfluidics in the presence of external stimuli.

Water management is an important factor for optimizing polymer electrolyte fuel cells (PEFC) under high current density conditions as required for the automotive application. The characteristics of the local liquid saturation of the gas diffusion layer (GDL) is of particular interest. Here we report on the development of in-situ X-ray tomographic microscopy (XTM) with a pixel sizes in the order of 2 μm and sensitivity for carbon and liquid water for the quantitative analysis of liquid water in GDLs. In-situ XTM of PEFC is a major experimental challenge. A complete cell needs to be operated under realistic conditions in the constraint space of the small field of view on the beamline sample stage. Further phase segmentation of the images is required to successfully analyze the quantitative properties of the different phases. For this a workflow, applying differential images between dry and wet structures has been developed. Cells with Toray TGP-H-060 GDLs were analyzed in-situ. Droplets that appear on the GDL surface are connected to a significant water structure inside the GDL. Further the water cluster size distribution in the GDL shows that while small droplets (<100 pl) are numerous, most of the water is contained in few larger clusters.

The nanostructure, primarily particle orientation, controls mechanical and functional (e.g., mouthfeel, cell compatibility, optical, morphing) properties when macroscopic materials are assembled from nanofibrils. Understanding and controlling the nanostructure is therefore an important key for the continued development of nanotechnology. We merge recent developments in the assembly of biological nanofibrils, X-ray diffraction orientation measurements, and computational fluid dynamics of complex flows. The result is a digital twin, which reveals the complete particle orientation in complex and transient flow situations, in particular the local alignment and spatial variation of the orientation distributions of different length fractions, both along the process and over a specific cross section. The methodology forms a necessary foundation for analysis and optimization of assembly involving anisotropic particles. Furthermore, it provides a bridge between advanced in operandi measurements of nanostructures and phenomena such as transitions between liquid crystal states and in silico studies of particle interactions and agglomeration.

We report a combined experimental and numerical investigation to decipher and delineate the role of fluid properties, flow parameters, and geometries on the dynamics of viscous thread formation in microchannels with miscible solvents. A methodological analysis based on the evolution of viscous threads unveils the significance of effective interfacial tension (EIT) induced by the virtue of concentration gradients between the non-equilibrium miscible fluid pair colloidal dispersions and their own solvent.  Functional scaling relationships developed with dimensionless capillary and Weber numbers, together with thread quantities thread detachment length, and thread width, shed light on the complex interplay of hydrodynamic effects and viscous microflow processes. The detachment of viscous threads inside microchannels is governed by the unified hydrodynamic effects of inertia, capillary, and viscous stresses in contrast to the natural phenomenon of self-lubrication,  bringing new insights to the physical phenomena involved in the confined microsystems. Exploiting the experimentally measured thread quantities, the scaling laws are practically applied to estimate the inherent fluid properties such as EIT between two inhomogeneous miscible fluids, and the fluid viscosities. In addition, the cross-sectional aspect ratio of the channels is varied numerically in conjunction with the converging shaped sections.  For specified flow rates and given rheologies of the fluids,  a flow-focusing configuration producing the shortest thread detachment length, and a longer region of strain rate along the centreline is identified. Overall, this work provides a consolidated description of the effect of fluid properties, flow parameters, and geometry on the formation of miscible viscous threads in microchannel flows. 

We analyze the angular velocity of a small neutrally buoyant spheroid log rolling in a simple shear. When the effect of fluid inertia is negligible the angular velocity. equals half the fluid vorticity. We compute by singular perturbation theory how weak fluid inertia reduces the angular velocity in an unbounded shear, and how this reduction depends upon the shape of the spheroid (on its aspect ratio). In addition we determine the angular velocity by direct numerical simulations. The results are in excellent agreement with the theory at small but not too small values of the shear Reynolds number Res, for all aspect ratios considered. For the special case of a sphere we find omega/s = -1/2 + 0.0540 Re-s(3/2) where s is the shear rate. The O( Re-s(3/2)) correction differs from that derived by Lin et al. who obtained a numerical coefficient roughly three times larger.

Biopolymer network dynamics play a significant role in both biological and materials science. This study focuses on the dynamics of cellulose nanofibers as a model system given their relevance to biology and nanotechnology applications. Using large-scale coarse-grained simulations with a lattice Boltzmann fluid coupling, we investigated the reptation behavior of individual nanofibers within entangled networks. Our analysis yields essential insights, proposing a scaling law for rotational diffusion, quantifying effective tube diameter, and revealing release mechanisms during reptation, spanning from rigid to semiflexible nanofibers. Additionally, we examine the onset of entanglement in relation to the nanofiber flexibility within the network. Microrheology analysis is conducted to assess macroscopic viscoelastic behavior. Importantly, our results align closely with previous experiments, validating the proposed scaling laws, effective tube diameters, and onset of entanglement. The findings provide an improved fundamental understanding of biopolymer network dynamics and guide the design of processes for advanced biobased materials. 

The ForMAX beamline at the MAX IV Laboratory provides multiscale and multimodal structural characterization of hierarchical materials in the nanometre to millimetre range by combining small- and wide-angle X-ray scattering with full-field microtomography. The modular design of the beamline is optimized for easy switching between different experimental modalities. The beamline has a special focus on the development of novel fibrous materials from forest resources, but it is also well suited for studies within, for example, food science and biomedical research.

A 3D lattice Boltzmann (LB) model with twenty-seven discrete velocities is presented and used for the simulation of three-dimensional porous media flows. Its accuracy in combination with the half-way bounce back boundary condition is assessed. Characteristic properties of the gas diffusion layers that are used in polymer electrolyte fuel cells can be determined with this model. Simulation in samples that have been obtained via X-ray tomographic microscopy, allows to estimate the values of permeability and relative effective diffusivity. Furthermore, the computational LB results are compared with the results of other numerical tools, as well as with experimental values.

We numerically analyze the rotation of a neutrally buoyant spheroid in a shear flow at small shear Reynolds number. Using direct numerical stability analysis of the coupled nonlinear particle-flow problem, we compute the linear stability of the log-rolling orbit at small shear Reynolds number Re-a. As Re-a -> 0 and as the box size of the system tends to infinity, we find good agreement between the numerical results and earlier analytical predictions valid to linear order in Re-a for the case of an unbounded shear. The numerical stability analysis indicates that there are substantial finite-size corrections to the analytical results obtained for the unbounded system. We also compare the analytical results to results of lattice Boltzmann simulations to analyze the stability of the tumbling orbit at shear Reynolds numbers of order unity. Theory for an unbounded system at infinitesimal shear Reynolds number predicts a bifurcation of the tumbling orbit at aspect ratio lambda(c) approximate to 0.137 below which tumbling is stable (as well as log rolling). The simulation results show a bifurcation line in the lambda-Re-a plane that reaches lambda approximate to 0.1275 at the smallest shear Reynolds number (Re-a = 1) at which we could simulate with the lattice Boltzmann code, in qualitative agreement with the analytical results.

Dispersed particle flows are encountered in many biological, geophysical but also in industrial situations, e.g. during processing of materials. In these flows, the particles usually are non-spherical and their angular dynamics play a crucial role for the final material properties. Generally, the angular dynamics of a particle is dependent on the local flow in the frame-of-reference of this particle. In this frame, the surrounding flow can be linearized and the linear velocity gradient will determine how the particle rotates. In this thesis, the main objective is to improve the fundamental knowledge of the angular dynamics of non-spherical particles related to two specific biobased material processes.

Firstly, the flow of suspended cellulose fibers in a papermaking process is used as a motivation. In this process, strong shear rates close to walls and the size of the fibers motivates the study of inertial effects on a single particle in a simple shear flow. Through direct numerical simulations combined with a global stability analysis, this flow problem is approached and all stable rotational states are found for spheroidal particles with aspect ratios ranging from moderately slender fibers to thin disc-shaped particles.

The second material process of interest is the production of strong cellulose filaments produced through hydrodynamic alignment and assembly of cellulose nanofibrils (CNF). The flow in the preparation process and the small size of the particles motivates the study of alignment and rotary diffusion of CNF in a strain flow. However, since the particles are smaller than the wavelength of visible light, the dynamics of CNF is not easily captured with standard optical techniques. With a new flow-stop experiment, rotary diffusion of CNF is measured using Polarized optical microscopy. This process is found to be quite complicated, where short-range interactions between fibrils seem to play an important role. New time-resolved X-ray characterization techniques were used to target the underlying mechanisms, but are found to be limited by the strong degradation of CNF due to the radiation.

Although the results in this thesis have limited direct applicability, they provide important fundamental stepping stones towards the possibility to control fiber orientation in flows and can potentially lead to new tailor-made materials assembled from a nano-scale.

The angular motion of a neutrally buoyant prolate spheroidal particle in simple shear flow has previously been found to follow two-dimensional dynamics similar to a Duffing-van der Pol oscillator as a consequence of inertia of the surrounding fluid. This behavior was however only present if the aspect ratio is large enough. When decreasing the particle aspect ratio, the particle could be found to perform period-doubled or chaotic orbits as effects of particle inertia also influence the dynamics. In this work, it is demonstrated that the onset of complex dynamics is through a Shilnikov bifurcation as the log-rolling state (particle is rotating around its symmetry axis, which is parallel to the vorticity direction) is transformed from a regular saddle node into a saddle focus when particle inertia is increased. Furthermore, it is shown that the same also applies for the two dimensional Duffing-van der Pol oscillator when including inertial terms. These results open up the possibility of developing a reduced model to mimic the influence of both fluid and particle inertia on the angular dynamics of spheroidal particles in simple shear flow, which can be used in fluid simulations with Lagrangian particles.

Dispersed particle flows occur in many industrial, biological and geophysical applications. The knowledge of how these flow behave can for example lead to improved material processes, better predictions of vascular diseases or more accurate climate models. These particle flows have certain properties that depend on single particle motion in fluid flows and especially how they are distributed both in terms of spatial position and, if they are non-spherical, in terms of orientation. Much is already known about the motion of perfectly spherical particles. For non-spherical particles, apart from their translation, it is important to know the the rotational motion due to local velocity gradients. Such studies have usually been restricted by the assumption that particles are extremely small compared to fluid length scales. In this limit, both inertia of the particle and inertia of the fluid can be neglected for the particle motion. This thesis gives a complete picture of how a spheroidal particle (a particle described by a rotation of an ellipse around one of its principal axes) behave in a linear shear flow when including both fluid and particle inertia, using numerical simulations. It is observed that this very simple problem possess very interesting dynamical behavior with different stable rotational states appearing as a competition between the two types of inertia. The effect of particle inertia leads to a rotation where the mass of the particle is concentrated as far away from the rotational axis as possible, i.e.\ a rotation around the minor axis. Typically, the effect of fluid inertia is instead that it tries to force the particle in a rotation where the streamlines of the flow remain as straight as possible. The first effect of fluid inertia is thus the opposite of particle inertia and instead leads to a particle rotation around the major axis. Depending on rotational state, the particles also affect the apparent viscosity of the particle dispersion. The different transitions and bifurcations between rotational states are characterized in terms of non-linear dynamics, which reveal that the particle motion probably can be described by some reduced model. The results in this theses provides fundamental knowledge and is necessary to understand flows containing non-spherical particles.

The increased availability and brilliance of new X-ray facilities have in the recent years opened up the possibility to characterize the alignment of dispersed anisotropic nanoparticles in various microfluidic applications, from hydrodynamic self-assemblies to flows in complex geometries. In such applications, it is vital to study the alignment of the nanoparticles in the flow, as this in turn affects the final properties of the self-assembled superstructures or those of the flow itself. Small-angle X-ray scattering (SAXS) is a well-suited characterization technique for this but typically provides the alignment in a projected plane perpendicular to the beam direction. In this work, we demonstrate a simple method to reconstruct the full three-dimensional orientation distribution function from a SAXS experiment through the assumption that the azimuthal angle of the nanoparticles around the flow direction is distributed uniformly, an assumption that is valid for a large range of nanoparticle flow processes. For demonstration purposes, the experimental results from previous works on hydrodynamic self-assembly of cellulose nanofibrils (CNFs) into filaments have been revised, resulting in a small correction to the presented order parameters. The results are then directly compared with simple numerical models to describe the increased alignment of CNFs both in the flowing system and during the drying of the filament. The proposed reconstruction method will allow for further improvements of theoretical or numerical simulations and consequently open up new possibilities for optimizing assembly processes, which include flow alignment of elongated nanoparticles.

This work describes the inertial effects on the rotational behavior of an oblate spheroidal particle confined between two parallel opposite moving walls, which generate a linear shear flow. Numerical results are obtained using the lattice Boltzmann method with an external boundary force. The rotation of the particle depends on the particle Reynolds number, Rep = Gd-2 nu(-1) (G is the shear rate, d is the particle diameter,. is the kinematic viscosity), and the Stokes number, St = alpha Re-p (a is the solid-to-fluid density ratio), which are dimensionless quantities connected to fluid and particle inertia, respectively. The results show that two inertial effects give rise to different stable rotational states. For a neutrally buoyant particle (St = Re-p) at low Re-p, particle inertia was found to dominate, eventually leading to a rotation about the particle's symmetry axis. The symmetry axis is in this case parallel to the vorticity direction; a rotational state called log-rolling. At high Re-p, fluid inertia will dominate and the particle will remain in a steady state, where the particle symmetry axis is perpendicular to the vorticity direction and has a constant angle phi(c) to the flow direction. The sequence of transitions between these dynamical states were found to be dependent on density ratio alpha, particle aspect ratio r(p), and domain size. More specifically, the present study reveals that an inclined rolling state (particle rotates around its symmetry axis, which is not aligned in the vorticity direction) appears through a pitchfork bifurcation due to the influence of periodic boundary conditions when simulated in a small domain. Furthermore, it is also found that a tumbling motion, where the particle symmetry axis rotates in the flow-gradient plane, can be a stable motion for particles with high r(p) and low alpha.

The rotational motion of a prolate spheroidal particle suspended in shear flow is studied by a lattice Boltzmann method with external boundary forcing (LB-EBF). It has previously been shown that the case of a single neutrally buoyant particle is a surprisingly rich dynamical system that exhibits several bifurcations between rotational states due to inertial effects. It was observed that the rotational states were associated with either fluid inertia effects or particle inertia effects, which are always in competition. The effects of fluid inertia are characterized by the particle Reynolds number Rep=4Ga²/ν, where G is the shear rate, a is the length of the particle major semi-axis and ν is the kinematic viscosity. Particle inertia is associated with the Stokes number St=α· Rep, where alpha is the solid-to-fluid density ratio. Previously, the neutrally buoyant case (St=Rep) was studied extensively. However, little is known about how these results are affected when St≢Rep, and how the aspect ratio rp (major axis/minor axis) influences the competition between fluid and particle inertia in the absence of gravity. This work gives a full description of how prolate spheroidal particles in the range 2≤ rp≤ 6 behave depending on the chosen St and Rep. Furthermore, consequences for the rheology of a dilute suspension containing such particles are discussed. Finally, grid resolution close to the particle is shown to affect the quantitative results considerably. It is suggested that this resolution is a major cause of quantitative discrepancies between different studies. Thus, the results of this work and previous direct numerical simulations of this problem should be regarded as qualitative descriptions of the physics involved, and more refined methods must be used to quantitatively pinpoint the transitions between rotational states.

Operating Polymer Electrolyte Fuel Cells (PEFC) under high current density conditions, causes significant losses related to liquid water saturation in the gas diffusion layer (GDL). The blockage of pores inside the material has a strong influence on its effective gas transport properties. Here we report on the combination of in-situ X-ray tomographic microscopy (XTM) of PEFC and the numerical determination of gas transport properties using Lattice Boltzmann and finite difference methods. The GDL domains (Toray TGP-H-060) of two identical cells, each with 11 mm(2) active area, were analyzed in sections of about 0.3 to 0.8 mm(2) size. Saturation levels between 0.1 and 0.4 were found, with higher saturation under the ribs. The saturated and the non-saturated states of the GDL samples were compared in order to quantify the dependence of gas phase permeability and effective relative diffusivity on liquid water saturation. Both these relative measures were found to follow power relationships of (1-s)(lambda), where the exponent. was approximately 3 for all cases except for the in-plane diffusivity where it was closer to 2.

We demonstrate a framework of interpreting data from x-ray photon correlation spectroscopy experiments with the aid of numerical simulations to describe nanoscale dynamics in soft matter. This is exemplified with the transport of passive tracer gold nanoparticles in networks of charge-stabilized cellulose nanofibers. The main structure of dynamic modes in reciprocal space could be replicated with a simulated system of confined Brownian motion, a digital twin, allowing for a direct measurement of important effective material properties describing the local environment of the tracers. 

Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. The cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.

Man-made continuous fibers play an essential role in society today. With the increase in global sustainability challenges, there is a broad spectrum of societal needs where the development of advanced biobased fibers could provide means to address the challenges. Biobased regenerated fibers, produced from dissolved cellulose are widely used today for clothes, upholstery, and linens. With new developments in the area of advanced biobased fibers, it would be possible to compete with high-performance synthetic fibers such as glass fibers and carbon fibers as well as to provide unique functionalities. One possible development is to fabricate fibers by spinning filaments from nanocellulose, Nature's nanoscale high-performance building block, which will require detailed insights into nanoscale assembly mechanisms during spinning, as well as knowledge regarding possible functionalization. If successful, this could result in a new class of man-made biobased fibers. This work aims to identify the progress made in the field of spinning of nanocellulose filaments, as well as outline necessary steps for efficient fabrication of such nanocellulose-based filaments with controlled and predictable properties.

The motion of a single ellipsoidal particle in simple shear flow can provide valuable insights toward understanding suspension flows with nonspherical particles. Previously, extensive studies have been performed on the ellipsoidal particle with rotational symmetry, a so-called spheroid. The nearly prolate ellipsoid (one major and two minor axes of almost equal size) is known to perform quasiperiodic or even chaotic orbits in the absence of inertia. With small particle inertia, the particle is also known to drift toward this irregular motion. However, it is not previously understood what effects from fluid inertia could be, which is of highest importance for particles close to neutral buoyancy. Here, we find that fluid inertia is acting strongly to suppress the chaotic motion and only very weak fluid inertia is sufficient to stabilize a rotation around themiddle axis. Themechanism responsible for this transition is believed to be centrifugal forces acting on fluid, which is dragged along with the rotational motion of the particle. With moderate fluid inertia, it is found that nearly prolate triaxial particles behave similarly to the perfectly spheroidal particles. Finally, we also are able to provide predictions about the stable rotational states for the general triaxial ellipsoid in simple shear with weak inertia.

The basic dynamics of a prolate spheroidal particle suspended in shear flow is studied using lattice Boltzmann simulations. The spheroid motion is determined by the particle Reynolds number (Re-p) and Stokes number (St), estimating the effects of fluid and particle inertia, respectively, compared with viscous forces on the particle. The particle Reynolds number is defined by Re-p = 4Ga(2)/nu, where G is the shear rate, a is the length of the spheroid major semi-axis and nu is the kinematic viscosity. The Stokes number is defined as St = alpha . Re-p, where alpha is the solid-to-fluid density ratio. Here, a neutrally buoyant prolate spheroidal particle (St = Re-p) of aspect ratio (major axis/minor axis) r(p) = 4 is considered. The long-term rotational motion for different initial orientations and Re-p is explained by the dominant inertial effect on the particle. The transitions between rotational states are subsequently studied in detail in terms of nonlinear dynamics. Fluid inertia is seen to cause several bifurcations typical for a nonlinear system with odd symmetry around a double zero eigenvalue. Particle inertia gives rise to centrifugal forces which drives the particle to rotate with the symmetry axis in the flow-gradient plane (tumbling). At high Re-p, the motion is constrained to this planar motion regardless of initial orientation. At a certain critical Reynolds number, Re-p = Re-c, a motionless (steady) state is created through an infinite-period saddle-node bifurcation and consequently the tumbling period near the transition is scaled as vertical bar Re-p - Re-c vertical bar(-1/2). Analyses in this paper show that if a transition from tumbling to steady state occurs at Re-p = Re-c, then any parameter beta (e. g. confinement or particle spacing) that influences the value of Re-c, such that Re-p = Re-c as beta = beta(c), will lead to a period that scales as vertical bar beta - beta c vertical bar(-1/2) and is independent of particle shape or any geometric aspect ratio in the flow.

Hydrodynamic alignment of proteinaceous or polymeric nanofibrillar building blocks can be utilized for subsequent assembly into intricate three-dimensional macrostructures. The non-equilibrium structure of flowing nanofibrils relies on a complex balance between the imposed flow-field, colloidal interactions and Brownian motion. The understanding of the impact of non-equilibrium dynamics is not only weak, but is also required for structural control. Investigation of underlying dynamics imposed by the flow requiresin situdynamic characterization and is limited by the time-resolution of existing characterization methods, specifically on the nanoscale. Here, we present and demonstrate a flow-stop technique, using polarized optical microscopy (POM) to quantify the anisotropic orientation and diffusivity of nanofibrils in shear and extensional flows. Microscopy results are combined with small-angle X-ray scattering (SAXS) measurements to estimate the orientation of nanofibrils in motion and simultaneous structural changes in a loose network. Diffusivity of polydisperse systems is observed to act on multiple timescales, which is interpreted as an effect of apparent fibril lengths that also include nanoscale entanglements. The origin of the fastest diffusivity is correlated to the strength of velocity gradients, independent of type of deformation (shear or extension). Fibrils in extensional flow results in highly anisotropic systems enhancing interfibrillar contacts, which is evident through a slowing down of diffusive timescales. Our results strongly emphasize the need for careful design of fluidic microsystems for assembling fibrillar building blocks into high-performance macrostructures relying on improved understanding of nanoscale physics.

A spheroidal particle in simple shear flow shows surprisingly complicated angular dynamics; caused by effects of fluid inertia (characterized by the particle Reynolds number Re_p) and particle inertia (characterized by the Stokes number St). Understanding this behavior can provide important fundamental knowledge of suspension flows with spheroidal particles. Up to now only qualitative analysis has been available at moderate Re_p. Rigorous analytical methods apply only to very small Re_p and numerical results lack accuracy due to the difficulty in treating the moving boundary of the particle. Here we show that the dynamics of the rotational motion of a prolate spheroidal particle in a linear shear flow can be quantitatively analyzed through the eigenvalues of the log-rolling particle (particle aligned with vorticity). This analysis provides an accurate description of stable rotational states in terms of Re_p,St, and particle aspect ratio (r_p). Furthermore we find that the effect on the orientational dynamics from fluid inertia can be modeled with a Duffing-Van der Pol oscillator. This opens up the possibility of developing a reduced-order model that takes into account effects from both fluid and particle inertia.

Time-resolved in situ characterization of well-defined mixing processes using small-angle X-ray scattering (SAXS) is usually challenging, especially if the process involves changes of material viscoelasticity. In specific, it can be difficult to create a continuous mixing experiment without shearing the material of interest; a desirable situation since shear flow both affects nanoscale structures and flow stability as well as resulting in unreliable time-resolved data. Here, we demonstrate a flow-focusing mixing device for in situ nanostructural characterization using scanning-SAXS. Given the interfacial tension and viscosity ratio between core and sheath fluids, the core material confined by sheath flows is completely detached from the walls and forms a zero-shear plug flow at the channel center, allowing for a trivial conversion of spatial coordinates to mixing times. With this technique, the time-resolved gel formation of dispersed cellulose nanocrystals (CNCs) was studied by mixing with a sodium chloride solution. It is observed how locally ordered regions, so called tactoids, are disrupted when the added monovalent ions affect the electrostatic interactions, which in turn leads to a loss of CNC alignment through enhanced rotary diffusion. The demonstrated flow-focusing scanning-SAXS technique can be used to unveil important kinetics during structural formation of nanocellulosic materials. However, the same technique is also applicable in many soft matter systems to provide new insights into the nanoscale dynamics during mixing.

During the past decade, cellulose nanofibrils (CNFs) have shown tremendous potential as a building block to fabricate new advanced materials that are both biocompatible and biodegradable. The excellent mechanical properties of the individual CNF can be transferred to macroscale fibers through careful control in hydrodynamic alignment and assembly processes. The optimization of such processes relies on the understanding of nanofibril dynamics during the process, which in turn requires in situ characterization. Here, we use a shear-free mixing experiment combined with scanning small-angle X-ray scattering (scanning-SAXS) to provide time-resolved nanoscale kinetics during the in situ assembly of dispersed cellulose nanofibrils (CNFs) upon mixing with a sodium chloride solution. The addition of monovalent ions led to the transition to a volume-spanning arrested (gel) state. The transition of CNFs is associated with segmental aggregation of the particles, leading to a connected network and reduced Brownian motion, whereby an aligned structure can be preserved. Furthermore, we find that the extensional flow seems to enhance the formation of these segmental aggregates, which in turn provides a comprehensible explanation for the superior material properties obtained in shear-free processes used for spinning filaments from CNFs. This observation clearly highlights the need for different assembly strategies depending on morphology and interactions of the dispersed nanoparticles, where this work can be used as a guide for improved nanomaterial processes.

Nanostructured materials made through flow-assisted assembly of proteinaceous or polymeric nanosized fibrillar building blocks are promising contenders for a family of high-performance biocompatible materials in a wide variety of applications. Optimization of these processes relies on improving our knowledge of the physical mechanisms from nano- to macroscale and especially understanding the alignment of elongated nanoparticles in flows. Here, we study the full projected orientation distributions of cellulose nanocrystals (CNCs) and nanofibrils (CNFs) in confined flow using scanning microbeam SAXS. For CNCs, we further compare with a simulated system of dilute Brownian ellipsoids, which agrees well at dilute concentrations. However, increasing CNC concentration to a semidilute regime results in locally arranged domains called tactoids, which aid in aligning the CNC at low shear rates, but limit alignment at higher rates Similarly, shear alignment of CNF at semidilute conditions is also limited owing to probable bundle or flock formation of the highly entangled nanofibrils. This work provides a quantitative comparison of full projected orientation distributions of elongated nanoparticles in confined flow and provides an important stepping stone towards predicting and controlling processes to create nanostructured materials on an industrial scale.

In this study, the gelation behavior of TEMPO-oxidized wood-based cellulose nanofiber (CNF) suspensions in two different glycols, ethylene glycol (EG) and propylene glycol (PG), was investigated near the overlap concentration and compared with that of aqueous CNF suspensions. The flow property of these non-aqueous and aqueous CNF suspensions was characterized by rheological, UV-vis, and rheo-optical techniques. It was found that the CNF(PG) suspensions exhibited stirring-reversible gelation behavior, where gelation could be induced simply by resting (i.e., prolonged holding time). However, this behavior was not observed for CNF(EG) and CNF(aq) suspensions. Higher temperature and higher CNF concentration could accelerate the gelation process of CNFs in PG, but no large-scale phase separation was detected by the optical techniques. Our study suggests that the reduced hydrophilic attraction between CNFs in PG is the main driving force for forming CNF-rich micro-domains, yielding a physically crosslinked network. This study suggests that the choice of solvent can be used to tailor and control the flow behavior of CNF suspensions, leading to designs of new cellulose-enabled nanocomposites for varying applications. 

Flow-assisted alignment of anisotropic nanoparticles is a promising route for the bottom-up assembly of advanced materials with tunable properties. While aligning processes could be optimized by controlling factors such as solvent viscosity, flow deformation, and the structure of the particles themselves, it is necessary to understand the relationship between these factors and their effect on the final orientation. In this study, we investigated the flow of surface-charged cellulose nanocrystals (CNCs) with the shape of a rigid rod dispersed in water and propylene glycol (PG) in an isotropic tactoid state. In situ scanning small-angle X-ray scattering (SAXS) and rheo-optical flow-stop experiments were used to quantify the dynamics, orientation, and structure of the assigned system at the nanometer scale. The effects of both shear and extensional flow fields were revealed in a single experiment by using a flow-focusing channel geometry, which was used as a model flow for nanomaterial assembly. Due to the higher solvent viscosity, CNCs in PG showed much slower Brownian dynamics than CNCs in water and thus could be aligned at lower deformation rates. Moreover, CNCs in PG also formed a characteristic tactoid structure but with less ordering than CNCs in water owing to weaker electrostatic interactions. The results indicate that CNCs in water stay assembled in the mesoscale structure at moderate deformation rates but are broken up at higher flow rates, enhancing rotary diffusion and leading to lower overall alignment. Albeit being a study of cellulose nanoparticles, the fundamental interplay between imposed flow fields, Brownian motion, and electrostatic interactions likely apply to many other anisotropic colloidal systems.

Understanding the morphology and flow behavior of cellulose nanofibers (CNFs) dispersed in organic solvents can improve the process of fabricating new cellulose-based nanocomposites. In this study, jute-based 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized CNFs with two different charge densities (0.64 and 1.03 mmol/g) were dispersed in ethylene glycol (EG) and propylene glycol (PG) using the solvent exchange method. The morphology and dimensions of CNFs in dry and suspension states were characterized using transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering techniques. The results showed that the cross-sectional dimensions remained the same in different solvents. Rheological measurements revealed that CNF suspensions in water or glycol (EG and PG) behaved similar to typical polymer solutions with a solvent-independent overlap concentration corresponding to the crowding factor of about 14. Furthermore, a thixotropic behavior was found in the concentrated CNF/glycol systems as observed in typical CNF aqueous suspensions. The fact that TEMPO-oxidized CNFs can be well dispersed in organic solvents opens up new possibilities to improve the CNF–polymer matrix blending, where the use of a viscous solvent can delay the transition to turbulence in processing and improve the control of fiber orientation because of a slower Brownian diffusive motion.