Cellulose Nanocrystals Suspensions Research Articles

Liquid crystal phase behavior of oxalated cellulose nanocrystal and optical films with controllable structural color induced by centripetal force

Cellulose nanocrystal (CNC) is a sustainable bio-nanomaterial. The distinctive left-handed polarization properties render cellulose nanocrystal a promising candidate for optical film. Due to eco-friendliness, reliability, mildness and simplicity, the oxalate hydrolysis method stands out among various preparation methods for CNC. This study delved into the liquid crystal phase behavior of oxalated cellulose nanocrystal derived from pulp, and discovered the influences of CNC concentration and pH on suspension stability and phase transition, and evaluated its optical properties. The results demonstrated that oxalated CNC presented two different liquid crystal phases, the nematic phase and the cholesteric phase. The stability mechanism of CNC suspension and the regulatory principle of the liquid crystal phase transition were revealed. A novel CNC film-forming technology, the multilayer spin-coating technique, was developed for cellulose nanocrystal optical films. Driven by centrifugal force, cellulose nanocrystals were induced to self-assembly and formed the optical film with circular dichroism and structural color. This simple and efficient film-forming technology promised rapid processing (1 h) and controllable film structure and optical properties compared to traditional technologies. This work provided a theoretical understanding and practical prospects for integrating oxalated cellulose nanocrystal into sustainable advanced optical film materials.

Investigation of cellulose nanocrystals fabricated via sulfuric acid combined with deep eutectic solvent route

To make full use of tobacco waste in cigarette production and enhance resource utilization efficiency, cellulose nanocrystals (CNCs) were prepared by a method of sulfuric acid combined with a deep eutectic solvent. This method was compared with conventional methods, and the CNCs were thoroughly characterized. The results indicated that the yield of CNCs prepared by the sulfuric acid combined with a deep eutectic solvent method exceeded 26 %, with the highest yield reaching 29.5 %, surpassing the yields from two other methods of 12.5 %, 17.2 %, corresponding to sulfuric acid and sulfuric acid-oxalic acid, respectively. Scanning electron microscopy revealed a laminar morphology of CNCs, in which the CNCs maintained a cellulose type I structure with well-preserved crystallinity. In addition, CNCs prepared by the sulfuric acid combined with a deep eutectic solvent method exhibited good thermal stability, with maximum mass loss at temperature of 342.8 °C during third pyrolysis stage, higher than that of sulfuric acid at 316.7 °C and sulfuric acid-oxalic acid at 335.9 °C. Steady-state rheological testing revealed that the viscosity of the CNCs suspension decreased with an increasing shear rate, which is characteristic of pseudoplastic fluid shear thinning behavior. CNCs prepared by the sulfuric acid combined with DES method reduced the amount of sulfuric acid, and the yield was much higher than that of the other two methods. Moreover, the method using sulfuric acid combined with DES method was simple and safe, and the obtained CNCs had high thermal stability and viscosity, which expands the application prospects in biocomposite material fields.

Tailoring of steel fiber surface by coating cellulose nanocrystal for enhanced flexural properties of UHPC

Ultra-high-performance concrete (UHPC) is an advanced generation of cementitious composites with excellent compressive strength and durability. However, the relatively poor interfacial transition zone (ITZ) between steel fibers and UHPC matrix leads to insufficient flexural properties and hinders its further applications. This study proposed a cost-effective, sustainable, and highly reactive coating material, cellulose nanocrystals (CNCs), to densify the ITZ of steel fiber surfaces, thus enhancing the flexural properties of UHPC. Utilizing the Herschel-Bulkley model, the critical concentration of 1.0 % is determined for enabling uniform dispersion of CNCs, enhancing the coating performance and reliability. The performance of CNCs as coating materials was evaluated by flexural test of UHPC with CNCs-coated steel fibers, pull-off test, scanning electron microscope (SEM), atomic force microscope (AFM), energy-dispersive spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FTIR). Results showed that compared to UHPC with pristine steel fibers, the flexural strength and toughness of UHPC with CNCs-coated steel fibers were increased by up to 14 % and 18 %, because the single fiber pull-off energy was increased by 50 %. It can be attributed to the densified ITZ which is validated by the increased UHD C-S-H and HD C-S-H on ITZ. However, when the concentration of CNCs suspension (i.e., 1.5 %) exceeds the critical value, the CNCs coating film would stick the uniformly dispersed steel fibers together and then affect their distribution, thus reducing the mechanical performance of UHPC. This work provides a green and effective approach for promoting flexural properties and an in-depth understanding of CNCs coating mechanism.

Examination of flow birefringence induced by the shear components along the optical axis using a parallel-plate-type rheometer

In this study, the concept of rheo-optics was applied to explore the flow birefringence induced by the stress components along the camera’s optical axis since it is often overlooked in the traditional theories of photoelastic flow measurement. A novel aspect of this research is that it involved conducting polarization measurements on simple shear flows, specifically from a perspective in which a shear-velocity gradient exists along the camera’s optical axis. A parallel-plate-type rheometer and a polarization camera are employed for these systematic measurements. The experimental findings for dilute aqueous cellulose nanocrystal suspensions demonstrate that the flow birefringence can be expressed as a power law based on the power of the second invariant of the deformation-rate tensor. This suggests that flow birefringence can be universally characterized by the coordinate-independent invariants and a pre-factor determined by the direction of polarization measurement. By adjusting the nonlinear term in the stress-optic law, its applicability could be expanded to include three-dimensional fluid stress fields in which the stress is distributed along the camera’s optical axis.

Influence of buffer on colloidal stability, microstructure, and rheology of cellulose nanocrystals in hyaluronic acid suspensions

Hyaluronic acid (HA) is a natural biopolymer found in various human tissues, while cellulose nanocrystals (CNCs) extracted from pulp fibers have unique rheological properties and biocompatibility. Due to the superior biomechanical properties of CNC and HA, a CNC-based HA suspension may be useful in biomedical applications. While buffers are an essential constituent of any suspension used for biomedical applications to maintain the desired pH level, they can significantly affect the properties of the suspension, including colloidal stability, microstructure, and rheological characteristics.To our knowledge, this is the first study analyzing the influence of buffer solutions on the suspension characteristics of HA/CNC systems, integrating both theoretical and experimental approaches. The results revealed an alignment between predictions of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and results from experiments characterizing a buffer-specific trend in colloidal stability. Suspensions with a higher energy barrier showed higher colloidal stability, with a lower tendency for phase separation and agglomerate formations. The microstructural analysis of CNC tactoids in the suspension revealed the existence of the hedgehog defect when dispersed in different buffer solutions. The defect is predicted to be caused by the pH-dependent protonation and deprotonation of HA. Furthermore, steady shear viscometry showed a microstructural-dependent shear viscosity trend, which, in turn, depends on the buffer solution.The study provides novel insights into the microstructural and bulk properties of HA and CNC suspensions in various buffer solutions. The results highlight the importance of solvent choice in tailoring the properties of the suspension for specific biomedical applications. These findings may be helpful in formulating HA and CNC suspensions for different biomedical applications, including drug delivery systems and viscosupplement injections.

Surface reconstruction of sulfonated polysulfone ultrafiltration membrane with cellulose nanocrystals for enhancing anti-fouling performance

The fouling issues of ultrafiltration membranes is one of limitations for their long-term effectiveness. Here, we developed an effective and environmentally friendly approach for constructing anti-fouling ultrafiltration membrane, achieved by the surface modification of sulfonated polysulfone (SPSF) ultrafiltration membrane with cellulose nanocrystals (CNCs). The composite ultrafiltration membrane was obtained by only filtering CNC suspension through SPSF ultrafiltration membrane, and showed good hydrophilicity that its water contact angle is only 53° which is much lower than that of SPSF ultrafiltration membrane (74°). Its retention rate for the pollutants with particle size greater than 10 nm is close to 100 %. Its water flux is almost twice that of SPSF ultrafiltration membrane under the sewage condition. After three cycles of filtering severe sewage, its flux recovery rate is still 95 %, far higher than that of SPSF ultrafiltration membrane (60 %). Therefore, the surface modification strategy of SPSF ultrafiltration membrane with CNCs is effective and green for improving the anti-fouling properties of ultrafiltration membranes, which is a valuable reference for enhancing the anti-fouling performance of ultrafiltration membranes from various materials. The as-prepared CNCs/SPSF ultrafiltration membrane has a promising application in the purification of wastewater containing hydrophobic particles.

Flow birefringence of cellulose nanocrystal suspensions in three-dimensional flow fields: revisiting the stress-optic law

This study systematically investigates the flow birefringence of cellulose nanocrystal (CNC) suspensions. The aim is to clarify the importance of the stress component along the camera’s optical axis in the stress-optic law (SOL), which describes the relationship between birefringence, the retardation of transmitted polarized light, and the stress field. More than 100 datasets pertaining to the retardation of CNC suspensions (concentrations of 0.1, 0.3, 0.5, and 1.0 wt%) in a laminar flow field within a rectangular channel (aspect ratios of 0.1, 1, and 3) are systematically obtained. The measured retardation data are compared with the predictions given by the conventional SOL excluding the stress component along the camera’s optical axis and by the SOL including these components as second-order terms (2nd-order SOL). The results show that the 2nd-order SOL gives a significantly better agreement with the measurements. Based on the 2nd-order SOL, the retardation at the center of the channel, where the effect of the stress component along the camera’s optical axis is most pronounced, is predicted to be proportional to the square of the flow rate, which agrees with the experimental data. The results confirm the importance of considering the stress component along the camera’s optical axis in the flow birefringence of CNC suspensions at high flow rates, even for quasi-two-dimensional channel flow.

Visualization Of Nanoparticle Orientation Structures Inside Complex Fluids Using Polarized Light Imaging Technique

The present paper reports on the effect of 3D-oriented particles on birefringence using the concept of 'rheooptics', a technique for identifying changes in the internal structure or flow dynamics of complex fluids from changes in optical anisotropy (birefringence). We used the photoelastic method, as a kind of polarized light imaging technique, to visualize the internal orientation structure induced by applying shear stress to cellulose nanocrystal (CNC) suspensions under shear flow. Two different rheometers (concentric cylinder and parallel plate-type) that can easily combine a birefringence measurement system were introduced to Transverse rotation Longitudinal rotation perform the shear flow induction, and the birefringence was measured and compared from vertical and horizontal directions for shear. The birefringence measurements from different directions provide an opportunity to investigate the effect of 3D-oriented CNCs on birefringence, which is a novelty of the present study. The measured birefringence was fitted with the empirical equation proposed in the previous study and followed the power law of applied shear rate with the same exponent, independent of the shear direction at the time of measurement This result suggests that there is a common physical background that gives birefringence a power law. This exponent was different from the values given in previous studies and is explained by differences in the particle interaction behaviour based on the concentration of suspensions and CNC length. Note that the proportionality coefficients differ by a factor of 10, clearly indicating differences due to the direction of birefringence measurement. These results indicate that birefringence due to transverse rotation of the CNC is more sensitive to shear stress than to longitudinal rotation.

Cross-Linked Cellulose Nanocrystal Membranes with Cholesteric Assembly.

Forming membranes by tangential flow deposition of cellulose nanocrystal (CNC) suspensions is an attractive new approach to bottom-up membrane fabrication, providing control of separation performance using shear rate and ionic strength. Previously, the stabilization of these membranes was achieved by irreversibly coagulating the deposited layer upon the permeation of a high-ionic-strength salt solution. Here, we demonstrate for the first time the chemical cross-linking of carboxyl-containing TEMPO-oxidized CNCs by Ag(I)-catalyzed oxidative decarboxylation and the stabilization of CNC membranes using this post-treatment. Cross-linking of TEMPO-CNCs was first demonstrated in suspension via turbidity, dynamic light scattering, and storage (G') and loss (G″) moduli measurements. Membranes were formed by filtering a 0.15 wt % TEMPO-CNC suspension onto a porous support, followed by permeation of the cross-linking solution containing AgNO3 and KPS through the deposited layer. Rejection for Blue Dextran with a 5 kDa molecular weight was 95.3 ± 1.9%, 90.6 ± 3.7%, and 95.9 ± 1.0% for membranes made from suspensions of TEMPO-CNC, desulfated TEMPO-CNC. and TEMPO-CNC with 100 mM NaCl, respectively. Suspensions with added NaCl led to membranes with improved stability and cholesteric self-assembly in the membrane layer. Membranes subjected to cross-linking post-treatment remained intact upon drying, while those stabilized physically using 200 mM AlCl3 solution were cracked, demonstrating the advantage of the cross-linking approach for scale-up, which requires drying of the membranes for module preparation and storage.

Flexible, Photonic Films of Surfactant‐Functionalized Cellulose Nanocrystals for Pressure and Humidity Sensing

Most paints contain pigments that absorb light and fade over time. A robust alternative can be found in nature, where structural coloration arises from the interference of light with submicron features. Plant‐derived, cellulose nanocrystals (CNCs) mimic these features by self‐assembling into a cholesteric liquid crystal that exhibits structural coloration when dried. While much research has been done on CNCs in aqueous solutions, less is known about transferring CNCs to apolar solvents that are widely employed in paints. This study uses a common surfactant in agricultural and industrial products to suspend CNCs in toluene . Surprisingly, a stable liquid crystal phase is formed within hours, even with concentrations of up to 50 wt%. Evaporating the apolar CNC suspensions results in photonic films with peak wavelengths ranging from 660 to 920 nm. The resulting flexible films have variable mechanical properties with surfactant content, allowing for an optical response with applied force. The films also act as humidity sensors, with increasing relative humidity swelling the films, yielding a redshift in the reflected wavelength. With the addition of a single surfactant, CNCs can be made compatible with existing production methods of industrial coatings, while improving the strength and responsiveness of structurally colored films to external stimuli.

Nonlinear oscillatory rheology of aqueous suspensions of cellulose nanocrystals and nanofibrils

In this work, the nonlinear rheological behavior of aqueous suspensions composed of two typical nanocellulose [rod-like cellulose nanocrystals (CNCs) and filamentous cellulose nanofibrils (CNFs)] was examined and compared by using various large-amplitude oscillatory shear (LAOS) analysis methods, such as Fourier-transform rheology, stress decomposition, Chebyshev polynomials, and the sequence of physical processes. From our analysis, the nonlinear rheological parameters of higher harmonics, dissipation ratio, strain hardening ratio, shear thickening ratio, transient modulus, and cage modulus were obtained and quantitatively analyzed. CNCs tend to assemble to form anisotropic structures in an aqueous medium while the CNFs are entangled to form gels. The CNF suspensions demonstrated a significant viscous modulus overshoot and had stronger yield stresses, but the yield of CNC suspensions was more ductile. In the case of low concentrations, the CNF suspensions demonstrated stronger intracycle shear thickening behavior in medium-amplitude oscillatory shear region and lower dissipation ratios at small strain amplitudes. Although both nanocellulose suspensions revealed the existence of four intracycle rheological transition processes (viscoplastic deformation, structural recovery, early-stage yielding, and late-stage yielding), the CNF suspensions exhibited a stronger structural recovery ability. Larger strain amplitudes did not invariably result in a broader range of intracycle rheological transitions, which are also affected by the excitation frequency. The application of the various LAOS analysis methods provided valuable intracycle nonlinear rheological insights into nanocellulose suspensions, which are of great importance for enhancing their industrial perspectives.

Chiral nematic nanocomposites with pitch gradient elaborated by filtration and ultraviolet curing of cellulose nanocrystal suspensions

An innovative method combining frontal filtration with ultraviolet (UV) curing has been implemented to design cellulosic nanocomposite films with controlled anisotropic textures from nanometric to micrometric length scales. Namely, an aqueous suspension containing poly (ethylene glycol) diacrylate polymer (PEGDA) as a photocurable polymer and cellulose nanocrystals (CNCs) at a 70/30 mass ratio was processed by frontal filtration, followed by in-situ UV-curing in a dedicated cell. This procedure allowed designing nanocomposite films with highly oriented and densely-packed CNCs, homogeneously distributed in a PEGDA matrix over a thickness of ca. 500 μm. The nanocomposite films were investigated with small-angle X-ray scattering (SAXS), by raster-scanning along their height with a 25 μm vertically-collimated X-ray beam. The CNCs exhibited a high degree of orientation, with their director aligned parallel to the membrane surface, combined with an increase in the degree of alignment as concentration increased towards the membrane surface. Scanning electron microscopy images of fractured films showed the presence of regularly spaced bands lying perpendicular to the applied transmembrane pressure, highlighting the presence of a chiral nematic (cholesteric) organization of the CNCs with a pitch gradient that increased from the membrane surface to the bulk.

Flexible multiple-stimulus-responsive photonic films based on layer-by-layer assembly of cellulose nanocrystals and deep eutectic solvents

Photonic crystal materials responding to environmental stimuli are important in sensors, intelligent detection, and anti-counterfeiting. However, traditional photonic materials usually lack tunable color and sufficient color suppleness, hindering their practical applications. Here, we report a facile strategy to achieve mechanical and color-tunable photonic films by doping deep eutectic solvents (DES) into cellulose nanocrystals (CNC) using layer-by-layer assembly. The amount of DES and several assembly layers were vital in determining the structure color and mechanical and response properties in the CNC photonic films. The experimental results revealed that DES could endow CNC suspension systems with high zeta potential, high viscoelasticity, and low transmittance. The tiny DES compensated for the insufficient flexibility of the CNC film, resulting in a wide color range, high solvent discrimination ability, and multi-color at several view angles. Moreover, photonic crystal film also played an important role in intelligent display and could be applied to traffic reflective signs to remind pedestrians and drivers of road safety and as smart labels for indoor humidity detection. These characteristics of the CNC photonic films could provide a promising strategy for developing advanced intelligent sensors, detection, and anti-counterfeiting materials.

Recent Progress on Photonic Cellulose Nanocrystal Films for Sensing Applications

Abstract: Cellulose nanocrystals (CNCs) have triggered considerable research interest in the last few years owing to their unique optical, biodegradation, and mechanical behavior. Herein, recent progress on the sensing application of photonic CNC films is summarized and discussed based on the analyses of the latest studies. We briefly introduce the three approaches for pre-paring CNCs: mechanical treatment, acid hydrolysis, and enzymatic hydrolysis, recapitulating their differences in preparation and properties. Then, when the aqueous suspension of cellu-lose nanocrystals (CNCs) reaches a specific concentration, it will self-assemble to form a left-handed nematic liquid crystal structure, and this structure can be maintained in films after water evaporation, which has strong photonic crystal properties. The periodic layered structure in the film interferes and diffracts with light, showing a rainbow color. Photonic CNC com-posites that combine CNCs and functional materials have good properties and broad prospects. Finally, we highlight the advanced applications of photonic CNC films, including mechanical sensing, thermal sensing, and humidity sensing. The prospects and ongoing challenges of pho-tonic CNC films were summarized.

Effects of different salt ions on the structure and rheological behavior of sulfated cellulose nanocrystal hydrogel

Cellulose nanocrystal (CNC) hydrogels are increasingly used in various applications. Here, CNC hydrogels were formed by adding four salt ions (NaCl, KCl, MgCl2, and CaCl2) to sulfated CNC suspensions. NaCl and KCl are monovalent salt ions and MgCl2 and CaCl2 are divalent salt ions; each pair has similar cation charges but different cation radii. This study compared the effects of four salt ions on the structure and rheological behavior of CNC hydrogels. At the same ion concentration, compared with NaCl and KCl, the addition of MgCl2 and CaCl2 significantly reduced the distance between the CNC particles, forming pronounced aggregates and denser network structures. Furthermore, the G′ and G″ of the CNC hydrogels with salt ions followed the order NaCl < KCl < MgCl2 < CaCl2 in the small-amplitude oscillatory shear (SAOS) test, and more viscoelastic hydrogels exhibited relatively lower deformability in the creep-recovery test. Under large-amplitude oscillatory shear (LAOS) conditions, the CNC hydrogels with salt ions exhibited LAOS type III behavior, and the change in yield stress followed the same order as the SAOS results. Among them, CNC hydrogel with CaCl2 exhibited stronger nonlinear response and enhanced strain-stiffening behavior (higher I3/I1 and e3/e1) to resist deformation before 20% strain, as well as an enhanced softening effect (higher |v3/v1|) as the structure was destroyed and rearranged at strains ranging from 20% to 100%. Such CNC hydrogels with different salt ions, which can regulate structural and rheological properties, provide basis for designing hydrogels and meet potential requirements in food and biomedicine fields.

Orthotropic organization of a cellulose nanocrystal suspension realized via the combined action of frontal ultrafiltration and ultrasound as revealed by in situ SAXS

HypothesisRodlike cellulose nanocrystals (CNCs) exhibit significant potential as building blocks for creating uniform, sustainable materials. However, a critical hurdle lies in the need to enhance existing or devise novel processing that provides improved control over the alignment and arrangement of CNCs across a wide spatial range. Specifically, the challenge is to achieve orthotropic organization in a single-step processing, which entails creating non-uniform CNC orientations to generate spatial variations in anisotropy. ExperimentsA novel processing method combining frontal ultrafiltration (FU) and ultrasound (US) has been developed. A dedicated channel-cell was designed to simultaneously generate (1) a vertical acoustic force thanks to a vibrating blade at the top and (2) a transmembrane pressure force at the bottom. Time-resolved in situ small-angle X-ray scattering permitted to probe the dynamical structural organization/orientation of CNCs during the processing. FindingsFor the first time, a typical three-layer orthotropic structure that resembles the articular cartilage organization was achieved in one step during the FU/US process: a first layer composed of CNCs having their director aligned parallel to the horizontal membrane surface, a second intermediate isotropic layer, and a third layer of CNCs with their director vertically oriented along the direction of US wave propagation direction.

Multiscale study of the chiral self-assembly of cellulose nanocrystals during the frontal ultrafiltration process.

The structural organization of cellulose nanocrystal (CNC) suspensions at the membrane surface during frontal ultrafiltration has been characterized, for the first time, at the nano- and microscale by in situ small-angle X-ray and light scattering (SAXS and SALS, respectively). During filtration, the particles assembled at the membrane surface and formed the so-called concentration polarization layer (CPL), which contains CNCs arranged in a chiral nematic (cholesteric) helicoidal structure, with the long axis of the CNCs oriented parallel to the membrane surface, and the helical axis of the cholesteric structure oriented perpendicular to the membrane surface. The self-organization of CNCs in the form of oriented cholesteric structures was further characterized by a pitch gradient in the CPL. The structure of the CPL was also investigated upon release of the transmembrane pressure. SAXS data revealed a relaxation process associated with a diffusion of the CNCs from the membrane surface towards the bulk, while SALS measurements revealed a re-organization of the cholesteric phase that was preserved all along the deposit. The preservation of the observed structure after 14 days of continuous filtration followed by air-drying was confirmed using scanning electron microscopy and wide-angle X-ray diffraction, demonstrating the feasibility of the process scale-up.

Angle-resolved optical spectroscopy of photonic cellulose nanocrystal films reveals the influence of additives on the mechanism of kinetic arrest.

Cellulose nanocrystals (CNCs) are rod-like nanoparticles whose chiral self-assembly into photonic films has been promoted as a sustainable source of colouration. Upon drying, an aqueous CNC suspension passes through two regimes: first, a liquid phase, where the CNCs self-organise into a cholesteric liquid crystal, followed by a kinetically-arrested phase, where the helicoidal structure compresses upon loss of solvent, resulting in a solid film with vibrant structural colour. The transition between these two regimes plays an important role in the visual appearance of photonic CNC films, but details on when and how kinetic arrest occurs have remained elusive. In this work, we combine angle-resolved optical spectroscopy of photonic films (approx. 100 vol% CNC) with a model for compressed helicoidal structures to retrieve the suspension conditions during kinetic arrest (approx. 10 vol% CNC). This analysis indicates a shift in the mechanism of kinetic arrest from a glass transition at lower ionic strength to gelation at higher ionic strength, explaining the trends in domain size and film colour. In contrast, neutral additives (glucose, poly(ethylene glycol)) appear to primarily reduce the compression upon drying without affecting cholesteric behaviour, as supported by a general analytical model. These findings deepen our understanding of CNC co-assembly with various commonly-used additives, enabling better control over the production of multifunctional structurally coloured materials.

Two-dimensional strain rate imaging study using a polarization camera and birefringent aqueous cellulose nanocrystal suspensions

The birefringence response of aqueous cellulose nanocrystal (CNC) suspensions in a two-dimensional laminar flow is measured and studied. The suspensions have CNC concentrations of 1.0 wt% (weight percentage) and 1.2 wt%. Cellulose nanocrystals are optically anisotropic rod-like particles that align when subjected to local velocity gradients, whereas at rest, they remain randomly orientated by Brownian motion. The alignment causes birefringence, a phenomenon also known as flow-induced birefringence. We study the flow through an additively manufactured flow channel and measure the amount of birefringence as well as the position of the refractive index axes by using polarizers and a polarization camera. With the help of reference data published in a previous study (Lane, Rode, et al., 2022a), strain rates are derived from the birefringence measurements and compared with numerical simulations. Two flow situations are studied, a plane Poiseuille flow and the flow around a cosine-shaped constriction. The experimentally derived shear rates for the plane Poiseuille flow are consistent with theoretical and computational results. The derived strain rates for the flow around the cosine-shaped constriction show an unexpected asymmetric profile, with the strain rates in the contraction zone being larger than in the expansion zone. The averaged orientation of the CNCs in the flow is linked to the position of the refractive index axes. In the contraction zone, the CNCs tend to align parallel to the flow, whereas in the expansion zone, the CNCs tend to align perpendicular to the flow. The results of this study are discussed in the context of previous, similar studies. The asymmetric strain rate profile around the cosine-shaped constriction is thought to originate from history effects, and the alignment of the CNCs is influenced by extensional rates.

Investigating the phase behaviour of binary suspensions of cellulose nanocrystals and montmorillonite with nonlinear rheology, SAXS and polarized optical microscopy

Using microscopy imaging techniques, X-ray scattering, and nonlinear rheological measurements, we have examined microstructural changes, and phase behavior of cellulose nanocrystals (CNC)/montmorillonite (MMT) composite colloidal systems. Fourier-transform (FT) rheology-stress decomposition methods, Lissajous-Bowditch plots, and other techniques are used to both qualitatively and quantitatively determine the various phases that the suspensions exhibit. In the MAOS (medium amplitude oscillatory shear) region, multiple scaling regions, as well as quadratic scaling regions are obtained. The dependence of the normalized third relative intensity (I3/1) values on angular frequency (ω) also provided new insights into how nonlinear parameters depend on the various CNC/MMT phases. These findings allow us to differentiate various phases exhibited by the composite system, including the isotropic, biphasic, and chiral nematic liquid crystalline (LC) phases. The CNC/MMT nanocomposite system exhibits a variety of liquid crystalline phases, which may contribute to improved mechanical properties for the system, including increased mixture strength, stiffness, and toughness because of the particle alignment in the LC phase. Additionally, the field of optics and photonics may find use for this nanocomposite system in the fabrication of sensors, polarizers, and optical films; energy storage applications where the aligned structures facilitate ion transport; and the formulation of paints and coatings where the strain stiffening and shear thinning behavior of the CNC/MMT composite system are critical.