Linear Viscoelastic Regime Research Articles

Organic reinforcement of an ethylene propylene diene monomer with the in situ synthesis of a polyimide dispersed phase by reactive extrusion

AbstractEthylene‐propylene‐diene monomer rubber, grafted with maleic anhydride functions (EPDM‐g‐MA) was organically reinforced by reactive extrusion from the in situ synthesis of a polyimide (PI) phase. The blends were reactively processed at 200°C in a twin‐screw extruder, with the PI content varying from 5 to 40 wt%. Transmission Electron Microscopy (TEM) revealed a very fine nodular dispersion of the PI phase with diameters ranging from 130 to 240 nm depending on the PI concentration. The reinforcement of the elastomer was evidenced with a sharp increase of the Young's modulus and the tensile strength, and the stiffness of the material was further increased with the PI content. The linear viscoelastic regime, as measured by the variation in storage modulus as a function of strain, was unaffected by this organic reinforcement, thus opening up an original way of controlling the Payne effect. Additionally, the cross‐linking of the blend with 20 wt% of PI with dicumyl peroxide (DCP) showed that the PI phase did not impact the creation of the cross‐linked network. The decrease of the swelling ratio and the improvement of the elastic recovery suggested that EPDM‐g‐PI copolymers can create a second network in the material, resulting in a higher apparent cross‐linking density. The mechanical properties of the cured blend showed a doubling of the Young's modulus and maximal stress values compared to those obtained for the pure matrix as well as a constant strain at break.Highlights Ethylene‐propylene‐diene monomer rubber, grafted with maleic anhydride functions (EPDM‐g‐MA) was organically reinforced by reactive extrusion. The reinforcement was obtained from the in situ synthesis of a polyimide (PI) phase. The Young's modulus of cross‐linked EPDM containing 20 wt% PI was doubled. The linear viscoelastic regime was unaffected by this organic reinforcement. This original way of reinforcement opens the control of the Payne effect.

Hemp Protein Isolate-Based Natural Thermal-Reversible Hydrogel as a Novel Wound Dressing Material.

Hydrogels, due to their excellent microstructure and mechanical strength, have become a novel biomaterial in wound dressing. However, plant proteins have never been considered because of their poor original gelling performances and insufficient rheological properties. Here, we reported the fabrication of a plant protein-based thermal-reversible gel using a reverse micelle-extracted hemp protein isolate (HPI). A systematic study was conducted to fully reveal their microstructure, rheological properties, and anti-inflammatory effect to lay a foundation for this newly developed plant protein hydrogel as a potential natural wound dressing. By modulating protein concentration (4% HPI) and temperature (85 °C), a thermal-reversible HPI gel appeared as a filament structure with the major molecular driving force of hydrophobic interactions and hydrogen bonds. By characterizing the rheological properties, lower gel strength and wider linear viscoelastic regime were determined in the thermal-reversible HPI gel compared with a thermal-irreversible HPI gel. Besides, large amplitude oscillatory shear data identified the thermal-reversible gel as a soft gel which demonstrated intracycle strain stiffening and shear thinning behavior. Moreover, the thermal-reversible HPI gel is nontoxic and has benefits in neutrophil growth with injectability and perfect wound coverage. This study opens a novel means to form a natural thermal-reversible hydrogel that can be a new material source for wound dressing.

Interfacial property determination from dynamic pendant-drop characterizations.

The properties of the interface between materials have practical implications in various fields, encompassing capillary action, foam and emulsion stability, adhesion properties of materials and mass and heat transfer processes. Studying the dynamics of interfaces is also fundamental for understanding intermolecular interactions, change of molecular conformations and molecular aggregations. Pendant-drop tensiometry and its extension, the oscillating drop method, are simple, versatile methods used to measure surface tension, interfacial tension and interfacial rheological properties. These methods can, however, generate unreliable results because of inadequate material preparation, an incorrect calibration method, inappropriate selection of data for analysis, neglect of optical influences or operating the system outside the linear viscoelastic regime. In addition, many studies fail to report accurate uncertainties. This protocol addresses all these critical points and provides detailed descriptions of some operation tips relating to purifying methods for different kinds of material, the time frame for analyzing measurement data, the correction method for optical effects, implementation of the oscillating method with a common programmable pump and remedies for some common problems encountered during the measurement. Examples of interfacial tension measurements for two- and three-phase systems, as well as interfacial dilational modulus measurements for N2 and surfactant solutions, are provided to illustrate procedural details and results. A single measurement takes minutes to hours to complete, while the entire protocol, including the leak test, cleaning, repeated measurements and data analysis, may take several days.

Thermomechanical characterisation and plane stress linear viscoelastic modelling of ethylene-tetra-fluoroethylene foils

Ethylene-tetra-fluoroethylene (ETFE) is a polymer employed in tension membrane structures with mechanical properties that strongly depend on time and temperature effects. A comprehensive understanding of the mutual influence of these variables and a unified viscoelastic constitutive model design can enable wider exploitation of ETFE in sustainable lightweight construction. This study presents a thermomechanical characterisation of ETFE foils through quasi-static tensile experiments spanning two orders of magnitude of strain rates, creep, relaxation, shear and dynamic cyclic tests in a wide range of temperatures suitable for building applications, from −20∘ C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$-20^{\\circ }\ ext{ C}$\\end{document} to 60∘ C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$60^{\\circ }\ ext{ C}$\\end{document}. The experimental results in different material orientations are used to identify the limits of the linear viscoelastic domain, define the direction-dependent creep compliance master curves and calibrate the parameters of a plane stress orthotropic linear viscoelastic model, employing the Boltzmann superposition and the time-temperature superposition principles. The model has been numerically implemented using a recursive integration algorithm and its code is provided open source. A validation on independently acquired data shows the accuracy of the constitutive model in predicting ETFE behaviour within the linear viscoelastic regime usually adopted during structural design, with excellent extrapolation capabilities outside the range of the calibration data.

The Rheological and Structural Properties of Aqueous Graphene Oxide Dispersions: Concentration and pH Dependence.

A modified Hummer's method was used to synthesize aqueous dispersions of graphene oxide (GO). The morphology, chemical structure, and exfoliation state of GO were analyzed by combining scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The structural and rheological properties of the GO dispersions were studied as a function of GO concentration and pH. Increasing the concentration of GO revealed shorter interparticle distances between GO sheets. This induced a transition from fluid to nematic gel-like structures, as observed by polarized optical microscopy (POM). The Herschel-Bulkley model was used to fit the shear thinning curves and to demonstrate the viscoelastic behavior. Both the yield stress and viscoelastic moduli in the linear viscoelastic regime increased. As pH increases, the color of the aqueous GO dispersions becomes darker, the negative values of the zeta potential increase, the distances between the GO sheets decrease as observed by a slight shift of the correlation peak toward higher values of the scattering vector modulus in small-angle X-ray scattering (SAXS), and the rheological properties (yield stress and viscoelastic moduli in the linear viscoelastic region) decrease. These results can be explained by a change in the morphology of GO related to their hydrophilicity. This work presents relationships between rheological and structural properties of GO sheet dispersions, with particular emphasis on the effects of concentration and pH.

Impact of Deformability and Rigidity of Starch Granules on Linear and Non-Linear Rheological Behavior of Waxy Rice Starch Gels and Applicability for Food End Uses.

The objective of this study was to investigate granule size and distribution and deformability of granules and their effect on the rheological properties of waxy starch gels. Native (granular) waxy rice gels (10%) were prepared, and their response in oscillatory shear was investigated in the linear and non-linear viscoelastic regime. The results show the gels were mainly composed of aggregated and deformed swollen granules. Significance of granule size and its distribution, deformability of granules, and the molecular characteristics of amylopectin (AP) on storage modulus of those gels was demonstrated. A low degree of deformability of granules, typical for small granules with a broad size distribution and small molecular size of AP with short external chains, resulted in rigid and brittle gels. Highly deformed granules and high AP leachates, however, yielded soft gels. It was found that the transition of elastic to plastic behavior in the non-linear regime (LAOS) was gradual when AP had long external chains, but an abrupt transition was observed with the gel with short exterior chains of AP. Differences in rheological properties of cohesive waxy starch gels appear to be mainly impacted by the varying degrees of granule deformability and rigidity, which is further attributed to a combination of factors, including granule size, particle size distribution, molecular size, the external chain length of amylopectin (AP), and lipid content. The significance of this study is that it will assist the food industry in selecting suitable waxy rice starches to gain desired textural properties of end products.

Interfacial rheological properties of pepsin-hydrolyzed lentil protein isolate at oil-water interfaces

Lentil protein isolate (LPI) was investigated for its potential as a plant protein-based emulsifier. LPI consists mainly of globulins with high molecular weights which are relatively slow to adsorb and stabilize oil-water interfaces. Smaller proteins, such as whey protein, can stabilize the interface much faster, quickly forming a viscoelastic film that slows down the rate of droplet recoalescence, leading to smaller droplets. To increase the rate of adsorption, LPI was enzymatically hydrolyzed by pepsin at 1.5% and 4.5% degree of hydrolysis (DH), to obtain small peptides. The behavior of these peptides was studied at the oil-water interface in comparison to whey protein isolate (WPI) and native lentil protein isolate (LPI). Interfacial properties were investigated using dilatational and interfacial shear rheology in the linear viscoelastic regime (LVE) and nonlinear viscoelastic regime (NLVE) and these were related to protein characteristics and emulsion formation. The 1.5% and 4.5%DH LPI showed high surface hydrophobicity, and consisted mainly of low molecular weight peptides, which contributed to faster adsorption kinetics and consequently covered the interface faster than LPI. In dilatation, the native and hydrolyzed LPI-stabilized interfaces had comparable stiffness and were clearly weaker than WPI-stabilized interfaces, which contrasts with the results in shear deformations, where the former both had higher stiffness than WPI. Both hydrolyzed LPI and WPI formed more brittle and less stretchable interfaces compared to native LPI in both dilatational and shear rheology. In emulsification tests, native LPI produces the largest droplets, and the 4.5% DH LPI and WPI have the smallest droplet size. But, bridging flocculation was observed when emulsions were prepared with both hydrolyzed LPI, which may be attributed to inter-droplet hydrophobic interactions between small polypeptides. This can be linked to an increase in the surface hydrophobicity of hydrolyzed LPI. Thus, the use of native LPI as a stabilizer in emulsion preparation is preferable over the hydrolyzed samples, despite its larger droplet size.

Influence of cellulose nanofibers on the behavior of Pickering emulsions. Part II: Thixotropy and dynamic-mechanical tests

Nonlinear rheology of Pickering emulsions is used to further investigate the nonlinear and unrecoverable transformation of inner structures, which is beyond the linear viscoelastic regime of tiny structural disturbances. Exploring various rheological methods plays a vital role in emulsion applications, such as simulating the macroscopic structural transformation between static and liquidlike flow states, strain overshoot, and regeneration for broken structures. According to our previous studies, cellulose nanofibers (CNFs) Pickering emulsions are a typical system for investigating polymer-based emulsions with the auxiliary surfactant [didodecyldimethylammonium bromide (DDAB)] for enhancing CNF absorption. To further study different rheological properties by varying CNF or DDAB contents, multiple interval thixotropic test, large amplitude oscillatory shear, and concentration-time-dependent superposition are employed to study the linear viscoelasticity and structural transformation of nonlinear range. This research was conducted based on the previous published works [Cui et al., Materials 15, 8285 (2022)] as a further characterization for the same sample series.

Laboratory evaluation of a nanostructured lubricating grease for tram runflat tires

PurposeThis paper aims to develop a stable gel-type lubricant emulating commercial conditions. This encompassed rheological and tribological assessments, alongside field trials on the Medellín tram system.Design/methodology/approachThe gel-type lubricant with graphite and aluminum powder is synthesized. Rheological tests, viscosity measurements and linear viscoelastic regime assessments are conducted. Subsequently, tribological analyses encompassing four-ball and twin disc methods are executed. Finally, real-world testing is performed on the Medellín tram system.FindingsAn achieved lubricant met the stipulated criteria, yielding innovative insights into the interaction of graphite and aluminum powder additives under varying tests.Originality/valueNovel findings are unveiled regarding the interaction of graphite and aluminum powder additives in tribological, rheological and real-world trials. In addition, the wear behavior of polymers is observed, along with the potential utilization of such additives in tramway systems.

Viscoelasticity of a carbon nanotube-laden air-water interface.

The viscoelasticity of a carbon nanotube (CNT)-laden air-water interface was characterized using two different experimental methods. The first experimental method used a Langmuir-Pockels (LP) trough coupled with a pair of oscillating barriers. The second method is termed the Bicone-Trough (BT) method, where a LP trough was custom-built and fit onto a rheometer equipped with a bicone fixture to standardize the preparation and conditioning of a particle-laden interface especially at high particle coverages. The performance of both methods was evaluated by performing Fast Fourier Transform (FFT) analysis to calculate the signal-to-noise ratios (SNR). Overall, the rheometer-based BT method offered better strain control and considerably higher SNRs compared to the Oscillatory Barriers (OB) method that oscillated barriers with relatively limited positional and speed control. For a CNT surface coverage of 165mg/m2 and a frequency of 100mHz, the interfacial shear modulus obtained from the OB method increased from 39 to 57mN/m as the normal strain amplitude increased from 1 to 3%. No linear viscoelastic regime was experimentally observed for a normal strain as small as 0.5%. In the BT method, a linear regime was observed below a shear strain of 0.1%. The interfacial shear modulus decreased significantly from 96 to 2mN/m as the shear strain amplitude increased from 0.025 to 10%.

Enhancing nanoscale viscoelasticity characterization in bimodal atomic force microscopy.

Polymeric, soft, and biological materials exhibit viscoelasticity, which is a time dependent mechanical response to deformation. Material viscoelasticity emerges from the movement of a material's constituent molecules at the nano- and microscale in response to applied deformation. Therefore, viscoelastic properties depend on the speed at which a material is deformed. Recent technological advances, especially in atomic force microscopy (AFM), have provided tools to measure and map material viscoelasticity with nanoscale resolution. However, to obtain additional information about the viscoelastic behavior of a material from such measurements, theoretical grounding during data analysis is required. For example, commercially available bimodal AFM imaging maps two different viscoelastic properties of a sample, the storage modulus, E', and loss tangent, tan δ, with each property being measured by a different resonance frequency of the AFM cantilever. While such techniques provide high resolution maps of E' and tan δ, the different measurement frequencies make it difficult to calculate key viscoelastic properties of the sample such as: the model of viscoelasticity that describes the sample, the loss modulus, E'', at either frequency, elasticity E, viscosity η, and characteristic response times τ. To overcome this difficulty, we present a new data analysis procedure derived from linear viscoelasticity theory. This procedure is applied and validated by performing amplitude modulation-frequency modulation (AM-FM) AFM, a commercially available bimodal imaging technique, on a styrene-butadiene rubber (SBR) with known mechanical behavior. The new analysis procedure correctly identified the type of viscoelasticity exhibited by the SBR and accurately calculated SBR E, η, and τ, providing a useful means of enhancing the amount of information gained about a sample's nanoscale viscoelastic properties from bimodal AFM measurements. Additionally, being derived from fundamental models of linear viscoelasticity, the procedure can be employed for any technique where different viscoelastic properties are measured at different and discrete frequencies with applied deformations in the linear viscoelastic regime of a sample.

The effects of stem bromelain on the gelation behavior of kappa carrageenan under linear and nonlinear rheological regimes

Carrageenans have shown a versatile and wide range of applications in the food and biomedical fields. To tune the rheological properties and improve the biological functions of carrageenan gels, the effect of stem bromelain (SBr) on the intermolecular interaction and rheological property of κ-carrageenan (κC) was investigated. The viscoelastic properties and gel network structure of pure SBr, κC, and SBr/κC mixtures were studied using dynamic rheology in the linear and nonlinear viscoelastic regimes. Different SBr/κC mixtures were prepared with varying final pH levels (pH 6.06, 6.95, and 8.08). The time series and frequency dependence of SBr/κC mixtures in the linear viscoelastic regime showed that the elastic modulus is (3–10 times) greater than the viscous modulus, indicating network structure formation. The temperature dependence of the viscoelastic moduli SBr/κC mixtures exhibited a significantly improved physical property than the pure SBr and κC, demonstrating synergistic relation between SBr and κC via enhanced electrostatic interaction. By increasing the pH level of the mixtures, a decrease in the shear moduli was observed attributed to the increasing repulsive interaction between SBr and κC. The observed nonlinear rheological responses suggest a transiently crosslinked network. Accordingly, with the gentle imposition of increasing stress levels, the nonlinear responses suggest that SBr/κC is a stress-mediated, highly entangled complex network with a pH-controlled dynamic viscoelastic property. Therefore, our results provide structural insights into the microscopic origins of the rheological behavior of SBr/κC mixtures as a basis for precise material design.

Rheology of edible soft glassy materials

In this paper we investigate the rheology of three different classes of edible yield stress fluids: a) cookie doughs, b) vegetable/fruit purees, and c) protein-rich doughs as used in meat analogs and 3D food printing. Strains sweeps of different formulations within one class can be mapped to a (partial) master curve, with at least the same strain softening index, and a similar crossover point. For classes showing only a partial master curve, the formulation differs in the response of the loss modulus in the linear viscoelastic (LVE) regime, and the transition regime between LVE and strain softening regimes, where several formulations also show a weak strain overshoot. Amongst different classes, different behaviour in strain softening has been observed. Meat analogs and fruit purees show a ratio of 2 between strain softening indices of elastic and loss modulus, while for cookie doughs and protein-rich inks, the ratio is near unity. A constitutive model using a configurational tensor with shear rate-dependent viscosity and strain-dependent elastic modulus can reproduce all features observed for the different classes and for the various formulations within a class. We conclude that our constitutive model is a good basis to design edible yield stress fluids for fiber-enrichment, starch and/or sugar replacement.

Effect of fiber properties and orientation on the shear rheology and Poynting effect in meat and meat analogues

The development of plant-based meat analogues is an important aspect of the transition towards using more plant proteins. Production of such products with texture (and rheology) adequate for consumer acceptance like meats is a great challenge. However, there is a current lack in quantitative methods to compare whole cut meats and plant-based analogues that also consider its fibrous structures. We tackled this problem by combining non-linear shear rheology and shear-induced normal stress measurements on whole cut meats (beef and chicken) and plant-based fibrous model systems for meat analogues (soy and pea protein isolates combined with wheat gluten). We found different response in the linear viscoelastic regime for different samples, and the non-linear viscoelastic regime provided a deeper understanding into the role of structural components. Meat samples showed rearrangements at small strains and lower energy dissipation, higher intracycle strain stiffening, and a larger normal stress response at large strains than plant-based fibrous products, due to more elastic fibers. The plant-based fibrous products behave more solid-like until a larger strain, but the fibrous structures break down at large deformations resulting in higher energy dissipation, and show a lower normal stress response than meat. We therefore explore the importance of fiber properties and orientation on the nonlinear rheology of fibrous model systems for meat analogues, and provide a robust methodology to quantitatively compare different mechanical responses of meat and plant-based fibrous meat analogues. These results thereby allow comparison and tuning mechanical responses of plant-based meat analogue products towards real meat.

Rheological response of ferrofluids undergoing unsteady shear flows in the presence of a magnetic field

The rheological response of two commercial ferrofluids to transient shearing flows using a parallel disk rheometer device equipped with a magnetic cell is investigated. The basic difference between the ferrofluids is their volume fraction of magnetic particles. The first transient shear flow examined is a step-strain under the influence of a magnetic field, from which the stress relaxation functions for both magnetic fluids studied are obtained in terms of the magnetic field strength and the intensity of the step strain. The main relaxation times of both fluids are determined and shown to increase with the applied magnetic field parameter after some critical value. We also observed that the shear stress relaxes to a residual stress, which is strongly dependent on both magnetic field and strain strengths. This remarkable residual stress increases as the intensity of the magnetic field rises. In terms of the strain strength, this residual stress is found to have two interesting behaviors. First, for small values of strain, the residual stress increases linearly until a maximum is reached. Further increases in the strain strength lead to a nonlinear decrease in the residual stress. We conjecture that the linear regime is associated with a predominance of elastic deformation of the fluid microstructure while the nonlinear one to its plastic deformation or even to the structure breakup. The second experimental investigation of the magnetic fluids is carried out under the condition of oscillatory shear in a linear viscoelastic regime and in the presence of an applied magnetic field. The main viscoelastic moduli of the ferrofluids as functions of the non-dimensional frequency and the magnetic field intensity are presented. In addition, it is also shown, for both ferrofluids, that viscous and elastic characteristics are severely increased when the applied magnetic field intensity is enhanced. We also determine the shear elastic modulus for both magnetic fluids in the limit of low Deborah number as a function of the magnetic parameter. Compatibility checks between the viscous modulus and the apparent shear viscosity under conditions of the same frequency and shear rate are performed, and the first normal stress difference is calculated.

Modeling the rheological behavior of silica filled rubber compounds

The rheological behavior of styrene–butadiene rubber (SBR) compounds filled with silica is investigated as a function of silica volume fraction. To predict the mechanical response, a continuum model for entangled polymer melts filled with nanoparticles is herein introduced. This model is capable of describing the rheological response in both the linear and nonlinear viscoelastic regimes in the context of non-equilibrium thermodynamics to guarantee its thermodynamic admissibility. The constitutive model describes the polymer nanocomposite melts at a mesoscopic level of description by considering the conformation tensor between successive entanglement points, and the orientation tensor for the, in general, spheroidal nanoparticles that describes their average orientation. Evolution equations are developed for nanoparticles with an arbitrary shape but are eventually specified to the case of spherical ones. The multimode version of the new constitutive model provides a very accurate prediction of the rheological behavior of the processability range of SBR/silica nanocomposites. Thus, the new model is a tool able to provide answers to the several difficulties that rubber-producing manufacturers face when processing rubber compounds.

Thermomechanical Stress Analysis of Hydrated Vital Gluten with Large Amplitude Oscillatory Shear Rheology.

Vital gluten is increasingly researched as a non-food product for biodegradable materials. During processing, the protein network is confronted with increased thermal and mechanical stress, altering the network characteristics. With the prospect of using the protein for materials beyond food, it is important to understand the mechanical properties at various processing temperatures. To achieve this, the study investigates hydrated vital gluten under thermomechanical stress based on large amplitude oscillatory shear (LAOS) rheology. LAOS rheology was conducted at increasing shear strains (0.01-100%), various frequencies (5-20 rad/s) and temperatures of 25, 45, 55, 65, 70 and 85 °C. With elevating temperatures up to 55 °C, the linear viscoelastic moduli decrease, indicating material softening. Then, protein polymerization and the formation of new cross-links due to thermal denaturation cause more network connectivity, resulting in significantly higher elastic moduli. Beyond the linear viscoelastic regime, the strain-stiffening ratio rises disproportionately. This effect becomes even more evident at higher temperatures. Lacking a viscous contribution, the highly elastic but also stiff network shows less mechanical resilience. Additionally, at these elevated temperatures, structural changes during the protein's denaturation and network shrinkage due to water evaporation could be visualized with confocal laser scanning microscopy (CLSM).

Creep Properties of a Viscoelastic 3D Printed Sierpinski Carpet-Based Fractal

In this paper, the phenomenon of creep compliance and the creep Poisson’s ratio of a 3D-printed Sierpinski carpet-based fractal and its bulk material (flexible resin Resione F69) was experimentally investigated, as well as the quantification of the change in the viscoelastic parameters of the material due to the fractal structure. The samples were manufactured via a vat photopolymerization method. The fractal structure of the samples was based on the Sierpinski carpet at the fourth iteration. In order to evaluate the response of both the fractal and the bulk material under the creep phenomenon, 1 h-duration tensile creep tests at three constant temperatures (20, 30 and 40 °C) and three constant stresses (0.1, 0.2 and 0.3 MPa) were conducted. A digital image correlation (DIC) technique was implemented for strain measurement in axial and transverse directions. From the results obtained, the linear viscoelastic behavior regime of the fractal and the bulk material was identified. The linear viscoelastic parameters of both fractal and bulk materials were then estimated by fitting the creep Burgers model to the experimental data to determine the effect of the fractal geometry on the viscoelastic properties of the samples. Overall, it was found that the reduction in stiffness induced by the fractal porosity caused a more viscous behavior of the material and a reduction in its creep Poisson’s ratio, which means an increase in the compliance of the material.

Nanostructures, Linear Rheological Responses, and Tunable Mechanical Properties of Microphase-Separated Cellulose-graft-Diblock Bottlebrush Copolymer Elastomers.

A series of cellulose-graft-diblock bottlebrush copolymer elastomers (cellulose-graft-poly(n-butyl acrylate)-block-poly(methyl methacrylate) (Cell-g-PBA-b-PMMA)) with short side chains were synthesized via successive atom transfer radical polymerization (ATRP) to study the influence of varying compositions and lengths of the graft diblock side chains on microphase morphologies and properties. The microphase-separated morphologies from misaligned spheres to cylinders were observed by atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) measurements. These bottlebrush copolymer elastomers possessed thermal stability and enhanced mechanical properties because the PMMA outer block could self-assemble into hard microdomains, which served as physical cross-links. The viscoelastic responses of these bottlebrush copolymers within the linear viscoelastic (LVE) regime were carried out by the oscillatory shear rheology. The time-temperature superposition (tTs) principle was applied to construct the master curves of the dynamic moduli, and the sequential relaxation of dense bottlebrush copolymers with different PMMA hard outer block lengths was analyzed. The rheological behaviors in this work could be utilized to build up the connection of microstructures and properties for the application of these bottlebrush copolymers as high-performance thermoplastic elastomers.

Skin substitutes based on gellan gum with mechanical and penetration compatibility to native human skin.

The study reports on a simple system to fabricate skin substitutes consisting of a naturally occurring bacterial polysaccharide gellan gum. Gelation was driven by the addition of a culture medium whose cations induced gellan gum crosslinking at physiological temperature, resulting in hydrogels. Human dermal fibroblasts were incorporated in these hydrogels and their mechanical, morphological, and penetration characteristics were studied. The mechanical properties were determined by means of oscillatory shear rheology, and a short linear viscoelastic regime was noted up to less than 1% of strain amplitude. The storage modulus increased with an increasing polymer concentration. The moduli were in the range noted for native human skin. After 2 weeks of fibroblast cultivation, the storage moduli showed signs of deterioration, so that a culture time of 2 weeks was proposed for further studies. Microscopic and fluorescent staining observations were documented. These depicted a crosslinked network structure in the hydrogels with a homogeneous distribution of cells and an assured cell viability of 2 weeks. H&E staining was also performed, which showed some traces of ECM formation in a few sections. Finally, caffeine penetration experiments were carried out with Franz diffusion cells. The hydrogels with a higher concentration of polymer containing cells showed an improved barrier function against caffeine compared to previously studied multicomponent hydrogels as well as commercially available 3D skin models. Therefore, these hydrogels displayed both mechanical and penetration compatibility with the ex vivo native human skin.