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Odors are one of the most diverse and complicated gaseous mixtures so that their discrimination is challenging yet attractive because of the rich information about their origin. The more similar the properties of odors are, the more difficult the discrimination becomes. The practical applications, however, often demand such discrimination, especially with a compact sensing platform. In this paper, we show that a nanomaterial designed for a specific type of odors can clearly discriminate them even with a single nanomechanical sensing channel. Fuel oils and their mixture are used as a model target that has similar chemical properties but different compositions mainly consisting of paraffinic, olefinic, naphthenic, and aromatic hydrocarbons. We demonstrate using octadecyl functionalized silica–titania nanoparticles that the difference in the compositions is successfully picked up based on their high affinity for the aliphatic hydrocarbons and alkyl chain length dependent nonlinear viscoelastic behavior. Such a properly designed material is proved to derive sufficient information from a series of analytes to discriminate them even with a single sensing element. This approach provides a guideline to prepare various sensors whose response properties are distinct and optimized depending on applications.

Monoolein-based cubic and hexagonal mesophases were investigated as matrices for insulin loading, at low pH, as a function of temperature and in the presence of increasing amounts of oleic acid, as a structural stabilizer for the hexagonal phase. Synchrotron small angle X-ray diffraction, rheological measurements, and attenuated total reflection-Fourier transform infrared spectroscopy were used to study the effects of insulin loading on the lipid mesophases and of the effect of protein confinement in the 2D- and 3D-lipid matrix water channels on its stability and unfolding behavior. We found that insulin encapsulation has only little effects both on the mesophase structures and on the viscoelastic properties of lipid systems, whereas protein confinement affects the response of the secondary structure of insulin to thermal changes in a different manner according to the specific mesophase: in the cubic structure, the unfolding toward an unordered structure is favored, while the prevalence of parallel β-sheets, and nuclei for fibril formation, is observed in hexagonal structures.

Understanding the pressure dependence of the nonlinear behavior of ultrasonically excited phospholipid-stabilized nanobubbles (NBs) is important for optimizing ultrasound exposure parameters for implementations of contrast enhanced ultrasound, critical to molecular imaging. The viscoelastic properties of the shell can be controlled by the introduction of membrane additives, such as propylene glycol as a membrane softener or glycerol as a membrane stiffener. We report on the production of high-yield NBs with narrow dispersity and different shell properties. Through precise control over size and shell structure, we show how these shell components interact with the phospholipid membrane, change their structure, affect their viscoelastic properties, and consequently change their acoustic response. A two-photon microscopy technique through a polarity-sensitive fluorescent dye, C-laurdan, was utilized to gain insights on the effect of membrane additives to the membrane structure. We report how the shell stiffness of NBs affects the pressure threshold (Pt) for the sudden amplification in the scattered acoustic signal from NBs. For narrow size NBs with 200 nm mean size, we find Pt to be between 123 and 245 kPa for the NBs with the most flexible membrane as assessed using C-Laurdan, 465-588 kPa for the NBs with intermediate stiffness, and 588-710 kPa for the NBs with stiff membranes. Numerical simulations of the NB dynamics are in good agreement with the experimental observations, confirming the dependence of acoustic response to shell properties, thereby substantiating further the development in engineering the shell of ultrasound contrast agents. The viscoelastic-dependent threshold behavior can be utilized for significantly and selectively enhancing the diagnostic and therapeutic ultrasound applications of potent narrow size NBs.

The high dosage of surfactant terribly restrains the extensive application of viscoelastic surfactant (VES) fracturing fluid. In this study, a novel gemini surfactant (GLO) with long hydrophobic tails and double bonds was prepared and a VES fracturing fluid with a low concentration of GLO was developed. Because of the long tails bending near the double bonds, there is a significant improvement of the surfactant aggregate architecture, which realized the favorable viscosity of the VES fluid at a more economical concentration than the conventional VES fracturing fluids. Fourier transform infrared spectrometry (FT-IR), nuclear magnetic resonance spectrometry (1H NMR, 13C NMR), and high-resolution mass spectrometry (HRMS) were employed to study the formation of the product and the structure of GLO. The designed GLO was produced according to the results of the structure characterizations. The formula of the VES fracturing fluid was optimized to be 2.0 wt % GLO + 0.4 wt % sodium salicylate (NaSal) + 1.0 wt % KCl based on the measurements of the viscosity. The viscosity of the VES fluid decreased from 405.5 to 98.7 mPa·s as the temperature increased from 18 to 80 °C and reached equilibrium at about 70.2 mPa·s. The VES fluid showed a typical elastic pseudoplastic fluid with a yield stress of 0.5 Pa in the rheological tests. It realized a proppant setting velocity as low as 0.08 g/min in the dynamic proppant transport test carried by GLO-based VES fracturing fluid. Compared to the formation water, the filtrate of the VES fracturing fluid decreased the water contact angle (CA) from 56.2 to 45.4° and decreased the water/oil interfacial tension (IFT) from 19.5 to 1.6 mN/m. Finally, the VES fracturing fluid induced a low permeability loss rate of 10.4% and a low conductivity loss rate of 5.4% for the oil phase in the experiments of formation damage evaluation.

Although single-particle level studies on prolate ellipsoidal colloids are relatively abundant, similar studies on oblate ellipsoids are rare because suitable model systems are scarcely available. Here, we present the preparation of monodisperse hard core–shell oblate ellipsoids that can be imaged and tracked in 3D with confocal laser scanning microscopy. Using a thermomechanical squeezing method, we transform spherical core–shell polymethyl-methacrylate (PMMA) particles into oblate ellipsoids. We show how the shape polydispersity as well as the aspect ratio of the obtained oblate ellipsoids can be controlled. In addition, we discuss how the core–shell geometry limits the range of aspect ratios because of the different viscoelastic properties of the cross-linked PMMA core and linear PMMA shell. We further demonstrate imaging of the core–shell oblate dispersions on a single-particle level in real space and time and the tracking of position and orientation using our recently developed tracking algorithm for anisotropic core–shell colloids. Our results thus provide the tools for the future investigation of the behavior of oblate ellipsoids, especially in dense suspensions.

Supramolecular polymers are known to form strong and resilient hydrogels which can take up large amounts of water while exhibiting ease of processing and self-healing. They also possess similarities with networks of biological macromolecules. The combination of these features makes supramolecular polymers ideal candidates for studying mechanisms and consequences of self-assembly, which are relevant to biological materials. At the same time, this renders investigations of mixed hydrogels based on different supramolecular compounds necessary, since this substantially widens their applicability. Here, we address unusual viscoelastic properties of a class of binary hydrogels made by mixing fibrillar supramolecular polymers that are formed from two compounds: 1,3,5-benzene-tricarboxamide decorated with aliphatic chains terminated by tetra(ethylene glycol) (BTA) and a 20 kg/mol telechelic poly(ethylene glycol) decorated with the same hydrogen bonding BTA motif on both ends (BTA-PEG-BTA). Using a suite of experimental and simulation techniques, we find that the respective single-compound-based supramolecular systems form very different networks which exhibit drastically different rheology. More strikingly, mixing the compounds results in a non-monotonic dependence of modulus and viscosity on composition, suggesting a competition between interactions of the two compounds, which can then be used to fine-tune the mechanical properties. Simulations offer insight into the nature of this competition and their remarkable qualitative agreement with the experimental results is promising for the design of mixed hydrogels with desired and tunable properties. Their combination with a sensitive dynamic probe (here rheology) offer a powerful toolbox to explore the unique properties of binary hydrogel mixtures., A two-component hydrogel system, comprising two different supramolecular molecules based on the same hydrogen bonding motif, is shown to exhibit a non-monotonic dependence of modulus and viscosity on composition. This binary hydrogel consists of fibrillar supramolecular polymers formed from two compounds, 1,3,5-benzene-tricarboxamide decorated with aliphatic chains terminated by tetra(ethylene glycol) (BTA) and a 20 kg/mol telechelic poly(ethylene glycol) decorated with the same hydrogen bonding BTA motif on both ends (BTA-PEG-BTA). The powerful combination of rheometric and cryo-TEM experiments with simulations provides detailed insights into the origin of the observed behavior, which is the competition between the dynamic interactions of the two compounds. The coarse-grained model used in simulations implies a universal validity of these findings for a variety of different chemical compounds. It is concluded that interactions between not only the single associating units, but also their changing organization in space with changing relative composition, play a crucial role in the emerging mechanics of binary and multicomponent gels, and therefore have implications in understanding and tailoring the viscoelastic properties of biological networks or designing mixed hydrogels with desired properties.

The control of physical properties of soft matters via external stimuli is useful for various applications. Poly(ionic liquid)s are versatile liquid polymers exhibiting ionic conductivity, though the development of photoresponsive poly(ionic liquid)s is still limited. Here, we report the synthesis and properties of a photoreactive poly(ionic liquid) 1a consisting of a Ru sandwich complex [Ru(C5H5){C6H3(OC6H12CN)3}]+ and a polymeric anion -[-CH2–CH(SO2N–SO2CF3)-]n-. Upon UV photoirradiation, the liquid transformed into a rubbery elastomer 2a through the photochemical reaction of the cations. The resultant elastomer is a unique hybrid coordination polymer comprising a cationic coordination network and anionic covalent chains. The elastomer returned to 1a upon heating. The application of light and heat resulted in a coordination structure transformation that caused reversible changes in viscoelasticity and ionic conductivity. The liquid 1a was synthesized by polymerization of ionic liquid 1b containing an H2C═CHSO2N–SO2CF3 anion. UV photoirradiation transformed 1b into a viscous elastomer 2b consisting of a coordination network, though the elastomer changed into 1a upon heating via polymerization of the anion.

Polymer latexes have long been used as coating binders by various branches of industry due to their capacity to adhere coating components and increase the strength of the dried final coatings. In addition, these latexes have been known to affect the rheology of coating dispersions. Currently, emulsion polymerization is the most widely used method of producing polymer latexes. While the stability of these latexes is primarily provided by electrostatic repulsion between surfactants, this property also causes foaming problems during coating processes. In this research, these problems were addressed by preparing polymer-stabilized (PS) latexes that contained different concentrations of acrylic acid. Steric protection of the latexes was provided by a protective shell consisting of starch and poly(vinyl alcohol) (PVA). The viscosity, particle size, ζ-potential, and viscoelastic behavior of the prepared latexes were investigated as a function of pH, and their surface tension and foaming tendencies were evaluated. The latexes were applied as coating cobinders in calcium carbonate and clay coating dispersions, and the viscoelastic properties, surface tensions, and foaming tendencies of these mixtures were studied. The presence of acrylic acid monomers was found to be an important factor affecting the viscosity, particle size, and ζ-potential of the PS latexes prepared in this work, which were further found to generate less foam than comparable emulsion-polymerized latexes. Finally, coating color viscoelastic properties were modified via the partial substitution of styrene-butadiene (S/B) latexes with PS latexes.

The development of high-resolution, label-free, noninvasive, and subsurface microscopy methods of living cells remains a formidable problem. Force-microscopy-based stiffness measurements contribute to our understanding of single-cell nanomechanics. The elastic properties of the cell's outer structures, such as the plasma membrane and actin cytoskeleton, dominate stiffness measurements, which in turns prevents the imaging of intracellular structures. We propose that the above limitation could be overcome by combining 2D sections of the cell's viscoelastic properties. We show the simultaneous imaging of the outer cell's cytoskeleton and the organelles inside the nucleus. The elastic component of interaction force carries information on the cell's outer elements as the cortex and the actin cytoskeleton. The inelastic component is sensitive to the hydrodynamic drag of the inner structures such the nucleoli.

[EN] High-speed atomic force microscopy (AFM) enabled the imaging of protein interactions with millisecond time resolutions (10 fps). However, the acquisition of nanomechanical maps of proteins is about 100 times slower. Here, we developed a high-speed bimodal AFM that provided high-spatial resolution maps of the elastic modulus, the loss tangent, and the topography at imaging rates of 5 fps. The microscope was applied to identify the initial stages of the self-assembly of the collagen structures. By following the changes in the physical properties, we identified four stages, nucleation and growth of collagen precursors, formation of tropocollagen molecules, assembly of tropocollagens into microfibrils, and alignment of microfibrils to generate microribbons. Some emerging collagen structures never matured, and after an existence of several seconds, they disappeared into the solution. The elastic modulus of a microfibril (∼4 MPa) implied very small stiffness (∼3 × 10–6 N/m). Those values amplified the amplitude of the collagen thermal fluctuations on the mica plane, which facilitated microribbon build-up., Financial support from the Ministerio de Ciencia e Innovación (PID2019-106801GB-I00; MAT2016-76507-R), Comunidad de Madrid S2018/NMT-4443 (Tec4Bio-CM), and European Commission Marie Sklodowska-Curie grant agreement No.721874 are acknowledged.

The ability to precisely control particle migration within microfluidic systems is essential for focusing, separating, counting, and detecting a wide range of biological species. To date, viscoelastic microfluidic systems have primarily been applied to the focusing, separation, and isolation of micrometer-sized species, with their use in nanoparticle manipulations being underdeveloped and underexplored, due to issues related to nanoparticle diffusivity and a need for extended channel lengths. To overcome such issues, we herein present sheathless oscillatory viscoelastic microfluidics as a method for focusing and separating both micrometer and sub-micrometer species. To highlight the efficacy of our approach, we segment our study into three size regimes, namely, micrometer (where characteristic particle dimensions are above 1 μm), sub-micrometer (where characteristic dimensions are between 1 μm and 100 nm), and nano (where characteristic dimensions are below 100 nm) regimes. Based on the ability to successfully manipulate particles in all these regimes, we demonstrate the successful isolation of p-bodies from biofluids (in the micrometer regime), the focusing of λ-DNA (in the sub-micrometer regime), and the focusing of extracellular vesicles (in the nanoregime). Finally, we characterize the physics underlying viscoelastic microflows using a dimensionless number that relates the lateral velocity (due to elastic effects) to the diffusion constant of the species within the viscoelastic carrier fluid. Based on the ability to precisely manipulate species in all three regimes, we expect that sheathless oscillatory viscoelastic microfluidics may be used to good effect in a range of biological and life science applications.

The delicate flow-induced morphology of immiscible polypropylene/polystyrene blends in the presence of silica nanoparticles (NPs) is investigated in a multiparameter space. The morphology map constructed based on in situ morphology observation reveals that a critical ratio of NP concentration to droplet concentration, which strongly depends on the NP surface chemistries and the ratio of the NP concentration to the droplet concentration, exists. Below or above the critical ratio, the NPs display diverse effects on the morphology (promote or suppress droplet coalescence). These results can be interpreted by the competition between the bridging mechanism (acceleratory effect) and the enhanced viscoelasticity (inhibitory effect) exerted by the NPs.

Colloidal gels with various architectures and different types of interactions provide a unique opportunity to shed light on the interplay between microscopic structures and mechanical properties of soft glassy materials. Here, we prepare acetylated cellulose nanofibrils with 2 degrees of substitution and make a structural and rheological characterization of their hydrogels. Two-step yielding processes are observed in the shear experiments, which allow us to deduce more precise knowledge regarding localized structural changes of the fibrils. We separate the viscoelastic response into two contributions: the establishment of cross-linked clusters on a fibril level and the arrested phase separation on a cluster level. We hypothesize that with the addition of salt, the hydrogels exhibit different arrested states that are identified as unable to access the thermodynamic equilibrium. Our results highlight that the coexistence of gelation and glass transitions are experimentally recognized in the hydrogels, with a global gelation driven by a local glasslike arrest during spinodal decomposition.

In this study, the effect of chemical surface functionalization through oxidation of exfoliated graphite nanoplatelets in the transport properties of their aqueous nanofluids has been analyzed. With this objective, thermal conductivity and viscoelastic properties have been determined for original and oxidized nanoplatelets. The results show that the functionalization completely changes the internal structure of the suspension, which is reflected in shifts of even orders of magnitude on viscosity, yield stress, or storage or loss moduli. It is evident that this influences thermal conduction properties as well, as it has been also demonstrated. This shows that nanostructure surface functionalization can be a useful strategy to tune nanofluid thermophysical properties.

We investigate the influence of the environment on the relaxation dynamics of well-defined H-polymers diluted in a matrix of linear chains. The molar mass of the linear chain matrix is systematically varied and the relaxation dynamics of the H-polymer is probed by means of linear viscoelastic measurements, with the aim to understand its altered motion in different blends, compared to its pure melt state. Our results indicate that short unentangled linear chains accelerate the relaxation of both the branches and the backbone of the H-polymers by acting as an effective solvent. On the other hand, the relaxation of the H-polymer in an entangled matrix is slowed-down, with the degree of retardation depending on the entanglement number of the linear chains. We show that this retardation can be quantified by considering that the H-polymers are moving in a dilated tube at the rhythm of the motion of the linear matrix.

[Image: see text] Peptide hydrogels are excellent candidates for medical therapeutics due to their tuneable viscoelastic properties, however, in vivo they will be subject to various osmotic pressures, temperature changes, and biological co-solutes, which could alter their performance. Peptide hydrogels formed from the synthetic peptide I(3)K have a temperature-induced hardening of their shear modulus by a factor of 2. We show that the addition of uncross-linked poly(N-isopropylacrylamide) chains to the peptide gels increases the gels’ temperature sensitivity by 3 orders of magnitude through the control of osmotic swelling and cross-linking. Using machine learning combined with single-molecule fluorescence microscopy, we measured the modulation of states of prestress in the gels on the level of single peptide fibers. A new self-consistent mixture model was developed to simultaneously quantify the energy and the length distributions of the states of prestress. Switching the temperature from 20 to 40 °C causes 6-fold increases in the number of states of prestress. At the higher temperature, many of the fibers experience constrained buckling with characteristic small wavelength oscillations in their curvature.

Liquid intrusion into zeolitic imidazolate framework 7 (ZIF-7) has been observed for the first time. Among the three typical phases of ZIF-7, we discover that only the guest-free ZIF-7-II structure can be intruded by mechanical pressure, and intriguingly, this pressurized liquid intrusion behavior is detected only in nanocrystals, indicating the crystal size effect. Because of its unique combination of non-outflow property and high intrusion pressure, water intrusion into ZIF-7-II generates a marked energy dissipation capacity of ∼2 J/g despite its limited pore volume. We present several strategies that can be easily implemented to tune its intrusion pressure and energy dissipation and accomplish material reusability. Remarkably, we found that the pore cavities of ZIF-7-II can accommodate water molecules without experiencing any phase transition, which is entirely different from other solvents whose incorporation will trigger a spontaneous conversion into ZIF-7-I. Our pressure-vs-volume data further reveal that the process of water infiltration and retainment is controlled by the gate-opening/closing mechanism, which has enabled us to probe the viscoelasticity of ZIF-7 via cyclic liquid intrusion experiments. This study has deepened our understanding of the time-dependent mechanical properties of ZIFs and shed new light on the structural flexibility central to the novel applications of metal-organic framework materials.

Nanocomposites consisting of polymers reinforced with filler particles are important for a wide variety of industries and processes, but although they exhibit unique viscoelastic properties and as such are widely applied in e.g. tires, the precise mechanism of their reinforcement is at best incompletely understood at present. In order to understand it at a fundamental level, and ultimately control it in practice, it is essential to determine the impact of interactions between filler particles and polymer matrix on the nanocomposite microstructure and its macroscopic dynamic mechanical properties. To this end, we performed experiments on two model systems as well as molecular dynamics simulations, aiming to determine to what extent widely used shear-distortion models of the reinforcement are applicable as well as the role played by molecular interactions on the enhancement of the mechanical properties. In both experiments and simulations a linear dependence of the reinforcement on the inverse radius of the nanoparticles was obtained. Deformation simulations of a linearly increasing strain showed an overall increase of 50% in the linear modulus when fillers were added to the polymer matrix, regardless of the use of direct interactions among the nanoparticles. Furthermore, the use of attractive nanoparticle interactions resulted in a higher matrix densification at the interfaces and to a sharp increase in the reinforcement.

Classical lubrication theory is unable to explain a variety of phenomena and experimental observations involving soft viscoelastic materials, which are ubiquitous and increasingly used in e.g. engineering and biomedical applications. These include unexpected ruptures of the lubricating film and a friction–speed dependence, which cannot be elucidated by means of conventional models, based on time-independent stress–strain constitutive laws for the lubricated solids. A new modeling framework, corroborated through experimental measurements enabled via an interferometric technique, is proposed to address these issues: Solid/fluid interactions are captured thanks to a coupling strategy that makes it possible to study the effect that solid viscoelasticity has on fluid film lubrication. It is shown that a newly defined visco-elasto-hydrodynamic lubrication (VEHL) regime can be experienced depending on the degree of coupling between the fluid flow and the solid hysteretic response. Pressure distributions show a marked asymmetry with a peak at the flow inlet, and correspondingly, the film thickness reveals a pronounced shrinkage at the flow outlet; friction is heavily influenced by the viscoelastic hysteresis which is experienced in addition to the viscous losses. These features show significant differences with respect to the classical elasto-hydrodynamic lubrication (EHL) regime response that would be predicted when solid viscoelasticity is neglected. A simple yet powerful criterion to assess the importance of viscoelastic solid contributions to soft matter lubrication is finally proposed.

Many 3D printing technologies are based on the development of inks and pastes to build objects through droplet or filament deposition (the latter also known as continuous extrusion, robocasting, or direct ink writing). Controlling and tuning rheological behavior is key for successful manufacturing using these techniques. Different formulations have been proposed, but the search continues for approaches that are clean, flexible, robust and that can be adapted to a wide range of materials. Here, we show how graphene oxide (GO) enables the formulation of water-based pastes to print a wide variety of materials (polymers, ceramics, and steel) using robocasting. This work combines flow and oscillatory rheology to provide further insights into the rheological behavior of suspensions combining GO with other materials. Graphene oxide can be used to manipulate the viscoelastic response, enabling the formulation of pastes with excellent printing behavior that combine shear thinning flow and a fast recovery of their elastic properties. These inks do not contain other additives, only GO and the material of interest. As a proof of concept, we demonstrate the 3D printing of additive-free graphene oxide structures as well as polymers, ceramics, and steel. Due to its amphiphilic nature and 2D structure, graphene oxide plays multiple roles, behaving as a dispersant, viscosifier, and binder. It stabilizes suspensions of different powders, modifies the flow and viscoelasticity of materials with different chemistries, particle sizes and shapes, and binds the particles together, providing green strength for manual handling. This approach enables printing complex 3D ceramic structures using robocasting with similar properties to alternative formulations, thus demonstrating the potential of using 2D colloids in materials manufacturing.

Understanding the interaction between liquids and deformable solid surfaces is a fascinating fundamental problem, in which interaction and coupling of capillary and viscoelastic effects, due to solid substrate deformation, give rise to complex wetting mechanisms. Here we investigated as a model case the behavior of water drops on two smooth bitumen substrates with different rheological properties, defined as hard and soft (with complex shear moduli in the order of 10(7) and 10(5) Pa, respectively, at 1 Hz), focusing both on wetting and on dewetting behavior. By means of classical quasi-static contact angle measurements and drop impact tests, we show that the water drop behavior can significantly change from the quasi-static to the dynamic regime on soft viscoelastic surfaces, with the transition being defined by the substrate rheological properties. As a result, we also show that on the hard substrate, where the elastic response is dominant under all investigated conditions, classical quasi-static contact angle measurements provide consistent results that can be used to predict the drop dynamic wetting behavior, such as drop deposition or rebound after impact, as typically observed for nondeformable substrates. Differently, on soft surfaces, the formation of wetting ridges did not allow to define uniquely the substrate intrinsic advancing and receding contact angles. In addition, despite showing a high adhesion to the soft surface in quasi-static measurements, the drop was surprisingly able to rebound and escape from the surface after impact, as it is typically observed for hydrophobic surfaces. These results highlight that measurements of wetting properties for viscoelastic substrates need to be critically used and that wetting behavior of a liquid on viscoelastic surfaces is a function of the characteristic time scales.

We investigated the rheology of a series of anionically synthesized, model symmetric Cayley tree poly(methylmethacrylates) having from 1 to 4 generations of identical molar mass. The hierarchical relaxation of the different generations was assessed from the linear data by accounting for both the plateau modulus and the characteristic relaxation times. Using a tube-model time-marching analysis based on the concept of hierarchy of motion, we described quantitatively the frequency spectra without adjustable parameters. We also performed uniaxial extensional measurements using the Sentmanat extensional rheometer fixture. The samples tested exhibited significant strain hardening compared to their linear analogs at lower and intermediate Hencky strain rates. This hardening was more pronounced with increasing number of generations, hence branch points. The extracted effective steady extensional viscosity was found to scale with the extensional rate with a power exponent of about -0.5, in agreement with earlier findings with linear polystyrenes. We also extended the time-marching-algorithm to predict the extensional behavior of these polymers using the conceptual framework developed recently for pom-pom and Cayley-tree polymers. Comparison between theoretical and experimental results was satisfactory when the maximum stretch which can be supported by the molecule was estimated by accounting for the recently proposed inter-chain pressure effects. (C) 2010 The Society of Rheology. [DOI: 10.1122/1.3368724]

The analysis of nanoindentation force curves collected on polymers through the common Oliver and Pharr procedure does not lead to a correct evaluation of Young’s modulus. In particular, the estimated elastic modulus is several times larger than the correct one, thus compromising the possibility of a nanomechanical characterization of polymers. Pile-up or viscoelasticity is usually blamed for this failure, and a deep analysis of their influences is attempted in this work. Piling-up can be minimized by indenting on a true nanometer scale, i.e., at penetration depth smaller than 200 nm. On the other side, it is common knowledge that fast indentations minimize the effect of viscoelasticity. However, changing the indentation time in a broad range of contact time (fractions of second up to hundreds of seconds) did not allow the correct estimation of Young’s modulus for the polymers used in this work. The final result is that the Oliver and Pharr procedure as well as any other procedure analyzing the unloading curve with elastic contact mechanics models cannot be employed to measure Young’s modulus of polymers because its application is incorrect from a theoretical point of view, unless the analysis is limited to the very first nanometers of penetration depth when the contact is perfectly elastic. Viscoelastic contact mechanics models should instead be employed to characterize these materials.

Oil in water (o/w) Pickering emulsion stabilized by a nanoparticle-surfactant-polymer system shows better thermal stability than the one stabilized by a surfactant-polymer system. The knowledge of the viscoelastic properties of these emulsion systems is important for their successful application for high pressure and high temperature conditions related to enhanced oil recovery (EOR). In this work, the viscoelastic behavior (G? and G?) of the Pickering emulsion stabilized by a nanoparticle-surfactant-polymer system has been investigated as a function of pressure (0.1-30 MPa) and temperature (298-371 K) and compared with conventional emulsion stabilized by a surfactant-polymer system. An oilfield polymer polyacrylamide (PAM) along with nanoparticles (SiO2 and clay) and conventional surfactants are used for the formulation of Pickering o/w emulsion systems. Both the emulsion systems showed liquid-like behavior at 0.1 MPa with G? dominance over the complete range of strain amplitude. It is observed that Pickering emulsions are found to be more stable at high pressure conditions as the pressure effect did not show any significant influence on the viscoelastic properties. Pickering emulsions behave like viscoelastic fluid at all pressure conditions as compared to the surfactant-polymer stabilized emulsion, wherein the storage modulus has shown rapid increase with increase in pressure from 0.1 to 30 MPa. In addition, Pickering emulsions showed better flowability by showing stable G? values for varying conditions of temperature as compared to the surfactant-polymer stabilized emulsion. The stable viscoelastic response for Pickering emulsion is beneficial for their implementation at complex reservoir conditions. � 2015 American Chemical Society.

We present a study on flow-induced crystallization of polymers filled with rigid particles. The numerical simulations reveal the interplay between filler particles, the polymer melt, flow, and flow-induced crystallization. Both crystallization kinetics and the resulting crystal orientation are affected, and they are crucial for the material properties that are created during flow. In the analysis of the problem, first a direct 2D numerical simulation technique for viscoelastic particle suspensions is applied to determine the local molecular conformation during the flow. Subsequently, we use this conformation as the driving force for flow-induced crystallization. Local anisotropic crystalline structures are formed due to high molecular orientation, especially near the particles. Because of the presence of the same particles, regions of the melt are shielded from the flow, and therefore, hardly any effect of the flow is seen in these regions. Both coupled and decoupled simulations were performed. In the last approximation the flow problem is solved using a generalized Newtonian viscous fluid model, and the velocity gradients obtained are plugged into a viscoelastic constitutive model that provides the molecular conformation. It is found that the decoupled method gives incorrect results, especially with respect to the molecular and crystalline structure orientation.

We demonstrate the influence of molecular weight and molecular weight asymmetry across an interface on the transient behavior of the interfacial tension. The interfacial tension was measured as a function of time for a range of polymer combinations with a broad range of interfacial properties using a pendant/sessile drop apparatus. The results show that neglecting mutual solubility, assumed to be a reasonable approximation in many cases, very often does not sustain. Instead, a diffuse interface layer develops in time with a corresponding transient interfacial tension. Depending on the specific combination of polymers, the transient interfacial tension is found to increase or decrease with time. The results are interpreted in terms of a recently proposed model [Shi et al., Macromolecules 37, 1591 (2004)], giving relative characteristic diffusion time scales in terms of molecular weight, molecular weight distribution, and viscosities. However, the time scales obtained from this theoretical approach do not give a conclusive trend. Using oscillatory dilatational interfacial experiments the viscoelastic behavior of these diffusive interfaces is demonstrated. The time evolution of the interfacial tension and the dilatational elasticity show the same trend as predicted by the theory of diffuse interfaces, supporting the idea that the polymer combinations under consideration indeed form diffuse interfaces. The dilatational elasticity and the dilatational viscosity show a frequency dependency that is described qualitatively by a simple Fickian diffusion model and quantitatively by a Maxwell model. The characteristic diffusion times provided by the latter show that the systems with thick interfaces (tens of microseconds and more) can be considered as slower diffusive systems compared to the systems with thinner interfaces (a few micrometers in thickness and less) can be considered as fast diffusive systems.

When polyolefins are produced on heterogeneous catalysts, they encapsulate the catalyst fragments and present diffusional resistance to further monomer transport to the catalyst fragments. In addition, the deposited polymer layer brings in viscoelastic resistance, since it must be deformed to make space for the polymer being formed at the catalyst surface. In the present work, we analyze the influence of the growing polymer layer on the development of the stress and the concentration profiles and, hence, on the polymerization rate.

The demulsification mechanism of asphaltene-stabilized water-in-toluene emulsions by an ethylene-oxide-propylene oxide (EO-PO) based polymeric demulsifier was studied. Demulsification efficiency was determined by bottle tests and correlated to the physicochemical properties of asphaltene interfacial films after demulsifier addition. From bottle tests and droplet coalescence experiments, the demulsifier showed an optimal performance at 2.3 ppm (mass basis) in toluene. At high concentrations, the demulsification performance deteriorated due to the intrinsic stabilizing capacity of the demulsifier, which was attributed to steric repulsion between water droplets. Addition of demulsifier was shown to soften the asphaltene film (i.e., reduce the viscoelastic moduli of asphaltene films) under both shear and compressional interfacial deformations. Study of the macrostructures and the chemical composition of asphaltene film at the toluene-water interface after demulsifier addition demonstrated gradual penetration of the demulsifier into the asphaltene film. Demulsifier penetration in the asphaltene film changed the asphaltene interfacial mobility and morphology, as probed with Brewster angle and atomic force microscopy.

This work is focused on the conductivity study of viscoelastic liquids, taking as a model poly(2,3-dimethoxybenzyl methacrylate). Each isotherm, displaying the conductivity in the frequency domain, shows a plateau in the low frequency region, representing the dc conductivity. The covered frequency range by the plateau increases with the temperature. The frequency corresponding to the end of the plateau, ωc, marks the onset of the ac conductivity, which correspond in increasing order of frequency to Maxwell− Wagner−Sillars, glass−rubber transition and secondary relaxations. The contributions of the relaxation processes to the ac conductivity in the wholly frequencies range were analyzed. The time−temperature correspondence principle holds for the reduced ac conductivity. However, this principle does not hold for the components of the complex dielectric permittivity due, among other things, to the different temperature dependences of each dipolar relaxation processes. Analogueies and differences between the conductivity behavior of viscoelastic liquids and disordered inorganic solids are discussed., This work was financially supported by the DGCYT and CAM through the Grant MAT2012-33483. This work is dedicated in memoriam of Professor Emeritus Evaristo Riande in recognition of his contribution to polymer science.

This paper reports the rheological behavior of chitosan solutions that have been cross-linked with different amounts of genipin, at body temperature and physiological pH. The effect of the cross-linker loading on the rheological properties of hydrogels has been evaluated. The oscillatory time sweep method was used to monitor the dynamic viscoelastic parameters during in situ (i.e., in the rheometer) gelation experiments, enabling the determination of the gelation time. The stress and frequency sweeps were employed to measure G' of the cured hydrogels. It was found that the solutions of chitosan cross-linked with genipin, under physiological conditions, could form relatively strong elastic gels when compared to those of pure chitosan. Moreover, the gelation time obtained from the crossover of G'' and G' was in excellent agreement with the value obtained from the Winter-Chambon criterion. A significant reduction on this parameter was achieved even at low genipin concentrations. This behavior suggests that these formulations are able to be produced in situ and thus constitute promising matrices for cells and bioactive molecule encapsulations.

We used energy transfer experiments to examine the rates of polymer diffusion in latex films of two P(VAc-DBM) copolymer samples: one of nominal M w = 250 000 (by GPC, M 250K) and the other, the high-M sample, with a substantial (50%) gel content. An important feature of this sample is that its sol fraction had a similar molecular weight distribution (similar GPC curves) to that of the M 250K sample. Films of both samples exhibited the viscoelastic response at high frequencies expected for entangled polymers. At low frequencies, the G' and G″ values for the high-M sample were comparable in magnitude over a wide range of frequencies and were proportional to ω 0.5. This type of behavior is often seen as a signature of a critical gel but appears here for a mixture of gel and randomly branched polymer. Our most important finding is that the rates of intercellular polymer diffusion were very similar in latex films of the two polymers. This result indicates that the diffusion rate depends primarily on the molecular weight and degree of branching of the diffusing species and is much less sensitive to the cross-linked nature of the matrix present in one of the samples. Fil: Wu, Jun. University of Toronto; Canadá Fil: Tomba, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina. University of Toronto; Canadá Fil: Winnik, Mitchell A.. University of Toronto; Canadá Fil: Farwaha, Rajeev. Vinamul Polymers; Estados Unidos Fil: Rademacher, Jude. ICI Paints; Estados Unidos

The influence of the cross-linking degree on the dynamics of the segmental motions close to the glass transition of poly(methyl methacrylate), PMMA, networks was investigated by three different mechanical spectroscopy techniques: thermally stimulated recovery (TSR), dynamic mechanical analysis (DMA), and creep. The application of the time-temperature superposition principle to isothermal DMA and creep results permitted to successfully construct master curves for PMMA networks with distinct cross-linking degrees. The former results were fitted to the KWW equation. The obtained variation of beta(KWW) for the distinct networks indicated that the relaxation curves tend to broaden as the cross-linking degree increases. TSR results clearly revealed a significant shift of the alpha-relaxation to longer times and a broader relaxation as the cross-linking degree increases, what was also observed by DMA and creep. A change from a Vogel to an Arrhenius behavior was detected by the three techniques with the decrease of temperature below T-g. The temperature dependence of the apparent activation energies (E-a) was calculated from DMA, creep, and TSR experiments; above T-g a good agreement was seen between the E-a values for all the techniques. Furthermore, the effect of the cross-linking degree on the fragility of PMMA networks was evaluated. For these materials an increase of fragility with increasing cross-linking degree was observed.

A numerical method to compute the viscoelastic melt-spinning model with radial resolutions of temperature and stress fields is formulated and applied to the low speed range. The starting framework is the reduction of the complete continuous model into both the perturbed two-dimensional model and the perturbed average model obtained from a first-order regular perturbation analysis available in the literature. The polymer rheology is described with the nonisothermal Phan-Thien and Tanner and Giesekus constitutive equations. By using the implicit tridiagonal scheme of finite differences coupled to the fourth-order Runge−Kutta method, an iterative numerical algorithm is proposed for the computation of the coupled balance equations. The temperature and stress fields in the filament as functions of axial and radial positions are obtained for a well-refined mesh and with high numerical precision. The numerical algorithm considers the appropriate interplay between axial and radial varying temperature and stress fields and the rigorous averaged balances of momentum and energy and averaged constitutive equation. The development of a skin-core structure is predicted with the two rheological models. Fil: Ottone, Mariel Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina Fil: Deiber, Julio Alcides. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina

This book deals with the increasingly 'diminishing' interfaces that are resulting as device dimensions scale down. Chapter topics include nanomechanical properties and stuctures of thin films in contrast to their bulk counterparts, from both experimental and theoretical perspectives; viscoelasticity, micro-roughness, and friction, particularly in polymers; advances in instrumentation such as scanning probes, X-ray scattering, sum frequency generation spectroscopy and nanorheometers; the origin of film properties via tailored molecular modification of film components; molecular dynamics simulations and modelling of interfaces.

This volume is a study of polymer surfaces and interfaces from the the perspective of polymer scientists, tribologists, and mechanical engineers. The book is divided into four sections that address a range of problems, from contact mechanics of viscoelastic materials to relationships between polymer microstructures and surface properties. Special attention is paid to micromechanical and microtribological properties and composites, with an emphasis on scanning probe-based microscopy studies. Industrial applications of the work are discussed, including automotive coatings, computer hard discs, medical devices, and microelectromechanical systems.

I. INTRODUCTION In numerous applications of surfactants the rheological behavior of their aqueous solutions is of great practical importance. Surfactant systems can have very complex flow properties. For example, concentrated solutions of certain surfactants are Newtonian liquids and their viscosities are only slightly higher than that of pure water. On the other hand, solutions of other surfactants have viscosities that are 106 to 107 times higher than the water viscosity although the surfactant concentration is still below 1 wt %, and such systems are also highly elastic. The viscosities of such samples can be varied within ~ 6 orders of magnitude by only a small change of different parameters like surfactant concentration, ionic strength, temperature, or concentration of additives [1].