Soft Polymer Research Articles

Is Ficoll a Colloid or Polymer? A Multitechnique Study of a Prototypical Excluded-Volume Macromolecular Crowder

The in-cell environment is crowded with macromolecules, and the consequent reduction in free volume, based on the hard-sphere paradigm, is central to understanding macromolecular motions. A much-used model crowder, Ficoll, often assumed to be a compact, if not rigid, colloidal particle, is studied by rheology, small-angle neutron scattering, nuclear magnetic resonance diffusometry, and relaxometry. We find that the Ficoll suspension viscosity scales linearly with concentration cF in the dilute limit and as ∼cF3.8 at high cF, i.e, consistent with the 15/4 (de Gennes) scaling for a reptating polymer. The form factor of Ficoll, obtained via small-angle neutron scattering (SANS), resembles either a Gaussian polymer or a soft polymer blob. From NMR diffusion measurements, we obtain an effective volume fraction for Ficoll that accounts for Ficoll-bound water in two ways and show that each results in a volume occupancy of 60% to 70% in the crowding limit, much larger than the traditionally reported values of around 30%. If we persist with the colloid paradigm and examine the dependence of the zero-q structure factor obtained via SANS in terms of this effective volume fraction, we find that only a combination of particle softness and interparticle attractions, quantified using a computational model, can replicate the experimental S(0). The stark difference between effective and traditional volume occupancies affects the interpretation of previous experiments on macromolecular crowding and might explain the intriguing non-monotonicity observed in the dependence of protein relaxation rates on crowder concentration.

CNT/PVDF Composite Coating Layer on Cu with a Synergy of Uniform Current Distribution and Stress Releasing for Improving Reversible Li Plating/Stripping.

The uncontrollable formation of polymorphous Li deposits, e.g., whiskers, mosses, or dendrites resulting from nonuniform interfacial current distribution and internal stress release in the upward direction on the conventional current collector (e.g., Cu foil) of Li metal rechargeable batteries with a lithium-metal-free negatrode (LMFRBs), leads to rapid performance degradation or serious safety problems. The 3D carbon nanotubes (CNTs) skeleton has been proven to effectively reduce the current density and eliminate the internal accumulated stress. However, remarkable electrolyte decomposition, inherent Li source consumption due to repeated SEI formation, and Li+ intercalation in CNTs limit the application of 3D CNTs skeleton. Thus, it is necessary to avoid the side effects of the 3D CNTs skeleton and retain uniform interfacial current distribution and stress mitigation. In this work, we integrate the CNTs network with a soft functional polymer polyvinylidene fluoride (PVDF) to form a relatively dense coating layer on Cu foil, which can shield the contact between the internal surface of the 3D CNTs framework and the electrolyte. Simultaneously, the Li-F-rich SEI resulting from the partial reduction of PVDF with deposited Li and the soft nature of the coating layer release the accumulation of internal stress in the horizontal direction, resulting in mosses/whisker-free Li deposition. Thus, improved Li deposition/dissolution and stable cycling performance of the LMFRBs can be achieved.

Silver-Reduced Poly(Ethylene Glycol) Diacrylate Composites with Microline Arrays for Directional Bending Sensors.

Herein, a soft and flexible polymer composite sensor with a surface structure is manufactured that is sensitive to a wide range of mechanical stimuli, including small actions and large motions. A polymer sensor performing with a piezoresistive mechanism is proposed by synthesizing a new conductive polymer composite to fabricate a microline structure by itself, named Ag-reduced poly(ethylene glycol) diacrylate (PEGDA) composite directional bending sensor (ACBS). A simple but effective process of forming nanoparticles (NPs) and surface structures is a notable characteristic. High sensitivity to a small stimulus was achieved by forming Ag NPs within PEGDA, particularly concentrating on the surface and applying the microline structure. With the structural characteristics of a line structure, the ACBS achieved anisotropic sensitivity to bulk motion along the arranged line direction. The excellent sensitivity of this polymer sensor was experimentally demonstrated via water droplets, blowing, and breathing. Combining the advantages of a simple synthetic and simple fabrication process along with the fabrication ability of the microsurface structure with the material itself and the conductive Ag/PEGDA integrated layer, this ACBS is outstanding as a soft and flexible polymer composite sensor and has potential application in physical devices such as wearable devices and biosensors.

Machine Learning Approach to Characterize the Adhesive and Mechanical Properties of Soft Polymers Using PeakForce Tapping AFM

Machine Learning Approach to Characterize the Adhesive and Mechanical Properties of Soft Polymers Using PeakForce Tapping AFM

Improved piezoelectricity of porous cellulose material via flexible polarization-initiate bridge for self-powered sensor

Self-powered piezoelectric sensors based on cellulose nanocrystal (CNC) porous materials are light-weight and portable, whereas using unmodified CNCs can hardly obtain enough piezoelectric properties without external strong polarization due to its irreversible deformation caused by low toughness. Here, we bonded rod-like CNCs with a soft polymer, poly ethylene glycol (PEG), and hypothesized that PEG could toughen the material and its dielectric signal could induce the CNC polarization. We further adsorbed graphene (GR) as surface electrodes to prepare a CNC-PEG-GR piezoelectric porous material with density of 0.096 g·cm−3. The voltage output reached maximum when the frequency matched the dielectric relaxation frequency of PEG. We also increased the length-diameter ratio of porous material pores from 1.1 to 3.3 by adjusting its freeze-drying process, and the voltage output could reach to 0.7 V at a moderate ratio. They could be conveniently integrated into portable self-powered sensors applied to the intelligent wearable electronic devices.

Enhanced deep-tissue photoacoustics by using microcomposites made of radiofrequency metamaterials and soft polymers: Double- and triple-resonance phenomena

Photoacoustic imaging systems offer a platform with high resolution to explore body tissues, food, and artwork. On the other hand, plasmonics constitutes a source of resonant heating and thermal expansion to generate acoustic waves. However, its associated techniques are seriously limited to laser penetration and nonspecific hyperthermia in the sample. To address this issue, the present work adopts a paradigm shift in photoacoustics. By simulating microparticles made of random composites, the calculated pressure can be made similar or superior to that calculated via plasmonic optoacoustics. The improvement is due to a phenomenon called double or triple resonance, which is the excitation of one or both electric and magnetic plasmons within radiofrequency range and the simultaneous excitation of the particle’s acoustic mode. Given that electromagnetic pulses are restricted to nanosecond pulse widths and MHz frequencies, the proposed method overcomes the poor penetration in tissues and reduces thermal damage, thereby offering a noninvasive technique of theragnosis. Moreover, the resonant pressure obtained lasts longer than with conventional photoacoustic pressure, providing a central feature to enhance detection. To fully comprehend the multi-resonance framework, we develop a complete photoacoustic solution. The proposed approach could pave the way to thermoacoustic imaging and manipulation methods for sensitive materials and tissues with micrometer resolution.

Origin of the Acoustic Bandgaps in Hypersonic Colloidal Phononics: The Role of the Elastic Impedance.

How phonons propagate in nanostructures determines the flow of elastic and thermal energy in dielectric materials. However, a reliable theoretical prediction of the phonon dispersion relation requires experimental verification both near to and far from the Brillouin zone of the nanostructure. We report on the experimental hypersonic phonon dispersion of hard (SiO2) and soft (polymer) fcc colloidal crystals infiltrated in liquid polydimethylsiloxane with different elastic impedance contrast using Brillouin light spectroscopy. We discuss the distinct differences with first-principles full elastodynamic calculations involving a multiple-scattering theory. Interparticle contacts strongly impact the long-wavelength speed of sound and the nature of the particle vibration resonance-induced hybridization hypersonic bandgap. The absence of the order-induced Bragg bandgap in SiO2 and its presence in soft opals cannot be fully accounted for by the theory, limiting its predictive power. Bridging the elasticity of the two colloidal crystals with suitable SiO2 core–shell (polymer) particles reveals an unprecedented crossover behavior in the dispersion relation. In view of many conversational parameters, the control tuning of phonon propagation in soft matter-based hypersonic phononics remains challenging.

Temperature-dependent vibration energy harvesting performance of polyimide/(Na,K)NbO3 piezoelectric composites

A composite structure of piezoelectric particles and soft polymer composite material is one of the candidates that converts environmental vibration energy into electrical energy. Presently, expanding the usage of applications is needed in terms of the working environment at harsh temperatures. Polyimide is flexible and temperature-stable polymer. In this research, we report a synthesis of polyimide/(Na,K)NbO3 (PI/NKN) flexible composites. We constructed a setup, where vibration and heat are simultaneously applied to the PI/NKN composites. The frequency and temperature dependence of the output voltage were investigated at room temperature up to 200 °C. Relative permittivity, piezoelectric constant, and output voltage of the PI/NKN showed temperature stability. Flexibility and glass transition temperature of a polymer matrix are important factors. PI/NKN composites are potential energy harvesting materials with flexibility and excellent high-temperature stability.

PVC gel smart sensor for robotics sensing applications: an experimental and finite element simulation study * * Montassar Aidi Sharif (M. A. S.) has a PhD degree in Electrical and Computer Engineering from Michigan State University (MSU) - USA. Currently, Dr. Sharif is with the Department of Electronic and Control Engineering and Computer Engineering Departments, Technical Engineering College—Kirkuk, Northern Technical

Research is now being done on soft electroactive polymers (EAPs), such as polyvinyl chloride (PVC) gel, as an example, for use in soft robotics and smart sensors. Although the sensing behavior of PVC gel has not yet been thoroughly investigated, it has been determined that this material reacts in some way to the stimuli that come from the outside. PVC gels are being utilized to construct a broad variety of different kinds of smart sensors due to the fact that their deformation may be endlessly configured by variations in electrode arrangement, applied mechanical stress, and the amount of plasticizer contained within the gel. In this study, experimental characterizations and the results of finite element simulations are discussed for a PVC gel compression sensor. The finite element simulation of what happens to PVC gel when it is compressed from the outside using mechanical force has been built using the COMSOL Multiphysics, which is a finite element simulation software. Additional experimental measurements of PVC gels are carried out in order to validate the underlying principles that have been presented thus far by providing context for the results of the simulations and to validate the findings effectively. Based on the findings, it appears that the suggested sensor is able to detect compression at a variety of amplitudes and rates . This study sheds light on the sensing capabilities of PVC gel in sensing investigations and provides a framework for conducting such investigations, thereby laying the groundwork for an increase in the use of PVC gel sensors in soft robotics research in the future.

3D Printing of Soft Magnetoactive Devices with Thiol‐Click Photopolymer Composites

Magnetoresponsive polymers have gained increased attention in the design of soft actuators as they can be spatially as well as temporally activated and enable an external noninvasive control of movement. By introducing the magnetoresponsive properties in photocurable resins, one can fabricate personalized and complex structures (via vat photopolymerization 3D printing), whose movement can be conveniently controlled by an external magnetic field. Advancing from acrylate‐based photopolymers, which often suffer from shrinkage stress, low monomer conversion, and oxygen inhibition, the fabrication of magnetoresponsive thiol‐click photopolymers containing Fe3O4 nanoparticles as magnetic fillers is highlighted. The addition of the thiol crosslinker yields soft and flexible polymer composites, whose cure kinetics, viscosity, thermal, and mechanical properties are studied as a function of the thiol and filler content. Although cure rate and final monomer conversion decrease with rising filler concentration, the cure kinetics is reasonably fast at 6 wt%. The short pot life, a result of thiol‐Michael reactions induced by Fe3O4 nanoparticles, and a high thiol content, are overcome by the addition of an appropriate stabilizer. As proof of concept, 3D structures are fabricated by digital light processing (DLP) 3D printing and their magnetically driven movement is demonstrated.

Fifty years of Schallamach waves: from rubber friction to nanoscale fracture.

The question of how soft polymers slide against hard surfaces is of significant scientific interest, given its practical implications. Specifically, such systems commonly show interesting stick-slip dynamics, wherein the interface moves intermittently despite uniform remote loading. The year 2021 marked the 50th anniversary of the publication of a seminal paper by Adolf Schallamach (Wear, 1971), which first revealed an intimate link between stick-slip and moving detachment waves, now called Schallamach waves. We place Schallamach's results in a broader context and review subsequent investigations of stick-slip, before discussing recent observations of solitary Schallamach waves. This variant is not observable in standard contacts so that a special cylindrical contact must be used to quantify its properties. The latter configuration also reveals the occurrence of a dual wave-the so-called separation pulse-that propagates in a direction opposite to Schallamach waves. We show how the dual wave and other, more general, Schallamach-type waves can be described using continuum theory and provide pointers for future research. In the process, fundamental analogues of Schallamach-type waves emerge in nanoscale mechanics and interface fracture. The result is an ongoing application of lessons learnt from Schallamach-type waves to better understand these latter phenomena. This article is part of the theme issue 'Nanocracks in nature and industry'.

Soft wetting with (a)symmetric Shuttleworth effect.

The wetting of soft polymer substrates brings in multiple complexities when compared with the wetting on rigid substrates. The contact angle of the liquid is no longer governed by Young’s Law, but is affected by the substrate’s bulk and surface deformations. On top of that, elastic interfaces exhibit a surface energy that depends on how much they are stretched—a feature known as the Shuttleworth effect (or as surface-elasticity). Here, we present two models through which we explore the wetting of drops in the presence of a strong Shuttleworth effect. The first model is macroscopic in character and consistently accounts for large deformations via a neo-Hookean elasticity. The second model is based on a mesoscopic description of wetting, using a reduced description of the substrate’s elasticity. While the second model is more empirical in terms of the elasticity, it enables a gradient dynamics formulation for soft wetting dynamics. We provide a detailed comparison between the equilibrium states predicted by the two models, from which we deduce robust features of soft wetting in the presence of a strong Shuttleworth effect. Specifically, we show that the (a)symmetry of the Shuttleworth effect between the ‘dry’ and ‘wet’ states governs horizontal deformations in the substrate. Our results are discussed in the light of recent experiments on the wettability of stretched substrates.

Large-Area 3D Printable Soft Electronic Skin for Biomedical Applications.

Soft electronic skin (soft-e-skin) capable of sensing touch and pressure similar to human skin is essential in many applications, including robotics, healthcare, and augmented reality. However, most of the research effort on soft-e-skin was confined to the lab-scale demonstration. Several hurdles remain challenging, such as highly complex and expensive fabrication processes, instability in long-term use, and difficulty producing large areas and mass production. Here, we present a robust 3D printable large-area electronic skin made of a soft and resilient polymer capable of detecting touch and load, and bending with extreme sensitivity (up to 150 kPa-1) to touch and load, 750 times higher than earlier work. The soft-e-skin shows excellent long-term stability and consistent performance up to almost a year. In addition, we describe a fabrication process capable of producing large areas and in large numbers, yet is cost-effective. The soft-e-skin consists of a uniquely designed optical waveguide and a layer of a soft membrane with an array of soft structures which work as passive sensing nodes. The use of a soft structure gives the liberty of stretching to the soft-e-skin without considering the disjoints among the sensing nodes. We have shown the functioning of the soft-e-skin under various conditions.

Microfluidic Nanomaterial Synthesis and In Situ SAXS, WAXS, or SANS Characterization: Manipulation of Size Characteristics and Online Elucidation of Dynamic Structural Transitions.

With the ability to cross biological barriers, encapsulate and efficiently deliver drugs and nucleic acid therapeutics, and protect the loaded cargos from degradation, different soft polymer and lipid nanoparticles (including liposomes, cubosomes, and hexosomes) have received considerable interest in the last three decades as versatile platforms for drug delivery applications and for the design of vaccines. Hard nanocrystals (including gold nanoparticles and quantum dots) are also attractive for use in various biomedical applications. Here, microfluidics provides unique opportunities for the continuous synthesis of these hard and soft nanomaterials with controllable shapes and sizes, and their in situ characterization through manipulation of the flow conditions and coupling to synchrotron small-angle X-ray (SAXS), wide-angle scattering (WAXS), or neutron (SANS) scattering techniques, respectively. Two-dimensional (2D) and three-dimensional (3D) microfluidic devices are attractive not only for the continuous production of monodispersed nanomaterials, but also for improving our understanding of the involved nucleation and growth mechanisms during the formation of hard nanocrystals under confined geometry conditions. They allow further gaining insight into the involved dynamic structural transitions, mechanisms, and kinetics during the generation of self-assembled nanostructures (including drug nanocarriers) at different reaction times (ranging from fractions of seconds to minutes). This review provides an overview of recently developed 2D and 3D microfluidic platforms for the continuous production of nanomaterials, and their simultaneous use in in situ characterization investigations through coupling to nanostructural characterization techniques (e.g., SAXS, WAXS, and SANS).

Dendrite-Free and Long-Cycling Lithium Metal Battery Enabled by Ultrathin, 2D Shield-Defensive, and Single Lithium-Ion Conducting Polymeric Membrane.

Polymeric membranes are considered as promising materials to realize safe and long-life lithium metal batteries (LMBs). However, they are usually based on soft 1D linear polymers and thus cannot effectively inhibit piercing of lithium dendrites at high current density. Herein, single lithium-ion conducting molecular brushes (GO-g-PSSLi) are successfully designed and fabricated with a new 2D "soft-hard-soft" hierarchical structure by grafting hairy lithium polystyrenesulfonate (PSSLi) chains on both sides of graphene oxide (GO) sheets. The ultrathin GO-g-PSSLi membrane is further constructed by evaporation-induced layer-by-layer self-assembly of GO-g-PSSLi molecular brushes. Unlike conventional soft 1D linear polymeric structure, the rigid 2D extended aromatic structure of intralayer GO backbones can bear the shield effect of preventing the dendrites possibly generated at high current density from piercing. More importantly, such a shield effect can be significantly strengthened by layer-by-layer stacking of 2D molecular brushes. On the other hand, the 3D interconnected interlayer channels and the soft single lithium-ion conducting PSSLi side-chains on the surface of channels provide rapid lithium-ion transportation pathways and homogenize lithium-ion flux. As a result, LMBs with GO-g-PSSLi membrane possess long-term reversible lithium plating/striping (6months) at high current density.

CENTAUR-The small- and wide-angle neutron scattering diffractometer/spectrometer for the Second Target Station of the Spallation Neutron Source.

CENTAUR has been selected as one of the eight initial instruments to be built at the Second Target Station (STS) of the Spallation Neutron Source at Oak Ridge National Laboratory. It is a small-angle neutron scattering (SANS) and wide-angle neutron scattering (WANS) instrument with diffraction and spectroscopic capabilities. This instrument will maximally leverage the high brightness of the STS source, the state-of-the-art neutron optics, and a suite of detectors to deliver unprecedented capabilities that enable measurements over a wide range of length scales with excellent resolution, measurements on smaller samples, and time-resolved investigations of evolving structures. Notably, the simultaneous WANS and diffraction capability will be unique among neutron scattering instruments in the United States. This instrument will provide much needed capabilities for soft matter and polymer sciences, geology, biology, quantum condensed matter, and other materials sciences that need in situ and operando experiments for kinetic and/or out-of-equilibrium studies. Beam polarization and a high-resolution chopper will enable detailed structural and dynamical investigations of magnetic and quantum materials. CENTAUR's excellent resolution makes it ideal for low-angle diffraction studies of highly ordered large-scale structures, such as skyrmions, shear-induced ordering in colloids, and biomembranes. Additionally, the spectroscopic mode of this instrument extends to lower momentum transfers than are currently possible with existing spectrometers, thereby providing a unique capability for inelastic SANS studies.

EXPANSE: A time-of-flight EXPanded Angle Neutron Spin Echo spectrometer at the Second Target Station of the Spallation Neutron Source

EXPANSE, an EXPanded Angle Neutron Spin Echo instrument, has been proposed and selected as one of the first suite of instruments to be built at the Second Target Station of the Spallation Neutron Source at the Oak Ridge National Laboratory. This instrument is designed to address scientific problems that involve high-energy resolution (neV-μeV) of dynamic processes in a wide range of materials. The wide-angle detector banks of EXPANSE provide coverage of nearly two orders of magnitude in scattering wavenumbers, and the wide wavelength band affords approximately four orders of magnitude in Fourier times. This instrument will offer unique capabilities that are not available in the currently existing neutron scattering instruments in the United States. Specifically, EXPANSE will enable direct measurements of slow dynamics in the time domain over wide Q-ranges simultaneously and will also enable time-resolved spectroscopic studies. The instrument is expected to contribute to a diverse range of science areas, including soft matter, polymers, biological materials, liquids and glasses, energy materials, unconventional magnets, and quantum materials.

Identification of Phthalates from Artificial Products in Chinese Kindergarten Classrooms and the Implications for Preschool Children's Exposure Assessments.

Phthalates are typical chemical pollutants in kindergarten classrooms since numerous artificial products (e.g., polyvinyl chloride (PVC) floorings, soft polymers and plastic toys) that might contain phthalates are widely distributed in kindergarten classrooms. Although Chinese preschool children spend a considerable amount of their waking hours (>8 h/day) in kindergartens, phthalate exposure in such indoor environment has not been given much attention. In this study, the mass fractions of six phthalates in twenty-six artificial products (fifteen flat decoration materials and eleven plastic toys) commonly found in Chinese kindergarten classrooms were measured. Di-2-ethylhexyl phthalate (DEHP) was the most predominant compound in all materials. The emission characteristics of the DEHP from these materials were further investigated. The measured emission characteristics were used for predicting multi-phase DEHP concentrations in kindergarten classrooms by applying a mass transfer model. The modeled concentrations were comparable with those measured in the real environment, indicating that these products might be the major sources of DEHP in Chinese kindergarten classrooms. Preschool children’s exposure to DEHP was found to be 0.42 μg/kg/day in kindergartens under baseline conditions, accounting for 18% of the total exposure to DEHP in Chinese indoor environments.

Design and Mechanical Characterization Using Digital Image Correlation of Soft Tissue-Mimicking Polymers.

Present and future anatomical models for biomedical applications will need bio-mimicking three-dimensional (3D)-printed tissues. These would enable, for example, the evaluation of the quality-performance of novel devices at an intermediate step between ex-vivo and in-vivo trials. Nowadays, PolyJet technology produces anatomical models with varying levels of realism and fidelity to replicate organic tissues. These include anatomical presets set with combinations of multiple materials, transitions, and colors that vary in hardness, flexibility, and density. This study aims to mechanically characterize multi-material specimens designed and fabricated to mimic various bio-inspired hierarchical structures targeted to mimic tendons and ligaments. A Stratasys® J750™ 3D Printer was used, combining the Agilus30™ material at different hardness levels in the bio-mimicking configurations. Then, the mechanical properties of these different options were tested to evaluate their behavior under uni-axial tensile tests. Digital Image Correlation (DIC) was used to accurately quantify the specimens’ large strains in a non-contact fashion. A difference in the mechanical properties according to pattern type, proposed hardness combinations, and matrix-to-fiber ratio were evidenced. The specimens V, J1, A1, and C were selected as the best for every type of pattern. Specimens V were chosen as the leading combination since they exhibited the best balance of mechanical properties with the higher values of Modulus of elasticity (2.21 ± 0.17 MPa), maximum strain (1.86 ± 0.05 mm/mm), and tensile strength at break (2.11 ± 0.13 MPa). The approach demonstrates the versatility of PolyJet technology that enables core materials to be tailored based on specific needs. These findings will allow the development of more accurate and realistic computational and 3D printed soft tissue anatomical solutions mimicking something much closer to real tissues.

Cardiac Radiofrequency Ablation Simulation Using a 3D-Printed Bi-Atrial Thermochromic Model

Radiofrequency ablation (RFA) is a treatment used in the management of various arrhythmias including atrial fibrillation. Enhanced training for electrophysiologists through the use of physical simulators has a significant role in improving patient outcomes. The requirements for a high-fidelity simulator for cardiac RFA are challenging and not fully met by any research or commercial simulator at present. In this study, we have produced and evaluated a 3D-printed, bi-atrial model contained in a custom-made enclosure for RFA simulation using a new soft tissue-mimicking polymer, Layfomm-40, combined with thermochromic pigment and barium sulphate in an acrylic paint carrier. We evaluated the conductive properties of Layfomm-40, its sensitivity to RFA, and its visibility in X-ray imaging, and carried a full simulation of RFA in the cardiac catheterization laboratory by an electrophysiologist. We demonstrated that a patient-specific 3D-printed Layfomm-40 bi-atrial model coated with a custom thermochromic/barium sulphate paint was compatible with the CARTO3 electroanatomic mapping system and could be effectively imaged using X-ray fluoroscopy. We demonstrated the effective delivery and visualization of radiofrequency ablation lesions in this model. The simulator meets nearly all the requirements for high-fidelity physical simulation of RFA. The use of such simulators is likely to have impact on the training of electrophysiologists and the evaluation of novel RFA devices.