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At least 109 records · Page 6

On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers

For many decades, silicone elastomers with oil incorporated have served as fouling-release coating for marine applications. In a comprehensive study involving a series of laboratory-based marine fouling assays and extensive global field studies of up to 2-year duration, we compare polydimethylsiloxane (PDMS) coatings of the same composition loaded with oil via two different methods. One method used a traditional, one-pot pre-cure oil addition approach (o-PDMS) and another method used a newer post-cure infusion approach (i-PDMS). The latter displays a substantial improvement in biofouling prevention performance that exceeds established commercial silicone-based fouling-release coating standards. We interpret the differences in performance between one-pot and infused PDMS by developing a mechanistic model based on the Flory–Rehner theory of swollen polymer networks. Using this model, we propose that the chemical potential of the incorporated oil is a key consideration for the design of future fouling-release coatings, as the improved performance is driven by the formation and stabilization of an anti-adhesion oil overlayer on the polymer surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanically tunable elastomer and cellulose nanocrystal composites as scaffolds for in vitro cell studies

Considering the range of properties that various materials offer for tissue engineering it has come clear that no one size fits all, as no one material can be fully effective for all types of cell and ensuing tissues. Scaffolds need to address the delicate balance between cell-scaffold interactions and the particular requirements of different cell types. To address the specific needs for the controlled growth of tissues it is imperative to match scaffold stiffness and elasticity to cells and tissues of interest to promote regeneration success. We here report an efficient method for creating scaffolds of tunable elasticity by generating a range of composites based on ε-caprolactone-D,L-lactide-based elastomer with cellulose nanocrystals (CNC). Two specific composites with different Young's modulus (E) values (~5 MPa and ~15 MPa) were selected and fully evaluated by tensile tests, Fourier Transform-Infrared (FT-IR), Scanning Electron Microscopy (SEM), contact angle measurements, and X-ray scattering. As a proof of concept this work studies how matching the scaffold's mechanical properties to neuroblastomas and fibroblasts cells affects cell behavior. Specifically, the composite with lower E, by design with less CNC content, is more suitable for neuroblastomas, whereas the one with higher E via higher CNC content is more suited for human dermal fibroblasts. The approach of matching cells with appropriate mechanical environments can provide important insights into fundamental cell behaviors.

36 MATERIALS SCIENCE↗

PolyDODT: a macrocyclic elastomer with unusual properties

The effect of reaction conditions on the structure of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H 2 O 2 and air was investigated. 800 MHz (1 and 2D) NMR was used to investigate the polymer structures. Sensitivity analysis provided direct evidence for high purity cyclic polyDODT up to M n ~ 100 000 g mol –1 . Here, comparative analysis by High Resolution Multidetector Size Exclusion Chromatography (SEC) using integrated data showed that the cycles had lower viscosity and were more compact (both for R g and R h ) than linear samples of similar molecular weight. However, differential data revealed unusual behavior. While lower molecular weight cyclic polymers eluted later and had lower intrinsic viscosity than their linear counterparts at the same molecular weight, at higher molecular weights the polymers showed strange behavior: both the diffusion coefficient measured by Quasielastic Light Scattering (QELS) and Mark–Houwink–Sakurada plots of intrinsic viscosity for linear and cyclic polyDODT were found to converge. R3P, an aqueous based “green” method is capable of producing polymers at the 10–100 g scale in the lab, which will allow more detailed studies of this new class of biodegradable elastomers so further experimentation can be performed to elucidate the reasons for the unusual findings.

36 MATERIALS SCIENCE↗

Tunable thermoplastic elastomer gels derived from controlled-distribution triblock copolymers with crystallizable endblocks

Thermoplastic elastomers (TPEs), a commercially important category of triblock copolymers, are employed alone or upon physical modification with a midblock-selective oil (to form TPE gels, TPEGs) in a broad range of contemporary technologies. While most copolymers in this class of self-networking macromolecules possess glassy polystyrene endblocks and a rubbery polydiene or polyolefin midblock, we investigate TPEGs fabricated from a novel controlled-distribution copolymer with crystallizable polyolefin endblocks and a random-copolymer midblock. According to both electron microscopy and small-angle scattering, the morphologies of these TPEGs remain largely invariant up to 40 wt% oil and then transform considerably at higher oil levels. Although reductions in endblock melting point and crystallinity measured by thermal calorimetry accompany increasing oil content, mechanical properties such as the uniaxial strain at break and fracture toughness improve in some cases by over 50% between 5 and 40 wt% oil. In fact, the strain at break can reach 2500% within this range, thereby confirming that (i) the structure–property relationships of these unique TPEGs are highly composition-tunable and (ii) these TPEGs, stabilized by crystallizable endblocks, provide an attractive alternative for ultrasoft and stretchy recyclable materials.

36 MATERIALS SCIENCE↗

The effect of polymer stiffness on magnetization reversal of magnetorheological elastomers

Ultrasoft magnetorheological elastomers (MREs) offer convenient real-time magnetic field control of mechanical properties that provides a means to mimic mechanical cues and regulators of cells in vitro. Here, we systematically investigate the effect of polymer stiffness on magnetization reversal of MREs using a combination of magnetometry measurements and computational modeling. Poly-dimethylsiloxane-based MREs with Young’s moduli that range over two orders of magnitude were synthesized using commercial polymers Sylgard™ 527, Sylgard 184, and carbonyl iron powder. The magnetic hysteresis loops of the softer MREs exhibit a characteristic pinched loop shape with almost zero remanence and loop widening at intermediate fields that monotonically decreases with increasing polymer stiffness. A simple two-dipole model that incorporates magneto-mechanical coupling not only confirms that micrometer-scale particle motion along the applied magnetic field direction plays a defining role in the magnetic hysteresis of ultrasoft MREs but also reproduces the observed loop shapes and widening trends for MREs with varying polymer stiffnesses.

36 MATERIALS SCIENCE↗

Twist again: Dynamically and reversibly controllable chirality in liquid crystalline elastomer microposts

Photoresponsive liquid crystalline elastomers (LCEs) constitute ideal actuators for soft robots because their light-induced macroscopic shape changes can be harnessed to perform specific articulated motions. Conventional LCEs, however, do not typically exhibit complex modes of bending and twisting necessary to perform sophisticated maneuvers. Here, we model LCE microposts encompassing side-chain mesogens oriented along a magnetically programmed nematic director, and azobenzene cross-linkers, which determine the deformations of illuminated posts. On altering the nematic director orientation from vertical to horizontal, the post’s bending respectively changes from light-seeking to light-avoiding. Moreover, both modeling and subsequent experiments show that with the director tilted at 45°, the initially achiral post reversibly twists into a right- or left-handed chiral structure, controlled by the angle of incident light. We exploit this photoinduced chirality to design “chimera” posts (encompassing two regions with distinct director orientations) that exhibit simultaneous bending and twisting, mimicking motions exhibited by the human musculoskeletal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Topology control of human fibroblast cells monolayer by liquid crystal elastomer

Eukaryotic cells in living tissues form dynamic patterns with spatially varying orientational order that affects important physiological processes such as apoptosis and cell migration. The challenge is how to impart a predesigned map of orientational order onto a growing tissue. Here, we demonstrate an approach to produce cell monolayers of human dermal fibroblasts with predesigned orientational patterns and topological defects using a photoaligned liquid crystal elastomer (LCE) that swells anisotropically in an aqueous medium. The patterns inscribed into the LCE are replicated by the tissue monolayer and cause a strong spatial variation of cells phenotype, their surface density, and number density fluctuations. Unbinding dynamics of defect pairs intrinsic to active matter is suppressed by anisotropic surface anchoring allowing the estimation of the elastic characteristics of the tissues. The demonstrated patterned LCE approach has potential to control the collective behavior of cells in living tissues, cell differentiation, and tissue morphogenesis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Programming liquid crystal elastomers for multistep ambidirectional deformability

Ambidirectionality, which is the ability of structural elements to move beyond a reference state in two opposite directions, is common in nature. However, conventional soft materials are typically limited to a single, unidirectional deformation unless complex hybrid constructs are used. We exploited the combination of mesogen self-assembly, polymer chain elasticity, and polymerization-induced stress to design liquid crystalline elastomers that exhibit two mesophases: chevron smectic C (cSmC) and smectic A (SmA). Inducing the cSmC-SmA–isotropic phase transition led to an unusual inversion of the strain field in the microstructure, resulting in opposite deformation modes (e.g., consecutive shrinkage or expansion and right-handed or left-handed twisting and tilting in opposite directions) and high-frequency nonmonotonic oscillations. Further, this ambidirectional movement is scalable and can be used to generate Gaussian transformations at the macroscale.

36 MATERIALS SCIENCE↗

Apparatus, system, and method for radiation hardened plastic and flexible elastomer scintillator

A scintillating material that is a radiation hardened plastic and flexible elastomer is disclosed. The material is useful in a wide range of high energy particle environments and can be used to create detectors. Such detectors can be used in physics experiments or in medical treatment or imaging. The scintillator can be radiation hardened so as to allow for an extended lifetime over other materials.

Akgun, Ugur↗

Stereolithography additive manufacturing of photoaligned liquid crystal elastomers

A method of forming a three-dimensional structure of liquid crystal (LC) elastomers includes contacting a resin layer of LC oligomers with a layer of photoalignment material, and exposing a portion of photoalignment material to light for aligning the portion of photoalignment material in a first orientation. The LC oligomers adjacent the illuminated portion of photoalignment material align to the first orientation of the illuminated portion. The portion of aligned LC oligomers of the resin layer are cured. Operations for forming additional layers include creating a relative movement of the resin layer away from the photoalignment material, contacting another resin layer with the photoalignment material, and exposing another portion of photoalignment material to light for aligning the photoalignment material in a different orientation. The LC oligomers adjacent the illuminated portion of photoalignment material align to the different orientation, and the portion of aligned LC oligomers of the resin layer are cured.

Moran, Bryan D.↗

Effect of Molecular Weight on the Morphology of a Polymer Semiconductor–Thermoplastic Elastomer Blend

Abstract Polymer semiconductors (PSCs) are essential active materials in mechanically stretchable electronic devices. However, many exhibit low fracture strain due to their rigid chain conformation and the presence of large crystalline domains. Here, a PSC/elastomer blend, poly[((2,6‐bis(thiophen‐2‐yl)‐3,7‐bis(9‐octylnonadecyl)thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene)‐5,5′‐diyl)(2,5‐bis(8‐octyloctadecyl)‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione)‐5,5′‐diyl]] (P2TDPP2TFT4) and polystyrene‐ block ‐poly(ethylene‐ran‐butylene)‐ block ‐polystyrene (SEBS) are systematically investigated. Specifically, the effects of molecular weight of both SEBS and P2TDPP2TFT4 on the resulting blend morphology, mechanical, and electrical properties are explored. In addition to commonly used techniques, atomic force microscopy‐based nanomechanical images are used to provide additional insights into the blend film morphology. Opposing trends in SEBS‐induced aggregation are observed for the different P2TDPP2TFT4 molecular weights upon increasing the SEBS molecular weight from 87 to 276 kDa. Furthermore, these trends are seen in device performance trends for both molecular weights of P2TDPP2TFT4. SEBS molecular weight also has a substantial influence on the mesoscale phase separation. Strain at fracture increases dramatically upon blending, reaching a maximum value of 640% ± 20% in the blended films measured with film‐on‐water method. These results highlight the importance of molecular weight for electronic devices. In addition, this study provides valuable insights into appropriate polymer selections for stretchable semiconducting thin films that simultaneously possess excellent mechanical and electrical properties.

36 MATERIALS SCIENCE↗

H-Mat Hydrogen Compatibility of Polymers and Elastomers

The H2@Scale program of the U.S. Department of Energy (DOE) Fuel Cell Technologies Office is supporting work on the hydrogen compatibility of polymers to improve the durability and reliability of materials for hydrogen infrastructure. The hydrogen compatibility program (H-Mat) seeks “to address the challenges of hydrogen degradation by elucidating the mechanisms of hydrogen-materials interactions with the goal of providing science-based strategies to design materials, (micro)structures, and morphology with improved resistance to hydrogen degradation.” This research has observed interactions of hydrogen and pressure with model rubber-material compounds resulting in volume change and compression-set differences in the materials. The materials were investigated using helium-ion microscopy (HeIM), which revealed significant morphological changes in the plasticizer-incorporating compounds after exposure, as evidenced by time-of-flight secondary ion mass spectrometry. Additional studies using transmission electron microscopy and nuclear magnetic resonance were performed to correlate morphological change to potential chemical change in the materials.

08 HYDROGEN↗