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.

Preventing the spread of life-threatening gastrointestinal microbes on the surface of a continuously self-disinfecting block polymer.

Highly persistent, drug-resistant and transmissible healthcare pathogens such as Clostridioides difficile (C. difficile) and Candida auris (C. auris) are responsible for causing antibiotic-associated fatal diarrhea and invasive candidiasis, respectively. In this study, we demonstrate that these potentially lethal gastrointestinal microbes can be rapidly inactivated on the solid surface of a self-disinfecting anionic block polymer that inherently generates a water surface layer that is highly acidic (pH < 1) upon hydration. Due to thermodynamic incompatibility between its chemical sequences, the polymer spontaneously self-organizes into a nanostructure that enables proton migration from the interior of a film to the surface via contiguous nanoscale hydrophilic channels, as discerned here by scanning electron and atomic force microscopies, as well as X-ray photoelectron spectroscopy. Here, we report that two strains of C. difficile in the vegetative state and two species of Candida, Candida albicans (C. albicans) and C. auris, are, in most cases, inactivated to the limit of minimum detection. Corresponding electron and optical microscopy images reveal that, upon exposure to the hydrated polymer, the outer microbial membranes display evidence of damage and intracellular material is expelled. Combined with our previous studies of rapid bacterial and viral inactivation, these antimicrobial results are highly encouraging and, if translatable to clinical conditions in the form of self-standing polymer films or coatings, are expected to benefit the welfare of patients in healthcare facilities by continuously preventing the spread of such potentially dangerous microbes.

Surface Mechanical Properties and Topological Characteristics of Thermoplastic Copolyesters after Precisely Controlled Abrasion.

Due to the high probability of surface-to-surface contact of materials during routine applications, surface abrasion remains one of the most challenging factors governing the long-term performance of polymeric materials due to their broad range of tunable mechanical properties, as well as the varied conditions of abrasion (regarding, e.g., rate, load, and contact area). While this concept is empirically mature, a fundamental understanding of mechanical abrasion regarding thermoplastics remains lacking even though polymer abrasion can inadvertently lead to the formation of nano-/microplastics. In the present study, we introduce the concept of precision polymer abrasion (PPA) in conjunction with nanoindentation to elucidate the extent to which controlled wear is experienced by three chemically related thermoplastics under systematically varied abrasion conditions. While depth profiling of one polymer reveals a probe-dependent change in modulus, complementary results from positron annihilation lifetime spectroscopy confirm that the polymer density changes measurably, but not appreciably, with depth over the depth range explored. After a single PPA pass, the surface moduli of the polymers noticeably increase, whereas the corresponding increase in hardness is modest. The dependence of wear volume on the number of PPA passes is observed to reach limiting values for two of the thermoplastics, and application of an empirical model to the data yields estimates of these values for all three thermoplastics. These results suggest that the metrics commonly employed to describe the surface abrasion of polymers requires careful consideration of a host of underlying factors.

An integrated materials approach to ultrapermeable and ultraselective CO2 polymer membranes.

Advances in membrane technologies that combine greatly improved carbon dioxide (CO2) separation efficacy with low costs, facile fabrication, feasible upscaling, and mechanical robustness are needed to help mitigate global climate change. We introduce a hybrid-integrated membrane strategy wherein a high-permeability thin film is chemically functionalized with a patchy CO2-philic grafted chain surface layer. A high-solubility mechanism enriches the concentration of CO2 in the surface layer hydrated by water vapor naturally present in target gas streams, followed by fast CO2 transport through a highly permeable (but low-selectivity) polymer substrate. Analytical methods confirm the existence of an amine surface layer. Integrated multilayer membranes prepared in this way are not diffusion limited and retain much of their high CO2 permeability, and their CO2 selectivity is concurrently increased in some cases by more than ~150-fold.

Morphological Studies of Solution-Crystallized Thermoplastic Elastomers with Polyethylene Endblocks and a Random-Copolymer Midblock.

Styrenic thermoplastic elastomers (TPEs) in the form of triblock copolymers possessing glassy endblocks and a rubbery midblock account for the largest global market of TPEs worldwide, and typically rely on microphase separation of the endblocks and the subsequent formation of rigid microdomains to ensure satisfactory network stabilization. In this study, the morphological characteristics of a relatively new family of crystallizable TPEs that instead consist of polyethylene endblocks and a random-copolymer midblock composed of styrene and (ethylene-co-butylene) moieties are investigated. Copolymer solutions prepared at logarithmic concentrations in a slightly endblock-selective solvent are subjected to crystallization under different time and temperature conditions to ascertain if copolymer self-assembly is directed by endblock crystallization or vice versa. According to transmission electron microscopy, semicrystalline aggregates develop at the lowest solution concentration examined (0.01 wt%), and the size and population of crystals, which dominate the copolymer morphologies, are observed to increase with increasing aging time. Real-space results are correlated with small- and wide-angle X-ray scattering to elucidate the concurrent roles of endblock crystallization and self-assembly of these unique TPEs in solution.

Anion-Specific Water Interactions with Nanochitin: Donnan and Osmotic Pressure Effects as Revealed by Quartz Microgravimetry.

The development of new materials emphasizes greater use of sustainable and eco-friendly resources, including those that take advantage of the unique properties of nanopolysaccharides. Advances in this area, however, necessarily require a thorough understanding of interactions with water. Our contribution to this important topic pertains to the swelling behavior of partially deacetylated nanochitin (NCh), which has been studied here by quartz crystal microgravimetry. Ultrathin films of NCh supported on gold-coated resonators have been equilibrated in aqueous electrolyte solutions (containing NaF, NaCl, NaBr, NaNO3, Na2SO4, Na2SO3, or Na3PO4) at different ionic strengths. As anticipated, NCh displays contrasting swelling/deswelling responses, depending on the ionic affinities and valences of the counterions. The extent of water uptake induced by halide anions, for instance, follows a modified Hofmeister series with F- producing the highest swelling. In marked contrast, Cl- induces film dehydration. We conclude that larger anions promote deswelling such that water losses increase with increasing anion valence. Results such as the ones reported here are critical to ongoing efforts designed to dry chitin nanomaterials and develop bio-based and sustainable materials, including particles, films, coatings, and other nanostructured assemblies, for various devices and applications.

Toward Universal Photodynamic Coatings for Infection Control.

The dual threats posed by the COVID-19 pandemic and hospital-acquired infections (HAIs) have emphasized the urgent need for self-disinfecting materials for infection control. Despite their highly potent antimicrobial activity, the adoption of photoactive materials to reduce infection transmission in hospitals and related healthcare facilities has been severely hampered by the lack of scalable and cost-effective manufacturing, in which case high-volume production methods for fabricating aPDI-based materials are needed. To address this issue here, we examined the antimicrobial efficacy of a simple bicomponent spray coating composed of the commercially-available UV-photocrosslinkable polymer N-methyl-4(4'-formyl-styryl)pyridinium methosulfate acetal poly(vinyl alcohol) (SbQ-PVA) and one of three aPDI photosensitizers (PSs): zinc-tetra(4-N-methylpyridyl)porphine (ZnTMPyP4+), methylene blue (MB), and Rose Bengal (RB). We applied these photodynamic coatings, collectively termed SbQ-PVA/PS, to a variety of commercially available materials. Scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the successful application of the coatings, while inductively coupled plasma-optical emission spectroscopy (ICP-OES) revealed a photosensitizer loading of 0.09-0.78 nmol PS/mg material. The antimicrobial efficacy of the coated materials was evaluated against methicillin-susceptible Staphylococcus aureus ATCC-29213 and human coronavirus strain HCoV-229E. Upon illumination with visible light (60 min, 400-700 nm, 65 ± 5 mW/cm2), the coated materials inactivated S. aureus by 97-99.999% and HCoV-229E by 92-99.999%, depending on the material and PS employed. Photobleaching studies employing HCoV-229E demonstrated detection limit inactivation (99.999%) even after exposure for 4 weeks to indoor ambient room lighting. Taken together, these results demonstrate the potential for photodynamic SbQ-PVA/PS coatings to be universally applied to a wide range of materials for effectively reducing pathogen transmission.

Rapid and Repetitive Inactivation of SARS-CoV-2 and Human Coronavirus on Self-Disinfecting Anionic Polymers.

While the ongoing COVID-19 pandemic affirms an urgent global need for effective vaccines as second and third infection waves are spreading worldwide and generating new mutant virus strains, it has also revealed the importance of mitigating the transmission of SARS-CoV-2 through the introduction of restrictive social practices. Here, it is demonstrated that an architecturally- and chemically-diverse family of nanostructured anionic polymers yield a rapid and continuous disinfecting alternative to inactivate coronaviruses and prevent their transmission from contact with contaminated surfaces. Operating on a dramatic pH-drop mechanism along the polymer/pathogen interface, polymers of this archetype inactivate the SARS-CoV-2 virus, as well as a human coronavirus surrogate (HCoV-229E), to the minimum detection limit within minutes. Application of these anionic polymers to frequently touched surfaces in medical, educational, and public-transportation facilities, or personal protection equipment, can provide rapid and repetitive protection without detrimental health or environmental complications.

Mesophase characteristics of cellulose nanocrystal films prepared from electrolyte suspensions.

Cellulose nanocrystals (CNCs) exhibit a cholesteric mesophase above a critical concentration in aqueous suspensions. Above this concentration, CNCs self-organize into left-handed helicoidal structures that can be preserved in dried, stratified films. In this systematic study, we have prepared optically-active CNC films cast from different electrolyte suspensions and investigated, via circular dichroism and other techniques, the effects of counterion type (six mono/divalent salts, including those responsible for promoting "salting-out" and "salting-in" in the Hofmeister series) and ionic strength on mesomorphic behavior and cholesteric arrangement. The presence of electrolytes influences CNC colloidal stability by compressing the electric double layer and altering interactions among neighboring CNCs and water, thereby affecting the extent to which the CNCs form a mesophase. Interestingly, mesomorphic behavior and CNC alignment appear to be sensitive to cationic radius and charge valence, in which case the optical properties of CNC films can be adjusted for targeted sustainable applications. Such heuristic rules can be valuable for predicting the stability and characteristics of CNC microstructure in designer coatings and thin films prepared by introducing suitable cations prior to film formation.

Cellulose nanofibers and the film-formation dilemma: Drying temperature and tunable optical, mechanical and wetting properties of nanocomposite films composed of waterborne sulfopolyesters.

HYPOTHESIS: Waterborne sulfopolyesters have gained considerable interest as coating materials due to their excellent film-forming and optical properties. Their commercial use has been limited, however, due to their fragile nature. Incorporating cellulose nanofiber (CNF), a sustainable biopolymer, into the polymer matrix is expected to enhance the mechanical integrity of the nanocomposite as these two components synergistically interact. EXPERIMENTS: In this study, we have investigated the suspension and film characteristics of three sulfopolyesters varying in charge density, glass transition temperature and molecular weight, as well as their mixtures with CNF. We have performed steady-shear rheology on mixtures with different CNF loading levels, and resulting films have been subjected to quasistatic uniaxial tensile and water contact-angle tests to elucidate the effects of CNF on mechanical and surface properties. FINDINGS: Addition of CNF to waterborne polyester promotes shear-thinning behavior that remains unaffected by the CNF content. Solid films cast from these suspensions possess enhanced mechanical properties, as well as tailorable surface hydrophilicity, depending on composition and film-drying temperature. Tensile tests reveal that films containing 10 wt% CNF display the greatest mechanical improvements, suggesting the existence of a previously unidentified Goldilocks composition window.

Photodynamic Coatings on Polymer Microfibers for Pathogen Inactivation: Effects of Application Method and Composition.

A substantial increase in the risk of hospital-acquired infections (HAIs) has greatly impacted the global healthcare industry. Harmful pathogens adhere to a variety of surfaces and infect personnel on contact, thereby promoting transmission to new hosts. This is particularly worrisome in the case of antibiotic-resistant pathogens, which constitute a growing threat to human health worldwide and require new preventative routes of disinfection. In this study, we have incorporated different loading levels of a porphyrin photosensitizer capable of generating reactive singlet oxygen in the presence of O2 and visible light in a water-soluble, photo-cross-linkable polymer coating, which was subsequently deposited on polymer microfibers. Two different application methods are considered, and the morphological and chemical characteristics of these coated fibers are analyzed to detect the presence of the coating and photosensitizer. To discern the efficacy of the fibers against pathogenic bacteria, photodynamic inactivation has been performed on two different bacterial strains, Staphylococcus aureus and antibiotic-resistant Escherichia coli, with population reductions of >99.9999 and 99.6%, respectively, after exposure to visible light for 1 h. In response to the current COVID-19 pandemic, we also confirm that these coated fibers can inactivate a human common cold coronavirus serving as a surrogate for the SARS-CoV-2 virus.

Network topology and stability of homologous multiblock copolymer physical gels.

The mechanical properties of physical gels generated by selectively swelling a homologous series of linear multiblock copolymers are investigated by quasistatic uniaxial tensile tests. We use the slip-tube network model to extract the contributions arising from network crosslinks and chain entanglements. The composition dependence of these contributions is established and considered in terms of simulations that identify the probabilities associated with chain conformations. Dynamic rheology provides additional insight into the characteristics and thermal stability of the molecular networks.

Optimization of the Rubber Formulation for Footwear Applications from the Response Surface Method.

Impact force remains the primary cause of foot injury and general discomfort with regard to footwear. The footwear industry traditionally relies on modified elastomers (including natural rubber) whose properties can be physically adjusted by varying the constituents in the rubber formulations. This work aims to investigate the effect of filler/plasticizer fractions on shock attenuation of natural rubber soles. The statistical response surface method (RSM) was used to optimize the loading of natural rubber, fillers (carbon black and china clay) and a plasticizer (paraffinic oil). A novel predictive equation addressing the effects of additives on the physical and mechanical properties of the shoe sole was successfully created using the RSM. Our results demonstrate how the concentrations of these components regulate final properties, such as impact force absorption and hardness, in the commercial manufacture of shoe soles. While a higher loading level of plasticizer promotes reductions in hardness and impact force, as well as energy dissipation, in these modified elastomers, these properties were improved by increasing the filler content.

Quantitative Calorimetric Studies of the Chiral Nematic Mesophase in Aqueous Cellulose Nanocrystal Suspensions.

Aqueous suspensions of cellulose nanocrystals (CNCs) can spontaneously form a chiral nematic mesophase at a critical concentration (c*). Unfortunately, no current analytical technique permits rapid detection of c*. Herein, we introduce a facile and accurate approach to assess c* rapidly (<2 h) from a small sample volume and compare our results with those obtained by conventional methods. Our strategy employs isothermal titration calorimetry (ITC) to measure the heat associated with interactions in the suspension, which can identify the onset of mesophase formation as the heat signature is sensitive to the suspension viscosity and thus capable of detecting small changes in the suspension environment. We measure c* for CNC samples differing in surface charge and aspect ratio, and find that both lower aspect ratios and higher surface charges increase c*. Our ITC results reveal the role of CNC interactions prior to the visual observation of mesophase formation and elucidate mesomorphic effects related to nanocrystals and their suspensions.

Shear-Dependent Structures of Flocculated Micro/Nanofibrillated Cellulose (MNFC) in Aqueous Suspensions.

Cellulosic nanomaterials constitute a topic of growing commercial interest for numerous applications, many of which demand a working knowledge of the rheology of the materials. We demonstrate here that aqueous suspensions of micro/nanofibrillated cellulose (MNFC) exhibit complex shear behavior governed primarily by fibrillar floc dynamics. Regimes corresponding to structure formation, persistence, and breakdown are quantitatively differentiated. We assess the recovery of the network structure as a function of the applied breakdown conditions and identify critical conditions that characterize the floc dynamics as isotropic or anisotropic. A two-step yield behavior generates persistent anisotropic flocs that effectively prohibit recovery of the initial gel structure under certain conditions. Processing within this stress window entails a risk of generating heterogeneous, potentially irreproducible structures and properties. An in-depth understanding of the rheology of aqueous MNFC suspensions and their floc-dominated, rather than fibril-dominated, nature is critical to rationally tailoring properties through judicious selection of processing conditions.

Ionic complexation of endblock-sulfonated thermoplastic elastomers and their physical gels for improved thermomechanical performance.

Thermoplastic elastomers (TPEs) composed of nonpolar triblock copolymers constitute a broadly important class of (re)processable network-forming macromolecules employed in ubiquitous commercial applications. Physical gelation of these materials in the presence of a low-volatility oil that is midblock-selective yields tunably soft TPE gels (TPEGs) that are suitable for emergent technologies ranging from electroactive, phase-change and shape-memory responsive media to patternable soft substrates for flexible electronics and microfluidics. Many of the high-volume TPEs used for these purposes possess styrenic endblocks that are inherently limited by a relatively low glass transition temperature. To mitigate this shortcoming, we sulfonate and subsequently complex (and physically crosslink) the endblocks with trivalent Al3+ ions. Doing so reduces the effective hydrophilicity of the sulfonated endblocks, as evidenced by water uptake measurements, while concurrently enhancing the thermomechanical stability of the corresponding TPEGs. Chemical modification results, as well as morphological and property development, are investigated as functions of the degree of sulfonation, complexation and TPEG composition.

Spectroscopic and Rheological Cross-Analysis of Polyester Polyol Cure Behavior: Role of Polyester Secondary Hydroxyl Content.

The sol-gel transition of a series of polyester polyol resins possessing varied secondary hydroxyl content and reacted with a polymerized aliphatic isocyanate cross-linking agent is studied to elucidate the effect of molecular architecture on cure behavior. Dynamic rheology is utilized in conjunction with time-resolved variable-temperature Fourier-transform infrared spectroscopy to examine the relationship between chemical conversion and microstructural evolution as functions of both time and temperature. The onset of a percolated microstructure is identified for all resins, and apparent activation energies extracted from Arrhenius analyses of gelation and average reaction kinetics are found to depend on the secondary hydroxyl content in the polyester polyols. The similarity between these two activation energies is explored. Gel point suppression is observed in all the resin systems examined, resulting in significant deviations from the classical gelation theory of Flory and Stockmayer. The magnitude of these deviations depends on secondary hydroxyl content, and a qualitative model is proposed to explain the observed phenomena, which are consistent with results previously reported in the literature.

Self-Assembly of a Midblock-Sulfonated Pentablock Copolymer in Mixed Organic Solvents: A Combined SAXS and SANS Analysis.

Ionic, and specifically sulfonated, block copolymers are continually gaining interest in the soft materials community due to their unique suitability in various ion-exchange applications such as fuel cells, organic photovoltaics, and desalination membranes. One unresolved challenge inherent to these materials is solvent templating, that is, the translation of self-assembled solution structures into nonequilibrium solid film morphologies. Recently, the use of mixed polar/nonpolar organic solvents has been examined in an effort to elucidate and control the solution self-assembly of sulfonated block copolymers. The current study sheds new light on micellar assemblies (i.e., those with the sulfonated blocks comprising the micellar core) of a midblock-sulfonated pentablock copolymer in polar/nonpolar solvent mixtures by combining small-angle X-ray and small-angle neutron scattering. Our scattering data reveal that micelle size depends strongly on overall solvent composition: micelle cores and coronae grow as the fraction of nonpolar solvent is increased. Universal model fits further indicate that an unexpectedly high fraction of the micelle cores is occupied by polar solvent (60-80 vol %) and that partitioning of the polar solvent into micelle cores becomes more pronounced as its overall quantity decreases. This solvent presence in the micelle cores explains the simultaneous core/corona growth, which is otherwise counterintuitive. Our findings provide a potential pathway for the formation of solvent-templated films with more interconnected morphologies due to the greatly solvated micellar cores in solution, thereby enhancing the molecular, ion, and electron-transport properties of the resultant films.

Dielectric and Resistive Heating of Polymeric Media: Toward Remote Thermal Activation of Stimuli-Responsive Soft Materials.

Stimuli-responsive soft materials are becoming increasingly important in a wide range of contemporary technologies, and methods by which to promote thermal stimulation remotely are of considerable interest for controllable device deployment, particularly in inaccessible environments such as outer space. Until now, remote thermal stimulation of responsive polymers has relied extensively on the use of nanocomposites wherein embedded nanoparticles/structures are selectively targeted for heating purposes. In this study, an alternative remote-heating mechanism demonstrates that the dielectric and resistive thermal losses introduced upon application of an alternating current generate sufficient heat to raise the temperature of a neat polyimide by over 70 °C within ≈10 s. Thermal imaging is used here to measure current-induced temperature changes of polymeric media, and a proposed analytical model yields predictions that compare reasonably well with experimental data, confirming that such remote heating is viable. Conditions permitting a shape-memory polymer possessing a melting transition and susceptible to dielectric actuation to achieve continuous electrostrain-temperature cycling are identified.

Incorporation of Metallic Species into Midblock-Sulfonated Block Ionomers.

Block ionomers can, in the same fashion as their neutral block copolymer analogs, microphase-order into various nanoscale morphologies. The added benefit of a copolymer possessing a charged species is that the resultant block ionomer becomes amphiphilic and capable of imbibing polar liquids, including water. This characteristic facilitates incorporation of metallic species into the soft nanostructure for a wide range of target applications. In this study, the nonpolar and polar constituents of solvent-templated midblock-sulfonated block ionomers (SBIs) are first selectively metallated for complementary morphological analysis. Next, four different salts, with cationic charges ranging from +1 to +3, are introduced into three hydrated SBIs varying in their degree of sulfonation (DOS), and cation uptake is measured as a function of immersion time. These results indicate that uptake generally increases with increasing salt concentration, cationic charge, and specimen DOS. Swelling and nanoindentation measurements conducted at ambient temperature demonstrate that water uptake decreases, while the surface modulus increases, with increasing cationic charge. Chemical spectra acquired from energy-dispersive X-ray spectroscopy (EDS) confirm the presence of each of the ion-exchanged species, and corresponding EDS chemical maps reveal that the spatial distribution of these species is relatively uniform throughout the block ionomer films.