Using the Quartz Crystal Microbalance to Monitor the Curing of Drying Oils.

Drying oils such as linseed oil form a polymer network through a complex free-radical polymerization process. We have studied polymerization in this challenging class of polymers using a quartz crystal microbalance (QCM). The QCM is able to measure the evolution of polymer mass and mechanical properties as the oil transitions from a liquid-like to a solid-like state. Measurements using bulk materials and thin films provide information about the initial polymerization phase as well as the evolution of the mass and mechanical properties over the first two years of cure. The temperature-dependent response of the cured linseed oil films was also measured. These results were combined with previously published results obtained from traditional dynamic mechanical analysis to give a unified picture of the properties of these materials across a very broad temperature range.

Tailoring Interactions of Random Copolymer Polyelectrolyte Complexes to Remove Nanoplastic Contaminants from Water.

We investigate the usage of polyelectrolyte complex materials for water remediation purposes, specifically their ability to remove nanoplastics from water, on which there is currently little to no prior research. We demonstrate that oppositely charged random copolymers are effective at quantitatively removing nanoplastic contamination from aqueous solution. The mechanisms underlying this remediation ability are explored through computational simulations, with corroborating quartz crystal microbalance adsorption experiments. We find that hydrophobic nanostructures and interactions likely play an important role.

Functionalizing a Polyelectrolyte Complex with Chitosan Derivatives to Tailor Membrane Surface Properties.

Polyelectrolyte complex (PEC) materials show promise in the development of tunable membranes for aqueous and organic solvent separations, as well as in the creation of surface layers for fouling control. In this study, we developed a polyelectrolyte complex (PEC) functionalized by negatively charged carboxymethyl chitosan (CMC-) and positively charged quaternized chitosan (QC+) to tailor its surface properties and antibacterial efficacy. CMC- and QC+ were prepared and characterized using FT-IR and 1H NMR, which confirmed the presence of the carboxymethyl group and trimethylammonium group in CMC- and QC+ with 65.6% and 83.9% substitution, respectively. The CMC- functionalized PEC (CMC-/PEC) and QC+ functionalized PEC materials (QC+/PEC) were evaluated for their stability in water, resistance to organic and inorganic adsorption, and antibacterial action against a model microorganism, Pseudomonas putida. The results showed no release of chitosan derivatives after adsorption, and CMC-/PEC and QC+/PEC exhibited charge-based, selective repulsion of model organic and inorganic substances. Moreover, the functionalized PEC surfaces displayed lower bacterial attachment due to their smoother surfaces as compared to the bare ceramic membrane and their antimicrobial properties. Among the PEC samples, CMC-/PEC had the lowest cell attachment, while QC+/PEC showed the highest attachment due to electrostatic attraction. The ceramic and bare PEC surfaces were negligibly bactericidal, while cell viability decreased to 34.4 ± 10.2% and 30.6 ± 8.2% with the CMC-/PEC and QC+/PEC surfaces, respectively. In the filtration experiments, the unmodified PEC and CMC-/PEC showed lower rates of flux decline due to organic fouling than did the bare ceramic or QC+/PEC due to electrostatic repulsion. Furthermore, PECs as protective layers promoted much higher flux recoveries than simply backwashing the uncoated membranes. This surface tunability, then, enhances the potential of PECs either as fouling resistant materials or as a method to create a sacrificial, protective layer on surfaces that once fouled can be dissolved and re-established.

Quantitative Rheometry of Thin Soft Materials Using the Quartz Crystal Microbalance with Dissipation.

In the inertial limit, the resonance frequency of the quartz crystal microbalance (QCM) is related to the coupled mass on the quartz sensor through the Sauerbrey expression that relates the mass to the change in resonance frequency. However, when the thickness of the film is sufficiently large, the relationship becomes more complicated and both the frequency and damping of the crystal resonance must be considered. In this regime, a rheological model of the material must be used to accurately extract the adhered film's thickness, shear modulus, and viscoelastic phase angle from the data. In the present work we examine the suitability of two viscoelastic models, a simple Voigt model ( Physica Scripta 1999, 59, 391-396) and a more realistic power-law model ( Langmuir 2015, 31, 4008-4017), to extract the rheological properties of a thermoresponsive hydrogel film. By changing temperature and initial dry film thickness of the gel, the operation of QCM was traversed from the Sauerbrey limit, where viscous losses do not impact the frequency, through the regime where the QCM response is sensitive to viscoelastic properties. The density-shear modulus and the viscoelastic phase angle from the two models are in good agreement when the shear wavelength ratio, d/λ n, is in the range of 0.05-0.20, where d is the film thickness and λ n is the wavelength of the mechanical shear wave at the nth harmonic. We further provide a framework for estimating the physical properties of soft materials in the megahertz regime by using the physical behavior of polyelectrolyte complexes. This provides the user with an approximate range of allowable film thicknesses for accurate viscoelastic analysis with either model, thus enabling better use of the QCM-D in soft materials research.

pH-Controlled Electrochemical Deposition of Polyelectrolyte Complex Films.

Polyelectrolyte complex (PEC) films made from oppositely charged polymer chains have applications as drug-delivery vehicles, separation membranes, and biocompatible coatings. Conventional layer-by-layer techniques for polyelectrolyte coatings are low-throughput and multistep processes that are quite slow for building films on the order of micrometers. In this work, PEC films are electrochemically deposited using a rapid one-pot method, yielding thick (1 µm) films within short experimental time scales (5 min). This rapid electrodeposition is achieved by exploiting the reduction of hydrogen peroxide at mild electrode potentials that avoid water electrolysis yet trigger the pH-responsive self-assembly of a PEC film composed of poly(acrylic) acid and poly(allylamine) HCl. In situ rheology using an electrochemical quartz crystal microbalance quantified the shear modulus-density product of the deposited layer to be on the order of 107 Pa g/cm3 at a frequency of 15 MHz, with a viscoelastic phase angle of approximately 50°. This electrodeposition scheme furthers the development of PEC coatings for more high-throughput applications, where a fast and efficient single-step approach would be desirable for obtaining coatings.

Solubility and interfacial segregation of salts in ternary polyelectrolyte blends.

Solid Polymer Electrolytes (SPEs) consisting of ternary blends of charged polymer, neutral polymer, and plasticizer or salt have received much interest for their low volatility and high flexibility of polymers with ion-selective conductivity of the charge-carrying backbone. It has been shown that in these polyelectrolyte blends, where the dielectric constant is relatively low, ionic correlations can significantly influence the miscibility, inducing phase separation even at negative values of χN. Here we present a comprehensive study of phase behavior and interfacial segregation upon the addition of a tertiary component in blends of charged and neutral homopolymers. Using a hybrid of self-consistent field and liquid state theories (SCFT-LS), we investigate the bulk miscibility and the distribution of ions across the interface, looking at interfacial adsorption and selectivity of the minority component. We demonstrate that the competition between ionic correlations and ion entropy induces complex charge-dependent selectivity that can be tuned by the value of Γ, the ionic correlation strength. We show that charge interactions can have a pronounced effect on the interfacial width and tension, especially at low χN.

Anodic Electrodeposition of a Cationic Polyelectrolyte in the Presence of Multivalent Anions.

The electrochemical quartz crystal microbalance (QCM) was used to investigate the deposition of poly(allylamine hydrochloride) (PAH) with molybdate anions under anodic conditions. The PAH-molybdate complex was used as a model system to understand possible deposition criteria which may be relevant to the formation of proteinaceous films on CoCrMo hip implants. Data indicate that PAH deposition will occur above ∼0.60 V vs SCE if molybdate anions are present in the electrolyte above a critical concentration, and if the polymer concentration remains below a critical value. Numerical modeling and dynamic light scattering (DLS) studies were performed to understand the conditions that enable deposition to occur at these potentials. The results indicate that PAH-molybdate complexes form most efficiently when the polyvalent positive charge and polyvalent negative charge in the system are in an optimum range with respect to each other.

Viscoelastic properties of electrochemically deposited protein/metal complexes.

The interfacial gelation of proteins at metallic surfaces was investigated with an electrochemical quartz crystal microbalance (QCM). When Cr electrodes were corroded in proteinaceous solutions, it was found that gels will form at the Cr surfaces if molybdate ions are also present in the solution. Gelation is reversible and can also be controlled with the electrochemical potential at the electrode. Further, a method was developed to characterize the viscoelastic properties of thin films in liquid media using the QCM as a high-frequency rheometer. By measuring the frequency and dissipation at multiple harmonics of the resonance frequency, the viscoelastic phase angle, density-modulus product, and areal mass of a film can be determined. The method was applied to characterize the protein films, demonstrating that they have a phase angle near 55° and a density-modulus product of ≈10(7) Pa·g/cm(3). Data imply that the gels are composed of a weakly cross-linked proteinaceous network with properties similar to albumin solutions with concentrations in the range of ≈40 wt %.

High-frequency rheological characterization of homogeneous polymer films with the quartz crystal microbalance.

We utilize quartz crystal resonators operating at multiple resonant harmonics to measure the high-frequency rheological properties of materials with a broad range of viscoelastic properties. The technique is demonstrated with poly(t-butyl acrylate) films in the vicinity of the calorimetrically determined glass transition and with rubbery polyisoprene films. The technique is a noncontact technique that can be used to quantify the temperature or time-dependent viscoelastic response in homogeneous films with thicknesses in the micrometer range. This work complements the ability of the resonators to quantify the viscoelastic behavior of viscoelastic polymer solutions and simple Newtonian liquids. For each material we obtain the density-shear modulus product and the viscoelastic phase angle at frequencies of 5 and 15 MHz. A standardized analysis protocol is described that enables this information to be obtained reliably and accurately. The polyisoprene data are found to be in good agreement with measurements obtained by dynamic mechanical analysis using extrapolated temperature shift factors.

Formation and mechanical characterization of ionically crosslinked membranes at oil-water interfaces.

Here we report on the preparation and mechanical characterization of a 2-D self-assembled membrane formed by ionically crosslinking the polyelectrolyte parts of a gradient amphiphilic copolymer at oil and water interfaces. To fabricate these membranes, chloroform solutions of styrene-acrylic acid copolymers were suspended as pendant drops in an aqueous embedding phase. Due to the amphiphilic nature of these molecules, the copolymer chains migrate to the oil-water interface creating an interfacial layer. Upon the addition of zinc acetate to the embedding phase, crosslinks between copolymer molecules are formed via zinc-carboxylate complexes. While ionically crosslinked block copolymer membranes were critically damaged after one expansion cycle, ionically crosslinked gradient copolymers formed durable membranes that maintained their physical integrity through multiple expansion-compression-expansion cycles. This difference in mechanical behavior is attributed to the fact that gradient copolymers are more effective interfacial modifiers and have a significantly different molecular alignment at the oil-water interface. Additionally by changing the incubation time from 20 to 30 minutes, the low-strain dilatational modulus of these membranes was significantly increased due to higher interfacial coverage and crosslinking density. Longer incubation times also led to a distinct yield point and plastic deformation behavior at larger strains. Further mechanical characterization of the membranes showed that they can be quite robust and that by replacing the internal oil phase with an aqueous solution, future testing of membrane filtration and permeation may be possible.

Dominant role of molybdenum in the electrochemical deposition of biological macromolecules on metallic surfaces.

The corrosion of CoCrMo, an alloy frequently used in orthopedic implants, was studied with an electrochemical quartz crystal microbalance (QCM) in three physiologically relevant solutions. Mass changes were measured during potentiodynamic tests, showing material deposition in protein solutions at potential levels that caused mass loss when the proteins were not present. X-ray photoelectron spectroscopy (XPS) data indicated that the deposited material was primarily organic and therefore was most likely derived from proteins in the electrolyte. Material deposition consistently occurred at a critical potential and was not dependent on the current density or total charge released into solution. Corrosion studies on pure Co, Cr, and Mo in protein solutions found material deposition only on Mo. We hypothesize that organic deposition results from the interaction of Mo(VI) with proteins in the surrounding solution. The organic layer is reminiscent of tribochemical reaction layers that form on the surface of CoCrMo hip bearings, suggesting that these types of layers can be formed by purely electrochemical means.

Large deformation and adhesive contact studies of axisymmetric membranes.

A model membrane contact system consisting of an acrylic copolymer membrane and a PDMS substrate was utilized to evaluate a recently developed nonlinear large-deformation adhesive contact analysis. Direct measurements of the local membrane apex strain during noncontact inflation indicated that the neo-Hookean model provides an accurate measure of membrane strain and supports its use as the strain energy function for the analysis. Two membrane contact geometries, exhibiting significantly different strain distributions during withdrawal, were investigated. The first examines the wet contact of an air pressurized membrane. The second looks at the dry contact of a fluid deformed membrane in which a stepper motor controls membrane-substrate separation. A time-dependent modulus emerges from the analysis, with principal tensions obtained from a comparison of predicted and experimental membrane profiles. The applicability of this numerical analysis for determining membrane tension, however, is limited by wrinkling instabilities and viscoelasticity. For this reason, a conceptually simpler method, based on the direct measurement of the membrane tension and contact angle, was also utilized. The traditional peel energy defined with this direct measurement accurately described the membrane/substrate adhesive interactions, giving well-defined peel energies that were independent of the detailed strain state of the membrane.

In vitro assessment of varying peptide surface density on the suppression of angiogenesis by micelles displaying αvß3 blocking peptides.

Ligand targeted therapy (LTT) is a precision medicine strategy that can selectively target diseased cells while minimizing off-target effects on healthy cells. Integrin-targeted LTT has been developed recently for angiogenesis-related diseases. However, the clinical success is based on the optimal design of the nanoparticles for inducing receptor clustering within the cell membrane. The current study focused on determining the surface density of Ser-Asp-Val containing anti-integrin heptapeptide on poly (ethylene glycol)-b-poly(propylene sulfide) micelles (MC) required for anti-angiogenic effects on HUVECs. Varying peptide density on PEG-b-PPS/Pep-PA MCs (Pep-PA-Peptide-palmitoleic acid) was used in comparison to a random peptide (SGV) and cRGD (cyclic-Arginine-Glycine-Aspartic acid) construct at 5%-density on MCs. Immunocytochemistry using CD51/CD31 antibody was performed to study the integrin blocking by MCs. In addition, the expression of VWF and PECAM-1, cell migration and tube formation was evaluated in the presence of PEG-b-PPS/Pep-PA MCs. The results show PEG-b-PPS/SDV-PA MCs with 5%-peptide density to achieve significantly higher αvß3 blocking compared to random peptide as well as cRGD. In addition, αvß3 blocking via MCs further reduced the expression of vWF and PECAM-1 angiogenesis protein expression in HUVECs. Although a significant level of integrin blocking was observed for 1%-peptide density on MCs, the cell migration and tube formation were not significantly affected. In conclusion, the results of this study demonstrate that the peptide surface density on PEG-b-PPS/Pep-PA MCs has a significant impact in integrin blocking as well as inhibiting angiogenesis during LTT. The outcomes of this study provides insight into the design of ligand targeted nanocarriers for various disease conditions.

Crack Surface Analysis of Elastomers Using Transfer Learning.

Cracks that form during fatigue offer critical information regarding the fracture process of the associated material, such as the crack speed, energy dissipation, and material stiffness. Characterization of the surfaces formed after these cracks have propagated through the material can provide important information complementary to other in-depth analyses. However, because of the complex nature of these cracks, their characterization is difficult, and most of the established characterization techniques are inadequate. Recently, Machine Learning techniques are being applied to image-based material science problems in predicting structure-property relations. Convolutional neural networks (CNNs) have proven their capacity on modeling complex and diverse images. The downside of CNNs for supervised learning is that that they require large amounts of training data. One work-around is using a pre-trained model, i.e., transfer learning (TL). However, TL models cannot be used directly without modification. In this paper, to use TL for crack surface feature-property mapping, we propose to prune the pre-trained model to retain the weights of the first several convolutional layers. Those layers are then used to extract relevant underlying features from the microstructural images. Next, principal component analysis (PCA) is used to further reduce the feature dimension. Finally, the extracted crack features together with the temperature effect are correlated with the properties of interest using regression models. The proposed approach is first tested on artificial microstructures created by spectral density function reconstruction. It is then applied to experimental data of silicone rubbers. With the experimental data, two analyses are performed: (i) analysis of the correlation of the crack surface feature and material property and (ii) predictive model for property estimation, whereby the experiments can be potentially replaced altogether.

Quantitative high-throughput measurement of bulk mechanical properties using commonly available equipment.

Machine learning approaches have introduced an urgent need for large datasets of materials properties. However, for mechanical properties, current high-throughput measurement methods typically require complex robotic instrumentation, with enormous capital costs that are inaccessible to most experimentalists. A quantitative high-throughput method using only common lab equipment and consumables with simple fabrication steps is long desired. Here, we present such a technique that can measure bulk mechanical properties in soft materials with a common laboratory centrifuge, multiwell plates, and microparticles. By applying a homogeneous force on the particles embedded inside samples in the multiwell plate using centrifugation, we show that our technique measures the fracture stress of gels with similar accuracy to a rheometer. However, our method has a throughput on the order of 103 samples per run and is generalizable to virtually all soft material systems. We hope that our method can expedite materials discovery and potentially inspire the future development of additional high-throughput characterization methods.

Electric Field Controlled Self-Assembly of Hierarchically Ordered Membranes.

Self-assembly in the presence of external forces is an adaptive, directed organization of molecular components under nonequilibrium conditions. While forces may be generated as a result of spontaneous interactions among components of a system, intervention with external forces can significantly alter the final outcome of self-assembly. Superimposing these intrinsic and extrinsic forces provides greater degrees of freedom to control the structure and function of self-assembling materials. In this work we investigate the role of electric fields during the dynamic self-assembly of a negatively charged polyelectrolyte and a positively charged peptide amphiphile in water leading to the formation of an ordered membrane. In the absence of electric fields, contact between the two solutions of oppositely charged molecules triggers the growth of closed membranes with vertically oriented fibrils that encapsulate the polyelectrolyte solution. This process of self-assembly is intrinsically driven by excess osmotic pressure of counterions, and the electric field is found to modify the kinetics of membrane formation, and also its morphology and properties. Depending on the strength and orientation of the field we observe a significant increase or decrease of up to nearly 100% in membrane thickness, as well as the controlled rotation of nanofiber growth direction by 90 degrees, resulting in a significant increase in mechanical stiffness. These results suggest the possibility of using electric fields to control structure in self-assembly processes involving diffusion of oppositely charged molecules.

Extreme strain localization and sliding friction in physically associating polymer gels.

Model physically associating gels deformed in shear over a wide range of reduced rates displayed evidence of strain localization. The nonlinear stress responses and inhomogeneous velocity profiles observed during shear rheometry coupled with particle tracking velocimetry were associated with the occurrence of rate-dependent banding and fracture-like responses in the gel. Scaling law analysis from traditional sliding friction studies suggests that, at the molecular level, deformation is confined to a shear zone with thickness comparable to the mesh size of the gel, the smallest structurally relevant length scale in the gel.

Sterilizable and Reusable UV-Resistant Graphene-Polyurethane Elastomer Composites.

Shortages of personal protective equipment (PPE) at the start of the COVID-19 pandemic caused medical workers to reuse medical supplies such as N95 masks. While ultraviolet germicidal irradiation (UVGI) is commonly used for sterilization, UVGI can also damage the elastomeric components of N95 masks, preventing effective fit and thus weakening filtration efficacy. Although PPE shortage is no longer an acute issue, the development of sterilizable and reusable UV-resistant elastomers remains of high interest from a long-term sustainability and health perspective. Here, graphene nanosheets, produced by scalable and sustainable exfoliation of graphite in ethanol using the polymer ethyl cellulose (EC), are utilized as UV-resistant additives in polyurethane (PU) elastomer composites. By increasing the graphene/EC loading up to 1 wt %, substantial UV protection is imparted by the graphene nanosheets, which strongly absorb UV light and hence suppress photoinduced degradation of the PU matrix. Additionally, graphene/EC provides mechanical reinforcement, such as increasing Young's modulus, elongation at break, and toughness, with negligible changes following UV exposure. These graphene/EC-PU composites remain mechanically robust over at least 150 sterilization cycles, enabling safe reuse following UVGI. Beyond N95 masks, these UVGI-compatible graphene/EC-PU composites have potential utility in other PPE applications to address the broader issue of single-use waste.

Thickness-dependent autophobic dewetting of thin polymer films on coated substrates.

We demonstrate that the wetting behavior of a thin liquid film, poly(4-bromostyrene) (PBrS), on top of a solid substrate may be effectively controlled with the insertion of a secondary liquid film, poly(4-vinyl pyridine) (P4VP), underneath the primary film. This secondary film remains stable under all conditions, and can be viewed as an extension of the substrate itself. On the basis of results from X-ray standing waves generated via total external reflection from an X-ray mirror, time-of-flight secondary ion mass spectroscopy, optical microscopy, and atomic force microscopy, we construct the full Helmholtz free energy versus PBrS thickness curve using existing theories that account for both long- and short-range interactions. The form of the free energy curve, which contains an inflection point and an absolute minimum at a nonzero PBrS thickness, accurately reflects our observation that thick PBrS films undergo autophobic dewetting on top of the stable P4VP, while sufficiently thin PBrS films remain stable. The thickness of the autophobic wetting layer is controlled by the range of the repulsive interaction between the film and the substrate, and is found to be ∼4 nm for the PBrS/P4VP interface.