Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues.

The functionality inherent in lignin-derivable bisguaiacols/bissyringols can improve the processability and performance of the resulting polymers. Herein, non-isocyanate polyurethanes (NIPUs) were synthesized from bisguaiacols/bissyringols with varying degrees of methoxy substitution and differing bridging groups. Notably, the presence of increasing numbers of methoxy groups (0, 2, and 4) in bisphenol F (BPF)-, bisguaiacol F (BGF)-, and bissyringol F (BSF)-NIPUs led to higher percentages of hydrogen-bonded -OH/-NH groups (i.e., ∼65%, ∼85%, ∼95%, respectively). Increased hydrogen bonding between chains improved the elongation-at-break (εbreak) and toughness of lignin-derivable NIPUs over their petroleum counterparts without a reduction in Young's moduli and tensile strengths. For example, BSF-NIPU exhibited the highest εbreak ∼210% and toughness ∼62 MJ m-3, followed by BGF-NIPU (εbreak ∼185% and toughness ∼58 MJ m-3), and then BPF-NIPU (εbreak ∼140% and toughness ∼42 MJ m-3). Similar trends were found in the dimethyl-substituted analogues, particularly for the bisphenol A-NIPU and bisguaiacol A-NIPU. Importantly, the melt rheology of the lignin-derivable NIPUs was comparable to that of the petroleum-derived analogues, with a slightly lower viscosity (i.e., improved melt flow) for the bio-derivable NIPUs. These findings suggested that the added functionalities (methoxy groups) derived from lignin precursors improved thermomechanical stability while also offering increased processability. Altogether, the structure-property-processing relationships described in this work can help facilitate the development of sustainable, performance-advantaged polymers.

Increase in the effective viscosity of polyethylene under extreme nanoconfinement.

Understanding polymer transport in nanopores is crucial for optimizing heterogeneously catalyzed processes in polymer upcycling and fabricating high-performance nanocomposite films and membranes. Although confined polymer dynamics have been extensively studied, the behavior of polyethylene (PE)-the most widely used commodity polymer-in pores smaller than 20 nm remains largely unexplored. We investigate the effects of extreme nanoconfinement on PE transport using capillary rise infiltration in silica nanoparticle packings with average pore radii ranging from ∼1 to ∼9 nm. Using in situ ellipsometry and the Lucas-Washburn model, we discover a previously unknown inverse relationship between effective viscosity (ηeff) and average pore radius (Rpore). Additonally, we determine that PE transport under these extreme conditions is primarily governed by physical confinement, rather than pore surface chemistry. We refine an existing theory to provide a generalized formalism to describe the polymer transport dynamics over a wide range of pore radii (from 1 nm and larger). Our results offer valuable insights for optimizing catalyst supports in polymer upcycling and improving infiltration processes for nanocomposite fabrication.

Peptide-polyurea hybrids: a platform for tunable, thermally-stable, and injectable hydrogels.

Drawing inspiration from natural systems, such as the highly segmented structures found in silk fibroin, is an important strategy when designing strong, yet dynamic biomaterials. Polymer-peptide hybrids aim to incorporate the benefits of hierarchical polypeptide structures into synthetic platforms that are promising materials for hydrogel systems due to aspects such as their biocompatibility and structural tunability. In this work, we demonstrated the utility of poly(ethylene glycol) (PEG) peptide-polyurea hybrids as self-assembled hydrogels. Specifically, poly(ε-carbobenzyloxy-L-lysine)-b-PEG-b-poly(ε-carbobenzyloxy-L-lysine) and poly(ß-benzyl-L-aspartate)-b-PEG-b-poly(ß-benzyl-L-aspartate) triblock copolymers were used as the soft segments in linear peptide-polyurea (PPU) hybrids. We systematically examined the effect of peptide secondary structure and peptide segment length on hydrogelation, microstructure, and rheological properties of our PPU hydrogels. Polymers containing α-helical secondary structures resulted in rapid gelation upon the addition of water, as driven by hierarchical assembly of the peptide segments. Peptide segment length dictated gel strength and resistance to deformation via complex relationships. Simulated injection experiments demonstrated that PPU hydrogels recover their original gel network within 10 s of cessation of high shear. Finally, we showed that PPU hydrogels remain solid-like within the range of 10 to 80 °C; however, a unique softening transition occurs at temperatures corresponding to slight melting of secondary structures. Overall, this bioinspired PPU hybrid platform provides opportunities to design synthetic, bioinspired polymers for hydrogels with tunable microstructure and mechanics for a wide range of thermal and injection-based applications.

Finding the sweet spot: a library of hydrogels with tunable degradation for tissue model development.

In vitro models are valuable tools for applications including understanding cellular mechanisms and drug screening. Hydrogel biomaterials facilitate in vitro models by mimicking the extracellular matrix and in vivo microenvironment. However, it can be challenging for cells to form tissues in hydrogels that do not degrade. In contrast, if hydrogels degrade too much or too quickly, tissue models may be difficult to assess in a high throughput manner. In this paper, we present a poly(allylamine) (PAA) based synthetic hydrogel system which can be tuned to control the mechanical and chemical cues provided by the hydrogel scaffold. PAA is a polycation with several biomedical applications, including the delivery of small molecules, nucleic acids, and proteins. Based on PAA and poly(ethylene glycol) (PEG), we developed a synthetic non-degradable system with potential applications for long-term cultures. We then created a second set of gels that combined PAA with poly-L-lysine (PLL) to generate a library of semi-degradable gels with unique degradation kinetics. In this work, we present the hydrogel systems' synthesis, characterization, and degradation profiles along with cellular data demonstrating that a subset of gels supports the formation of endothelial cell cord-like structures.

The effect of pyrolysis on the chemical, thermal and rheological properties of pitch.

Pitch-based carbon fibers are of considerable interest as high-performance materials. There are reports over the last several decades detailing (i) methods of improving pitch-based carbon fiber performance, and (ii) reducing the cost of production via novel processing techniques. However, there remain considerable challenges in producing high-performance pitch-based carbon fibers consistently on an industrial scale. This is arguably due to the difficulty of scaling the melt-spinning process to compensate for variability in pitch feedstock quality and a lack of understanding of processing-structure-performance relationships. This work focuses on the early stages of heat treatment (pyrolysis) of isotropic pitch and its effect on the chemical, thermal, and rheological properties of the pitch, which help determine its processability. More specifically, we quantify significant changes in chemical structure, Mw, Tg, Ts, and shear and extensional rheology as a function of pyrolysis time at 400 °C. The extensional rheology, in particular, shows that the 'stretchability' of the pitch samples strongly depends on pyrolysis severity, and is important for characterizing 'drawability'. Using a novel analysis of the uniaxial stretching kinematics, we show an isothermal 'drawability window' that allows for the largest axial and radial Hencky strains at constant rate. We hypothesize that this extensional drawability window could facilitate the successful processing of pitch into high quality fiber, minimizing the trial-and-error approach currently used in the field.

Surface tensions at elevated pressure depend strongly on bulk phase saturation.

HYPOTHESIS: Understanding interfacial phenomena at elevated pressure is crucial to the design of a variety of processes, modeling important systems, and interpreting interfacial thermodynamics. While many previous studies have offered insight into these areas, current techniques have inherent drawbacks that limit equilibrium measurements. EXPERIMENTS: In this work, we adapt the ambient microtensiometer of Alvarez and co-workers into a high pressure microtensiometer (HPMT) capable of experimentally quantifying a wide range of interfacial phenomena at elevated pressures. Particularly, the HPMT uses a microscale spherical interface pinned to the tip of a capillary to directly measure surface tension via the Laplace equation. The stream of microscale bubbles used to pressurize the system ensures quick saturation of the bulk phases prior to conducting measurements. The HPMT is validated by measuring the surface tension of air-water as a function of pressure. We then measure the surface tension of CO2 vapor and water as a function of pressure, finding lower equilibrium surface tension values than originally reported in the literature. FINDINGS: This work both introduces further development of a useful experimental technique for probing interfacial phenomena at elevated pressures and demonstrates the importance of establishing bulk equilibrium to measure surface tension. The true equilibrium state of the CO2-water surface has a lower tension than previously reported. We hypothesize that this discrepancy is likely due to the long diffusion timescales required to ensure saturation of the bulk fluids using traditional tensiometry. Thus we argue that previously reported elevated pressure measurements were performed at non-equilibrium conditions, putting to rest a long standing discrepancy in the literature. Our measurements establish an equilibrium pressure isotherm for the pure CO2-water surface that will be essential in analyzing surfactant transport at elevated pressures.

Nylon-6/Ti3C2T z MXene Nanocomposites Synthesized by in Situ Ring Opening Polymerization of ε-Caprolactam and Their Water Transport Properties.

Clay-reinforced nylon-6 nanocomposites (NCs)-characterized by the full exfoliation of the nanoreinforcement-were introduced in the marketplace in the 1990s. Herein, we demonstrate, for the first time, that Ti3C2T z MXene can be incorporated into nylon-6 to synthesize melt-processable nanocomposites with excellent water barrier properties (94% reduction in water vapor permeation). To intercalate the ε-caprolactam monomer between the MXene multilayers, the latter were first treated with 12-aminolauric acid, a low-cost, nontoxic, biodegradable, and long shelf life compound. Upon heating to 250 °C, in the presence of 6-aminocaproic acid, in situ polymerization occurred, yielding melt-processable nylon-6/MXene NCs that were, in turn, studied by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, and dynamic vapor sorption analysis. Using the latter, moisture-sorption isotherms of a neat and a 1.9 vol % NC, at 60 °C, were fit to the Guggenheim, Anderson, and de Boer equation. Solubility, permeation, and diffusion coefficients of water through the NCs were measured as a function of temperature and found to be the lowest ever reported for nylon-6, despite the fact that, at ∼1.9 and 5.0 vol %, the MXene loads were relatively low. This record low diffusivity is ascribed to the very large aspect ratios-500 to 1000-of Ti3C2T z flakes and their dispersion. The water permeation rate is a factor of 5 lower than the best reported in the much more mature nylon/clay field, suggesting lower values can be achieved with further optimization. Lastly infrared spectroscopy spectra of neat and NC samples suggest the surface terminations of the 12-Ti3C2T z flakes bind with nylon-6, limiting water adsorption sites, resulting in reduced solubility in the NC films.

Accounting for optical errors in microtensiometry.

HYPOTHESIS: Drop shape analysis (DSA) techniques measure interfacial tension subject to error in image analysis and the optical system. While considerable efforts have been made to minimize image analysis errors, very little work has treated optical errors. There are two main sources of error when considering the optical system: the angle of misalignment and the choice of focal plane. Due to the convoluted nature of these sources, small angles of misalignment can lead to large errors in measured curvature. We demonstrate using microtensiometry the contributions of these sources to measured errors in radius, and, more importantly, deconvolute the effects of misalignment and focal plane. Our findings are expected to have broad implications on all optical techniques measuring interfacial curvature. EXPERIMENTS: A geometric model is developed to analytically determine the contributions of misalignment angle and choice of focal plane on measurement error for spherical cap interfaces. This work utilizes a microtensiometer to validate the geometric model and to quantify the effect of both sources of error. For the case of a microtensiometer, an empirical calibration is demonstrated that corrects for optical errors and drastically simplifies implementation. FINDINGS: The combination of geometric modeling and experimental results reveal a convoluted relationship between the true and measured interfacial radius as a function of the misalignment angle and choice of focal plane. The validated geometric model produces a full operating window that is strongly dependent on the capillary radius and spherical cap height. In all cases, the contribution of optical errors is minimized when the height of the spherical cap is equivalent to the capillary radius, i.e. a hemispherical interface. The understanding of these errors allow for correct measure of interfacial curvature and interfacial tension regardless of experimental setup. For the case of microtensiometry, this greatly decreases the time for experimental setup and increases experiential accuracy. In a broad sense, this work outlines the importance of optical errors in all DSA techniques. More specifically, these results have important implications for all microscale and microfluidic measurements of interface curvature.