Morgana M. Trexler

Scalable, bottom‐up chemical synthesis and electrospinning of novel Cl‐substituted poly(para‐phenylene terephthalamide) (PPTA) nanofibers are herein reported. To achieve Cl‐PPTA nanofibers, the chemical reaction between the monomers was precisely controlled, and dissolution of the polymer into solvent was tailored to enable anisotropic solution formation and sufficient entanglement molecular weight. Electrospinning processing parameters were studied to understand their effects on fiber formation and mat morphology and then optimized to yield consistently high quality fibers. Importantly, the control of relative humidity during the fiber formation process was found to be critical, likely because water promotes hydrogen bond formation between the PPTA chains. The fiber and mat morphologies resulting from different combinations of chemistry and spinning conditions were observed using scanning electron microscopy, and observations were used as inputs to the optimization process. Tensile properties of single Cl‐PPTA nanofibers were characterized for the first time using a nanomanipulator mounted inside a scanning electron microscope (SEM), and fiber moduli measuring up to 70 GPa, and strengths exceeding 1 GPa were achieved. Given the excellent mechanical properties measured for the nanofibers, this chemical synthesis procedure and electrospinning protocol appear to be a promising route for producing a new class of nanofibers with ultrahigh strength and stiffness. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 563–573

The synthesis and electrospinning of novel N‐substituted aramid nanofibers (ANFs) prepared from basic dispersions of commercial microscale Kevlar fibers are herein reported. The functionalized ANFs were characterized via Fourier transform infrared spectroscopy, ¹³C solid‐state nuclear magnetic resonance spectroscopy, and X‐ray diffraction to confirm proper N‐substitution of the side groups and to determine changes to the polymer crystallinity and stability. These analyses suggested that the electrospun ANFs consisted of numerous crystalline domains in the transverse fiber direction with large amorphous regions that were void of defects commonly found in commercial Kevlar fibers. A semi‐empirical study of the variations in the solubility parameter due to various side chain moieties was conducted to facilitate solvent selection and to elucidate the enhanced solubility effects with selected organic solvents. These initial findings suggest a promising route for obtaining a new class of nanofibers with ultrahigh strength and stiffness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44082.

Prompt emergency treatment for ocular injury, particularly in a battlefield setting, is essential to preserve vision, reduce pain, and prevent secondary infection. A bandage contact lens that could be applied in the field, at the time of injury, would protect the injured ocular surface until hospital treatment is available. Cellulose, a natural polymer, is widely used in biomedical applications including bandage materials. Hydrogels synthesized from different cellulose sources, such as plants, cotton, and bacteria, can have the optical transparency and mechanical strength of contact lenses, by tailoring synthesis parameters. Thus, we optimized the fabrication of cellulose-based hydrogels and evaluated their in vivo biocompatibility and related physical properties. Our data demonstrate that along with tailorable physical properties, our novel cellulose-based hydrogels could be made with contact lens geometry, exhibit no significant signs of material toxicity after 22 days of in vivo testing, and show significant promise for use as a corneal bandage immediately following ocular trauma.

Cellulose‐based hydrogels show great potential for a wide range of applications. However, the structure of these hydrated gels is not fully understood. The impact of moisture on the structure and stability of cellulose based hydrogels is reported in this article. Analytical data based on GPC, NMR, and rheology are discussed. It was found that moisture‐induced gelation greatly reduces the crystallinity of the hydrogels, and the release of water from the hydrogels leads to permanent structural changes in the network structure due to the reformation of hydrogen bonding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42071.

Hydrogels with four different plant‐based microcrystalline cellulose concentrations were prepared using the self‐assembly technique. The interaction parameter between cellulose and water was determined by the classical Flory‐Huggins theory, and was found to be around 0.44 with weak concentration dependence. The crosslinking density in these hydrogels was measured by both the Mooney‐Rivlin equation and the Flory‐Rehner theory. Reasonable consistency was found between the two methods albeit results from the Flory‐Rehner theory were slightly higher due to the contribution from the physical crosslinks. The crosslinking density values for all four hydrogels determined from both methods were found to range from 19 to 56 mol/m³. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Predicting spinal injury under high rates of vertical loading is of interest, but the success of computational models in modeling this type of loading scenario is highly dependent on the material models employed. Understanding the response of these biological materials at high strain rates is critical to accurately model mechanical response of tissue and predict injury. While data exists at lower strain rates, there is a lack of the high strain rate material data that are needed to develop constitutive models. The Split Hopkinson Pressure Bar (SHPB) has been used for many years to obtain properties of various materials at high strain rates. However, this apparatus has mainly been used for characterizing metals and ceramics and is difficult to apply to softer materials such as biological tissue. Recently, studies have shown that modifications to the traditional SHPB setup allow for the successful characterization of mechanical properties of biological materials at strain rates and peak strain values that exceed alternate soft tissue testing techniques. In this paper, the previously-reported modified SHPB technique is applied to characterize human intervertebral disc material under simple shear. The strain rates achieved range from 5 to 250 strain s-1. The results demonstrate the sensitivity to the disc composition and structure, with the nucleus pulposus and annulus fibrosus exhibiting different behavior under shear loading. Shear tangent moduli are approximated at varying strain levels from 5 to 20% strain. This data and technique facilitates determination of mechanical properties of intervertebral disc materials under shear loading, for eventual use in constitutive models.