Flexible Unidirectional (UD) composite laminates are commonly being used for ballistic-resistant body armor. These laminates comprise UD layers, each constructed by laminating thin layers of high-performance fibers held in place using very low modulus binder resins, with the fibers in each layer oriented parallel to each other. As these materials are used in body armor, it is important to investigate their long-term reliability, particularly with regards to exposure to temperature and humidity as these are known causes of degradation in other commonly used body armor materials. This work investigates the tensile behavior of a poly(p-phenylene terephthalamide), or PPTA flexible UD laminate aged for up to 150 d at accelerated conditions of 70 °C and 76 % relative humidity (RH). Tests were performed at three different crosshead displacement rates and three different gauge lengths. The effect of ageing on the mechanical properties of the material resulted in less than 10 % degradation in tensile strength, with a more significant reduction in longer specimens when tested at slower rates.

To improve the reliability and design of body armor, it is imperative to understand the failure modes and the degradation rates of the materials used in armor. Despite the best efforts of manufacturers, some vulnerability of armor materials to aging due to hydrolytic or oxidative environments is expected and may result in the degradation of material properties such as tensile strength. In this work, p-aramid yarns from two manufacturers were exposed to environmental conditions of various fixed temperature and humidity combinations. The maximum temperature and humidity condition was 70℃ and 76% relative humidity (RH). Tensile tests were performed on specimens extracted at several different times over the course of at least 1 year to determine the change in ultimate tensile strength and failure strain as a function of time, temperature, and humidity. Molecular spectroscopy was used to investigate any chemical changes as a result of the aging. The p-aramid materials were found to be generally resistant to degradation at most conditions, showing changes of less than 10% only at the highest temperature and humidity conditions.

Carbon nanotube (CNT) grafted glass fiber reinforced epoxy nanocomposites (GFRP) present a range of stiffnesses (MPa to GPa) and length scales (μm to nm) at the fiber-matrix interface. The contribution of functionalized CNT networks to the local and bulk polymer dynamics is studied here by using a combination of torsion dynamical mechanical thermal analysis (DMTA), positron annihilation lifetime spectroscopy (PALS), and neutron scattering (NS) measurements. DMTA

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The self-assembly of lipids into nanoscale vesicles (liposomes) is routinely accomplished in water. However, reports of similar vesicles in polar organic solvents like glycerol, formamide, and ethylene glycol (EG) are scarce. Here, we demonstrate the formation of nanoscale vesicles in glycerol, formamide, and EG using the common phospholipid lecithin (derived from soy). The samples we study are simple binary mixtures of lecithin and the solvent, with no additional cosurfactants or salt. Lecithin dissolves readily in the solvents and spontaneously gives rise to viscous fluids at low lipid concentrations (∼2–4%), with structures ∼200 nm detected by dynamic light scattering. At higher concentrations (>10%), lecithin forms clear gels that are strongly birefringent at rest. Dynamic rheology confirms the elastic response of gels, with their elastic modulus being ∼20 Pa at ∼10% lipid. Images from cryo-scanning electron microscopy (cryo-SEM) indicate that concentrated samples are “vesicle gels,” where multilamellar vesicles (MLVs, also called “onions”), with diameters between 50 and 600 nm, are close-packed across the sample volume. This structure can explain both the elastic rheology as well as the static birefringence of the samples. The discovery of vesicles and vesicle gels in polar solvents widens the scope of systems that can be created by self-assembly. Interestingly, it is much easier to form vesicles in polar solvents than in water, and the former are stable indefinitely, whereas the latter tend to aggregate or coalesce over time. The stability is attributed to refractive index-matching between lipid bilayers and the solvents, i.e., these vesicles are relatively “invisible” and thus experience only weak attractions. The ability to use lipids (which are “green” or eco-friendly molecules derived from renewable natural sources) to thicken and form gels in polar solvents could also prove useful in a variety of areas, including cosmetics, pharmaceuticals, and lubricants.

Cells assemble dynamic protein-based nanostructures far from equilibrium, such as microtubules, in a process referred to as dissipative assembly. Synthetic analogues have utilized chemical fuels and reaction networks to form transient hydrogels and molecular assemblies from small molecule or synthetic polymer building blocks. Here, we demonstrate dissipative cross-linking of transient protein hydrogels using a redox cycle, which exhibit protein unfolding-dependent lifetimes and mechanical properties. Fast oxidation of cysteine groups on bovine serum albumin by hydrogen peroxide, the chemical fuel, formed transient hydrogels with disulfide bond cross-links that degraded over hours by a slow reductive back reaction. Interestingly, despite increased cross-linking, the hydrogel lifetime decreased as a function of increasing denaturant concentration. Experiments showed that the solvent-accessible cysteine concentration increased with increasing denaturant concentration due to unfolding of secondary structures. The increased cysteine concentration consumed more fuel, which led to less direction oxidation of the reducing agent and affected a shorter hydrogel lifetime. Increased hydrogel stiffness, disulfide cross-linking density, and decreased oxidation of redox-sensitive fluorescent probes at a high denaturant concentration provided evidence supporting the unveiling of additional cysteine cross-linking sites and more rapid consumption of hydrogen peroxide at higher denaturant concentrations. Taken together, the results indicate that the protein secondary structure mediated the transient hydrogel lifetime and mechanical properties by mediating the redox reactions, a feature unique to biomacromolecules that exhibit a higher order structure. While prior works have focused on the effects of the fuel concentration on dissipative assembly of non-biological molecules, this work demonstrates that the protein structure, even in nearly fully denatured proteins, can exert similar control over reaction kinetics, lifetime, and resulting mechanical properties of transient hydrogels.

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