RESUMO
Polymers that extend covalently in two dimensions have attracted recent attention1,2 as a means of combining the mechanical strength and in-plane energy conduction of conventional two-dimensional (2D) materials3,4 with the low densities, synthetic processability and organic composition of their one-dimensional counterparts. Efforts so far have proven successful in forms that do not allow full realization of these properties, such as polymerization at flat interfaces5,6 or fixation of monomers in immobilized lattices7-9. Another frequently employed synthetic approach is to introduce microscopic reversibility, at the cost of bond stability, to achieve 2D crystals after extensive error correction10,11. Here we demonstrate a homogenous 2D irreversible polycondensation that results in a covalently bonded 2D polymeric material that is chemically stable and highly processable. Further processing yields highly oriented, free-standing films that have a 2D elastic modulus and yield strength of 12.7 ± 3.8 gigapascals and 488 ± 57 megapascals, respectively. This synthetic route provides opportunities for 2D materials in applications ranging from composite structures to barrier coating materials.
RESUMO
Reversible Diels-Alder chemistry was utilized to manipulate the surface energy of glass substrates. Hydrophobic dieneophiles were prepared and attached to glass slides and capillaries to yield a nonwetting surface. Thermal treatment of the surfaces cleaved the Diels-Alder linkage, and resulted in the fabrication of a hydrophilic surface. Preliminary analysis utilized contact angle (CA) measurements to monitor the change in surface energy, and observed a hydrophilic state (CA - 70 +/- 3 degrees) before attachment of the dieneophile to a hydrophobic state (CA - 101 +/- 9 degrees) followed by regeneration of the hydrophilic state (CA - 70 +/- 6 degrees) upon cleavage of the Diels-Alder linkage. The treatments were then applied to glass capillaries, with effective treatment confirmed by fluid column measurements. Patterned treatments were also demonstrated to provide effective flow gating. Finally, attempts to create self-pressurizing capillaries were unsuccessful due to pronounced contact angle hysteresis for the hydrophobic surface treatment.
RESUMO
The linear polymer poly(p-phenylene terephthalamide), better known by its tradename Kevlar, is an icon of modern materials science due to its remarkable strength, stiffness, and environmental resistance. Here, we propose a new two-dimensional (2D) polymer, "graphamid", that closely resembles Kevlar in chemical structure, but is mechanically advantaged by virtue of its 2D structure. Using atomistic calculations, we show that graphamid comprises covalently-bonded sheets bridged by a high population of strong intermolecular hydrogen bonds. Molecular and micromechanical calculations predict that these strong intermolecular interactions allow stiff, high strength (6-8 GPa), and tough films from ensembles of finite graphamid molecules. In contrast, traditional 2D materials like graphene have weak intermolecular interactions, leading to ensembles of low strength (0.1-0.5 GPa) and brittle fracture behavior. These results suggest that hydrogen-bonded 2D polymers like graphamid would be transformative in enabling scalable, lightweight, high performance polymer films of unprecedented mechanical performance.
RESUMO
Two-dimensional (2D) materials can uniquely span the physical dimensions of a surrounding composite matrix in the limit of maximum reinforcement. However, the alignment and assembly of continuous 2D components at high volume fraction remain challenging. We use a stacking and folding method to generate aligned graphene/polycarbonate composites with as many as 320 parallel layers spanning 0.032 to 0.11 millimeters in thickness that significantly increases the effective elastic modulus and strength at exceptionally low volume fractions of only 0.082%. An analogous transverse shear scrolling method generates Archimedean spiral fibers that demonstrate exotic, telescoping elongation at break of 110%, or 30 times greater than Kevlar. Both composites retain anisotropic electrical conduction along the graphene planar axis and transparency. These composites promise substantial mechanical reinforcement, electrical, and optical properties at highly reduced volume fraction.
RESUMO
The behavior of polydisperse granular materials, composed of mixtures of particles of different sizes, is studied under conditions of high pressure and confinement. Two types of experiments are performed. In the first type, granular mixtures are compressed, with the resulting force-displacement curve used to calculate density and volume modulus. In the second set of experiments, the drag force is measured by pulling a cylinder, horizontally, through a compressed granular mixture. The density, volume modulus, and drag forces for the mixtures are quantified in terms of the mixture composition. The results show that the behavior of these mixtures depends strongly on the mass fractions of the different sized particles, with density, volume modulus, and drag force all reaching values significantly higher than observed in the monodisperse granular materials. Furthermore, the trends for density and drag force show strong correlation, suggesting that drag resistance of confined granular media could be directly related to packing effects. These results should prove useful in understanding the physics of drag in granular materials under high pressure, such as ballistic penetration of soils or ceramic armors.
RESUMO
The resistance offered by a cylindrical rod to creeping cross flow of granular materials under pressure is investigated. The experimental system consists of a confined bed of granular particles, which are compacted under high pressure to consolidate the granular medium. A cylindrical rod is pulled at a constant and slow rate through the granular medium, and the measured pulling resistance is characterized as a drag force. The influence of various parameters such as the velocity of the cylindrical rod, the rod diameter and length, the granular particle size, and the compaction pressure on the required drag force is investigated experimentally. Nondimensional analysis is performed to simplify the relationships between these variables. The results show that the drag force is independent of the drag velocity, is linearly proportional to compaction pressure and rod diameter, and increases with rod length and particle size. Additional compaction experiments show that the effective density of the granular bed increases linearly with pressure, and similar behavior is noted for all particle sizes. These results should prove useful in the development of constitutive equations that can describe the motion of solid objects through compacted granular media under high pressure, such as during ballistic penetration of soils or ceramic armors.
RESUMO
The penetration behavior of Kevlar fabric intercalated with dry particles and shear thickening fluids (STF), highly concentrated fluid-particle suspensions, is presented. In particular, the role of particle hardness is explored by comparing fabric treatments containing SiO(2) particles, which are significantly harder than Kevlar, to treatments containing softer poly(methyl methacrylate) (PMMA) particles. The fabric testing includes yarn pull-out, quasi-static spike puncture, and ballistic penetration resistance, performed on single fabric layers. It was found that both dry particle and STF treatments resulted in improvements in fabric properties relative to neat or poly(ethylene glycol) (PEG) treated fabrics. On comparison of treatments with different particle hardness, the SiO(2) materials performed better in all tests than comparable PMMA materials, although the SiO(2) treatments caused yarn failure in pull-out testing, reducing the total pull-out energy. In addition, resistance to yarn pull-out was found to be substantially higher for STF-treated fabrics than for dry particle treated fabrics. However, both dry particle addition and STF treatments exhibited comparable enhancements in puncture and ballistic resistance. These observations suggest that viscous stress transfer, friction, and physical entrainment of hard particles into filaments contribute to the demonstrated improvements in the properties of protective fabrics treated with shear thickening fluids.