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At least 91 records · Page 5

Ethynylated aromatics as high temperature matrix resins

Difunctional and trifunctional arylacetylenes were used as monomers to form thermoset matrix resin composites. Composites can be hot pressed at 180 C to react 80 percent of the acetylene groups. Crosslinking is completed by postcuring at 350 C. The postcured resins are thermally stable to nominally 460 C in air. As a result of their high crosslink density, the matrix exhibits brittle failure when unaxial composites are tested in tension. Failure of both uniaxial tensile and flexural specimens occurs in shear at the fiber matrix interface. Tensile fracture stresses for 0 deg composites fabricated with 60 v/o Celion 6K graphite fiber were 827 MPa. The strain to failure was 0.5 percent. Composites fabricated with 8 harness satin Celion cloth (Fiberite 1133) and tested in tension also failed in shear at tensile stresses of 413 MPa.

Hurwitz, Frances I.↗

Blends of an ethynyl terminated imidothioether with ethynyl terminated arylene ether oligomers

An evaluation has been undertaken of blends of a novel ethynyl-terminated imidothioether with Udel P1700 polysulfone and ethynyl-terminated arylene ether oligomers. Good to excellent processability was obtained with these blends using compression molding; the cured blends displayed poor-to-good resistance to chloroform and low-to-moderately high fracture toughness, depending on the blends' crosslink density. The flexural strength and modulus of unidirectional carbon graphite laminates prepared with the blended resins were good.

Connell, J. W.↗

A predictive model for failure properties of thermoset resins

A predictive model for the three-dimensional failure behavior of engineering polymers has been developed in a recent NASA-sponsored research program. This model acknowledges the underlying molecular deformation mechanisms and thus accounts for the effects of different chemical compositions, crosslink density, functionality of the curing agent, etc., on the complete nonlinear stress-strain response including yield. The material parameters required by the model can be determined from test-tube quantities of a new resin in only a few days. Thus, we can obtain a first-order prediction of the applicability of a new resin for an advanced aerospace application without synthesizing the large quantities of material needed for failure testing. This technology will effect order-of-magnitude reductions in the time and expense required to develop new engineering polymers.

Caruthers, James M.↗

High Temperature Thermosets

A thermoset or network polymer is an organic material where the molecules are tied together through chemical bonds (crosslinks) and therefore they cannot move past one another. As a result, these materials exhibit a certain degree of dimensional stability. The chemical composition and the degree of crosslink density of the thermoset have a pronounced effect upon the properties. High temperature thermosets offer a favorable combination of properties that makes them attractive for many applications. Their most important features are the excellent processability particularly of the low molecular weight precusor forms, the chemical and solvent resistance and the dimensional stability. The market for high temperature thermosets will increase as new uses for them are uncovered and new thermosets with better combinations of properties are developed.

Hergenrother, Paul M.↗

Mechanical Properties of Graphene Nanoplatelet/Carbon Fiber/Epoxy Hybrid Composites: Multiscale Modeling and Experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite, while the effect on the axial properties is shown to be insignificant.

molecular dynamics↗

Mechanical Properties of Graphene Nanoplatelet Carbon Fiber Epoxy Hybrid Composites: Multiscale Modeling and Experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite, while the effect on the axial properties is shown to be insignificant.

computational mechanics↗

Mechanical Properties of Graphene Nanoplatelet/Carbon Fiber/Epoxy Hybrid Composites: Multiscale Modeling and Experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite while the effect on the axial properties is shown to be insignificant.

nanocomposites↗

Coal-based Bricks & Blocks (CBBs): Process Development to Prototype Fabrication Coupled with Techno-Economic Analysis and Market Survey

The decline of coal use for energy production provides an abundance of local feedstock for new innovative uses and value-added products. Expanding the U.S. coal-value chain to manufacture high-value carbon products can strengthen the nation’s energy and mineral security, enhance the U.S. national defense security, increase the United States’ economic prosperity, while achieving U.S. environmental objectives. The primary project goal is a relatively light-weight composite product with superior (or comparable) compressive strength. Both virgin and, where available, post-consumer recycled thermoplastic versions are tested for each thermoplastic species. A useful attribute of thermoplastics as binders is that they can be heated to their melting point, cooled, and reheated again without significant degradation. A key advantage of thermoset CBBs is that they require only mixing and molding. CBB advantages include low cost, availability, binding ability and processability. Coal-based bricks and blocks (CBBs) weigh about 50% less than clay bricks and can be manufactured with an interlocking design to promote ease of use for the novice builder. CBB formulation is evaluated according to a design-of-experiments (DoE) approach. DoE variables are a) relative weight fractions of binder, b) relative proportions of large versus small (milled) anthracite size fractions, and c) additive percentage. Fabrication methods include hot-press molding and extrusion, the later being the most commercially viable. CBBs are tested for compressive strength, modulus of rupture (by flexure test) and water absorption per ASTM C67, with density determined by the Archimedes drainage method. Fractured interfaces are examined by SEM (Scanning Electron Microscopy) to resolve fracture dynamics and interior microstructure uniformity. Differential scanning calorimetry (DSC) is used to compare plastic transition temperatures i.e., glass and melting temperatures to contrast virgin with post-consumer recycled thermoplastics and optimize their usage. These results are used in the DoE analysis to identify the binder and relative weight percentages for optimum strength, density, and porosity. Overall, CBBs possess strength comparable to clay-based bricks but are non-permeable and hydrophobic, and hence resistant to degradation by freeze-fracturing, corrosion, and efflorescence. The strongest composites have been made with the following thermoplastic binders (in order of strength): thermoset, high-density polyethylene crosslink resin, high-density polyethylene, nylon 6/6, and polypropylene. Results from a techno-economic analysis TEA show economy of scale for CBBs by modularization and reveal the binder as the cost driver for material costs. Ideally, the incorporation of post-consumer recycled thermoplastic will decrease material acquisition costs and increase product sustainability. Notably, CBBs do not require the high temperature calcination needed to produce cement, nor do they require firing in the 1600-2400 °F range for three days using natural gas, as do clay brick equivalents. Instead, CBBs are heated to a modest <600 °F according to the melt flow index of the thermoplastic binder. Existing anthracite mines can be expanded to produce CBBs to reduce aggregate transportation costs and emissions that exist for clay bricks. TEA reflects this reduced energy cost while a comparative CO2 emission analysis quantifies the reduced environmental footprint. The market survey identifies several commercialization opportunities, dependent upon the brick classification.

01 COAL, LIGNITE, AND PEAT↗

A Vitrimer Acts as a Compatibilizer for Polyethylene and Polypropylene Blends

Abstract Polymer compatibilization plays a critical role in achieving polymer blends with favorable mechanical properties and enabling efficient recycling of mixed plastic wastes. Nonetheless, traditional compatibilization methods often require tailored designs based on the specific chemical compositions of the blends. In this study, we propose a new approach for compatibilizing polymer blends using a dynamically crosslinked polymer network, known as vitrimers. By adding a relatively small amount (1–5 w/w%) of a vitrimer made of siloxane‐crosslinked high‐density polyethylene (HDPE), we successfully compatibilized unmodified HDPE and isotactic polypropylene (iPP). The vitrimer‐compatibilized blend exhibited enhanced elongation at break (120 %) and smaller iPP domain sizes (0.4 μm) compared to the control blend (22 % elongation at break, 0.9 μm iPP droplet size). Moreover, the vitrimer‐compatibilized blend showed significantly improved microphase stability during annealing at 180 °C. This straightforward method shows promise for applications across various polymer blend systems.

Yokoyama, Kosuke↗

A Vitrimer Acts as a Compatibilizer for Polyethylene and Polypropylene Blends

Polymer compatibilization plays a critical role in achieving polymer blends with favorable mechanical properties and enabling efficient recycling of mixed plastic wastes. Nonetheless, traditional compatibilization methods often require tailored designs based on the specific chemical compositions of the blends. In this study, we propose a new approach for compatibilizing polymer blends using a dynamically crosslinked polymer network, known as vitrimers. By adding a relatively small amount (1–5 w/w%) of a vitrimer made of siloxane‐crosslinked high‐density polyethylene (HDPE), we successfully compatibilized unmodified HDPE and isotactic polypropylene (iPP). The vitrimer‐compatibilized blend exhibited enhanced elongation at break (120 %) and smaller iPP domain sizes (0.4 μm) compared to the control blend (22 % elongation at break, 0.9 μm iPP droplet size). Moreover, the vitrimer‐compatibilized blend showed significantly improved microphase stability during annealing at 180 °C. This straightforward method shows promise for applications across various polymer blend systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Changes to the morphology and coefficient of thermal expansion in HDPE and UHMWPE following irradiation-based crosslinking

This work describes recent findings of the Los Alamos National Laboratory concerning the alterations to polyethylene’s (PE’s) mechanical and chemical properties after crosslinking via gamma irradiation. Three materials were examined as part of this study, including one HDPE and two UHMWPE specimens. Changes to degree of crystallinity (X C ) were qualitatively determined via measurements of density, and results suggest that X C is not necessarily correlated to crosslink density, depending on polymer manufacturing process and treatment following irradiation. TMA data suggests an anisotropic response in linear thermal expansion, and that the response may be more correlated to X C than crosslink density. Finally, FTIR analysis has led to the conclusion that oxidation occurs as a result of irradiation in open air, the degree of oxidation is proportional to the maximum radiation dose received, and that oxidation is largely a surface effect, penetrating no deeper than 1.5 mm. Due to time constraints, a full dataset could not be generated for changes in creep and thermal properties as a result of irradiation, and TMA analysis is only complete for one material tested in this study. These measurements are ongoing and will provide more context to the hypotheses drawn in this work.

36 MATERIALS SCIENCE↗

Understanding the origin of softness in structurally tailored and engineered macromolecular (STEM) gels: A DPD study

Structurally tailored and engineered macromolecular (STEM) gels are polymer networks containing a primary network (the “STEM-0” gel) and side chains that are anchored to this network (forming the “STEM-1” gel). The ability to vary the features of the side chains provides a robust means of tailoring the macroscopic properties of the material. We use dissipative particle dynamics (DPD) simulations to determine the mechanical response of STEM-1 gels to uniaxial compression for various values of the side chain length, n sc . While the Young’s modulus of the material is significantly decreased with increasing n sc (at a fixed density of grafted side chains), above a certain saturation value, increasing n sc does not lead to any further softening of the sample. Using the simulations, we calculate the relevant stresses, which are related to the Young’s modulus and the number of entanglements in the network. We show that the backbone chains become more spread out upon addition of sidechains, leading to a decrease in the physical entanglements between backbone segments. This observation accounts for the decrease of stress in the backbone network and the softening of the networks through the addition of sidechains. For long chains, however, the number density of physical crosslinks between side chains is independent of side chain length; this observation explains the observed stress saturation in the STEM-1 gels. Our approach allows us to correlate the molecular architecture of the gels to the resultant macroscopic mechanical behavior and provide guidelines for fabricating STEM gels with well-defined mechanical properties, which allow the materials to be used for a variety of applications.

36 MATERIALS SCIENCE↗

Crosslinking and Gelation of Polymer Brushes and Free Polymer Chains in a Confined Space during Controlled Radical Polymerization-A Computer Simulation Study

The confinement effect on crosslinking and gelation during controlled/living copolymerization of a monovinyl and a divinyl monomer was studied by Monte Carlo computer simulation using the dynamic lattice liquid method. The simulated reactions took place in plane-parallel slits of various widths for various grafting densities (GDs) and various initial initiator/crosslinker ratios ([X] 0 /[Ini] 0 ). Monomers and crosslinkers were initially randomly distributed in the slit, but initiators were either anchored to one solid plane (polymer brushes) or randomly distributed (free chains). For brushes, the gel point (GP) depended on GD and [X] 0 /[Ini] 0 . The higher these parameters, the lower was the gel point. The gel point was also affected by the slit width. For free, nongrafted chains, the dependence of GP on slit width was negligible. For brushes, a nonuniform density of crosslinks was found, the highest density was close to the wall. This asymmetry was high at the gel point and decreased at higher conversions.

36 MATERIALS SCIENCE↗

Electron-beam-deposited thin polymer films - Electrical properties vs bombarding current.

Polymer films about 150 A thick, deposited on glass substrates by electron bombardment of tetramethyltetraphenyltrisiloxane, were studied, after being sandwiched between evaporated aluminum electrodes, the top one semitransparent. The capacitance, conductance, and photoconductance of the sandwiches were measured at room temperature as a function of the electron bombarding current which formed the polymer. The polymer thickness was obtained independently from Christy's (1960) empirical formula for the rate of formation. The obtained results indicate that, with increasing bombarding current, the polymer undergoes an increase in both crosslinking bonds and dangling bonds. Exposure to air drastically reduces the density of dangling bonds, but does not affect the crosslinking.

Babcock, L. E.↗

Nanostructured polyelectrolytes for ion-selective membranes

Nanostructured polyelectrolyte bilayers deposited by Layer-by-Layer deposition on nanoporous membranes can be selectively crosslinked to modify the polyelectrolyte charge density and control ionic selectivity independent of ionic conductivity. For example, the polyelectrolyte bilayer can comprise a cationic polymer layer, such as poly(ethyleneimine), and an anionic polymer layer, such as poly(acrylic acid). Increasing the number of bilayers increases the cation selectivity when the poly(ethyleneimine) layer is crosslinked with glutaraldehyde. Crosslinking the membranes also increases the chemical and mechanical strength of the polyelectrolyte films. This controllable and inexpensive method can be used to create ion-selective and mechanically robust membranes on porous supports for a wide range of applications.

25 ENERGY STORAGE↗

The Compressive Behavior of Isocyanate-crosslinked Silica Aerogel at High Strain Rates

Aerogels are low-density, highly nano-porous materials. Their engineering applications are limited due to their brittleness and hydrophilicity. Recently, a strong lightweight crosslinked silica aerogel has been developed by encapsulating the skeletal framework of amine-modified silica aerogels with polyureas derived by isocyanate. The mesoporous structure of the underlying silica framework is preserved through conformal polymer coating, and the thermal conductivity remains low. Characterization has been conducted on the thermal, physical properties and the mechanical properties under quasi-static loading conditions. In this paper, we present results on the dynamic compressive behavior of the crosslinked silica aerogel (CSA) using a split Hopkinson pressure bar (SHPB). A new tubing pulse shaper was employed to help reach the dynamic stress equilibrium and constant strain rate. The stress-strain relationship was determined at high strain rates within 114-4386/s. The effects of strain rate, density, specimen thickness and water absorption on the dynamic behavior of the CSA were investigated through a series of dynamic experiments. The Young's moduli (or 0.2% offset compressive yield strengths) at a strain rate approx.350/s were determined as 10.96/2.08, 159.5/6.75, 192.2/7.68, 304.6/11.46, 407.0/20.91 and 640.5/30.47 MPa for CSA with densities 0.205, 0.454, 0.492, 0.551,0.628 and 0.731 g/cu cm, respectively. The deformation and failure behaviors of a native silica aerogel with density (0.472 g/cu cm ), approximately the same as a typical CSA sample were observed with a high speed digital camera. Digital image correlation technique was used to determine the surface strains through a series of images acquired using high speed photography. The relative uniform axial deformation indicated that localized compaction did not occur at a compressive strain level of approx.17%, suggesting most likely failure mechanism at high strain rate to be different from that under quasi-static loading condition. The Poisson s ratio was determined to be 0.162 in nonlinear regime under high strain rates. CSA samples failed generally by splitting, but were much more ductile than native silica aerogels.

Luo, H.↗