[Microtubule dynamics in relation to growth response to gravity in plant cells]
No abstract available
Non-NASA Center↗
SEARCH · Engineering Papers
Results for “Dynamic polymer”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Chemical, Physical, and Mechanical Characterization of Isocyanate Cross-linked Amine-Modified Silica Aerogels
We describe a new mechanically strong lightweight porous composite material obtained by encapsulating the skeletal framework of amine-modified silica aerogels with polyurea. The conformal polymer coating preserves the mesoporous structure of the underlying silica framework and the thermal conductivity remains low at 0.041 plus or minus 0.001 W m(sup -1 K(sup -1). The potential of the new cross-linked silica aerogels for load-carrying applications was determined through characterization of their mechanical behavior under compression, three-point bending, and dynamic mechanical analysis (DMA). A primary glass transition temperature of 130 C was identified through DMA. At room temperature, results indicate a hyperfoam behavior where in compression cross-linked aerogels are linearly elastic under small strains (less than 4%) and then exhibit yield behavior (until 40% strain), followed by densification and inelastic hardening. At room temperature the compressive Young's modulus and the Poisson's ratio were determined to be 129 plus or minus 8 MPa and 0.18, respectively, while the strain at ultimate failure is 77% and the average specific compressive stress at ultimate failure is 3.89 x 10(exp 5) N m kg(sup -1). The specific flexural strength is 2.16 x 10(exp 4) N m kg(sup -1). Effects on the compressive behavior of strain rate and low temperature were also evaluated.
Katti, Atul↗
Spatiotemporal Formation and Growth Kinetics of Polyelectrolyte Complex Micelles with Millisecond Resolution
We have directly observed the in situ self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. A synthesized neutral-charged diblock polycation and homopolyanion that we have previously investigated as a model charge-matched, core-shell micelle system were selected for this work. The initial micellization of the oppositely charged polyelectrolytes was completed within the dead time of mixing of 100 ms, followed by micelle growth and equilibration up to several seconds. By combining the structural evolution of the radius of gyration (R-g) with complementary molecular dynamics simulations, we show how the self-assemblies evolve incrementally in size over time through a two-step kinetic process: first, oppositely charged polyelectrolyte chains pair to form nascent aggregates that immediately assemble into spherical micelles, and second, these PEC micelles grow into larger micellar entities. Furthermore, this work has determined one possible kinetic pathway for the initial formation of PEC micelles, which provides useful physical insights for increasing fundamental understanding self-assembly dynamics, driven by polyelectrolyte complexation that occurs on ultrafast time scales.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Shock initiation and hot spots in plastic-bonded 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)
TATB (1,3,5-triamino-2,4,6-trinitrobenzene) is a powerful explosive whose dynamical behavior is difficult to study because TATB is so insensitive to initiation by shock waves. We used a tabletop microscope equipped with 0–4.5 km/s laser-launched flyer plates to study shock initiation of TATB, which was fabricated in the form of an array of hundreds of plastic-bonded explosive minicharges (X-TATB = 80% TATB + 20% Sylgard 182 polymer). The 4 ns shocks from the flyer plates were not effective in initiating TATB, but we also developed a two-layer array where flyers first initiated a plastic-bonded PETN (pentaerythritol tetranitrate) charge (X-PETN = 80% PETN + 20% Sylgard), which drove an initiating 25 ns shock into the X-TATB. Thermal emission from shocked X-TATB was used to measure time-dependent temperature profiles with a resolution of 2 ns and to produce high-speed (5 ns) videos. In X-TATB, flyer plates produced 2500–3500 K hot spots and combustion at 2500 K. With X-PETN initiators, X-TATB had 3500–4000 K hot spots and a powerful volume explosion lasting a few nanoseconds. Prospects for producing TATB detonations on a tabletop are discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Curing behavior, chain dynamics, and microstructure of high Tg thiol-acrylate networks with systematically varied network heterogeneity
Explore the source record for details and available documents.
99 GENERAL AND MISCELLANEOUS↗
Novel Crash Sled with a Translating Support Mass
Background: A novel crash sled has been developed with a translating support, incorporating transducers that allow multiple methods of measuring energy absorption to fully characterize the dynamic crush response of composite components. Objective: The main goal of the current investigation was to demonstrate functionality, repeatability, and accuracy of crush testing using a crash sled with a translating support mass. Methods: A semi-automated algorithm for data reduction was developed based on impact mechanics principles. A preliminary set of tests was initially conducted using aluminum honeycomb specimens with a specified stable crushing force to quantify the accuracy and repeatability of the crush data. Following the success of these tests, triaxially-braided fiber-reinforced polymer (FRP) specimens were evaluated. Results: Crush tests with the aluminum honeycomb specimens showed excellent outcomes for all three specimens. These data provided close agreement with cumulative energy absorption between individual instruments and stable crushing forces at expected values. For the FRP specimens, specific energy absorption (SEA) and force-displacement curves were successfully measured; however, data from the translating support mass accelerometer was excluded from the dataset due to clipping. The SEA of the corrugated specimens was greater than the SEA for the C-channel specimens at both test speeds. Conclusions: The crash sled functionality was verified, the specimen geometry was found to contribute more to SEA than the impact speed in the speed range tested, and the support mass accelerometer will be upgraded to prevent clipping in future tests.
Dynamic Crush↗
Poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at intermediate temperatures
High temperature proton exchange membrane fuel cells are being lately investigated because of their high energy efficiency, their superior heat/water management, CO tolerance, and electrode reaction kinetics. To further advance this technology, the polymer membrane portfolio and performance should be improved for intermediate or high temperature operation (>100 °C). In this work we present new poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at 120 °C. First, new protic ionic liquids, hereafter called DAMAH + X - , were synthesized leading to diallylmethylammonium monomers with different counter-anions. By radical cyclopolymerization through thermal and photoinitiation mechanisms, self-standing protic polymeric membranes of poly(diallylmethylammonium X - ) were obtained. Membranes showed good thermal stability (>250 °C) and mechanical properties without the need of additives such as (protic) ionic liquids, solvents or inorganic charges. Great attention was paid to understand the effect of the different counter-anions on the membrane properties. As a general trend, fluorinated anions coming from strong acids confer high ionic conductivity and allow to reduce the hygroscopic properties on the protic polymeric membranes. Proton structural and dynamical stability at different temperatures and humidification conditions were investigated by Neutron Scattering (QENS and NR). The optimized poly(diallylmethylammonium X - ) shows similar ionic conductivity values than Nafion 212 under varying relative humidity conditions at 80 °C. Furthermore, it shows a high ionic conductivity value of 1.9 × 10 -3 Scm -1 at 120 °C under dry conditions.
08 HYDROGEN↗
Control of zeolite pore interior for chemoselective alkyne/olefin separations
The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. Additionally, in situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C 2 H 2 ) 3 ] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Deformation and Failure of a Multi-Wall Carbon Nanotube Yarn Composite
Forests of multi-walled carbon nanotubes can be twisted and manipulated into continuous fibers or yarns that exhibit many of the characteristics of traditional textiles. Macro-scale analysis and test may provide strength and stiffness predictions for a composite composed of a polymer matrix and low-volume fraction yarns. However, due to the nano-scale of the carbon nanotubes, it is desirable to use atomistic calculations to consider tube-tube interactions and the influence of simulated twist on the effective friction coefficient. This paper reports laboratory test data on the mechanical response of a multi-walled, carbon nanotube yarn/polymer composite from both dynamic and quasi-static tensile tests. Macroscale and nano-scale analysis methods are explored and used to define some of the key structure-property relationships. The measured influence of hot-wet aging on the tensile properties is also reported.
Gates, Thomas S.↗
Impact Behavior of Composite Fan Blade Leading Edge Subcomponent with Thermoplastic Polyurethane Interleave
Impact damage tolerance and damage resistance is a critical metric for application of polymer matrix composites where failure caused by impact damage could compromise structural performance and safety. As a result, several materials and/or design approaches to improve impact damage tolerance have been investigated over the past several decades. Many composite toughening methodologies impart a trade-off between increased fracture toughness and compromised in-plane strength and modulus. In large part, mechanical tests to evaluate composite damage tolerance include static methods such as Mode I, Mode II, and mixed mode failures. However, ballistic impact damage resistance does not always correlate with static properties. The intent of this paper is to evaluate the influence of a thermoplastic polyurethane veil interleave on the static and dynamic performance of composite test articles. Static coupon tests included tension, compression, double cantilever beam, and end notch flexure. Measurement of the resistance to ballistic impact damage were made to evaluate the composites response to high speed impact. The interlayer material showed a decrease of in-plane performance with only a moderate improvement to Mode I and Mode II fracture toughness. However, significant benefit to impact damage tolerance was observed through ballistic tests.
Damage Tolerance↗
Hysteresis-Free Nanoparticle-Reinforced Hydrogels
The elastic storage and release of mechanical energy has been key to many developments throughout the history of mankind. Resilience, absent hysteresis, has been an elusive goal to achieve, particularly at large deformations. Using a low-crosslink-density polyacrylamide hydrogel at 96% water content having hyperbranched silica nanoparticles (HBSPs) as the major junction points, a hysteresis-free material is realized. The fatigue-free characteristic of these composite hydrogels is evidenced by the invariance of the stress–strain curves at strain ratios of 4, even after 5000 cycles. At a strain ratio of 7, only a 1.3% hysteresis is observed. A markedly increased strain-ratio-at-break of 11.5 is observed. Finally, the unique attributes of these resilient hydrogels are manifested in the high-fidelity detection of dynamic deformations under cyclic loading over a broad range of frequencies, difficult to achieve with other materials.
36 MATERIALS SCIENCE↗
Counterintuitive Compatibilization of Poly(-Valerolactone) and Poly(L-Lactic Acid) by Statistical Copolymers toward Compostable and Recyclable Packaging
Poly(δ-valerolactone) (PVL) and poly(l-lactic acid) (PLLA) are bioderivable, compostable, and chemically recyclable plastics with synergistic properties for addressing plastic waste accumulation in receiving environments. Though recyclable-by-design polymers often fall short of competing with incumbent materials, blending affords a means to leverage individual component strengths toward ideal tunable properties. Polymer blends are often immiscible, but a range of methodologies are available to promote mixing. Here, we report on the compatibilization of 9 immiscible PVL and PLLA blends with three different compatibilization agents: thermoplastic starch, synthesized PVL-co-PLLA statistical copolymers (SCPs), and synthesized PVL-b-PLLA block-type copolymers. Resulting degrees of compatibilization are observed through scanning electron microscopy, corroborated by thermal and mechanical analyses monitoring performance as a function of microdomain size. Small-angle and wide-angle X-ray scattering experiments are conducted to observe the influence of compatibilizers on individual crystalline phases to further elucidate material behavior. Molecular dynamics simulations provide key insights into the interfacial interactions between homopolymers and compatibilizers. Finally, a suite of end-of-life avenues is established by biodegradation in industrial composting conditions, chemical recycling by deconstruction to hydroxymethyl esters, and direct chemical depolymerization to lactone precursors in mixed feed. Overall, we highlight several promising blends and the counterintuitive SCP compatibilization phenomenon toward high-performance, sustainable materials.
Compatibilization, copolymer compatibilizer, bio-b↗
Unraveling the Luminescence Quenching Mechanism in Strong and Weak Quantum-Confined CsPbBr 3 Triggered by Triarylamine-Based Hole Transport Layers
Luminescence quenching by hole transport layers (HTLs) is one of the major issues in developing efficient perovskite light-emitting diodes (PeLEDs), particularly prominent in blue-emitting devices. While a variety of material systems have been used as interfacial layers, the origin of such quenching and the type of interactions between perovskites and HTLs are still ambiguous. Here, we present a systematic investigation of the luminescence quenching of CsPbBr 3 by a commonly employed hole transport polymer, Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB) in LEDs. Strong and weakly quantum-confined CsPbBr 3 (nanoplatelets (NPLs)/nanocrystals (NCs)) are rationally selected to study the quenching mechanism by considering the differences in their morphology, energy level alignments, and quantum confinement. The steady-state and time-resolved Stern-Volmer plots unravel the dominance of dynamic and static quenching at lower and higher concentrations of TFB, respectively, with maximum quenching efficiency of 98%. The quenching rate in NCs is faster than in NPLs owing to their longer PL lifetimes and weak quantum confinement. The ultrafast transient absorption results support these dynamics and rule out the involvement of Forster or Dexter energy transfer. Finally, the 1D 1 H and 2D NOESY NMR study confirms the exchange of native ligands at the NCs surface with TFB, leading to dark CsPbBr 3 -TFB ensemble formation accountable for luminescence quenching. This highlights the critical role of the triarylamine functional group on TFB (also the backbone of many HTLs) in the quenching process. These results shed light on the underlying reasons for the luminescence quenching in PeLEDs and will help to choose the interfacial layers rationally for developing efficient LEDs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Anti-Icing Coatings using Ionomer Film Layer Structuring
This research effort examined the application of Nafion polymers in alcohol solvents as an anti-ice surface coating, as a mixture with hydrophilic polymers and freezing point depressant salt systems. Co-soluble systems of Nafion, polymer and salt were applied using dip coating methods to create smooth films for frost observation over a Peltier plate thermal system in ambient laboratory conditions. Cryo-DSC was applied to examine freezing events of the Nafion-surfactant mixtures, but the sensitivity of the measurement was insufficient to determine frost behavior. Collaborations with the Fog Chamber at Sandia-Albuquerque, and in environmental SAXS measurements with CINT-LANL were requested but were not able to be performed under the research duration. Since experimental characterization of these factors is difficult to achieve directly, computational modeling was used to guide the scientific basis for property improvement. Computational modeling was performed to improve understanding of the dynamic association between ionomer side groups and added molecules and deicing salts. The polyacrylic acid in water system was identified at the start of the project as a relevant system for exploring the effect of varying counterions on the properties of fully deprotonated polyacrylic acid (PAA) in the presence of water. Simulations were modeled with four different counterions, two monovalent counterions (K+ and Na+) and two divalent counterions (Ca2+ and Mg2+). The wt% of PAA in these systems was varied from ~10 to 80 wt% PAA for temperatures from 250K to 400K. In the second set of simulations, the interpenetration of water into a dry PAA film was studied for Na+ or Ca2+ counterions for temperatures between 300K and 400K. The result of this project is a sprayable Nafion film composite which resists ice nucleation at -20 °C for periods of greater than three hours. It is composed of Nafion polymer, hydrophilic polyethylene oxide polymer and CaCl2 anti-ice crosslinker. Durability and field performance properties remain to be determined.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermodynamically consistent algorithms for models of incompressible multiphase polymer solutions with a variable mobility
Here we present a general strategy for developing structure and property preserving numerical algorithms for thermodynamically consistent models of incompressible multiphase polymer solutions with a variable mobility. We first present a formalism to derive thermodynamically consistent, incompressible, multiphase polymer models. Then, we develop the general strategy, known as the supplementary variable method, to devise thermodynamically consistent numerical approximations to the models. We illustrate the numerical strategy using newly developed models of incompressible diblock copolymer solutions coupled with an electric and a magnetic field, respectively. Mesh refinement is conducted to verify convergence rates of the developed schemes. Some numerical examples are given to exhibit underlying dynamics absent from and driven by the external fields, respectively, highlighting differences between models with the variable and constant mobilities.
97 MATHEMATICS AND COMPUTING↗
Effect of Diphenyl Content on Viscoelasticity of Poly(dimethyl- co -diphenyl)siloxane Melt and Network
Polydimethylsiloxane (PDMS) is one of the most widely used polymeric materials for sealants, adhesives, lubricants, and thermal as well as electrical insulation. At low temperatures, however, PDMS is subject to crystallization that can cause deterioration in mechanical function. A common way to suppress such crystallization is through the incorporation of phenylsiloxane into the backbone of polysiloxane. Nevertheless, the introduction of phenyl components, even in small quantities, could potentially change the properties of the siloxane in a significant way. In this work, a series of mechanical tests and finite element simulations were performed to study the macroscale viscoelasticity of two poly(dimethyl-co-diphenyl)siloxane formulations in order to understand the effects of a few percent diphenyl contents on the viscoelasticity of the polysiloxane material. Here, we utilized the small-angle X-ray scattering to investigate the microscopic structures of the copolymers and broadband dielectric spectroscopy and rheology to probe the chain dynamics at the microscale. The results of these characterizations were used to inform the finite element simulations. We found that the degree of cross-linking does not significantly alter the microstructure but can profoundly affect the viscoelastic response of the copolymer networks. The corresponding hysteretic behavior is interpreted in terms of reptation-like motion and relaxation of the effective free chains in the cured polymer network. The relaxation of the copolymer chains is slowed significantly by even a small increase in the molar ratio of the diphenyl component.
36 MATERIALS SCIENCE↗
Lessons from intramolecular singlet fission with covalently bound chromophores
Molecular dimers, oligomers, and polymers are versatile components in photophysical and optoelectronic architectures that could impact a large variety of applications. We present a perspective on such systems in the field of singlet fission, which effectively multiplies excitons and produces a unique excited state species, the triplet pair. The choice of chromophore and the nature of the attachment between units, both geometrical and chemical, play a defining role in the dynamical scheme that evolves upon photoexcitation. Specific final outcomes (e.g., separated and uncorrelated triplet pairs) are being sought through rational design of covalently bound chromophore architectures built with guidance from recent fundamental studies that correlate structure with excited state population flow kinetics.
36 MATERIALS SCIENCE↗
Hydroporphyrin-Doped Near-Infrared-Emitting Polymer Dots for Cellular Fluorescence Imaging
We report Near-infrared (NIR) fluorescent semiconductor polymer dots (Pdots) have shown great potential for fluorescence imaging due to their exceptional chemical and photophysical properties. This paper describes the synthesis of NIR emitting Pdots with great control and tunability of emission peak wavelength. The Pdots were prepared by doping poly [(9,9-dioctylfluorenyl-2,7-diyl)-altco-(1,4-benzo-(2,1’,3)-thiadiazole)] (PFBT), a semiconducting polymer commonly used as a host polymer in luminescent Pdots, with a series of chlorins and bacteriochlorins with varying functional groups. Chlorins and bacteriochlorins are ideal dopants due to their high hydrophobicity, which precludes their use as molecular probes in aqueous biological media but on the other hand prevents their leakage when doped into Pdots. Additionally, chlorins and bacteriochlorins have narrow deep-red to NIR emission bands and the wide array of synthetic modifications available for modifying their molecular structure enables tuning their emission predictably and systematically. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements show the chlorin and bacteriochlorin-doped Pdots to be nearly spherical with an average diameter of 46±12 nm. Efficient energy transfer between PFBT and the doped chlorins or bacteriochlorins decreases the PFBT donor emission to near baseline level and increases the emission of the doped dyes that serve as acceptors. The chlorin and bacteriochlorindoped Pdots show narrow emission bands ranging from 640 nm to 820 nm depending on the doped dye. The paper demonstrates the utility of the systematic chlorin and bacteriochlorin synthesis approach by preparing Pdots of varying emission peak wavelength, utilizing them to visualize multiple targets using wide field fluorescence microscopy, binding them to secondary antibodies, and determining the binding of secondary antibody-conjugated Pdots to primary antibody-labeled receptors in plant cells. Additionally, the chlorin and bacteriochlorin doped Pdots show a blinking behavior that could enable their use in super resolution imaging methods like STORM.
13C-NMR↗