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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.

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At least 19 records

Indirect morphological analysis of particles in polymer particle composites via non-destructive permittivity measurements

We report polymers with specific properties (e.g. electrical, optical or mechanical) are commonly obtained via the addition of additives. The composites final properties rely on the preservation of these additives during embedding, which is, in particular, challenging for high aspect ratio particles, like shear-sensitive flaky particles (ssFP). Thus, in cases of ssFP off- or in-line monitoring is required. This study addresses the lack of suitable non-destructive monitoring methods appropriate for ssFP possessing a thickness below 1um and an area equivalent diameter of several 10 um. An elegant method was developed to validate the integrity of ssFP within composites, which is based on the measurement of the composite's permittivity and applying precise micro-structure property correlations to indirectly determine their morphological features. The main hypothesis tested was that a reduction of the particle’s aspect ratio by a factor of larger than 5 can be detected by the measurement of the composite's permittivity. In this study,the matrix polymer polyethylene or an epoxy resin together with mica-based ssFP with a mean area equivalent diameter of 42 um were used. The micro-structure property correlation presented by G. Ondracek [Z. f. Werkstofftechnik, 8:280-287, 1977] provided the necessary theoretical backbone to indirectly infer geometrical changes to the ssFP from permittivity measurements. An excellent match was obtained between the indirectly and the directly determined particle aspect ratios. This preliminary study established the presented technique as a promising non-destructive test method to monitor the integrity of ssFPs embedded in a polymer. In principle this technique is adaptable for in-line process monitoring.

36 MATERIALS SCIENCE↗

Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging

The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. Here, these findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dry particle coating of polymer particles for tailor-made product properties

Disperse polymer powders with tailor-made particle properties are of increasing interest in industrial applications such as Selective Laser Beam Melting processes (SLM). This study focuses on dry particle coating processes to improve the conductivity of the insulating polymer powder in order to assemble conductive devices. Therefore PP particles were coated with Carbon Black nanoparticles in a dry particle coating process. This process was investigated in dependence of process time and mass fraction of Carbon Black. The conductivity of the functionalized powders was measured by impedance spectroscopy. It was found that there is a dependence of process time, respectively coating ratio and conductivity. The powder shows higher conductivities with increasing number of guest particles per host particle surface area, i.e. there is a correlation between surface functionalization density and conductivity. The assembled composite particles open new possibilities for processing distinct polymers such as PP in SLM process. The fundamentals of the dry particle coating process of PP host particles with Carbon Black guest particles as well as the influence on the electrical conductivity will be discussed.

36 MATERIALS SCIENCE↗

Electromechanical characterization of individual micron-sized metal coated polymer particles

Micron-sized polymer particles with nanoscale metal coatings are essential in conductive adhesives for electronics assembly. The particles function in a compressed state in the adhesives. The link between mechanical properties and electrical conductivity is thus of the utmost importance in the formation of good electrical contact. A custom flat punch set-up based on nanoindentation has been developed to simultaneously deform and electrically probe individual particles. The set-up has a sufficiently low internal resistance to allow the measurement of sub-Ohm contact resistances. Additionally, the set-up can capture mechanical failure of the particles. Combining this data yields a fundamental understanding of contact behavior. We demonstrate that this method can clearly distinguish between particles of different sizes, with different thicknesses of metal coating, and different metallization schemes. The technique provides good repeatability and physical insight into the behavior of these particles that can guide adhesive design and the optimization of bonding processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Molecular simulation study of role of polymer–particle interactions in the strain-dependent viscoelasticity of elastomers (Payne effect)

The strain-amplitude dependence of viscoelastic behavior of model crosslinked elastomers containing various concentrations of spherical nanoparticles (NPs) was studied by non-equilibrium molecular dynamics simulation. All the filler NPs were in monodispersed state and the interactions between these particles were purely repulsive. The polymer–particle interactions were attractive and their interaction energies were tuned in a broad range. Through the computational study, many important features of the behavior of particle-reinforced elastomers observed in experiments, including the Payne effect, were successfully reproduced. It was shown that the magnitude of the Payne effect was found to depend on the polymer–particle interaction and the filler loading. By examining the microstructures of the simulation systems and their evolution during oscillatory shear, four different mechanisms for the role of the polymer–particle interactions in the Payne effect were revealed that consist of the debonding of polymer chains from NP surfaces, the breakage of polymer-shell-bridged NP network, the rearrangement of the NPs in the network into different layers and the shear-induced yielding of the rigid polymer shell in-between neighboring NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monodisperse porous polymer particles containing macrocyclic ether as a new class of sorbent for SR(II) separation

Strontium{sup 90} is one of the typical fission products that may be found in high level liquid waste (HLLW). Separation of Sr{sup 90} prior to the vitrification is beneficial to the final treatment of solid radioactive waste. In this study, a new class of sorbent for Sr(II) was developed by loading the macrocyclic ether DtBuCH18C6 into the monodisperse porous polymer particles (MPPPs). The MPPPs are well-known as a promising chromatographic material due to the uniform particle size, porous morphology, good compatibility with organic extractants, and rigid matrix. The structure and micro-morphology of the sorbent particles were characterized. The adsorption behavior towards Sr(II) in HNO{sub 3} media was investigated by both batch and column experiments. High adsorption efficiency and selective separation of Sr(II) was obtained. The sorbent particles can be recycled for at least several times before obvious lose of the adsorption ability. This kind of sorbent possesses the potential to be used for strontium separation in radioactive liquid waste.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrical four-point probing of spherical metallic thin films coated onto micron sized polymer particles

Micron-sized metal-coated polymer spheres are frequently used as filler particles in conductive composites for electronic interconnects. However, the intrinsic electrical resistivity of the spherical thin films has not been attainable due to deficiency in methods that eliminate the effect of contact resistance. In this work, a four-point probing method using vacuum compatible piezo-actuated micro robots was developed to directly investigate the electric properties of individual silver-coated spheres under real-time observation in a scanning electron microscope. Poly(methyl methacrylate) spheres with a diameter of 30 μm and four different film thicknesses (270 nm, 150 nm, 100 nm, and 60 nm) were investigated. By multiplying the experimental results with geometrical correction factors obtained using finite element models, the resistivities of the thin films were estimated for the four thicknesses. These were higher than the resistivity of bulk silver.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Laser-Induced Phase Transition in a Monolayer of Polymer Particles Levitating in a Low-Pressure Gas-Discharge Plasma

We report on the results of analysis of the mean kinetic energy and the pair correlation function of polymer particles in a plasma–dust structure under the action of laser radiation. We have observed experimentally the crystal–liquid phase transition in the monolayer of particles levitating in the near-electrode layer of a capacitive high-frequency discharge. The coupling parameter of the dust system has been estimated. The results of analysis of the modification of the polymer dust particle surface after holding in the plasma are considered. We propose an explanation of the phase transition taking into account the role of the photophoretic force in the motion of macroparticles. The effect of the photophoretic force is associated with the modification of the dust particle surface in the plasma, as a result of which the particles can effectively absorb laser radiation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Transparent Conductive Adhesives for Tandem Solar Cells Using Polymer-Particle Composites

Transparent conductive adhesives (TCAs) can enable conductivity between two substrates, which is useful for a wide range of electronic devices. Here, we have developed a TCA composed of a polymer-particle blend with ethylene-vinyl acetate as the transparent adhesive and metal-coated flexible poly(methyl methacrylate) microspheres as the conductive particles that can provide conductivity and adhesion regardless of the surface texture. This TCA layer was designed to be nearly transparent, conductive in only the out-of-plane direction, and of practical adhesive strength to hold the substrates together. The series resistance was measured at 0.3 and 0.8 O cm2 for 8 and 0.2% particle coverage, respectively, while remaining over 92% was transparent in both cases. For applications in photovoltaic devices, such as mechanically stacked multijunction III-V/Si cells, a TCA with 1% particle coverage will have less than 0.5% power loss due to the resistance and less than 1% shading loss to the bottom cell.

14 SOLAR ENERGY↗

Surface-selective laser sintering of thermolabile polymer particles using water as heating sensitizer

We report the implementation of a novel scheme for surface-selective laser sintering (SSLS) of polymer particles, based on using water as a sensitizer of laser heating and sintering of particles as well as laser radiation at a wavelength of 1.94 μm, corresponding to the strong absorption band of water. A method of sintering powders of poly(lactide-co-glycolide), a hydrophobic bioresorbable polymer, after modifying its surface with an aqueous solution of hyaluronic acid is developed. The sintering thresholds for wetted polymer are by 3 – 4 times lower than those for sintering in air. The presence of water restricts the temperature of the heated polymer, preventing its thermal destruction. Polymer matrices with a developed porous structure are obtained. The proposed SSLS method can be applied to produce bioresorbable polymer matrices for tissue engineering. (interaction of laser radiation with matter. laser plasma)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Design and scale-up of a semi-industrial downer-reactor for the rounding of irregular polymer particles

The recent development of rapid prototyping technologies towards additive manufacturing reveals some major drawbacks of processes such as laser beam melting (LBM). This contribution focuses on the lack of suitable polymer material with a fine particle size and good flowability. Polymer particles obtained by a wet grinding process 1 are treated in a heated downer reactor. This treatment changes the particles’ morphology from a chiselled state towards a spherical form by surface tension forces in a molten state 2 and leads to an improved flowability. To reach the required amount of rounded polymer powder, a downer reactor in semi-industrial scale has been established and will be characterized in this article. For the purpose of particle rounding it is necessary to avoid contact of molten particles with each other and with the hot reactor walls. Furthermore, the heat distribution has been investigated as one of the key parameters of the process. Finally, a proof of concept by rounding wet grinded PBT material was successfully conducted. The product was examined to obtain data about a change in particle size and flowability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Production of micron-sized polymer particles for additive manufacturing by melt emulsification

Melt emulsification is an advanced top-down approach that permits to produce spherical particles and thus widens the availability of polymer feed materials for additive manufacturing. In the process the polymer is molten in a continuous phase and droplet breakup is realized in a rotor-stator-device. The stabilization of the newly formed surfaces is quite challenging. Therefore, a new method to identify an appropriate emulsifier by measuring the interfacial tension between the polymer and continuous phase using a high pressure / high temperature cell is presented. The obtained powders are characterized by scanning electron microscopy (SEM) and by a Zimmermann tensile strength tester to determine the powder flowability. The processability of the polymer powders for additive manufacturing is investigated and demonstrated by building single layers by laser beam melting.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membrane fuel-cell catalyst layers. Characterization of an ink microstructure using oscillatory shear rheology showed that the catalyst particles (platinum on carbon) are significantly agglomerated in the absence of PAA or an ionomer. Both the ionomer and PAA promoted the stability of the particles against agglomeration via electrosteric stabilization by adsorbing onto the particle surface. Increasing the PAA concentration increased the stability of the particles (or reduced the agglomerated structure) due to increasing PAA coverage onto the free surface area of the particles. However, beyond a certain increase in concentration, PAA was found to predominantly remain as an excess free polymer in the ink due to an insufficient free/available surface area on the particles for further PAA coverage. Extensional rheology measurements demonstrated that PAA enhances the extensional viscosities of the inks. Consequently, increasing the PAA concentration in the ink promoted the evolution of uniform nanofibers. However, beyond a certain concentration, a significant increase in the shear viscosities of the inks led to defective fiber morphologies because of the onset of flow instabilities. Electrochemical performance comparisons between catalyst layers with different PAA concentrations showed maximum performance at the PAA concentration that led to the least agglomerated structure of the catalyst, most uniform fiber morphologies, and low concentrations of free (non-adsorbing) PAA in the electrode. These results provide a rationale for optimization of electrospun catalyst nanofibers for both spinnability and electrochemical performance.

25 ENERGY STORAGE↗

Solid-state polymer-particle hybrid electrolytes: Structure and electrochemical properties

Solid-state electrolytes (SSEs) are challenged by complex interfacial chemistry and poor ion transport through the interfaces they form with battery electrodes. Here, we investigate a class of SSE composed of micrometer-sized lithium oxide (Li 2 O) particles dispersed in a polymerizable 1,3-dioxolane (DOL) liquid. Ring-opening polymerization (ROP) of the DOL by Lewis acid salts inside a battery cell produces polymer-inorganic hybrid electrolytes with gradient properties on both the particle and battery cell length scales. These electrolytes sustain stable charge-discharge behavior in Li||NCM811 and anode-free Cu||NCM811 electrochemical cells. On the particle length scale, Li 2 O retards ROP, facilitating efficient ion transport in a fluid-like region near the particle surface. On battery cell length scales, gravity-assisted settling creates physical and electrochemical gradients in the hybrid electrolytes. By means of electrochemical and spectroscopic analyses, we find that Li 2 O particles participate in a reversible redox reaction that increases the effective CE in anode-free cells to values approaching 100%, enhancing battery cycle life.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗