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At least 19 records

Reprocessable polyhydroxyurethane networks reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS) and exhibiting excellent elevated temperature creep resistance

The rapid development of covalent adaptable networks or vitrimers shows promise for addressing the long-standing recycling issues associated with conventional, permanently cross-linked thermosets. At the same time, it is important to demonstrate that properties of reprocessable polymer networks can be optimized to meet the ongoing demand for high-performance materials. We have fabricated reprocessable polyhydroxyurethane (PHU) network composites reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS). With functionalized POSS serving as a fraction of the cross-linkers, the PHU–POSS network nanocomposites exhibit significantly enhanced storage modulus at the rubbery plateau region relative to the neat PHU network. With up to 10 wt% POSS loading, these network composites can undergo melt-state reprocessing at 140 °C with 100% property recovery associated with cross-link density. We also show that hydroxyurethane dynamic chemistry leads to excellent creep resistance at elevated temperature up to 90 °C and is unaffected by reactive incorporation of POSS. In conclusion, this study demonstrates the effectiveness of POSS as nanofillers for designing high-performance, organic-inorganic dynamic PHU networks with excellent reprocessability.

42 ENGINEERING↗

Discovering vanishing objects in POSS I red images using the Virtual Observatory

ABSTRACT In this paper, we report a search for vanishing sources in POSS I red images using virtual observatory (VO) archives, tools, and services. The search, conducted in the framework of the VASCO project, aims at finding POSS I (red) sources not present in recent catalogues like Pan-STARRS DR2 (limiting magnitude r = 21.4) or Gaia EDR3 (limiting magnitude G = 21). We found 298 165 sources visible only in POSS I plates, out of which 288 770 had a cross-match within 5 arcsec in other archives (mainly in the infrared), 189 were classified as asteroids, 35 as variable objects, 3592 as artefacts from the comparison to a second digitization (Supercosmos), and 180 as high proper motion objects without information on proper motion in Gaia EDR3. The remaining unidentified transients (5399) as well as the 172 163 sources not detected in the optical but identified in the infrared regime are available from a VO compliant archive and can be of interest in searches for strong M-dwarf flares, high-redshift supernovae, asteroids, or other categories of unidentified red transients. No point sources were detected by both POSS-I and POSS-II before vanishing, setting the rate of failed supernovae in the Milky Way during 70 yr to less than one in one billion.

Solano, Enrique↗

Experimental study of UV induced tensile properties deterioration and chemical aging of polyurea–POSS composites

Ultraviolet (UV) radiation present in natural sunlight degrades the chemical and mechanical properties of polymeric matrices in composites. Polyurea possess a unique set of chemical and mechanical properties due to its complex microstructure comprising of hard and soft segments (phases). The primary objective of the work presented here is to characterize the chemical and mechanical degradation of pure polyurea and polyurea - polyhedral oligomeric silsesquioxane (POSS) nanocomposites subjected to UV radiation exposure for 45 days. Control specimen in as-received condition (reference specimen) and UV-aged tensile test specimen are tested in the study. Analysis of Fourier transformed infrared (FTIR) spectra for UV-aged polyurea and polyurea-POSS composites reveals that the addition of POSS nanoparticles accelerate the deterioration of polyurea matrix by breaking the hard phase network and altering the mechanism of degradation for the soft phase present in polyurea microstructure. The deterioration of hard and soft segments cause a significant reduction in tensile properties of polyurea-POSS composites.

Materials Science↗

Novel Low-Temperature Poss-Containing Siloxane Elastomers

One route to increased aircraft performance is through the use of flexible, shape-changeable aerodynamics effectors. However, state of the art materials are not flexible or durable enough over the required broad temperature range. Mixed siloxanes were crosslinked by polyhedral oligomeric silsesquioxanes (POSS) producing novel materials that remained flexible and elastic from -55 to 94 C. POSS molecules were chemically modified to generate homogeneous distributions within the siloxane matrix. High resolution scanning electron microscope (HRSEM) images indicated homogenous POSS distribution up to 0.8 wt %. Above the solubility limit, POSS aggregates could be seen both macroscopically and via SEM (approx.60-120 nm). Tensile tests were performed to determine Young s modulus, tensile strength, and elongation at break over the range of temperatures associated with transonic aircraft use (-55 to 94 C; -65 to 200 F). The siloxane materials developed here maintained flexibility at -55 C, where previous candidate materials failed. At room temperature, films could be elongated up to 250 % before rupturing. At -55 and 94 C, however, films could be elongated up to 400 % and 125 %, respectively.

Belcher, Marcus A.↗

Oxygen Plasma Modification of Poss-Coated Kapton(Registered TradeMark) HN Films

The surface energy of a material depends on both surface composition and topographic features. In an effort to modify the surface topography of Kapton(Registered TradeMark) HN film, organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), were spray-coated onto the Kapton(Registered TradeMark) HN surface. Prior to POSS application, the Kapton(Registered TradeMark) HN film was activated by exposure to radio frequency (RF)-generated oxygen plasma. After POSS deposition and solvent evaporation, the films were exposed to various durations of RF-generated oxygen plasma to create a topographically rich surface. The modified films were characterized using optical microscopy, attenuated total reflection infrared (ATR-IR) spectroscopy, and high-resolution scanning electron microscopy (HRSEM). The physical properties of the modified films will be presented.

Wohl, C. J.↗

Modification of the Surface Properties of Polyimide Films using POSS Deposition and Oxygen Plasma Exposure

Topographically rich surfaces were generated by spray-coating organic solutions of a polyhedral oligomeric silsesquioxane, octakis (dimethylsilyloxy) silsesquioxane (POSS), on Kapton HN films and exposing them to radio frequency generated oxygen plasma. Changes in both surface chemistry and topography were observed. High-resolution scanning electron microscopy indicated substantial modification of the POSS-coated polyimide surface topographies as a result of oxygen plasma exposure. Water contact angles varied from 104 deg for unexposed POSS-coated surfaces to approximately 5 deg, for samples exposed for 5 h. Modulation of the dispersive and polar contributions to the surface energy was determined using van Oss Good Chaudhury theory.

Wohl, Christopher J.↗

Incorporating the APS Catalog of the POSS I and Image Archive in ADS

The primary purpose of this contract was to develop the software to both create and access an on-line database of images from digital scans of the Palomar Sky Survey. This required modifying our DBMS (called Star Base) to create an image database from the actual raw pixel data from the scans. The digitized images are processed into a set of coordinate-reference index and pixel files that are stored in run-length files, thus achieving an efficient lossless compression. For efficiency and ease of referencing, each digitized POSS I plate is then divided into 900 subplates. Our custom DBMS maps each query into the corresponding POSS plate(s) and subplate(s). All images from the appropriate subplates are retrieved from disk with byte-offsets taken from the index files. These are assembled on-the-fly into a GIF image file for browser display, and a FITS format image file for retrieval. The FITS images have a pixel size of 0.33 arcseconds. The FITS header contains astrometric and photometric information. This method keeps the disk requirements manageable while allowing for future improvements. When complete, the APS Image Database will contain over 130 Gb of data. A set of web pages query forms are available on-line, as well as an on-line tutorial and documentation. The database is distributed to the Internet by a high-speed SGI server and a high-bandwidth disk system. URL is http://aps.umn.edu/IDB/. The image database software is written in perl and C and has been compiled on SGI computers with MIX5.3. A copy of the written documentation is included and the software is on the accompanying exabyte tape.

Humphreys, Roberta M.↗

Enhancing and Archiving the APS Catalog of the POSS I

We have worked on two different projects: 1) Archiving the APS Catalog of the POSS I for distribution to NASA's NED at IPAC, SIMBAD in France, and individual astronomers and 2) The automated morphological classification of galaxies. We have completed archiving the Catalog into easily readable binary files. The database together with the software to read it has been distributed on DVD's to the national and international data centers and to individual astronomers. The archived Catalog contains more than 89 million objects in 632 fields in the first epoch Palomar Observatory Sky Survey. Additional image parameters not available in the original on-line version are also included in the archived version. The archived Catalog is also available and can be queried at the APS web site (URL: http://aps.umn.edu) which has been improved with a much faster and more efficient querying system. The Catalog can be downloaded as binary datafiles with the source code for reading it. It is also being integrated into the SkyQuery system which includes the Sloan Digital Sky Survey, 2MASS, and the FIRST radio sky survey. We experimented with different classification algorithms to automate the morphological classification of galaxies. This is an especially difficult problem because there are not only a large number of attributes or parameters and measurement uncertainties, but also the added complication of human disagreement about the adopted types. To solve this problem we used 837 galaxy images from nine POSS I fields at the North Galactic Pole classified by two independent astronomers for which they agree on the morphological types. The initial goal was to separate the galaxies into the three broad classes relevant to issues of large scale structure and galaxy formation and evolution: early (ellipticals and lenticulars), spirals, and late (irregulars) with an accuracy or success rate that rivals the best astronomer classifiers. We also needed to identify a set of parameters derived from the digitized images that separate the galaxies by type. The human eye can easily recognize complicated patterns in images such as spiral arms which can be spotty, blotchy affairs that are difficult for automated techniques. A galaxy image can potentially be described by hundreds of parameters, all of which may have some relation to the morphological type. In the set of initial experiments we used 624 such parameters, in two colors, blue and red. These parameters include the surface brightness and color measured at different radii, ratios of these parameters at different radii, concentration indices, Fourier transforms and wavelet decomposition coefficients. We experimented with three different classes of classification algorithms; decision trees, k-nearest neighbors, and support vector machines (SVM). A range of experiments were conducted and we eventually narrowed the parameters to 23 selected parameters. SVM consistently outperformed the other algorithms with both sets of features. By combining the results from the different algorithms in a weighted scheme we achieved an overall classification success of 86%.

Humphreys, Roberta M.↗

Properties of PMR Polyimides Improved by Preparation of Polyhedral Oligomeric Silsesquioxane (POSS) Nanocomposites

The field of hybrid organic-inorganic materials has grown drastically over the last several years. This interest stems from our ever-increasing ability to custom-build and control molecular structure at several length scales. This ability to control both the composition and structure of hybrid materials is sometimes broadly referred to as nanocomposite systems. One class of hybrid (organic-inorganic) nanostructured material is polyhedral oligomeric silsesquioxane (POSS), shown in the preceding diagram. The hybrid composition gives POSS materials dramatically enhanced properties relative to traditional hydrocarbons and inorganics. An important benefit of this technology is that it makes possible the formulations of nanostructured chemicals with excellent thermal and oxidative stability. This is largely due to the inorganic component.

Campbell, Sandi G.↗

Optimal Composite Material for Low Cost Fabrication of Large Composite Aerospace Structures using NASA Resins or POSS Nanoparticle Modifications

Thermoplastic laminates in situ consolidated via tape or tow placement require full mechanical properties. Realizing full properties requires resin crystallinity to be controlled - partial crystallinity leads to unacceptably low laminate compression properties. There are two approaches: utilize an amorphous matrix resin; or place material made from a semi-crystalline resin featuring kinetics faster than the process. In this paper, a matrix resin evaluation and trade study was completed with commercial and NASA amorphous polyimides on the one hand, and with PEKK mixed with POSS nanoparticles for accelerated crystallinity growth on the other. A new thermoplastic impregnated material, 6 mm wide (0.25-in) AS-4 carbon/LaRC(TradeMark)8515 dry polyimide tow, was fabricated. Since LaRC(TradeMark)8515 is fully amorphous, it attains full properties following in situ consolidation, with no post processing required to build crystallinity. The tow in situ processing was demonstrated via in situ thermoplastic filament winding it into rings.

Lamontia, Mark A.↗

Materials Data on POsS by Materials Project

PSOs crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Os5+ is bonded to three equivalent P3- and three equivalent S2- atoms to form distorted OsP3S3 octahedra that share corners with eight equivalent OsP3S3 octahedra, corners with three equivalent POs3S tetrahedra, corners with three equivalent SPOs3 tetrahedra, and edges with two equivalent OsP3S3 octahedra. The corner-sharing octahedra tilt angles range from 56–62°. There are a spread of Os–P bond distances ranging from 2.39–2.41 Å. There are one shorter (2.34 Å) and two longer (2.35 Å) Os–S bond lengths. P3- is bonded to three equivalent Os5+ and one S2- atom to form distorted POs3S tetrahedra that share corners with three equivalent OsP3S3 octahedra, corners with four equivalent POs3S tetrahedra, corners with nine equivalent SPOs3 tetrahedra, and an edgeedge with one POs3S tetrahedra. The corner-sharing octahedra tilt angles range from 66–71°. The P–S bond length is 2.28 Å. S2- is bonded to three equivalent Os5+ and one P3- atom to form SPOs3 tetrahedra that share corners with three equivalent OsP3S3 octahedra, corners with four equivalent SPOs3 tetrahedra, corners with nine equivalent POs3S tetrahedra, and an edgeedge with one SPOs3 tetrahedra. The corner-sharing octahedra tilt angles range from 74–78°.

36 MATERIALS SCIENCE↗

Materials Data on POsSe by Materials Project

OsPSe crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Os5+ is bonded to three equivalent P3- and three equivalent Se2- atoms to form OsP3Se3 octahedra that share corners with eight equivalent OsP3Se3 octahedra, corners with three equivalent POs3Se tetrahedra, corners with three equivalent SePOs3 tetrahedra, and edges with two equivalent OsP3Se3 octahedra. The corner-sharing octahedra tilt angles range from 55–60°. There are one shorter (2.40 Å) and two longer (2.41 Å) Os–P bond lengths. All Os–Se bond lengths are 2.47 Å. P3- is bonded to three equivalent Os5+ and one Se2- atom to form distorted POs3Se tetrahedra that share corners with three equivalent OsP3Se3 octahedra, corners with four equivalent POs3Se tetrahedra, corners with nine equivalent SePOs3 tetrahedra, and an edgeedge with one POs3Se tetrahedra. The corner-sharing octahedra tilt angles range from 64–72°. The P–Se bond length is 2.45 Å. Se2- is bonded to three equivalent Os5+ and one P3- atom to form SePOs3 tetrahedra that share corners with three equivalent OsP3Se3 octahedra, corners with four equivalent SePOs3 tetrahedra, corners with nine equivalent POs3Se tetrahedra, and an edgeedge with one SePOs3 tetrahedra. The corner-sharing octahedra tilt angles range from 73–82°.

36 MATERIALS SCIENCE↗

POSS(Registered TradeMark) Coatings for Solar Cells: An Update

Presently, solar cells are covered with Ce-doped microsheet cover glasses that are attached with Dow Corning DC 93-500 silicone adhesive. Various antireflection coatings are often applied to the cover glass to increase cell performance. This general approach has been used from the beginning of space exploration. However, it is expensive and time consuming. Furthermore, as the voltage of solar arrays increases, significant arcing has occurred in solar arrays, leading to loss of satellite power. The cause has been traced to differential voltages between strings and the close spacing between them with no insulation covering the edges of the solar cells. In addition, this problem could be ameliorated if the cover glass extended over the edges of the cell, but this would impact packing density. An alternative idea that might solve all these issues and be less expensive and more protective is to develop a coating that could be applied over the entire array. Such a coating must be resistant to atomic oxygen for low earth orbits below about 700 km, it must be resistant to ultraviolet radiation for all earth and near-sun orbits and, of course, it must withstand the damaging effects of space radiation. Coating flexibility would be an additional advantage. Based on past experience, one material that has many of the desired attributes of a universal protective coating is the Dow Corning DC 93-500. Of all the potential optical plastics, it appears to be the most suitable for use in space. As noted above, DC 93-500 has been extensively used to attach cover glasses to crystalline solar cells and has worked exceptionally well over the years. It is flexible and generally resistant to electrons, protons and ultraviolet (UV and VUV) radiation; although a VUV-rejection coating or VUV-absorbing ceria-doped cover glass may be required for long mission durations. It can also be applied in a thin coating (< 25 m) by conventional liquid coating processes. Unfortunately, when exposed to atomic oxygen (AO) DC 93-500 develops a frosty surface. Such frosting can lead to a loss of light transmitted into the cells and destroy the essential clarity needed for a concentrator lens.

Brandhorst, Henry↗

Reversible Changes in the Grain Structure and Conductivity in a Block Copolymer Electrolyte

Here, we study the phase behavior of a triblock organic–inorganic hybrid copolymer, poly(polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixture, as a function of temperature. The polymer exhibits a lamellar morphology both in the neat state and in the presence of salt. However, the average grain size increases substantially when the electrolyte is heated above 113 °C. The grain structure of this sample changes reversibly with temperature, that is, smaller grains reappear when the electrolyte is cooled below 113 °C. While annealing block copolymers at high temperatures often leads to an increase in the grain size, this change is generally irreversible. The reason for the reversible change in the grain structure of the POSS-PEO-POSS/LiTFSI electrolyte is discussed. The ionic conductivity of the electrolyte also exhibits reversible changes in this temperature window. Knowledge of the grain structure is crucial for understanding ion transport in nanostructured electrolytes.

25 ENERGY STORAGE↗

Improved Light Extraction in Organic Light‐Emitting Diodes via Semiconductor Dilution

Increasing the internal light extraction efficiency of organic light‐emitting diodes (OLEDs) is key to improving their performance for solid‐state lighting applications; however, it is challenging to do this in a way that is compatible with high volume manufacturing. Here, it is shown that the outcoupling efficiency of OLEDs can be improved by diluting their hole transport layer (HTL) with the low refractive index material trifluoropropyl oligomeric silsesquioxane (F‐POSS). Specifically, co‐evaporating 40 vol.% F‐POSS in the HTL of single and multi‐stack phosphorescent OLEDs decreases its refractive index by Δ n ≈ 0.2, which in turn yields a ≈12% increase in their outcoupling efficiency with no impact on electrical performance or operational lifetime. This result is significant because F‐POSS is a small molecule that sublimes cleanly, does not aggregate, and is compatible with state‐of‐the‐art HTL materials, making it a realistic path to increase light extraction in commercial OLEDs manufactured on existing production lines.

36 MATERIALS SCIENCE↗

Constructing Water‐Stable Porous Organic Salts via Suppressed Proton Integration Using Fluorinated Tetrazole Tectons

Porous organic salts (POSs) are an emerging class of materials with ordered ionic architectures, offering excellent proton transfer and water uptake properties. However, conventional POS synthesis via strong acid–base neutralization (e.g., ─SO₃H and ─NH₂) leads to extensive hydrogen bonding with water, compromising stability in aqueous and water-lean environments. Here, we address this challenge by designing POSs with hydrophobic porous channels and minimal hydrogen bonding formation. Our key innovation is the use of fluorinated tetrazole as a weak acid tecton and a tetra-substituted imidazole precursor devoid of active protons as the base. Single-crystal analysis and computational modeling reveal that the structural integrity of the synthesized POSs arises primarily from cation–anion interactions, with water confined as clusters in the pores, independent of hydrogen bonding with the scaffold. Robustness of the POS structure under aqueous and water-lean conditions is confirmed by X-ray and neutron scattering, as well as computational modeling, confirming preserved packing and crystal structures. The stability of POS is further demonstrated in aqueous iodine capture, with imidazolium cations and C–F functionalizations serving as strong adsorption sites. As a result, the approach developed herein further pushes the boundary of POS materials to withstand both aqueous and water-lean conditions.

Fluorinated tecton↗

Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes

Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.

25 ENERGY STORAGE↗