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DOE OSTI2026

Solid-State Side-Chain Functionalization of Conjugated Polymers for Expanded Chemical and Functional Versatility

Conjugated polymers that integrate diverse chemical functionalities with high electronic performance are essential for advanced organic electronic, optoelectronic, and biointerfaced technologies. Achieving such multifunctionality typically requires grafting functional units onto polymer side chains. However, conventional solution-phase approaches remain constrained by solubility limitations, side-chain-induced packing disruptions, and challenges in preserving charge transport. Here, we introduce a solid-state side-chain functionalization strategy that exploits a swellable polar side-chain architecture and azide–alkyne click chemistry to enable efficient molecular diffusion and reaction throughout predeposited polymer thin films. This approach substantially broadens the chemical compatibility of graftable units and mitigates the adverse effects on the electrical property. Moreover, the method supports spatially selective functionalization within a continuous film, enabling the patterned incorporation of chemically distinct groups to produce spatially defined optical properties. Here, this solid-state strategy thus provides a versatile platform for constructing conjugated polymers with expanded chemical versatility, preserved electronic performance, and programmable spatial functionality.

Conjugated polymers↗

NASA NTRS1994

Use of prismatic films to control light distribution

Piping light for illumination purposes is a concept which has been around for a long time. In fact, it was the subject of an 1881 United States patent which proposed the use of mirrors inside a tube to reflect light from wall to wall down the tube. The use of conventional mirrors for this purpose, however, has not worked because mirrors do not reflect well enough. On the other hand, optical fibers composed of certain glasses or plastics are known to transport light much more efficiently. The light that enters is reflected back and forth within the walls of the fiber until it reaches the other end. This is possible by means of a principle known as 'total internal reflection'. No light escapes through the walls and very little is absorbed in the bulk of the fiber. However, while optical fibers are very efficient in transporting light, they are impractical for transporting large quantities of light. Lorne Whitehead, as a student at the University of British Columbia, recognized that prismatic materials could be used to create a 'prism light guide', a hollow structure that can efficiently transport large quantities of light. This invention is a pipe whose transparent walls are formed on the outside into precise prismatic facets. The facets are efficient total internal reflection mirrors which prevent light travelling down the guide from escaping. Very little light is absorbed by the pipe because light travels primarily in the air space within the hollow guide. And, because the guide is hollow, weight and cost factors are much more favorable than would be the case with very large solid fibers. Recent advances in precision micromachining, polymer processing, and certain other manufacturing technologies have made the development of OLF (Optical Lighting Film) possible. The process is referred to as 'microreplication' and has been found to have broad applicability in a number of diverse product areas.

Kneipp, K. G.↗

DOE OSTI2023

Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

Stimuli-responsive microgels, composed of small beads with soft, deformable polymer networks swollen through a combination of synthetic control over the polymer and its interaction with water, form a versatile platform for development of multifunctional and biocompatible sensors. The interfacial structural variation of such materials at a nanometer length scale is essential to their function, but not yet fully comprehended. Here, we take advantage of the plasmonic response of a gold nanorod embedded in a thermoresponsive microgel (AuNR@PNIPMAm) to monitor structural changes in the hydrogel directly near the nanorod surface. By direct comparison of the plasmon response against measurements of the hydrogel structure from dynamic light scattering and nuclear magnetic resonance, we find that the microgel shell of batch-polymerized AuNR@PNIPMAm exhibits a heterogeneous volume phase transition reflected by different onset temperatures for changes in the hydrodyanmic radius (R H ) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with R H and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Transparent and Conductive Inorganic/Polymer‐Composite Encapsulants for Long‐Term Perovskite Solar Cells Operation

An innovative inorganic/polymer-composite encapsulation scheme comprising a polymer-based transparent conductive composite (TCC) coupled with a transparent conductive oxide is introduced to extend the lifetime of moisture-sensitive devices such as perovskite solar cells (PSC). The TCC comprises conductive silver-coated polymethyl methacrylate (Ag-PMMA) microsphere fillers protruding from a transparent non-conductive polymer matrix. TCC samples (5% Ag-PMMA by area) demonstrate high optical transparencies (%T approx. 85% in the 370–1200 nm region), low out-of-plane electrical resistivities (R < 0.2 Ω cm 2 ), and equilibrium permeabilities of less than 1 g mm/m 2 /day, all of which are well-maintained after 1,000 hours of environmental exposure. In practice, the TCC is employed between two indium zinc oxide (IZO) thin films, with the in-plane conductivity of IZO and the out-of-plane conductivity of TCC working collectively to function as a single encapsulating electrode. This encapsulation scheme is exemplified by benchmarking performances of PSCs subjected to accelerated aging conditions of quasi-maximum power point tracking under light soaking in air at 50 °C, 40% R.H. to 60% R.H. Notable improvements in operational lifetimes are observed, with a champion encapsulated PSC maintaining over 90% of its initial efficiency of 21.65% for up to 1,430 hours, compare to less than 300 hours for an unencapsulated control.

14 SOLAR ENERGY↗

DOE OSTI2022

Weather aging effects on modified asphalt with rubber-polyethylene composites

Weather aging may cause more severe degradation on asphalt than thermal-oxidative aging due to the synergistic effect among oxygen, heat, ultraviolet (UV) radiation, and moisture. This study aimed to investigate weather aging effects and anti-aging mechanisms on asphalt modified with rubber-polyethylene (PE) composites. The modified binder blends and asphalt mixtures were subjected to outdoor weather aging. Dynamic shear rheometer (DSR), Fourier transform infrared spectroscopy (FTIR), Gel permeation chromatography (GPC), and optical microscopy tests were adopted to characterize the rheological properties, aging resistance, polymer degradation, and anti-aging mechanisms of modified binder blends, respectively. Mixture performance tests including Asphalt Pavement Analyzer (APA) and Ideal-CT tests were used to evaluate rutting and cracking resistance of asphalt mixtures. Results showed that weather aging can cause more severe aging to asphalt binders than pressure aging vessel (PAV) due to the severe degradation of PE particles. Rubber-PE composites alloyed with an extruder proved to stabilize PE particles in asphalt and significantly improve the aging resistance of modified binder blends. Furthermore, the enhanced aging resistance is attributed to the dispersion of PE particles and carbon black released by soluble rubbers.

Aging resistance↗

DOE OSTI2025

Effects of Quantum Dot Loading on the Radioluminescence Efficiency in Quantum-Dot-Embedded Composites

Nanoparticle-embedded plastic scintillators are an emerging technology for fast, large-area, high-resolution radiation detection and imaging. Here, this study investigates the properties of such composites, focusing on the effects of the quantum dot (QD) concentration on the radioluminescence (RL) intensity, spectra, and dynamics. Experiments using CdSe/CdS QDs in a polymer reveal a superlinear increase in RL with the QD concentration despite optical losses from inner filtering and interparticle interactions. When corrected for inner filtering, RL shows a quadratic concentration dependence, consistent with simple analytical models of improving the secondary electron capture. Practically, the benefits of high QD concentrations are muted by optical losses, but the findings apply to other systems with insulating hosts. In addition to manipulating emission for large effective Stokes shifts, future improvements may come from hosts with higher stopping power and better charge transport, which enable more effective funneling of excitations but without concomitant optical losses associated with high nanoparticle concentrations.

Auger recombination↗

DOE OSTI2020

Prolate and oblate chiral liquid crystal spheroids

Liquid crystals are known to exhibit intriguing textures and color patterns, with applications in display and optical technologies. This work focuses on chiral materials and examines the palette of morphologies that arises when microdroplets are deformed into nonspherical shapes in a controllable manner. Specifically, geometrical confinement and mechanical strain are used to manipulate orientational order, phase transitions, and topological defects that arise in chiral liquid crystal droplets. Inspired by processes encountered in nature, where insects and animals often rely on strain and temperature to alter the optical appearance of dispersed liquid crystalline elements, chiral droplets are dispersed in polymer films and deformation induced by uniaxial or biaxial stretching. Our measurements are interpreted by resorting to simulations of the corresponding systems, thereby providing an in-depth understanding of the morphologies that arise in these materials. The reported structures and assemblies offer potential for applications in smart coatings, smart fabrics, and wearable sensors.

42 ENGINEERING↗

NASA NTRS1991

Interactions of atomic oxygen with material surfaces in low Earth orbit: Preliminary results from experiment A0114

The University of Alabama at Huntsville atomic oxygen experiment consisted of two trays of 64 one inch diameter solid samples. One tray was placed on the leading edge and one on the trailing edge of the spacecraft. Half of each sample was covered to provide a control. Thus it was intended that the effects of atomic oxygen and solar ultraviolet radiation on the surface properties of each material could be distinguised from each other and from the effects of aging. Sixteen of the samples were placed on a thermally isolated plate of highly polished aluminum, while the main plate was coated with the thermal control coating S13-GLO. Though the experiment was entirely passive, it was hoped that the effects of thermal activation might be observed, if present. The plates were expected to stabilize at temperatures differing by 20 to 30 C. The experiment also carried a device to measure the spacecraft altitude and several oxygen atom reflectometers which have not been analyzed to date. The samples included thin films of metals Os, Ir, Pt, Ni, W, Mo, and Al coated onto fused silica optical flats; metal carbides (WC, SiC), solid carbons of various types, eight polymers and some other coatings of various types.

Gregory, John C.↗

NASA NTRS1992

Interactions of atomic oxygen with material surfaces in low Earth orbit: Preliminary results from experiment A0114

The atomic oxygen experiment consisted of two trays (one-sixth of a Long Duration Exposure Facility (LDEF) tray each) of 64 one inch diameter solid samples. It was intended that the effects of atomic oxygen and solar ultraviolet irradiation on the surface properties of each material could be distinguished from each other and from the effects of aging. Sixteen of the samples were placed on a thermally isolated plate of highly polished aluminum, while the main plate was coated with the thermal control coating S13-GLO. Though the experiment was entirely passive, it was hoped that the effects of thermal activation might be observed, if present. The plates were expected to stabilize at temperatures differing by 20-30 C. The samples included thin films of metals Os, Ir, Pt, Ni, Mo, and Al coated onto silica optical flats, metal carbides (WC, SiC), solid carbons of various types, eight polymers, and some other coatings of various types. Analysis is essentially complete using stylus profilometry with high sensitivity Talystep and lower sensitivity Talysurf machines. Though the integrated fluence of O atoms on the LDEF was 30 times that of previous missions, etch depths of the polymers such as the polyimide Kapton show excellent agreement with extrapolations from previous flight data. However, some new effects were observed. We demonstrated on a previous experiment on STS-8 that profilometry of this kind can show steps of 50 A (for example those due to oxide film growth on metals) and this is now the preferred method for estimating etch depth (or mass loss) of erodible substances.

Gregory, John C.↗

NASA NTRS1999

A Compact Dual-Crystal Modulated Birefringence-Measurement System for Microgravity Applications

A compact modulated birefringence-measurement system has been developed for use in microgravity fluid physics applications with non-Newtonian fluids such as polymer solutions. This instrument uses a dual-crystal transverse electro-optical modulator capable of modulation frequencies in excess of 100 MHz. The two crystals are modulated 180 deg. out of phase from each other, The theoretical framework governing the development of this instrument using the Mueller-Stokes polarization matrices is discussed. Several ground-based experiments are performed to compare this system with the theoretical results. Results from this transverse electro-optical modulator-based birefringence-measurement system agree well with the theory. The instrument is also very stable and robust, making it suitable for the extreme acceleration environment to be encountered in a NASA Black Brandt sounding rocket.

Mackey, Jeffrey R.↗

NASA NTRS2000

Single-Arm Double-Mode Double-Order Planar Waveguide Interferometric Sensor

We have met the goals stated in section one for the project. We have demonstrated the feasibility of a single-arm double-mode double-order waveguide interferometer as a cost efficient alternative to an optical chemical sensor. Experimental prototype was built as a dye-doped polymer waveguide with propagating modes of orders <<0>> and <<1>> of the same TM polarization. The prototype demonstrated sensitivity to ammonia of the order of 200 ppm per one full oscillation of the signal. Sensor based on polyimide doped with BCP can operate at elevated temperature up to 150 C. Upon the future funding, we are planning to optimize the light source, material and the design in order to achieve sensitivity of the order of 1 ppm per full oscillations.

Sarkisov, Sergey S.↗

NASA NTRS2002

Fabry-Perot Interferometer-Based Electrooptic Modulator using LiNbO3 and Organic Thin Films

We report the study of a Fabry-Perot electro-optical modulator using thin crystalline film NPP, and Crystalline LiNbO3. We are able to observe 14, and 60 percent degree of modulation. Measurements were carried using a standard lock-in amplifier with a silicon detector. The proposal to design a Fabry-Perot electro-optic modulator with an intracavity electro-optically active organic material was based on the initial results using poled polymer thin films. The main feature of the proposed device is the observation that in traditional electrooptic modulators like a Packets cell, it requires few kilovolts of driving voltage to cause a 3 dB modulation even in high figure-of-merit electrooptic materials like LiNbO3. The driving voltage for the modulator can be reduced to as low as 10 volts by introducing the electrooptic material inside die resonant cavity of a Fabry-Perot modulator. This is because the transmission of the Fabry-Perot cavity varies nonlinearly with the change of refractive index or phase of light due to applied electric field.

Banks, C.↗

NASA NTRS1997

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

Non-NASA Center↗

NASA NTRS1997

Molecularly Oriented Polymeric Thin Films for Space Applications

The increased commitment from NASA and private industry to the exploration of outer space and the use of orbital instrumentation to monitor the earth has focused attention on organic polymeric materials for a variety of applications in space. Some polymeric materials have exhibited short-term (3-5 yr) space environmental durability; however, future spacecraft are being designed with lifetimes projected to be 10-30 years. This gives rise to concern that material property change brought about during operation may result in unpredicted spacecraft performance. Because of their inherent toughness and flexibility, low density, thermal stability, radiation resistance and mechanical strength, aromatic polyimides have excellent potential use as advanced materials on large space structures. Also, there exists a need for high temperature (200-300 C) stable, flexible polymeric films that have high optical transparency in the 300-600nm range of the electromagnetic spectrum. Polymers suitable for these space applications were fabricated and characterized. Additionally, these polymers were molecularly oriented to further enhance their dimensional stability, stiffness, elongation and strength. Both unoriented and oriented polymeric thin films were also cryogenically treated to temperatures below -184 C to show their stability in cold environments and determine any changes in material properties.

Fay, Catharine C.↗

NASA NTRS2017

Surface Monitoring of CFRP Structures for Adhesive Bonding

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding is essential in order to obtain a surface free from contaminants that may degrade structural performance. Two techniques which monitor the effectiveness of the laser surface treatment of carbon fiber reinforced polymer (CFRP) materials are being investigated: laser induced breakdown spectroscopy (LIBS) and optically stimulated electron emission (OSEE). The applicability of LIBS to detect silicone contaminants on CFRP composites is studied using ~35 ns Nd:YAG laser pulses at 355 nm with a pulse energy of 45 mJ. The LIBS regime in which pulse energies are < 100 mJ is referred to as mLIBS. CFRP surfaces were contaminated with polydimethylsiloxane (PDMS), a major component of silicone based mold release agents. The presence of PDMS is found by inspecting the Si I emission line at 288.2 nm. Untreated CFRP samples and CFRP contaminated with PDMS were tested. The PDMS areal density ranged from 0.36 Â+/- 0.04 to 0.51 Â+/- 0.16 mg/cm2. The results demonstrate the successful detection of PDMS on CFRP using mLIBS. In addition, OSEE was used to measure CFRP surface cleanliness pre- and post-treatment by laser ablation on specimens contaminated with PDMS coatings from 8 nm to 1311 nm in thickness. The results showed a significant increase in the OSEE photocurrent after laser surface treatment.

Ledesma, Rodolfo↗

DOE OSTI2020

Demonstration of Embedded Sensors in Ceramic Structures

The Transformational Challenge Reactor (TCR) program seeks to demonstrate an advanced 3D printed nuclear reactor core. A binder jet additive manufacturing process is used to fabricate the complex SiC ceramic components of the TCR core. After printing, the components are densified via chemical vapor infiltration (CVI). This process allows complex cavities to be created in which sensors can be placed at strategic locations. Inserting the sensors during the CVI process allows the sensors to be embedded within the component as it is infiltrated. The primary challenge for embedding the sensors is identifying the sensors and sensor sheath materials that can survive the temperatures (>1,000°C) and chemical exposure to H 2 and HCl during CVI. The embedded sensors that are being investigated for use during TCR operation include thermocouples, self-powered neutron detectors, and spatially distributed fiber-optic temperature sensors. This report describes the CVI materials compatibility tests and initial trials for embedding functional sensors. Mo is identified as the most suitable sensor sheath material based on its availability in small diameter tubing, relatively low neutron absorption cross section, and compatibility with H 2 , HCl, and the surrounding SiC matrix at the process temperatures. Amorphous SiO2 fiber-optic samples with Au and Cu metal coatings were successfully embedded in SiC along with bare fibers, although the metal coatings showed some evidence of localized melting during CVI. Initial experiments attempting to embed functional sensors showed that the sensors can be embedded in 3D printed SiC parts, but there are still challenges that must be overcome to ensure that the sensors and sensor sheaths do not fail during CVI. In particular, Nb-sheathed Mo-Nb thermocouples failed at temperatures far lower than expected despite thermodynamic calculations and materials compatibility tests that show the Nb sheath to be compatible with the CVI environment. One potential explanation for the large expansion of the Nb sheath could be related to hydride formation in the lower temperature region of the sheath. Future work will focus on Mo-sheathed thermocouples instead of Nb. The fiberoptic sensors tested during the instrumented experiment broke due to the lack of mechanical protection after their polymer-based coatings were vaporized. Future instrumented experiments will use metal-coated optical fibers for strain sensing to provide additional mechanical protection. However, custom coatings with higher melting points than commercially available Au and Cu might be required. Regardless, fiber-optic sensors are still candidates for spatially distributed temperature measurements since they can be inserted into an embedded metal sheath after CVI.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2021

A near-infrared optical nanosensor for measuring aerobic respiration in microbial systems

We developed a ratiometric oxygen-sensitive nanosensor and demonstrated application in monitoring metabolic oxygen consumption in microbial samples over time. Based on a near-infrared (NIR) emitting oxygen-quenched luminophore, platinum(II) octaethylporphine ketone (PtOEPK), along with a stable dioctadecyl dicarbocyanine reference dye (DiD), this nanosensor system provides an advantageous approach for overcoming imaging issues in biological systems, such as autofluorescence and optical scattering in the visible wavelength region. The dyes are encapsulated within a polymer-based nanoparticle matrix to maintain them at a constant ratio in biological samples, precluding the need for complex synthetic approaches. With this constant ratio of the two dyes, the nanosensor response can be measured as a ratio of their two signals, accounting for nanosensor concentration artifacts in measurements. The nanosensors are reversible, which enabled us to temporally monitor systems in which dissolved oxygen concentrations both increase and decrease. These sensors were applied for the monitoring of oxygen in samples of Saccharomyces cerevisiae (brewing yeast) in a 96-well optical fluorescence plate reader format over 60 h. By mixing the nanosensors directly into the sample well with the yeast, we were able to dynamically track metabolic activity changes over time due to varying cell concentration and exposure to an antimicrobial agent. As a result, this system could be a potential platform for high-throughput screening of various species or variants of microbes with unknown metabolic rates in response to external stimuli (antimicrobials, metabolites, etc.).

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2016

Propellantless Attitude Control of Solar Sail Technology Utilizing Reflective Control Devices

Solar sails offer an opportunity for a CubeSatscale, propellant-free spacecraft technology that enables long-term and long-distance missions not possible with traditional methods. Solar sails operate using the transfer of linear momentum from photons of sunlight reflected from the surface of the sail. To propel the spacecraft, no mechanically moving parts, thrusters, or propellant are needed. However, attitude control, or orientation, is still performed using traditional methods involving reaction wheels and propellant ejection, which severely limit mission lifetime. For example, the current state of the art solutions employed by upcoming missions couple solar sails with a state of the art propellant ejection gas system. Here, the use of the gas thruster has limited the lifetime of the mission. To solve the limited mission lifetime problem, the Propellantless Attitude Control of Solar Sail Technology Utilizing Reflective Control Devices project team is working on propellantless attitude control using thin layers of material, an optical film, electrically switchable from transparent to reflective. The technology is based on a polymer-dispersed liquid crystal (PDLC), which allows this switch upon application of a voltage. This technology removes the need for propellant, which reduces weight and cost while improving performance and lifetime.

Solar sail technology↗