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At least 271 records · Page 15

Process of end-capping a polyimide system

A process of endcapping a polyimide system with an endcapping agent in order to achieve a controlled decrease in molecular weight and melt viscosity along with predictable fracture resistance of the molded products is disclosed. The uncapped system is formed by combining an equimolar ratio of 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride (BDSDA) and 1,-bis (aminophenoxy) benzene (APB) dissolved in bis (2-methoxyethyl)ether. The endcapped system is formed by dissolving APB in bis-(2-methoxyethyl)ether, adding the BDSDA. By varying the amount of endcapping from 0 to 4%, molecular weight is decreased from 13,900 to 8660. At a processing temperature of 250 C, there is a linear relationship between molecular weight and viscosity, with the viscosity decreasing by two orders of magnitude as the molecular weight decreased from 13,900 to 8660.

Stclair, T. L.↗

LARC-IA: A flexible backbone polyimide

A new linear, aromatic, thermoplastic polyimide, prepared from oxydiphthalic anhydride (ODPA) and 3,4'-oxydianiline (ODA) in diglyme and identified as LARC-IA, was synthesized and evaluated. The monomers are relatively inexpensive and physiologically safe. Molecular weight was controlled by use of a monofunctional anhydride, phthalic anhydride (PA), in order to promote controlled flow and wetting properties. The polymer is considered a safe alternative to commercially available LARC-TPI which is prepared with an expensive diamine of uncertain carcinogenicity. The evaluation was based primarily on the polymer's adhesive properties as determined by thermal and water boil exposure of lap shear specimens. Strengths were determined at room temperature, 177, 204 and 232 C before and after exposure to determine the adhesive system's durability to adverse environments over a period of time. Other properties (FWT, G(1c), film and composite properties) were examined which were determined to be typical of a high temperature polyimide. Results of the study show a favorable comparison to LARC-TPI, a commercially available polyimide.

Progar, Donald J.↗

Synthesis of imide/arylene ether copolymers for adhesives and composite matrices

A series of imide/arylene ether copolymers were prepared from the reaction of an amorphous arylene ether oligomer and a semi-crystalline imide oligomer. These copolymers were thermally characterized and mechanical properties were measured. One block copolymer was endcapped and the molecular weight was controlled to provide a material that displayed good compression moldability and attractive adhesion and composite properties.

Jensen, B. J.↗

Imide/arylene ether copolymers. I

The preparation of a series of novel imide/arylene ether copolymers is described together with the results of viscosity and DSC Tg(Tm) measurements. The copolymers were synthesized from an arylene ether block and either an amorphous or semicrystalline imide block. One block copolymer was end-capped, and the molecular weight was controlled to improve compression moldability. The paper also presents results of mechanical properties tests on copolymer samples.

Jensen, B. J.↗

Gene Expression and Structural Skeletal Responses to Long-Duration Simulated Microgravity in Rats

Spaceflight has deleterious effects on skeletal structure and function, specifically causingprofound loss in bone mass, density, and strength, as well as changes in expression levels of genes related to oxidative stress [Hyeon et al., Smith et al.]. It is known that bone resorption remains elevated after spaceflight and that bone density and strength fail to recover completely even years following spaceflight [Smith et al., Carpenter et al.]. However, our current understanding of the signaling pathways and molecular mechanisms that control bone loss and that link oxidative stress, bone resorption, and mechanical unloading of skeletal tissue is incomplete. Here, we aim to examine skeletal responses to simulated long-duration spaceflight on bone loss using the ground-based hindlimb unloading (HU) model in adult (9 months old) male rats. We hypothesized that simulated microgravity leads to the temporal regulation of oxidative-defense genes and pro-osteoclastogenic factors, showing progression and eventual plateau during long-term unloading, and that transient changes at early timepoints in these pathways precede skeletal adaptations to long-duration unloading. We will identify oxidativestress and bone resorption-related changes using global gene expression analysis (Affymetrix arrays) for both acute (within 14 days) and long-term timepoints (90 days). We will also use quantitative PCR to examine changes in expression of genes related to oxidative metabolism (e.g. Nrf2, SOD-1), bone turnover (resorption and formation markers, e.g. TRAP, osteocalcin respectively, SOST), and osteoclastogenesis (e.g. RANKL, OPG) at both early and late timepoints. We will then use detailed microarchitectural and structural analysis through microcomputed tomography to relate gene expression changes with structural changes in bone, expecting that plateaus in gene expression correlate with long-term changes in bone microarchitecture.

Rael, Victoria E.↗

Experimental Measurements of the High-Temperature Oxidation of Carbon Fibers

We carried out laboratory experiments to study the decomposition of carbon fibers at high temperature and studied the material used in charring carbon phenolic ablators for planetary probe heatshields. Porous plug samples were exposed to controlled rates of molecular oxygen, carbon dioxide, and carbon monoxide at furnace-heated flow-tube reactor temperatures between 700 and 1500 K and pressures between 2000 and 6200 Pa. We used calibrated mass spectroscopy to make time-resolved quantitative measurements of decomposition products of the gases downstream of the test sample. Absolute and differential pressure measurements were used to determine the high-temperature permeability of the material and to monitor changes during material decomposition, and we characterized the microstructure of the porous sample using scanning electron microscopy. We found substantial carbon fiber oxidation for O2 flows, resulting in increasing CO/CO2 production ratios with increasing temperature. The CO2 was shown to react with carbon fibers following a Boudouard reaction at temperatures above 1200 K.

Francesco Panerai↗

Effects of Free Molecular Heating on the Space Shuttle Active Thermal Control System

During Space Transportation System (STS) flight 121, higher than predicted radiator outlet temperatures were experienced from post insertion and up until nominal correction (NC) burn two. Effects from the higher than predicted heat loads on the radiator panels led to an additional 50 lbm of supply water consumed by the Flash Evaporator System (FES). Post-flight analysis and research revealed that the additional heat loads were due to Free Molecular Heating (FMH) on the radiator panels, which previously had not been considered as a significant environmental factor for the Space Shuttle radiators. The current Orbiter radiator heat flux models were adapted to incorporate the effects of FMH in addition to solar, earth infrared and albedo sources. Previous STS flights were also examined to find additional flight data on the FMH environment. Results of the model were compared to flight data and verified against results generated by the National Aeronautics and Space Administration (NASA), Johnson Space Center (JSC) Aero-sciences group to verify the accuracy of the model.

McCloud, Peter L.↗

Genetic control of Drosophila nerve cord development

The Drosophila ventral nerve cord has been a central model system for studying the molecular genetic mechanisms that control CNS development. Studies show that the generation of neural diversity is a multistep process initiated by the patterning and segmentation of the neuroectoderm. These events act together with the process of lateral inhibition to generate precursor cells (neuroblasts) with specific identities, distinguished by the expression of unique combinations of regulatory genes. The expression of these genes in a given neuroblast restricts the fate of its progeny, by activating specific combinations of downstream genes. These genes in turn specify the identity of any given postmitotic cell, which is evident by its cellular morphology and choice of neurotransmitter.

Review↗

Molecular Engineering of Emissive Molecular Qubits Based on Spin-Correlated Radical Pairs

Spin chemistry of photogenerated spin-correlated radical pairs (SCRPs) offers a practical approach to control chemical reactions and molecular emissions by using weak magnetic fields. This capability to harness magnetic field effects (MFEs) paves the way for developing SCRPs-based molecular qubits. Here, in this work, we introduce a new series of donor–chiral bridge–acceptor (D–χ–A) molecules that demonstrate significant MFEs on fluorescence intensity and lifetime in solution at room temperature—critical for quantum sensing. By precisely tuning the donor site through torsional locking, distance extension, and planarization, we achieved remarkable control over key quantum properties, including field-response range and line width. In the most responsive systems, emission lifetimes increased by over 200%, and the total emission intensity was modulated by up to 30%. This level of tunability shows the power of synthetic spin chemistry. The rational design principle of optically addressable SCRP-based molecular systems, presented in this work, represents a major leap toward functional synthetic molecular qubits, advancing the field of molecular quantum technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multi-stage single photochrome system for controlled photoswitching responses

The ability of molecular photoswitches to convert on/off responses into large macroscale property change is fundamental to light-responsive materials. However, moving beyond simple binary responses necessitates the introduction of new elements that control the chemistry of the photoswitching process at the molecular scale. To achieve this goal, we designed, synthesized and developed a single photochrome, based on a modified donor–acceptor Stenhouse adduct (DASA), capable of independently addressing multiple molecular states. The multi-stage photoswitch enables complex switching phenomena. To demonstrate this, we show spatial control of the transformation of a three-stage photoswitch by tuning the population of intermediates along the multi-step reaction pathway of the DASAs without interfering with either the first or final stage. This allows for a photonic three-stage logic gate where the secondary wavelength solely negates the input of the primary wavelength. Finally, these results provide a new strategy to move beyond traditional on/off binary photochromic systems and enable the design of future molecular logic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solventless, curable fluid oligomeric systems for high performance microwave, acoustical and mechanical applications

While establishing the basis for a 'Technology 2000' product plan several years ago we plugged in the usual factors contributing toward product success: price/performance justifiable; profitable, warranting high quality maintenance, enhancement, and specific property improvement; narrow inventory requirements; and raw material integrable backwards with easily variable properties (molecular weight, functionality, and isomer control). We resolved this by selecting radical functional, low molecular weight polybutadiene liquid polymers. Encouraged by the need for solid rocket binders, several companies embarked on various perceptions of binder performance requirements over four decades ago. Initially dominated by progress of liquid polysulfides, soon a few settled primarily upon polybutadiene based binders. Such an approach in a few instances was exploited quite viably with a series of functional group terminated liquid polybutadienes: hydroxyl, mercaptan, carboxyl, vinyl, and amine. Good results are obtained for oligomers, liquid polymers, and their hybrids. The only significant limits on compounded products has been solvent resistance and oxidative sensitivity, unless sufficient proportion of sulfide or nitrile moiety is incorporated. For convenience, they have been grouped under the trademarks Nylane, Seamax, Oligomax, and Castomax.

Lefave, G. M.↗

QCM Thermo-Gravimetric Analysis (QTGA) Comparisons

The ASTM E-1559 apparatus has been used for years at NASA/Goddard Space Flight Center (GSFC) to determine in situ outgassing rate information, as well as pertinent in situ TML and multiple VCM values. The apparatus also affords the opportunity to experimentally compute the evaporation rates of molecular species that are reemitted as the Quartz Crystal Microbalances (QCMs) are gradually warmed up at some controlled temperature. Typically the molecular mass that accumulates onto the test QCMs are a compilation of species that are outgassing from the sample due to their respective activation energies and the desorption processes that the sample undergoes at various tested temperatures. It has been speculated that if there is too much molecular buildup of condensed water vapor (ice) onto the QCM crystal that a significantly higher temperature would be needed to break these "ice" bonds. ASTM E-1559 data plots will be used to demonstrate the thermogravimetric effects of water and other miscible molecular species with various water/ice thicknesses and at different evaporation rates.

Rosecrans, Glenn↗

Optimal control of coupled quantum systems based on the first-order Magnus expansion: Application to multiple dipole-dipole-coupled molecular rotors

This paper presents a method for performing approximate optimal control simulations for quantum systems with multiple coupled degrees of freedom. In this work, the time evolution is simulated using the first-order Magnus expansion in the interaction picture, where the couplings between different degrees of freedom are treated as the perturbation. A numerical implementation procedure is presented that leverages upon pairwise couplings and the separability of the zeroth-order time evolution operator to achieve a reduced computational cost, which is analyzed with respect to the number of degrees of freedom. The formulation is compatible with gradient-free methods to optimize the control field, and a stochastic hill climbing algorithm is adopted for this purpose. As illustrations, optimal control simulations are performed for systems of two and three dipole-dipole-coupled molecular rotors under the influence of a control field. For the two-rotor system, the field is optimized to achieve either orientation or entanglement objectives. For the three-rotor system, the field is optimized either to orient all three rotors in the same direction or to orient one rotor in a particular direction while the other two rotors point in the opposite direction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Growth of III-V films by control of MBE growth front stoichiometry

For the growth of strain-layer materials and high quality single and multiple quantum wells, the instantaneous control of growth front stoichiometry is critical. The process of the invention adjusts the offset or phase of molecular beam epitaxy (MBE) control shutters to program the instantaneous arrival or flux rate of In and As4 reactants to grow InAs. The interrupted growth of first In, then As4, is also a key feature.

Grunthaner, Frank J.↗

Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics

When molecules are coupled to an optical cavity, new light–matter hybrid states, so-called polaritons, are formed due to quantum light–matter interactions. With the experimental demonstrations of modifying chemical reactivities by forming polaritons under strong light–matter interactions, theorists have been encouraged to develop new methods to simulate these systems and discover new strategies to tune and control reactions. This review summarizes some of these exciting theoretical advances in polariton chemistry, in methods ranging from the fundamental framework to computational techniques and applications spanning from photochemistry to vibrational strong coupling. Even though the theory of quantum light–matter interactions goes back to the midtwentieth century, the gaps in the knowledge of molecular quantum electrodynamics (QED) have only recently been filled. We review recent advances made in resolving gauge ambiguities, the correct form of different QED Hamiltonians under different gauges, and their connections to various quantum optics models. Then, we review recently developed ab initio QED approaches which can accurately describe polariton states in a realistic molecule–cavity hybrid system. We then discuss applications using these method advancements. We review advancements in polariton photochemistry where the cavity is made resonant to electronic transitions to control molecular nonadiabatic excited state dynamics and enable new photochemical reactivities. When the cavity resonance is tuned to the molecular vibrations instead, ground-state chemical reaction modifications have been demonstrated experimentally, though its mechanistic principle remains unclear. We present some recent theoretical progress in resolving this mystery. Finally, we review the recent advances in understanding the collective coupling regime between light and matter, where many molecules can collectively couple to a single cavity mode or many cavity modes. We also lay out the current challenges in theory to explain the observed experimental results. We hope that this review will serve as a useful document for anyone who wants to become familiar with the context of polariton chemistry and molecular cavity QED and thus significantly benefit the entire community.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Properties of Thin Film Molecular Mixtures

Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, alpha, and low infrared emittance, epsilon. On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator. A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450C, a sharp transition at 1.8 micrometers is desired. The radiator completes the heat flow through the Carnot cycle. Additional work has been done supporting the use of molecular mixtures for terrestrial applications. Sputter deposition provides a means to apply coatings to the tubes that carry a working fluid at the focus of trough-style collectors. Sputtering offers considerable flexibility in coating conditions, including a wide variety of metal and dielectric targets. Coating designs range from simple two or three layer coatings to complex coatings that are purposely graded to be metal-rich at their base and oxide-rich at their surface in order to yield the desired solar selective properties. In these cermet coatings, molecular islands of metal are thought to be embedded in a three dimensional matrix of dielectric. Recent work has identified the use of custom made ion beam sputter deposition targets to produce coatings containing molecular mixtures of metal and dielectric. The targets are cylindrical and the surface consists of a gradually changing composition of metal and dielectric. Rotating the cylinder under the beam during ion beam sputter deposition yields a coating that is a molecular mixture of metal and dielectric, with the composition changing through the thickness of the coating. The optical properties of these coatings are not only dependent on their thickness and chemical composition, but are also dependent on the extent of the through thickness gradient established during deposition. This paper presents a summary of the optical properties of several thin film molecular mixtures designed as solar selective coatings. Optical performance is first identified as a function of wavelength, from the ultraviolet to the visible and infrared. Coating composition, thickness, and gradient from metal to dielectric also play an important role. Additional work for future activities is also identified.

Jaworske, Donald A.↗

Optical Properties of Thin Film Molecular Mixtures

Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, , and low infrared emittance, . On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator.1 A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450 C, a sharp transition at 1.8 micrometers is desired.2 The radiator completes the heat flow through the Carnot cycle.

Jaworske, Donald A.↗

Manipulating Pore Topology and Functionality to Promote Fluorocarbon-Based Adsorption Cooling

With the worldwide demand for refrigeration and cooling expected to triple, it is increasingly important to search for alternative energy resources to drive the refrigeration cycles with reduced electricity consumption. Recently, adsorption cooling has gained increased attention since energy reallocation in such systems is based on gas adsorption/desorption, which can be driven by waste/natural heat sources. Eco-friendly sorption-based cooling relies on the cyclic transfer of refrigerant gas from a high to low energy state by the pseudo-compression effect resulting from adsorption and desorption. The driving force for energy transfer relies on heat rather than electricity. The performance of a sorption chiller is primarily influenced by this cyclic sorption behavior, which is characterized as the working capacity of the porous sorbent. Thus increases in this working capacity directly translate to a more compact and efficient cooling system. How-ever, a lack of highly effective sorbent/refrigerant pairs lowers cooling performance, and therefore has limited applicability. To this end, synthetic metal-organic frameworks (MOFs) and covalent organic polymers (COPs) possess higher porosity and greater tunability leading to more substantial potential benefits for adsorption, compared to traditional sorbent materials. Similarly, hydrofluorocarbon refrigerants have more favorable applicability given ease of operation above atmospheric pressures due to suitable saturated vapor pressures and boiling points. For these reasons, our work focuses on an ongoing strategy to promote sorption cooling via improvements in the sorbent/refrigerant pair. Specifically, we target the interaction of hydrofluorocarbon refrigerants with MOF/COP materials at a molecular level by interpreting the host-guest chemistry and the role of framework pore topology. These molecular level differences translate to cooling performance, which is described herein. These strategies include engineering framework porosity (i.e., pore size, pore volume) by using elongated organic linkers and stereochemistry control during synthesis; manipulating the sorb-ate/sorbent interaction by introducing functional moieties or unsaturated metal centers to enhance working capacities in narrow pressure ranges; varying pore topology/morphology to impact adsorption isotherm behavior; and leveraging defective sites within the frameworks to further enhance adsorption capability. Here this atomic level understanding of sorb-ate-sorbent interactions is conducted using various in situ experimental techniques such as synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, in situ Fourier transform infrared spectroscopy, and direct sorption energies determinization with calorimetry. Moreover, the experimentally studied interactions and the corresponding adsorption mechanism are corroborated by computational studies using density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations. Using this approach, we envision the capability to engineer designed frameworks with precise molecular control to target refrigerant molecules and thereby enhance the performance of desired working pairs for sorption-based cooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗