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At least 235 records · Page 13

Evidence for Methane Segregation at the Surface of Pluto

In May 1995, a set of spectrophotometric curves of the system Pluto-Charon was recorded with the UKIRT telescope equipped with the spectrometer CGS4. As for the previous observations, the spectra cover a part of the near infrared range, between 1.4 and 2.55 micrometers, but with a higher resolution of approximately 700. In both the 1992 and 1995 data, the existence of solid methane is confirmed by numerous absorption bands, and the carbon monoxide and the nitrogen ices are identified by their respective signatures at 2.35 and 2.15 um. The solid nitrogen seems to be the principal icy component and forms a matrix in which the CH4 and CO molecules are diluted. However a spectroscopic analysis of the 1995 observations indicates that pure methane may coexist with its diluted phase in N2. In order to derive the horizontal and vertical distribution of these different species and to obtain some quantitative information about their characteristics, we have modeled the spectrum of May 15 that corresponds to the maximum of Pluto's visible light curve. This was achieved by means of a radiative transfer algorithm dealing with compact and stratified media. Among the various representations we have tested to describe the surface of Pluto, only a geographical mixture of three distinct units explains all the significant structures of the analyzed spectrum. The first unit is a thin granular layer of pure CH4 covering a compact polycrystalline substratum of N2-CH4-CO, which are in a molecular mixture (concentrations of and CO of the order of 0.45%, 0.1-0.2% respectively). It covers about 70% of the observed area and corresponds to volatile deposits that are sublimating under solar illumination. The second unit is either (a) a single thick layer of pure granular methane or (b) a unit similar to the first unit but with the two components inverted (i.e. with CH4 forming a substratum and the N2-CH4-CO mixture a superficial layer of fine grains). Covering 20% of the surface, it represents some old surfaces that have been sublimated for a long time, and eventually recovered later by very small amounts of fresh deposits of the molecular mixture N2-CH4-CO. Finally, the third unit may result from the condensation of very fine grains of nearly pure N2. It covers the remainder of the surface (about 10%). All these results allow a better understanding of the processes of deposition, metamorphism, sublimation and transport affecting the different ices detected on Pluto during its climatic cycles.

Doute, S.↗

Landform Degradation and Slope Processes on Io: The Galileo View

The Galileo mission has revealed remarkable evidence of mass movement and landform degradation on Io. We recognize four major slope types observed on a number of intermediate resolution (250 m/pixel) images and several additional textures on very high resolution (10 m/pixel) images. Slopes and scarps on Io often show evidence of erosion, seen in the simplest form as alcove-carving slumps and slides at all scales. Many of the mass movement deposits on Io are probably mostly the consequence of block release and brittle slope failure. Sputtering plays no significant role. Sapping as envisioned by McCauley et al. remains viable. We speculate that alcove-lined canyons seen in one observation and lobed deposits seen along the bases of scarps in several locations may reflect the plastic deformation and 'glacial' flow of interstitial volatiles (e.g., SO2) heated by locally high geothermal energy to mobilize the volatile. The appearance of some slopes and near-slope surface textures seen in very high resolution images is consistent with erosion from sublimation-degradation. However, a suitable volatile (e.g., H2S) that can sublimate fast enough to alter Io's youthful surface has not been identified. Disaggregation from chemical decomposition of solid S2O and other polysulfur oxides may conceivably operate on Io. This mechanism could degrade landforms in a manner that resembles degradation from sublimation, and at a rate that can compete with resurfacing.

Moore, Jeffrey M.↗

Integration of a Micro-Chip Amino Acid Chirality Detector into the MOD Instrument Concept

The MOD (Mars Organic Detector) instrument concept consists of a sublimation apparatus for organic compound isolation connected to a microfabricated microfluidic analyzer containing a sipper, pumps and a separation channel for organic compound characterization. The target organic compounds are amino acids and polycyclic aromatic hydrocarbons (PAHs). Solid samples are placed within the sublimation apparatus and heated to release organic compounds which sublime onto a cold finger. Half of the cold finger is coated with fluorescamine. which reacts with amino acids and other primary amines to generate an intense fluorescent derivative while the other half is uncoated and is used to directly detect PAH fluorescence, A capillary sipper is then used to dissolve and sample the labeled amino acids and integrated microfabricated pumps transport the labeled amino acids to the chip for analysis. The sample is separated using capillary zone electrophoresis (CZE) together with chiral dextrins to determine amino acid composition and chirality. During the grant period, the following steps have been completed toward the development of a robust instrument and chemistry.

Bada, Jeffrey L.↗

Space Suit Radiator Performance in Lunar and Mars Environments

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut's metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 3.48 lbs, an additional eight pounds of water are loaded into the unit of which about six to eight are sublimated and lost; this is the single largest expendable during an eight-hour EVA. Using a radiator to reject heat from the Astronaut during an EVA, we can significantly reduce the amount of expendable water consumed by the sublimator. Last year we reported on the design and initial operational assessment tests of our novel radiator designated the Radiator And Freeze Tolerant heat eXchanger (RAFT-X). Herein, we report on tests conducted in the NASA Johnson Space Center Chamber E Thermal Vacuum Test Facility. Up to 800 Btu/h of heat were rejected in lunar and Mars environments with temperatures as cold as -150 F. Tilting the radiator did not cause an observable loss in performance. The RAFT-X endured freeze / thaw cycles and in fact, the heat exchanger was completely frozen three times without any apparent damage to the unit. We were also able to operate the heat exchanger in a partially frozen configuration to throttle the heat rejection rate from 530 Btu/h at low water flow rate down to 300 Btu/h. Finally, the deliberate loss of a single loop heat pipe only degraded the heat rejection performance by about 2 to 5%.

Nabity, James↗

Space Suit Radiator Performance in Lunar and Mars Environments

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut's metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 1.58 kg (3.48 lbm), an additional 3.6 kg (8 lbm) of water are loaded into the unit, most of which is sublimated and lost to thus become the single largest expendable during an eight hour EVA. We can significantly reduce the amount of expendable water consumed in the sublimator by using a radiator to reject heat from the Astronaut during an EVA. Last year we reported on the design and initial operational assessment tests of our novel radiator designated the Radiator And Freeze Tolerant heat eXchanger (RAFT-X). Herein, we report on tests conducted in the NASA Johnson Space Center Chamber E Thermal Vacuum Test Facility. Up to 260 W (900 Btu/h) of heat were rejected in Lunar and Mars environments with temperatures as cold as -170 C (- 275 F). Further, the RAFT-X endured several freeze / thaw cycles and in fact, the heat exchanger was completely frozen three times without any apparent damage to the unit.

Nabity, James↗

A Freezable Heat Exchanger for Space Suit Radiator Systems

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut s metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 1.58 kg (3.48 lbm), an additional 3.6 kg (8 lbm) of water are loaded into the unit, most of which is sublimated and lost to space, thus becoming the single largest expendable during an eight-hour EVA. Using a radiator to reject heat from the astronaut during an EVA can reduce the amount of expendable water consumed in the sublimator. Radiators have no moving parts and are thus highly reliable. Past freezable radiators have been too heavy, but the weight can be greatly reduced by placing a small and freeze tolerant heat exchanger between the astronaut and radiator, instead of making the very large radiator freeze tolerant. Therefore, the key technological innovation to improve space suit radiator performance was the development of a lightweight and freezable heat exchanger that accommodates the variable heat load generated by the astronaut. Herein, we present the heat transfer performance of a newly designed heat exchanger that endured several freeze / thaw cycles without any apparent damage. The heat exchanger was also able to continuously turn down or turn up the heat rejection to follow the variable load.

Nabity, James A.↗

Space Suit Radiator Performance in Lunar and Mars Environments

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut's metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 3.48 lbs, an additional eight pounds of water are loaded into the unit of which about six to eight are sublimated and lost; this is the single largest expendable during an eight-hour EVA. Using a radiator to reject heat from the Astronaut during an EVA, we can significantly reduce the amount of expendable water consumed by the sublimator. Last year we reported on the design and initial operational assessment tests of our novel radiator designated the Radiator And Freeze Tolerant heat eXchanger (RAFT-X). Herein, we report on tests conducted in the NASA Johnson Space Center Chamber E Thermal Vacuum Test Facility. Up to 800 Btu/h of heat were rejected in lunar and Mars environments with temperatures as cold as 150 F. Tilting the radiator did not cause an observable loss in performance. The RAFT-X endured freeze/thaw cycles and in fact, the heat exchanger was completely frozen three times without any apparent damage to the unit. We were also able to operate the heat exchanger in a partially frozen configuration to throttle the heat rejection rate from 530 Btu/h at low water flow rate down to 300 Btu/h. Finally, the deliberate loss of a single loop heat pipe only degraded the heat rejection performance by about 2 to 5%.

Paul, Heather↗

Investigation of Condensing Ice Heat Exchangers for MTSA Technology Development

Metabolic heat regenerated Temperature Swing Adsorption (MTSA) technology is being developed for thermal, carbon dioxide (CO2) and humidity control for a Portable Life Support Subsystem (PLSS). Metabolically-produced CO2 present in the ventilation gas of a PLSS is collected using a CO2selective adsorbent via temperature swing adsorption. The temperature swing is initiated through cooling to well below metabolic temperatures. Cooling is achieved with a sublimation heat exchanger using water or liquid carbon dioxide (LCO2) expanded below sublimation temperature when exposed to low pressure or vacuum. Subsequent super heated vapor, as well as additional coolant, is used to further cool the astronaut. The temperature swing on the adsorbent is then completed by warming the adsorbent with a separate condensing ice heat exchanger (CIHX) using metabolic heat from moist ventilation gas. The condensed humidity in the ventilation gas is recycled at the habitat. The water condensation from the ventilation gas is a significant heat transfer mechanism for the warming of the adsorbent bed because it represents as much as half of the energy potential in the moist ventilation gas. Designing a heat exchanger to efficiently transfer this energy to the adsorbent bed and allow the collection of the water is a challenge since the CIHX will operate in a temperature range from 210K to 280K. The ventilation gas moisture will first freeze and then thaw, sometimes existing in three phases simultaneously. A NASA Small Business Innovative Research (SBIR) Phase 1 contract was performed to investigate condensing and icing as applied to MTSA to enable higher fidelity modeling and assess the impact of geometry variables on CIHX performance for future CIHX design optimization. Specifically, a design tool was created using analytical relations to explore the complex, interdependent design space of a condensing ice heat exchanger. Numerous variables were identified as having nontrivial contributions to performance such as hydraulic diameter, heat exchanger effectiveness, ventilation gas mass flow rate and surface roughness. Using this tool, four test articles were designed and manufactured to map to a full MTSA subassembly (the adsorbent bed, the sublimation heat exchanger for cooling and the condensing ice heat exchanger for warming). The design mapping considered impacts due to CIHX geometry as well as subassembly impacts such as thermal mass and thermal resistance through the adsorbent bed. The test articles were tested at simulated PLSS ventilation loop temperature, moisture content and subambient pressure. Ice accumulation and melting were observed. Data and test observations were analyzed to identify drivers of the condensing ice heat exchanger performance. This paper will discuss the analytical models, the test article designs, and testing procedures. Testing issues will be discussed to better describe data and share lessons learned. Data analysis and subsequent conclusions will be presented.

Padilla, Sebastian↗

The Origin of the Terra Meridiani Sediments: Volatile Transport and the Formation of Sulfate Bearing Layered Deposits on Mars

The chemistry, sedimentology, and geology of the Meridiani sedimentary deposits are best explained by eolian reworking of the sublimation residue of a large scale ice/dust deposit. This large ice deposit was located in close proximity to Terra Meridiani and incorporated large amounts of dust, sand, and SO2 aerosols generated by impacts and volcanism during early martian history. Sulfate formation and chemical weathering of the initial igneous material is hypothesized to have occurred inside of the ice when the darker mineral grains were heated by solar radiant energy. This created conditions in which small films of liquid water were created in and around the mineral grains. This water dissolved the SO2 and reacted with the mineral grains forming an acidic environment under low water/rock conditions. Subsequent sublimation of this ice deposit left behind large amounts of weathered sublimation residue which became the source material for the eolian process that deposited the Terra Meridiani deposit. The following features of the Meridiani sediments are best explained by this model: The large scale of the deposit, its mineralogic similarity across large distances, the cation-conservative nature of the weathering processes, the presence of acidic groundwaters on a basaltic planet, the accumulation of a thick sedimentary sequence outside of a topographic basin, and the low water/rock ratio needed to explain the presence of very soluble minerals and elements in the deposit. Remote sensing studies have linked the Meridiani deposits to a number of other martian surface features through mineralogic similarities, geomorphic similarities, and regional associations. These include layered deposits in Arabia Terra, interior layered deposits in the Valles Marineris system, southern Elysium/Aeolis, Amazonis Planitia, and the Hellas basin, Aram Chaos, Aureum Chaos, and Ioni Chaos. The common properties shared by these deposits suggest that all of these deposits share a common formation process which must have acted over a large area of Mars. The results of this study suggest a mechanism for volatile transport on Mars without invoking an early greenhouse. They also imply a common formation mechanism for most of the sulfate minerals and layered deposits on Mars, which explains their common occurrence.

Niles, P.B.↗

System Modeling of Metabolic Heat Regenerated Temperature Swing Adsorption (MTSA) Subassembly for Prototype Design

This paper describes modeling methods for the three core components of a Metabolic heat regenerated Temperature Swing Adsorption (MTSA) subassembly: the sorbent bed, a sublimation (cooling) heat exchanger (SHX), and a condensing icing (warming) heat exchanger (CIHX). The primary function of the MTSA, removing carbon dioxide from a ventilation loop, is performed via the sorbent bed. The CIHX is used to heat the sorbent bed for desorption and to remove moisture from the ventilation loop while the SHX is alternately employed to cool the sorbent bed via sublimation of a spray of water at low pressure to prepare the reconditioned bed for the next cycle. This paper describes a system level model of the MTSA as developed in Thermal Desktop and SINDA/FLUINT including assumptions on geometry and physical phenomena, modeling methodology and relevant pa ra mete rizatio ns. Several areas of particular modeling interest are discussed. In the sorbent bed, capture of the translating CO2 saturation front and associated local energy and mass balance in both adsorbing and desorbing modes is covered. The CIHX poses particular challenges for modeling in SINDA/FLUINT as accounting for solids states in fluid submodels are not a native capability. Methods for capturing phase change and latent heat of ice as well as the transport properties across a layer of low density accreted frost are developed. This extended modeling capacity is applicable to temperatures greater than 258 K. To extend applicability to the minimum device temperature of 235 K, a method for a mapped transformation of temperatures from below the limit temperatures to some value above is given along with descriptions for associated material property transformations and the resulting impacts to total heat and mass transfer. Similar considerations are shown for the SHX along with assumptions for flow mechanics and resulting model methods for sublimation in a flow.

Bower, Chad↗

Modeling Of Metabolic Heat Regenerated Temperature Swing Adsorption (MTSA) Subassembly For Prototype Design

This paper describes modeling methods for the three core components of a Metabolic heat regenerated Temperature Swing Adsorption (MTSA) subassembly: a sorbent bed, a sublimation (cooling) heat exchanger (SHX), and a condensing icing (warming) heat exchanger (CIHX). The primary function of the MTSA, removing carbon dioxide from a space suit Portable Life Support System (PLSS) ventilation loop, is performed via the sorbent bed. The CIHX is used to heat the sorbent bed for desorption and to remove moisture from the ventilation loop while the SHX is alternately employed to cool the sorbent bed via sublimation of a spray of water at low pressure to prepare the reconditioned bed for the next cycle. This paper describes subsystem heat a mass transfer modeling methodologies relevant to the description of the MTSA subassembly in Thermal Desktop and SINDA/FLUINT. Several areas of particular modeling interest are discussed. In the sorbent bed, capture of the translating carbon dioxide (CO2) front and associated local energy and mass balance in both adsorbing and desorbing modes is covered. The CIHX poses particular challenges for modeling in SINDA/FLUINT as accounting for solids states in fluid submodels are not a native capability. Methods for capturing phase change and latent heat of ice as well as the transport properties across a layer of low density accreted frost are developed. This extended modeling capacity is applicable to temperatures greater than 258 K. To extend applicability to the minimum device temperature of 235 K, a method for a mapped transformation of temperatures from below the limit temperatures to some value above is given along with descriptions for associated material property transformations and the resulting impacts to total heat and mass transfer. Similar considerations are given for the SHX along with functional relationships for areal sublimation rates as limited by flow mechanics in t1he outlet duct.

Bower, Chad E.↗

Study of Aerothermodynamic Modeling Issues Relevant to High-Speed Sample Return Vehicles

This paper examines the application of state-of-the-art coupled ablation and radiation simulations to highspeed sample return vehicles, such as those returning from Mars or an asteroid. A defining characteristic of these entries is that the surface recession rates and temperatures are driven by nonequilibrium convective and radiative heating through a boundary layer with significant surface blowing and ablation products. Measurements relevant to validating the simulation of these phenomena are reviewed and the Stardust entry is identified as providing the best relevant measurements. A coupled ablation and radiation flowfield analysis is presented that implements a finite-rate surface chemistry model. Comparisons between this finite-rate model and a equilibrium ablation model show that, while good agreement is seen for diffusion-limited oxidation cases, the finite-rate model predicts up to 50% lower char rates than the equilibrium model at sublimation conditions. Both the equilibrium and finite rate models predict significant negative mass flux at the surface due to sublimation of atomic carbon. A sensitivity analysis to flowfield and surface chemistry rates show that, for a sample return capsule at 10, 12, and 14 km/s, the sublimation rates for C and C3 provide the largest changes to the convective flux, radiative flux, and char rate. A parametric uncertainty analysis of the radiative heating due to radiation modeling parameters indicates uncertainties ranging from 27% at 10 km/s to 36% at 14 km/s. Applying the developed coupled analysis to the Stardust entry results in temperatures within 10% of those inferred from observations, and final recession values within 20% of measurements, which improves upon the 60% over-prediction at the stagnation point obtained through an uncoupled analysis. Emission from CN Violet is shown to be over-predicted by nearly and order-of-magnitude, which is consistent with the results of previous independent analyses. Finally, the coupled analysis is applied to a 14 km/s Earth entry representative of a Mars sample return. Although the radiative heating provides a larger fraction of the total heating, the influence of ablation and radiation on the flowfield are shown to be similar to Stardust.

Johnston, Christopher O.↗

Development of Naphthalene PLIF for Visualizing Ablation Products From a Space Capsule Heat Shield

The Orion Multi-Purpose Crew Vehicle (MPCV) will use an ablative heat shield. To better design this heat shield and others that will undergo planetary entry, an improved understanding of the ablation process would be beneficial. Here, a technique developed at The University of Texas at Austin that uses planar laser-induced fluorescence (PLIF) of a low-temperature sublimating ablator (naphthalene) to enable visualization of the ablation products in a hypersonic flow is applied. Although high-temperature ablation is difficult and expensive to recreate in a laboratory environment, low-temperature sublimation creates a limited physics problem that can be used to explore ablation-product transport in a hypersonic flow-field. In the current work, a subscale capsule reentry vehicle model with a solid naphthalene heat shield has been tested in a Mach 5 wind tunnel. The PLIF technique provides images of the spatial distribution of sublimated naphthalene in the heat-shield boundary layer, separated shear layer, and backshell recirculation region. Visualizations of the capsule shear layer using both naphthalene PLIF and Schlieren imaging compared favorably. PLIF images have shown high concentrations of naphthalene in the capsule separated flow region, intermittent turbulent structures on the heat shield surface, and interesting details of the capsule shear layer structure. It was shown that, in general, the capsule shear layer appears to be more unsteady at lower angels of attack. The PLIF images demonstrated that during a wind tunnel run, as the model heated up, the rate of naphthalene ablation increased, since the PLIF signal increased steadily over the course of a run. Additionally, the shear layer became increasingly unsteady over the course of a wind tunnel run, likely because of increased surface roughness but also possibly because of the increased blowing. Regions with a relatively low concentration of naphthalene were also identified in the capsule backshell recirculation region and are most likely the result of cross-flow-induced vortices on the capsule afterbody.

Combs, C. S.↗

Iodine Propellant Feed System Flow Modeling

The use of solid iodine as a propellant in Hall-effect thrusters (HETs) is currently being investigated for small-satellite applications. CubeSats offer an inexpensive mode of access to space; however, they currently lack significant propulsion capability. A high specific impulse (I (sub sp)) propulsion system would permit a significant change in velocity, delta v, to be imparted for orbital maintenance, transfers, or de-orbit maneuvers. An electric propulsion system that uses iodine as a propellant has a number of advantages. It has an exceptionally high rho times I (sub sp) figure of merit (density multiplied by the specific impulse), meaning that it can achieve a large total delta v with a relatively low combination of propellant mass and propellant tank volume. Also, the propellant feed system operates at low pressures (a few psia at most), as opposed to the use of super-critical xenon stored at very high pressure. Low pressure operation can lower system mass while greatly reducing the risk of propellant tank rupture, making low pressure a vitally important property for propellants on secondary payloads like CubeSats, where risks must be minimized. The iSAT mission aims to demonstrate iodine-fed HET technology, flying it in space onboard a 12U 912-unit) CubeSat. In the iSAT propellant feed system (PFS), solid iodine is sublimed through heating to produce gaseous propellant that is conducted through tubing to the thruster and cathode. The sublimation process is governed by the iodine (I2) vapor pressure, which is shown as a function of temperature in figure 1. As gaseous I2 flows out of the tank, the gas pressure in the volume containing the solid iodine propellant is reduced until a balance between the flow of iodine out of the tank and the sublimation rate of solid iodine at the equilibrium gas pressure and chosen tank temperature is reached.

Martin, A. K.↗

Effect of Sample Mass, Confinement, and Preheating Time on the Thermal Response of LLM‐105: Experiments and Kinetic Analysis

Various small-scale experiments were performed to provide data for developing a model to predict the thermal response of LLM-105 over a wide range of conditions. The thermal decomposition of LLM-105 was studied as a function of sample mass, confinement of volatile products, and preheating time in both isothermal and ramped heating experiments. The thermal decomposition of LLM-105 is a two-step process, as shown by the two exothermic peaks in the heat flow profiles, which were fitted to two nth-order autocatalytic reaction models with a similar activation energy of ∼289 kJ/mol. The magnitude and shape of these peaks varied with sample mass and confinement. Increasing sample mass enhanced the second exotherm with respect to the first one, while increasing the level of confinement promoted a transition from a sublimation-dominated regime towards thermal decomposition. The effect of LLM-105 particle size on the rate of weight loss was evident for open-pan experiments, where bigger particles sublimed at lower temperatures than smaller particles. Thermal response and solid residue composition of LLM-105 samples were analyzed following preheating for different durations. Longer preheating times caused a shift of the second exotherm to lower temperatures and a decrease in the reaction enthalpy, confirming that LLM-105 decay is a consecutive reaction mechanism, probably autocatalytic. In conclusion, the kinetic model derived from ramped experiments was validated against the measured LLM-105 fraction remaining and the enthalpy remaining of the solid residue as a function of preheating times and showed good agreement.

Chemistry - Chemical explosives↗

Solventless Dual‐Cure Liquid Resins Via Circular Use of Phthalic Anhydride for Recyclable Composite Applications

Abstract Fiber‐reinforced composites (FRCs) possess a remarkable strength‐to‐weight ratio, making them ideal light‐weighing alternative materials of metals used in automotive, aerospace, and outdoor equipment applications, but their recycling is challenging. Chemically recyclable thermoset polymers can enable fiber recovery and reuse; however, challenges remain in the separation and purification of depolymerized small molecules for efficient polymer recycling. To this end, a series of liquid resins for chemically recyclable polymer networks is designed based on phthalic anhydride, a widely produced and inexpensive chemical. The straightforward sublimation of phthalic anhydride is leveraged to enable a simple and efficient separation process for polymer recycling. To liquefy phthalic anhydride, five mono‐acryloyl‐phthalates are synthesized to obtain stable liquid resins together with phthalic diglycidyl ester. These liquid resins undergo dual‐cure reactions that comprise photopolymerization of acrylate and, subsequently, heat‐mediated epoxy‐acid polymerization reactions. These liquid resins exhibit moderate viscosities (2600–6400 cP @ 22 °C), fast curing, and robust thermomechanical properties (T g s from 71 to 116 °C). It is demonstrated that hydrolysis of the dual‐cured polymers completes within 2 h at 80 °C, and direct sublimation produces phthalic anhydride with 82% yield. This resin system is expected to provide a cost‐competitive, highly efficient platform for recyclable FRCs.

Polymer Science↗

Evolution of PTCDA-derived seeds prior to graphene nanoribbon growth on Ge(001)

The synthesis of graphene nanoribbons (GNRs) can be realized via CH4 chemical vapor deposition (CVD) on substrates such as Ge(001) that promote highly anisotropic growth kinetics. Small polycyclic aromatic hydrocarbons (PAHs) are first sublimed onto Ge near room temperature to form graphene-like seeds that subsequently initiate GNR growth with CH4 exposure at 1173 K. The behaviors of PAHs in the time in between their sublimation onto Ge and GNR growth are unclear. Here, we study an archetypical PAH, perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA), on Ge(001) using both scanning tunneling microscopy (STM) and density functional theory (DFT) to characterize PAH conformation, surface diffusivity, and clustering, versus temperature. PTCDA becomes mobile above 673 K (consistent with a DFT calculated diffusion barrier of 2.01 eV). The mobile PTCDA molecules meet, cluster, and fuse at Ge step edges. These clusters have an apparent height of 0.4 nm, similar to small graphene islands, and grow laterally with increasing temperature – reaching 1.2 – 2.1 nm in width at 1173 K, consistent with the seed size extrapolated from CVD experiments. These results provide a plausible picture for how PTCDA forms seeds for anisotropic GNR CVD and show that PAHs with reduced surface diffusivity and inter-molecular reactivity are needed to enable more monodisperse PAH-seeded GNR synthesis.

36 MATERIALS SCIENCE↗