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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination

Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12×. The primary dopant 2,5-diphenyloxazole had minimal impact on the printing process even when loaded at 25 % by mass of the resin. Working curve measurements, which relate energy dose to cure depth, were performed as a function of feature size to further assess the influence of dopants. Photopatterns smaller than 150 µm width had apparent increases in critical energy dose compared to larger photopatterns, while all resins maintained printed features in line gratings with 50 µm of separation. Printed scintillator monoliths were compared to scintillators cast by traditional molding, demonstrating that the layer-by-layer printing process does not decrease scintillation response. In conclusion, a maximum light output of 31 % of a benchmark plastic scintillator (EJ-200) and successful pulse shape discrimination were achieved with 20 % by mass 2,5-diphenyloxazole as the primary dopant and 0.1 % by mass 9,9-dimethyl-2,7-distyrylfluorene as the secondary dopant in printed scintillator samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Online thermal profile prediction for large format additive manufacturing: A hybrid CNN-LSTM based approach

Large format additive manufacturing (LFAM) is an advanced 3D printing technique that efficiently fabricates large-scale components through a layer-by-layer extrusion and deposition process. Accurate surface layer temperature monitoring is essential to prevent manufacturing failures and ensure final product quality. Traditional physics-based offline approaches for simulating thermal behavior are often inefficient and complex, posing challenges on real-time, in-situ monitoring. Here, to address this, we propose a data-driven hybrid CNN-LSTM model to predict sequential thermal images of arbitrary length using real-time infrared thermal imaging. In this approach, a Convolutional Neural Networks (CNN) is trained offline to capture spatial features, reduce dimensional complexity, and enhance time efficiency, while a stacked Long Short-Term Memory (LSTM) is applied online to capture temporal information for improved prediction of future thermal behavior in subsequent printing layers. Model performance is evaluated using MSE, SSIM, and PSNR metrics and is benchmarked against stacked LSTM and convolutional LSTM models, demonstrating superior accuracy and applicability. Additionally, to mitigate noise from moving extruders and gantry backgrounds in thermal images, a fine-tuned semantic segmentation model is implemented offline to extract printing geometry, enabling precise temperature tracking along the tool path for further thermal analysis. The frameworks developed in this study significantly advance temperature monitoring, thermal analysis, and in-situ manufacturing control for LFAM, bridging the gap between theoretical modeling and practical application.

Geometry extraction↗

Developing Benzodithiophene-Free donor polymer for 19.36% efficiency Green-Solvent-Processable organic solar cells

Here, in this work, a newly benzodithiophene-free D-A polymer donor, named PDTP-BDD, was developed for realizing green-solvent processed high-performance OSCs. By bridging two electron-rich unit of dithieno[3,2-b:2',3'-d]pyridin-5(4H)-one (DTP) and electron-deficient benzo[1,2-c:4,5c']dithiophene-4,8-dione (BDD) with thiophene units, PDTP-BDD possesses high absorption in the short wavelength range and a deep HOMO energy level. The rigid building blocks also make PDTP-BDD has strong aggregation and poor solubility in common halogen-free solvents (such as o-xylene) at room temperature, but it is readily dissolved and disaggregated at high temperature (120 °C). After cooling down to a lower temperature (60 °C), PDTP-BDD self-assembled and pre-aggregated slowly in the solution at a long time. By employing a delayed processing strategy in the layer-by-layer processed OSCs (LbL-OSCs), an optimized fibril network of the underling layer was realized, enabling the permeation of acceptor into the donor network. The optimized PDTP-BDD/L8-BO-based LbL-OSCs realized a high PCE of 18.42 %. By adding a small amount of D18 to further optimize the PDTP-BDD fibril network, an impressive PCE of 19.36 % was achieved finally in the resulting ternary LbL-OSCs, which is the highest value for OSCs processed by halogen-free solvents.

36 MATERIALS SCIENCE↗

Mineralogical and microstructural alterations in a portland cement paste after an accelerated decalcification process

Cement paste leaching and concomitant decalcification is a common cause of concrete structure deterioration. Such alterations entail microstructural changes that condition concrete durability. This study analysed those changes in cement pastes exposed to accelerated decalcification, layer-by-layer, from the surface in contact with the leaching agent, 6 M NH{sub 4}NO{sub 3,} to the unaltered area. The microstructural changes were analysed with BSEM, MIP and BET whilst the mineralogical and nanostructural alterations in each layer were assessed with XRD, FTIR, {sup 29}Si and {sup 27}Al MAS NMR and BSD. Decalcification affected not only portlandite and CSH gel, but also the anhydrous clinker and ettringite, inducing major micro- and nano-structural changes, particularly in the two layers closest to the leaching agent. CSH gel decalcification was more intense in the outer layers where long chain gels co-existed with silicon rich gels. BDS, in turn, revealed differences between the amount of bound water in the surface interfacing with the leaching agent and in the leaching front. More specifically, larger numbers of water molecules were tightly bound to silanol groups in the outer, whereas hydroxyl group distribution was more orderly in the inner layers.

36 MATERIALS SCIENCE↗

Optimal toolpath design of additive manufactured composite cylindrical structures

Structural design optimization for additive manufacturing is primarily focused on planar layer-by-layer processes and design of composite cylindrical structures does not often accommodate manufacturing constraints. In this study, we propose to optimize the toolpath trajectory of additively manufactured composite cylinders comprised of multiple thin cylindrical annuli. Additionally, our printing process is based on direct ink writing in which short carbon fibers in a thermoset resin are extruded through a moving nozzle to build up a structure. Since the fibers are primarily aligned in the flow direction of the extrudate, the printing trajectory influences the material properties of the composite structure. To accommodate this, we define the toolpaths as contours of parameterized level-set functions. This parameterization allows us to optimize the material properties and impose manufacturing constraints such as no-overlap, no-sag, minimum radius of curvature, and continuity of the toolpaths. Several examples illustrate the optimization procedure.

42 ENGINEERING↗

Combustion in the ZrF 4 -Mg-Si and ZrF 4 -Al-Si systems for preparation of zirconium silicides

The exothermic reactions in the ZrF 4 –Mg-Si and ZrF 4 -Al-Si systems are investigated by a fast temperature recording (thermocouple) technique, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). A quenching method is used to arrest the combustion process and conduct a layer-by-layer analysis of the products by x-ray diffraction (XRD) and electron microscopy. Two seemingly similar reactive systems exhibited considerably different combustion characteristics, composition, and morphology. Based on these investigations, we propose and discuss phase formation mechanisms at the early stages for each system. Three different pathways involving the reaction of ZrF 4 with other reagents and the Mg 2 Si intermediate are identified to occur in the ZrF 4 –Mg-Si system. Contrary to the complex mechanism in the ZrF 4 –Mg-Si system, the early stage of the combustion process for the ZrF 4 -Al-Si system involves the interaction of ZrF 4 with Al-Si eutectic melt. The exothermic reaction between reduced solid Zr and Si melt is the primary heat-generating step for both systems in spite of substantial differences in the early stages of the reactions. The silicon content in the reactive mixtures governs the phase composition of products. The ZrSi 2 phase, with a high growth rate, forms first on the Zr particle surfaces and then grows by a reactive diffusion mechanism. The ZrSi 2+ Zr reaction produces silicon-lean phases (e.g., ZrSi) when the silicon supply is limited. The combustion temperature also has a considerable influence on the phase compositions of the products. High combustion temperature in the ZrF 4 +2Mg+Si mixture enables the formation of multiphase products (α-ZrSi and β-ZrSi), whereas the relatively lower temperatures in the 3ZrF 4 +4Al+3Si mixture yields a single-phase α-ZrSi. As a result, lower combustion temperatures also make the ZrF 4 -Al-Si system more advantageous for the preparation of zirconium silicides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of different manufacturing methods on polyamide reverse-osmosis membranes for desalination: Insights from molecular dynamics simulations

Membranes are a key technology platform for a broad application of energy-efficient separations. To best serve the separation demands of industry, the manufacturing processes for these membranes are garnering increasing attention. In particular, for water desalination, the industry leading polyamide (PA) reverse osmosis (RO) membranes can be manufactured via molecular layer-by-layer (mLBL) deposition, interfacial polymerization (IP), and 3D-printing technique. However, the influence of different manufacturing methods on PA membrane’s properties is far from understood. Here, in this study, we present the high-pressure transport behavior of water and salt ions for PA membranes formed with IP, mLBL, and 3D-printing through non-equilibrium molecular dynamics simulations. Studies show that membranes fabricated with 3D-printing have similar performances to those manufactured using mLBL, quantified by water permeability, rejection of salt ions, structural integrity, and porosity features. However, the membranes formed with IP exhibit faster water transport, lower rejection, worse structural integrity, and more inhomogeneous network pores than those constructed using mLBL and 3D-printing. The unconnected water-accessible space governs water transport for PA membranes formed with mLBL and 3D-printing, which offers the impermanent open-closed pores that enable water to jump through PA membranes. In contrast, the permeated water-enterable space plays a prominent role in water movement across the PA membrane formed with IP, providing a continuous transport channel at high pressure. Importantly, we observe the more significant compaction features at high pressure for PA membranes formed with IP than mLBL and 3D printing. In short, these findings provide a comprehensive understanding of existing membrane preparation technologies. It also provides a guide for developing the new membrane preparation process at the molecular level.

3D-printing↗

Local prediction of Laser Powder Bed Fusion porosity by short-wave infrared imaging thermal feature porosity probability maps

We report that local thermal history can significantly vary in parts during metal Additive Manufacturing (AM), leading to local defects. However, the sequential layer-by-layer nature of AM facilitates in-situ part voxelmetric observations that can be used to detect and correct these defects for part qualification and quality control. The challenge is to relate this local radiometric data with local defect information to estimate process error likelihood in future builds. This paper uses a Short-Wave Infrared (SWIR) camera to record the temperature history for parts manufactured with Laser Powder Bed Fusion (LPBF) processes. The porosity from a cylindrical specimen is measured by ex-situ micro-computed tomography (μCT). Specimen data from the SWIR camera, combined with the μCT data, are used to generate thermal feature-based porosity probability maps. The porosity predictions made by various SWIR thermal feature-porosity probability maps of a specimen with a complex geometry are scored against the true porosity obtained via μCT. The receiver operating characteristic curves constructed from the predictions for the complex sample demonstrate the porosity probability mapping methodology’s potential for in-situ based porosity detection.

36 MATERIALS SCIENCE↗

Additively manufactured β-Ti5553 with laser powder bed fusion: Microstructures and mechanical properties of bulk and lattice parts

Ti5553 (Ti-5Al-5Mo-5V-3Cr wt%) is a titanium alloy widely used for its high strength-to-weight ratio and good formability at elevated temperatures. Unlike Ti-6Al-4V, Ti5553 does not undergo martensitic transformation, preventing cracking of brittle martensite upon rapid cooling. This makes it a strong candidate for additive manufacturing (AM), particularly laser powder bed fusion (L-PBF). L-PBF offers the unique opportunity to make fine lattice structures to reduce component weight. Despite the growing field of AM, there have been limited studies on L-PBF Ti5553 lattices and how their properties differ from the bulk. Here the present work addresses this knowledge gap by investigating microstructures and properties of L-PBF bulk and lattice parts and the effect of post L-PBF heat treatments. Electron microscopy and mechanical testing show that the high dislocation density formed during L-PBF increases bulk part’s yield strength by approximately 100 MPa compared to the conventional alloy. Digital image correlation during compression testing of octet truss lattices reveals a layer-by-layer failure mode. Compared to the bulk, the lattice contains copious ω nanoprecipitation, weaker <001> texture, smaller average grain sizes, and larger content of high-angle grain boundaries. These features elicit differences in Taylor factor distributions for the lattice depending on load direction, underlining challenges in predicting lattice mechanical response based on bulk properties. By examining the processing-structure-property relationships in the bulk and lattice, the present results delineate their microstructural and mechanical differences and establish a benchmark for the future design applications of L-PBF Ti5553.

36 MATERIALS SCIENCE↗

Phase stability and mechanical properties of wire + arc additively manufactured H13 tool steel at elevated temperatures

Wire + arc additive manufacturing (WAAM) is considered an innovative technology that can change the manufacturing landscape in the near future. WAAM offers the benefits of inexpensive initial system setup and a high deposition rate for fabricating medium- and large-sized parts such as die-casting tools. Here, AISI H13 tool steel, a popular die-casting tool metal, is manufactured by cold metal transfer (CMT)-based WAAM and is then comprehensively analyzed for its microstructural and mechanical properties. Location-dependent phase combinations are observed, which could be explained by nonequilibrium thermal cycles that resulted from the layer-by-layer stacking mechanism used in WAAM. In addition, remelting and reheating of the layers reduces welding anomalies (e.g., pores and voids). The metallurgical characteristics of the H13 strongly correlate with the mechanical properties. The combinations of phases at different locations of the additively manufactured part exhibit a periodic microhardness profile. Martensite, Retained Austenite, Ferrite, and Carbide phases are found in combination at different locations of the part based on the part’s temperature distribution during additive deposition. Moreover, the tensile properties at elevated temperatures (23 °C, 300 °C, and 600 °C) are comparable to those from other WAAM and additive manufacturing (AM) processes. The X-ray diffraction results verify that the microstructural stability of the fabricated parts at high temperatures would allow them to be used in high temperatures.

36 MATERIALS SCIENCE↗

Processing of tungsten through electron beam melting

Additive manufacturing (AM) presents a new design paradigm for the manufacture of engineering materials through the layer-by-layer approach combined with welding theory. In the instance of difficult to process materials such as tungsten and other refractory metals, AM offers an opportunity for radical redesign of critical components for next-generation energy technologies including fusion. In this work, electron beam powder bed fusion (EB-PBF) is applied to process pure tungsten to study the influence of process parameters on the defect density of the material. Here, an in-situ image analysis algorithm is applied to pure tungsten for the first time, and is used to visualize the defect structure in AM tungsten. Finally, a cracking mechanism for AM tungsten is proposed, and suggestions for suppression of cracks in pure tungsten are offered.

36 MATERIALS SCIENCE↗

Mechanical properties, strain hardening, and fracture behavior of ultrasonic additively manufactured Zircaloy-4 after low-temperature neutron irradiation

Ultrasonic additive manufacturing (UAM) is a solid-state, layer-by-layer advanced manufacturing process that has the potential to create custom spatially controlled composites with embedded wires and sensors for nuclear component manufacture. For this work, to assess the feasibility of using UAM for nuclear-relevant materials research, the technique was used to produce a 3.5-mm-thick Zircaloy-4 plate for irradiation testing. The UAM Zircaloy-4 specimens were irradiated in the High Flux Isotope Reactor at a target irradiation temperature of 117 °C to 2.9 displacements per atom (dpa) to assess differences in irradiation-hardening behavior as a function of alloy processing path. The UAM and reference baseplate (BP) materials increased in yield strength by 372±27 MPa and 346±21 MPa, respectively, and both suffered significant reductions in uniform and total elongation attributed to irradiation hardening at low-temperature. Although the materials had similar nanoscale defect structures, including nanoscale black dot/loop features and strain-induced dislocation channels, the UAM material’s processing-related defects resulted in accelerated strain localization and failure as demonstrated by lower post-irradiation uniform elongation of UAM specimens (0.5 %) compared to BP (1.5 %) material. The UAM material also showed considerable anisotropy in mechanical response due to crack propagation along weld boundaries, resulting in differences in strength & ductility when tested parallel and perpendicular to the prior UAM build orientation. Therefore, although the fundamental irradiation response of UAM-processed Zircaloy-4 was phenomenologically comparable to that of BP reference material, additional optimization of the UAM processing is needed to produce irradiation-resistant and nuclear-relevant materials.

Digital image correlation↗

Process-structure-property considerations for wire-based directed energy deposition of Ti-6Al-4V

Directed energy deposition (DED) is an attractive additive manufacturing (AM) process for large structural components. The rapid solidification and layer-by-layer process associated with DED results in non-ideal microstructures, such as large grains with strong crystallographic textures. These non-ideal microstructures can lead to severe anisotropy in the mechanical properties. Despite these challenges, DED has been identified as a potential solution for the manufacturing of near net shape Ti-6Al-4V preforms, replacing lost casting and forging capabilities. Two popular wire-based directed energy deposition (W-DED) processes were considered for the manufacturing of Ti-6Al-4V with assessments on their respective metallurgical and mechanical properties, as compared to a conventionally processed material. The two W-DED processes explored were wire arc additive manufacturing (WAAM) and electron beam additive manufacturing (EBAM). High throughput inspection and tensile testing procedures were utilized to generate statistically relevant data sets related to each process and sample orientation. The 2 AM technologies produced material with remarkably different microstructures and mechanical properties. Importantly, results revealed key differences in strength and ductility for the two disparate processes which were found to be related to differences in the metallurgical properties.

36 MATERIALS SCIENCE↗

Electrodialysis through nafion membranes coated with polyelectrolyte multilayers yields >99% pure monovalent ions at high recoveries

Separation of monovalent and multivalent ions is important in processes ranging from water softening to recycling of Li. Previous studies show that cation-exchange membranes coated with multilayer polyelectrolyte films exhibit monovalent/divalent ion selectivities as high as 1000 in electrodialysis (ED) under ideal conditions with low ion recoveries. This work shows that even at 60-80% monovalent-ion recoveries, ED through Nafion membranes coated with protonated poly(allylamine)/poly(4-styrenesulfonate) multilayers can separate equimolar K + and Mg 2+ or Li + and Mg 2+ to give 99.5% pure monovalent ion. Moreover, the use of a low-volume receiving phase allows ED to concentrate the monovalent ion. Typical current efficiencies are around 70% for these separations. Selectivities appear to increase when the membrane-coating procedure uses a higher polyelectrolyte concentration in the deposition solution. Because the limiting current declines with ED time due to depletion of the monovalent ion in the source phase, use of a gradually decreasing applied current enhances current efficiency compared to ED at a constant high current. Further, the membranes also show Li + /Mg 2+ selectivities around 100 when Mg 2+ is in a 20-fold excess in the source phase at an ionic strength of 0.6 M, but selectivity decreases at even higher ionic strengths.

15 GEOTHERMAL ENERGY↗

Correlating viscosity and die swell in 3D printing of polyphenylsulfone: A thermo-mechanical optimization modus operandi

Additive manufacturing (AM) of polyphenylsulfone (PPSU), an amorphous high-performance polymer (HPP), has shown promise in exhibiting structural integrity for many applications. With thermoplastic material extrusion 3D printing, parts consisting of layered melts exhibited voids, where the adhesion quality and void size depend on the processing parameters implemented during printing. However, the structure-process-property (SPP) relationships between the thermal properties and rheological and mechanical behavior of AM PPSU are poorly understood. Here, in this study, a comprehensive analysis of the thermal, thermo-mechanical, and layer-by-layer build-up of PPSU is investigated and correlated with viscosity and extrudate die swell behavior with void fraction volume as confirmed by high-resolution x-ray computed tomography (XCT). Gas chromatography–mass spectrometry (GC–MS) pyrolysis confirmed PPSU composition and degradation at 480 °C, consistent with thermo-gravimetric analysis TGA. A 141% difference in viscosity was observed when processing temperatures increased from 350 °C to 400 °C. Likewise, extrudate die swell decreased with increasing temperatures, resulting in a 17% difference. Tensile and compressive properties confirmed that higher extruding temperatures resulted in lower porosity and higher mechanical strength. In general, higher extruding temperatures lower the viscosity to allow for stronger cohesion between layers; however, increasing the temperature too high results in a below unity extrudate die swell, reducing mechanical properties. Therefore, to optimize the mechanical integrity of 3D printed amorphous PPSU parts, an increase in the viscosity, near unity of the extrudate die swell, and tempered extrusion temperature are needed.

36 MATERIALS SCIENCE↗

Pulsed laser deposition and structural evolution of BaF 2 nanolayers in Eu-doped BaF 2 /Al 2 O 3 layered optical nanocomposite thin films

Here, we have developed a pulsed laser deposition (PLD) geometry for the growth of uniform BaF 2 nanoscale thin films, through control of the deposition conditions. Our goal is to use the BaF 2 layers with controllable structure as component layers in layered optical nanocomposites. The structure of the BaF 2 nanolayer evolves as a function of the layer thickness: BaF 2 grows via a layer-by-layer growth mode on Al 2 O 3 ; the layers are amorphous for a thickness < 3 nm, and then become nanocrystalline as the layer thickness increases. The BaF 2 nanocrystals have an FCC crystal structure with a weak < 111 > texture that becomes stronger for thicker films. We then demonstrate that our BaF2 films can be introduced into layered Al 2 O 3 /BaF 2 /EuO x nanocomposite films, which allows for control of the relative position of the Eu ions and the BaF 2 layer. Cross-section samples of the multilayered films show interfacial intermixing between the layers, which is related to implantation during the PLD process. This intermixing enables the incorporation of Eu ions into BaF 2 layers and form a thin Eu-doped BaF 2 nanolayer at the interface. The layered nanocomposite films show photoluminescence (PL) emission from Eu 3+ ions, and the PL intensity changes can be correlated with the crystallinity and crystal size changes in the BaF 2 layer. Our results provide guidance for achieving thin film nanocomposite materials with controllable structure and photoluminescence behavior for light emitting diodes, photovoltaics and other optical applications.

36 MATERIALS SCIENCE↗

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications. This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2 H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature T g can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in T g and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of T g with increased confinement that is strongly influenced by the pore-liquid interface characteristics. This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. Finally, while the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗