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At least 109 records · Page 6

Modification of Radiator Pigments by Atomic Layer Deposition (ALD)

The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. Other examples include the application of variable emittance coatings such as the use of VO2 to optimize radiator size, allowing for a decrease in heater power budget. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. Modification of these coatings can be accomplished during coating application preprocessing by using a deposition technique prevalent in the semiconductor micro processing industry called Atomic Layer Deposition (ALD). The preprocessing is rendered directly on the coating dry pigment before binding. ALD is a cost effective nano-manufacturing technique that allows for the conformal coating of substrates with atomic-level thickness control in a benign temperature and pressure environment. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano-structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. We have demonstrated a method for the ALD of In2O3 and ITO films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments (patent pending). The results indicate excellent growth of 4-22 nm thick films demonstrating an order of magnitude decrease in resistivity on the pigments.

ITO↗

ToF-SIMS evaluation of PEG-related mass peaks and applications in PEG detection in cosmetic products

Polyethylene glycols (PEGs) are used in industrial, medical, health care, and personal care applications. The cycling and disposal of synthetic polymers like PEGs pose significant environmental concerns. Detecting and monitoring PEGs in the real world calls for immediate attention. This study unveils the efficacy of time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a reliable approach for precise analysis and identification of reference PEGs and PEGs used in cosmetic products. By comparing SIMS spectra, we show remarkable sensitivity in pinpointing distinctive ion peaks inherent to various PEG compounds. Moreover, the employment of principal component analysis effectively discriminates compositions among different samples. Notably, the application of SIMS two-dimensional image analysis visually portrays the spatial distribution of various PEGs as reference materials. The same is observed in authentic cosmetic products. The application of ToF-SIMS underscores its potential in distinguishing PEGs within intricate environmental context. ToF-SIMS provides an effective solution to studying emerging environmental challenges, offering straightforward sample preparation and superior detection of synthetic organics in mass spectral analysis. These features show that SIMS can serve as a promising alternative for evaluation and assessment of PEGs in terms of the source, emission, and transport of anthropogenic organics.

36 MATERIALS SCIENCE↗

Brush-modified fluorescent organic nanoparticles by ATRP with rigidity-regulated emission

Organic nanoparticles provide exceptional intraparticle tailorability, enabling the incorporation of functional molecules for diverse applications. In this study, we present the synthesis and characterization of fluorescent organic nanoparticles (FoNPs) with encapsulated aggregation-induced emission (AIE) luminogens with emission properties regulated by particle rigidity. Atom transfer radical polymerization (ATRP) was employed in dispersed media to develop various fluorescence colors tuned by precise control over particle rigidity. Comprehensive analyses revealed that increased particle rigidity significantly enhanced photoluminescence, achieving quantum yields of up to 22% in selected solvents. The high chain-end fidelity facilitated the grafting of hydrophilic polymer brushes from surfaces of FoNPs used as macroinitiators, enabling their dispersion in aqueous media while maintaining bright fluorescence. These findings highlight the potential of rigidity-regulated FoNPs as versatile platforms for advanced material applications, particularly in fluorescent waterborne films and aqueous-phase sensing systems.

Yin, Rongguan [Carnegie Mellon Univ., Pittsburgh, ↗

Predictability of Gaseous Impact Ignition Sensitivity from Autoignition Temperature Data

An analysis of cumulative binomial probabilities for a quantal-type test like ASTM G74 indicates that for a probability of reaction in a single trial of 0.05, the probability of obtaining zero reactions in 20 trials is only approximately 36 percent, Because the lack of precision with the ASTM G74 test logic could be potentially misleading, an investigation was conducted to determine if pneumatic impact sensitivity could be predicted more reliably from other, more precise test methods. Pneumatic impact sensitivity tests were conducted following ASTM G74, but employing more rigorous test logics; autoignition temperature tests were conducted per ASTM G72. Polytetrafluoroethylene (PTFE), Viton A, polyethylene, polyoxymethylene polyamide, and silicone were the polymers used. After a fixed number of pneumatic impact tests was performed at set pressures, a plot of reaction frequency over a 3.4 to 24.1 MPa impact pressure range indicated that PTFE, Viton A, and silicone would outperform other polymers. The 50 percent pneumatic impact reactivity level was determined with the Bruceton test method. The data obtained resulted in a strong correlation between the 50 percent reactivity level and the autoignition temperature of polymers, indicating similar ignition mechanisms.

Hirsh, David↗

Integrated Multilayer Insulation

Integrated multilayer insulation (IMLI) is being developed as an improved alternative to conventional multilayer insulation (MLI), which is more than 50 years old. A typical conventional MLI blanket comprises between 10 and 120 metallized polymer films separated by polyester nets. MLI is the best thermal- insulation material for use in a vacuum, and is the insulation material of choice for spacecraft and cryogenic systems. However, conventional MLI has several disadvantages: It is difficult or impossible to maintain the desired value of gap distance between the film layers (and consequently, it is difficult or impossible to ensure consistent performance), and fabrication and installation are labor-intensive and difficult. The development of IMLI is intended to overcome these disadvantages to some extent and to offer some additional advantages over conventional MLI. The main difference between IMLI and conventional MLI lies in the method of maintaining the gaps between the film layers. In IMLI, the film layers are separated by what its developers call a micro-molded discrete matrix, which can be loosely characterized as consisting of arrays of highly engineered, small, lightweight, polymer (typically, thermoplastic) frames attached to, and placed between, the film layers. The term "micro-molded" refers to both the smallness of the frames and the fact that they are fabricated in a process that forms precise small features, described below, that are essential to attainment of the desired properties. The term "discrete" refers to the nature of the matrix as consisting of separate frames, in contradistinction to a unitary frame spanning entire volume of an insulation blanket.

Dye, Scott↗

Structure–Function Relationships in Sequence-Controlled Copolymers for Rare Earth Element Chelation

The ability to tune material function through primary sequence is a defining feature of biological macromolecules, allowing precise control over structure and target interactions in complex aqueous environments. However, translating sequence–structure–function relationships to synthetic macromolecules is challenging due to their dispersity in sequence, conformation, and composition. Here, we report systematic studies of amphiphilic polymer chelators designed to probe how composition and patterning influence binding affinity and selectivity for rare earth elements (REEs), a series of technologically relevant metals with challenging separation profiles. A library of copolymers varying hydrophobic monomer composition and patterning was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization, spanning statistical, gradient, and block architectures. REE binding was quantified using a high-throughput colorimetric assay, and reconstruction of polymer ensembles using kinetic stochastic simulations enabled quantitative comparisons of sequence heterogeneity, linking local monomer colocalization to emergent REE binding. Further, we investigated the role of different hydrophobic comonomers in tuning metal coordination, with binding trends linked to structural features that influence binding site desolvation. Complementary dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements showed that both polymer and monomer architecture modulate metal-induced conformational changes, and that multichain assembly behavior emerges beyond critical hydrophobic thresholds. Sequence control also altered REE selectivity, with nonmonotonic differences observed across compositionally identical polymers with different sequence architectures. Together, these findings establish design principles that connect polymer sequence and structure to binding performance, guiding the design of macromolecular chelators with enhanced affinity and selectivity for applications in separations, sensing, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A novel digital lifecycle for Material‐Process‐Microstructure‐Performance relationships of thermoplastic olefins foams manufactured via supercritical fluid assisted foam injection molding

Abstract This research significantly enhances the applicability of thermoplastic olefins (TPOs) in the automotive industry using supercritical N 2 as a physical foaming agent, effectively addressing the limitations of traditional chemical agents. It merges experimental results with simulations to establish detailed material‐process‐microstructure‐performance (MP2) relationships, targeting 5–20% weight reductions. This innovative approach labeled digital lifecycle (DLC) helps accurately predict tensile, flexural, and impact properties based on the foam microstructure, along with experimentally demonstrating improved paintability. The study combines process simulations with finite element models to develop a comprehensive digital model for accurately predicting mechanical properties. Our findings demonstrate a strong correlation between simulated and experimental data, with about a 5% error across various weight reduction targets, marking significant improvements over existing analytical models. This research highlights the efficacy of physical foaming agents in TPO enhancement and emphasizes the importance of integrating experimental and simulation methods to capture the underlying foaming mechanism to establish material‐process‐microstructure‐performance (MP2) relationships. Highlights Establishes a material‐process‐microstructure‐performance (MP2) for TPO foams Sustainably produces TPO foams using supercritical (ScF) N 2 with 20% lightweighting Shows enhanced paintability for TPO foam improved surface aesthetics Digital lifecycle (DLC) that predicts both foam microstructure and properties DLC maps process effects & microstructure onto FEA mesh for precise prediction

Engineering↗

Plant metabolism and cell wall formation in space (microgravity) and on Earth

Variations in cell wall chemistry provide vascular plants with the ability to withstand gravitational forces, as well as providing facile mechanisms for correctional responses to various gravitational stimuli, e.g., in reaction wood formation. A principal focus of our current research is to precisely and systematically dissect the essentially unknown mechanism(s) of vascular plant cell wall assembly, particularly with respect to formation of its phenolic constituents, i.e., lignins and suberins, and how gravity impacts upon these processes. Formation of these phenolic polymers is of particular interest, since it appears that elaboration of their biochemical pathways was essential for successful land adaptation. By extrapolation, we are also greatly intrigued as to how the microgravity environment impacts upon 'normal' cell wall assembly mechanisms/metabolism.

Lewis, Norman G.↗

Advanced and functional composite materials via additive manufacturing: Trends and perspectives

Additive manufacturing (AM) has many advantages over conventional subtractive manufacturing methods. The cost-effective AM allows for precise fabrication of complex structures with less material waste, making it a popular manufacturing process in many applications. The recent development of AM materials has advanced significantly. Further, by precisely controlling material distribution and microstructural features, AM facilitates the creation of new composites with specific requirements. AM techniques have contributed considerably to integrating unique functionalities for various applications. This review emphasizes multiple categories of materials, including metal alloys, polymer-based composites, and sustainable composites, as well as applications of sensing materials and strategies and emerging artificial intelligence and machine learning.

36 MATERIALS SCIENCE↗

Patchy nanoparticles by atomic stencilling

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm, enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering.

36 MATERIALS SCIENCE↗

Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.

NASA Discipline Life Support Systems↗

Molecularly Imprinted Polymer Sensor Empowered by Bound States in the Continuum for Selective Trace-Detection of TGF-beta

The integration of advanced materials and photonic nanostructures can lead to enhanced biodetection capabilities, crucial in clinical scenarios and point-of-care diagnostics, where simplified strategies are essential. Herein, a molecularly imprinted polymer (MIP) photonic nanostructure is demonstrated, which selectively binding to transforming growth factor-beta (TGF-β), in which the sensing transduction is enhanced by bound states in the continuum (BICs). The MIP operating as a synthetic antibody matrix and coupled with BIC resonance, enhances the optical response to TGF-β at imprinted sites, leading to an augmented detection capability, thoroughly evaluated through spectral shift and optical lever analogue readout. The validation underscores the MIP-BIC sensor capability to detect TGF-β in spiked saliva, achieving a limit of detection of 10 fM and a resolution of 0.5 pM at physiological concentrations, with a precision of two orders of magnitude above discrimination threshold in patients. The MIP tailored selectivity is highlighted by an imprinting factor of 52, showcasing the sensor resistance to interference from other analytes. The MIP-BIC sensor architecture streamlines the detection process eliminating the need for complex sandwich immunoassays and demonstrates the potential for high-precision quantification. This positions the system as a robust tool for biomarker detection, especially in real-world diagnostic scenarios.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Single Transducer Ultrasonic Imaging Method that Eliminates the Effect of Plate Thickness Variation in the Image

This article describes a single transducer ultrasonic imaging method that eliminates the effect of plate thickness variation in the image. The method thus isolates ultrasonic variations due to material microstructure. The use of this method can result in significant cost savings because the ultrasonic image can be interpreted correctly without the need for machining to achieve precise thickness uniformity during nondestructive evaluations of material development. The method is based on measurement of ultrasonic velocity. Images obtained using the thickness-independent methodology are compared with conventional velocity and c-scan echo peak amplitude images for monolithic ceramic (silicon nitride), metal matrix composite and polymer matrix composite materials. It was found that the thickness-independent ultrasonic images reveal and quantify correctly areas of global microstructural (pore and fiber volume fraction) variation due to the elimination of thickness effects. The thickness-independent ultrasonic imaging method described in this article is currently being commercialized under a cooperative agreement between NASA Lewis Research Center and Sonix, Inc.

Roth, Don J.↗

Single‐Step Recovery of Water from Stable Crude Oil‐Water Emulsion Using Surface Engineered Hybrid Inorganic‐Polymer Membranes

ABSTRACT Separating crude oil from water remains one of the most stubborn challenges in environmental remediation, especially for surfactant‐stabilized emulsions that resist conventional demulsification methods. Here, we report a scalable strategy for achieving near‐zero‐discharge separation of crude oil emulsions using a single superhydrophilic membrane. By applying low‐temperature atomic layer deposition (ALD) of various metal oxides onto activated polyvinylidene fluoride (PVDF) membranes, we create atomically precise surface‐engineered (SE) membranes that maintain an exceptionally strong hydration layer at the membrane‐feed interface, even at high oil loadings. Among the various metal oxides, TiO 2 ‐modified SE membranes exhibit superior interfacial water stability, enabling sustained dewatering of complex crude oil‐water emulsions with >98% separation efficiency and >97% water recovery, compared to only 24.6% water recovery for the pristine membrane. This separation performance surpasses conventional hydrophilic membranes and is comparable to complex Janus channel membrane systems, demonstrating near‐complete emulsion separation using a single membrane. This low‐temperature membrane surface engineering process with atomic‐level precision and potential for scalability via roll‐to‐roll fabrication is promising for industrial‐scale, energy‐efficient water treatment and oil spill remediation applications.

Sengupta, Bratin [Applied Materials Division Argon↗

Fiber-Optic Sensor Would Monitor Growth of Polymer Film

A proposed optoelectronic sensor system would measure the increase in thickness of a film of parylene (a thermoplastic polymer made from para-xylene) during growth of the film in a vapor deposition process. By enabling real-time monitoring of film thickness, the system would make it possible to identify process conditions favorable for growth and to tailor the final thickness of the film with greater precision than is now possible. The heart of the sensor would be a pair of fiber-optic Fabry-Perot interferometers, depicted schematically in the figure. (In principle, a single such interferometer would suffice. The proposal calls for the use of two interferometers for protective redundancy and increased accuracy.) Each interferometer would include a light source, a fiber-optic coupler, and photodetectors in a control box outside the deposition chamber. A single-mode optical fiber for each interferometer would run from inside the control box to a fused-silica faceplate in a sensor head. The sensory tips of the optical fibers would be polished flush with the free surface of the faceplate. In preparation for use, the sensor head would be mounted with a hermetic seal in a feed-through port in the deposition chamber, such that free face of the faceplate and the sensory tips of the optical fibers would be exposed to the deposition environment. During operation, light would travel along each optical fiber from the control box to the sensor head. A small portion of the light would be reflected toward the control box from the end face of each fiber. Once growth of the parylene film started, a small portion of the light would also be reflected toward the control box from the outer surface of the film. In the control box, the two reflected portions of the light beam would interfere in one of the photodetectors. The difference between the phases of the interfering reflected portions of the light beam would vary in proportion to the increasing thickness of the film and the known index of refraction of the film, causing the photodetector reading to vary in proportion to a known sinusoidal function of film thickness. Electronic means of monitoring this variation and the corresponding variation in phase and thickness are well established in the art of interferometry. Hence, by tracking the cumulative change in phase difference from the beginning of deposition, one could track the growing thickness of the film to within a small fraction of a wavelength of light.

Beamesderfer, Michael↗

The developments in modifying functionality of lignin and its application in biocomposites

With the advancement of sustainable material innovations, renewable natural biopolymers are gradually replacing traditional metal and petroleum-based synthetic materials due to their environmental friendliness, biodegradability, and economic advantages. Lignin, the second most abundant natural aromatic polymer in the plant kingdom, has emerged as a key candidate raw material for the development of green polymer systems because of its unique phenylpropane unit network structure, high carbon content, and rich functional group characteristics. However, challenges such as the inherent structural complexity, chemical inertness, and uneven molecular weight distribution of lignin limit its direct application. By employing modification strategies such as chemical functionalization and physical regulation, researchers can precisely control its reactivity, thermal stability, and interfacial compatibility, enabling the preparation of high-performance lignin-based functional composites. Here, this paper systematically reviews the principles and methodological advancements in lignin's multi-dimensional modification technology. It analyzes the mechanisms by which various chemical and physical modification techniques enhance the mechanical properties, functional responsiveness, and environmental adaptability of materials, and discusses innovative applications in fields such as intelligent packaging, biomedical materials, and energy storage devices. Furthermore, this review addresses the key challenges encountered in the high-value transformation of lignin, with the aim of offering a theoretical framework and technical pathway for the transformative development of lignin from agricultural and forestry by-products to functional material platforms.

Functional composites↗

Single-Transducer, Ultrasonic Imaging Method for High-Temperature Structural Materials Eliminates the Effect of Thickness Variation in the Image

NASA Lewis Research Center's Life Prediction Branch, in partnership with Sonix, Inc., and Cleveland State University, recently advanced the development of, refined, and commercialized an advanced nondestructive evaluation (NDE) inspection method entitled the Single Transducer Thickness-Independent Ultrasonic Imaging Method. Selected by R&D Magazine as one of the 100 most technologically significant new products of 1996, the method uses a single transducer to eliminate the superimposing effects of thickness variation in the ultrasonic images of materials. As a result, any variation seen in the image is due solely to microstructural variation. This nondestructive method precisely and accurately characterizes material gradients (pore fraction, density, or chemical) that affect the uniformity of a material's physical performance (mechanical, thermal, or electrical). Advantages of the method over conventional ultrasonic imaging include (1) elimination of machining costs (for precision thickness control) during the quality control stages of material processing and development and (2) elimination of labor costs and subjectivity involved in further image processing and image interpretation. At NASA Lewis, the method has been used primarily for accurate inspections of high temperature structural materials including monolithic ceramics, metal matrix composites, and polymer matrix composites. Data were published this year for platelike samples, and current research is focusing on applying the method to tubular components. The initial publicity regarding the development of the method generated 150 requests for further information from a wide variety of institutions and individuals including the Federal Bureau of Investigation (FBI), Lockheed Martin Corporation, Rockwell International, Hewlett Packard Company, and Procter & Gamble Company. In addition, NASA has been solicited by the 3M Company and Allison Abrasives to use this method to inspect composite materials that are manufactured by these companies.

Roth, Don J.↗

Applications of Atomic Layer Deposition in the Modification of Carbon Nanotubes

Atomic Layer Deposition (ALD) is a cost-effective nanoadditive-manufacturing technique that allows for conformal coating of substrates with atomic control in a benign temperature and pressure environment. Using paired precursor gases, thin films can be deposited on flat or textured surfaces ranging from glass, polymers, aerogels, and metals. Through atomic layer control, where single layers of atoms are deposited, fabrication of metal transparent films, nano-laminates, and coatings of nano-channels and pores is achievable. Reaction mechanisms in ALD are normally self-limiting, allowing for atomically accurate control of nanometer (nm) thicknesses. Therefore, high uniformity and precise thickness control make ALD an attractive process for the creation of novel nano-scale devices. Decreases in resistivity and density of electrical wire are needed to improve the function of electronics, electric motors and cables. Such improvements may be accomplished by adding ballistically conducting, metallic carbon nanotubes (CNT) to Cu. ALD was used to coat multiple substrates including CNT with Cu in an effort to make CNT-Cu composites which is more conductive and less dense than Cu. In addition, ALD can be used to as a method to deposit the catalyst layer seed layer for CNT growth using Ni. The ALD of copper metallic films can follow multiple reaction pathways depending on the ALD precursors used. For this work the reaction pathway was deposition of copper oxide and then post process annealing in a hydrogen environment. Copper(II) diacetylacetonate (Cu(acac)2) and ozone are used as precursors for copper oxide. As-deposited copper oxide films prepared at 180°C resulted in a growth per cycle of 1.0 A/cycle with low film resistivity.

Dwivedi, Vivek H.↗