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At least 181 records · Page 10

Single particle impact explorations on the role of powder heat treatments in cold spray: Effects of strength and oxide structure

In cold spray, the optimization of the powder feedstock for improving the final properties of the coating and for improving the process itself are two different objectives. This paper explores the latter, studying the relationship between powder pre-heat treatment and the kinetic bonding between the individual particles and the substrate. Using a laser-induced particle impact test (LIPIT), we investigate the effect of different heat treatments on the critical adhesion velocity of Al 6061. Although heat treatments change the strength of the powders as well as the thickness of the native oxide layer each by as much as ∼50 %, the critical adhesion velocity remains constant to within only ∼10 %. A deeper analysis reveals that these two factors change in somewhat complementary ways for the heat treatments explored here, leading to counteracting effects. By quantitatively evaluating these two microstructural factors in tandem, we find that they are roughly equally important in determining the critical adhesion velocity. These observations thus provide insight for the development of new heat treatment regimens that might lower the adhesion velocity.

Al 6061↗

Review of the Effects of Polymer Binder Properties on Microstructure and Irreversible Volume Growth of Plastic Bonded Explosives Formulations

The rational design of effective polymeric binders for the formulation of plastic-bonded explosives (PBX) is challenging due to their inherent compositional complexity. The composites comprise irregularly shaped energetic material (EM) powders coated with low weight fractions of polymer via non-equilibrium processes such as slurry coating. Defects can deleteriously affect PBX stability and performance: nano- to micrometer-scale voids can act as loci for hot spots, lowering deflagration and detonation temperatures in unpredictable ways. Furthermore, some nominally desirable polymer properties are at odds with each other: e. g. good flow characteristics are desirable for coating and adhesion, but mechanical stiffness is needed to prevent deformation and cracking of PBX under mechanical stress. Good binder adhesion is critical, but the best means to predict and measure adhesion in PBX is not obvious. Experimental methods of determining binder adhesion on model surfaces may not capture polymer structural configurations relevant to deposition during coating. Molecular dynamics-based computational models have predicted key observables in PBX formulation, suggesting that they may be powerful tools for binder selection. In this review, primarily recent (~2006 and later) literature on polymeric binders for insensitive HE (IHE) is surveyed. We focus on how binder properties influence observable PBX properties as resistance to irreversible volume growth and void formation in PBX formulations mainly (but not exclusively) featuring 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) as the EM (e. g. PBX 9502, LX-17 and others). Conclusions from these studies yield useful guidelines for choosing HE binder candidates, as well as for the general design of highly-filled polymer composite materials. Finally, studies describing challenges in PBX formulation with the newer and more energetically dense high explosive, LLM-105, will be discussed.

adhesion↗

Dynamic Polymer Networks for On Demand Degradable Adhesives, Scaffolds, and Templates (Full Technical Report)

This feasibility study was motivated by a need for alternative mandrel materials to meet the next generation of inertial confinement fusion (ICF) ablator capsules. In response, a new polymer material based on reversible covalent bonds was proposed, with the objective to design thermosets to withstand elevated temperatures (140-200 degrees Celsius) while also being thermally degradable on-demand via controlled decomposition at temperatures above 200 degrees Celsius. A series of cyclopentadiene (Cp) containing thermosets were designed and synthesized to evaluate curing, reversibility and degradability via controlled retro-Diels Alder reactions using Cp-cycloaddition adducts as crosslinks. Ultimately, the current iteration of materials and strategy pursued in this study was assessed as impractical for meeting the needs and objectives of Lawrence Livermore National Laboratory’s (LLNL) target fabrication program.

36 MATERIALS SCIENCE↗

Dynamic Networks for On Demand Degradable Adhesives, Scaffolds and Templates (Abbreviated Final Report)

This feasibility study was motivated by a need for alternative mandrel materials to meet the next generation of inertial confinement fusion (ICF) ablator capsules. In response, a new polymer material based on reversible covalent bonds was proposed, with the objective to design thermosets to withstand elevated temperatures (140-200 degrees Celsius) while also being thermally degradable on-demand via controlled decomposition at temperatures above 200 degrees Celsius. A series of cyclopentadiene (Cp) containing thermosets were designed and synthesized to evaluate curing, reversibility and degradability controlled via retro-Diels Alder reactions using Cp-cycloaddition adducts as crosslinks. Ultimately, the current iteration of materials and strategy pursued in this study was assessed as impractical for meeting the needs and objectives of Lawrence Livermore National Laboratory’s (LLNL) target fabrication program.

36 MATERIALS SCIENCE↗

Size-Dependent Energy of Ni Nanoparticles on Graphene Films on Ni(111) and Adhesion Energetics by Adsorption Calorimetry

The use of carbon supports for late transition-metal nanoparticle catalysts has grown substantially in recent years due to efforts to develop electrocatalysts for clean energy applications and catalysts for new aqueous-phase biomass-related conversions and due to the evolution of new carbon materials with unique properties (e.g., graphene, carbon nanotubes, and so forth). However, much less is known about the bonding energetics of catalytic metal nanoparticles on carbon supports in comparison with oxide supports, which are more common for thermal catalysis. Here, we report the growth morphology and heats of adsorption of Ni vapor deposited onto graphene/Ni(111) at 300 K and 100 K using metal vapor single-crystal adsorption calorimetry and He + low-energy ion scattering (LEIS). These results provide the Ni chemical potential versus particle size, and the Ni/graphene adhesion energy. LEIS intensities suggest that Ni grows as flat-topped face-centered cubic islands with a nearly constant thickness of ~1.5 nm when deposited at 300 K. At 100 K, Ni grows as smaller nanoparticles, well modeled as hemispherical hexagonal close-packed nanoparticles with a density of ~2 × 10 16 particles/m 2 . The Ni chemical potential as a function of average particle diameter in the 0.5 to 4 nm range at 100 K was determined from the heats of Ni gas adsorption. Further, by fitting the measured chemical potential as a function of diameter, we determined an adhesion energy of 3.6 J/m 2 for large Ni particles on graphene/Ni(111). This adhesion energy is in good agreement with previous scanning tunneling microscopy and density functional theory investigations of Ni/graphene/Ni(111).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FWP FEAA149: “Next Generation Environmental Barrier Coatings”

Environmental barrier coatings (EBCs) are required coatings for utilization of SiC/SiC ceramic matrix composite (CMC) components in gas turbines, where the EBC represents the life-limiting factor for such components. EBC/CMC systems have shown success in aero-engine applications with increased turbine inlet temperatures and improved efficiencies, which are achieved through higher temperature stability, lower density, and decreased reliance on cooling air compared to traditional superalloys. While industrial gas turbines (IGTs) do not currently utilize SiC/SiC CMCs, the current shift towards low-carbon or carbon-free fuel sources for power generation could result in a need for EBC/CMC components with higher temperature capabilities. In this work, three tasks were outlined to improve understanding of EBC lifetimes to encourage use in IGTs with carbon-free fuel such as hydrogen: 1. Define the bond coating oxidation kinetics and EBC failure criteria, 2. Measure thermal expansion coefficients of each layered material, and 3. Perform advanced characterization and modeling to assess EBC lifetimes. Cyclic steam oxidation tests were conducted on various EBC/Si/SiC chemistries and EBC/SiC architectures to define substrate oxidation kinetics and EBC failure modes. An open-source code was developed to quantify the undulating thermally grown oxide thickness with thousands of measurements from specimen cross-section images. Bond coating oxidation kinetics were determined and used to develop a kinetic and thermodynamic model for predicting EBC lifetimes. High-temperature Raman spectroscopy was utilized for determining the SiO 2 thermally grown oxide phase transformation as the life-limiting feature for EBCs. Model efforts supported the claim that the SiO 2 phase transformation causes elevated stress during thermal cycling with associated cracking that decreases the adhesion strength of the EBC, eventually resulting in coating spallation. The finite element model subroutine will be made publicly available upon internal review. Further development of an EBC lifetime model for IGTs involves definition of a critical SiO 2 thickness for EBC spallation and must also consider both environmental (gas velocity, pressure, etc.) and specimen (EBC dopants, layer architectures, etc.) effects into predicted bond coating oxidation kinetics for long-lifetime components.

36 MATERIALS SCIENCE↗

Extreme Antiscaling Performance of Slippery Omniphobic Covalently Attached Liquids

Scale formation presents an enormous cost to the global economy. Classical nucleation theory dictates that to reduce the heterogeneous nucleation of scale, the surface should have low surface energy and be as smooth as possible. Past approaches have focused on lowering surface energy via the use of hydrophobic coatings and have created atomically smooth interfaces to eliminate nucleation sites, or both, via the infusion of low-surface-energy lubricants into rough superhydrophobic substrates. Although lubricant-based surfaces are promising candidates for antiscaling, lubricant drainage inhibits their utilization. Here, we develop methodologies to deposit slippery omniphobic covalently attached liquids (SOCAL) on arbitrary substrates. Similar to lubricant-based surfaces, SOCAL has ultralow roughness and surface energy, enabling low nucleation rates and eliminating the need to replenish the lubricant. To enable SOCAL coating on metals, we investigated the surface chemistry required to ensure high-quality functionalization as measured by ultralow contact angle hysteresis (<3°). Using a multilayer deposition approach, we first electrophoretically deposit (EPD) silicon dioxide (SiO 2 ) as an intermediate layer between the metallic substrate and SOCAL. The necessity of EPD SiO 2 is to smooth (<10 nm roughness) as well as to enable the proper surface chemistry for SOCAL bonding. To characterize antiscaling performance, we utilized calcium sulfate (CaSO 4 ) scale tests, showing a 20× reduction in scale deposition rate than untreated metallic substrates. Descaling tests revealed that SOCAL dramatically decreases scale adhesion, resulting in rapid removal of scale buildup. Furthermore, our work not only demonstrates a robust methodology for depositing antiscaling SOCAL coatings on metals but also develops design guidelines for the creation of antifouling coatings for alternate applications such as biofouling and high-temperature coking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Borylation of Poly(vinyl chloride) Produces Adhesive Materials

Postpolymerization functionalization of polymers can create new applications for existing materials, while retaining their most favorable, intrinsic properties. Polyvinyl chloride (PVC) is a widely used, commodity polymer that is particularly challenging to modify. We report a copper-catalyzed protocol that replaces a small fraction of the C-Cl bonds in PVC with C-B bonds to boronic esters. The reaction occurs with an inexpensive catalyst comprising copper(II) chloride and an NHC ligand derived from a common ionic liquid that is distinct from the N-heterocyclic carbene (NHC) used for the borylation of small alkyl halides. The resulting materials adhere strongly to common surfaces, such as glass and metals, even more strongly than do commercial glues.

D’Angelo, Kyan A↗

Autonomous Changes in Polymer Materials Driven by Chemical Fuels

Time-dependent properties in polymer materials can be achieved through coupling to out-of-equilibrium chemical fuel reactions that mimic biological processes. Through transient changes in bonding in polymers, transient gelation, changes in mechanical stiffness, swelling, self-healing, or self-assembly can be achieved. Recent advances in these categories are discussed. These out-of-equilibrium behaviors enable applications ranging from smart adhesives to actuators for soft robotics. However, challenges remain, including waste accumulation, bio-compatibility, and achieving functionally useful performance. Addressing these issues is essential for advancing the practical use of chemically driven polymer materials and unlocking their full potential for future technologies.

36 MATERIALS SCIENCE↗

Energetics and Structure of Nickel Atoms and Nanoparticles on MgO(100)

The growth morphology and interfacial energetics of vapor deposited Ni on the MgO(100) surface at 300 and 100 K have been studied using single crystal adsorption calorimetry (SCAC), He + low-energy ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED). At 300 K, the Ni atoms grow as three-dimensional nanoparticles with a saturation number density of 5 × 10 16 particles/m 2 . The differential heat of adsorption at 300 K increases rapidly with coverage, from 276 (initially) to 311 kJ/mol by 0.4 ML. Thereafter, it slowly increases asymptotically to the sublimation enthalpy of bulk Ni (430 kJ/ml) by 9 ML. The Ni 2p 3/2 XPS peak binding energy at 300 K is initially (i.e., at 0.16 ML) 1.4 eV higher than that for bulk Ni(solid), but it decreases to that value at high coverage. The Ni atoms form a metastable phase at 300 K when in nanoparticles with diameter <2.5 nm, and the adhesion energy of such Ni nanoparticles to MgO(100) was found to be 3.05 J/m 2 . At 100 K, the Ni atoms form single adatoms and then 0.17 nm thick 2D islands at low coverage with fewer Ni-Ni bonds compared to the Ni nanoparticles formed at 300 K. Thus, the initial heat (i.e., for the first ~0.03 ML) is 148 kJ/mol at 100 K, 128 kJ/mol lower than at 300 K, and remains lower for the 2D islands. With increasing coverage at 100 K, the tiny 2D Ni islands grow in size to cover nearly the entire surface before thickening. Lastly, the XPS Ni 2p 3/2 peak binding energy for 0.21 ML Ni on MgO(100) at 100 K is 2.2 eV higher than that for bulk Ni(solid), suggesting charge transfer from Ni to MgO(100) and formation of Ni 2+ at very low coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure-property relationship between lignin structures and properties of 3D-printed lignin composites

Lignin is a low-cost and renewable bioresource with a huge annual production promising to prepare sustainable materials. However, the poor interfacial adhesion between many lignin-polymer pairs deteriorates the mechanical performance of the composites, which seriously limits the application of lignin in 3D printing via fused depositional modeling. This work examined lignin-polyamide 12 (PA 12) intermolecular interactions (e.g., hydrogen bonding) to address the interface challenge. To realize this goal, the phenolic hydroxyl content was increased for a kraft softwood lignin using a LiBr/HBr demethylation procedure, increasing phenoxy content by 61.7%. Increased hydrogen bonding interactions between modified lignin (Pine-Lig-OH) and PA 12 demonstrated a significantly improved molten dynamic modulus by rheological analysis. Regarding mechanical properties, by adding 20 wt% of Pine-Lig-OH, the tensile strength and Young's modulus reached 46.6 MPa and 1.62 GPa, 30.2% and 33.9% higher than PA 12, respectively. Further morphological analysis proved the interfacial interactions are enhanced by showing the difference in the phase gaps. The dynamic mechanical analysis (DMA) supported the conclusion that Pine-Lig-OH could interact with polymer chains, alternating segmental movements due to the strong interaction. Here, this study presents a method to enhance lignin composite properties by promoting interactions with the polymer matrix through modified functional groups, guiding future lignin composite research.

36 MATERIALS SCIENCE↗

Degradation Studies of Silicone Rubbers in Direct Contact with Corrosive Solids Under Compression

Silicone elastomers are polymer materials widely used within the complex, serving as cushions, adhesives, binders, and potting compounds. Excellent high-temperature resistance combined with low-temperature flexibility, high resistance to chemicals and long-term age-related stability, make silicones first-choice materials in many application areas. However, the siloxane bonds comprising the backbone of silicone elastomers are susceptible to hydrolysis when catalytic amounts of acid or base are present. Hydrolysis is a form of degradation that results in chain-cleavage and rearrangement reactions, which can manifest in changes to the physical response and mechanical properties of the elastomer. This task aims to assess and quantify the extent of degradation and/or corrosion of silicone elastomer materials when placed in direct compressive contact with an Arrhenius base under varying environments (oxidative/nonoxidative, relative humidity, temperature, time, etc.).

36 MATERIALS SCIENCE↗

Tough and circular glass fiber composites via a tailored dynamic boronic ester interface

Glass fiber reinforced polymer (GFRP) composites are valued for their strength and cost-effectiveness. However, traditional GFRPs often face challenges for end-of-life recycling due to their non-depolymerizable thermoset matrices, and long-term performance due to inadequate interfacial adhesion, which can lead to fiber–matrix delamination. Here, in this work, we have designed dynamic fiber–matrix interfaces to allow tough and closed-loop recyclable GFRPs by utilizing a vitrimer, derived from upcycled polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) with boronic ester (S-Bpin) and amine-based diol crosslinker. The boronic ester groups in S-Bpin form dynamic covalent bonds with the naturally present hydroxyl groups on the unsized GF surface, which eliminates the need for fiber sizing and enables facile closed-loop recyclability of both the fibers and the vitrimer matrix. The resulting strong fiber–matrix interface, depicted by the Raman mapping, leads to a 552% increase in-plane shear toughness (6.2 ± 0.3 MJ m -3 ) and 27% ultimate tensile strength (361 ± 89.2 MPa) compared to those of the conventional epoxy-based matrix (0.95 ± 0.05 MJ m -3 and 264 ± 59.7 MPa, respectively). The network rearrangement through dynamic boronic ester exchange enables fast thermoformability and repairability of micro-cracks at elevated temperatures. Additionally, both the matrix and composite demonstrate strong adhesion to various surfaces including steel and glasses exhibiting ≥6 MPa lap shear strength, which expands their suitability for diverse industrial applications. The readily created dynamic interface between boronic ester functionalized vitrimer and neat GFs presents a promising strategy for developing closed-loop recyclable, multifunctional structural materials, offering a sustainable alternative to non-recyclable thermoset GFRPs and contributes to a circular economy in composite materials.

36 MATERIALS SCIENCE↗

Ameliorating the sodium storage performance of hard carbon anode through rational modulation of binder

Hard carbon anodes have emerged as promising candidates for sodium-ion batteries due to their inherent advantages. Nevertheless, the surface imperfections in these materials often culminate in irreversible electrolyte consumption, fostering the development of a heterogeneous and fragile solid electrolyte interface (SEI), thereby compromising the initial Coulombic efficiency (ICE). Here, drawing inspiration from the catalytic potential of C=O (carbonyl) bonds in directing preferential salt reduction, we introduce a novel strategy that leverages the modulation of the binder, a long-term overlooked pivotal components in the electrode process. Specifically, Polymethyl methacrylate (PMMA), abundant in C=O groups, is partially substituted for PVDF, ensuring robust adhesion of the electrode material to the current collector while preserving superior mechanical properties. The accurate combination of two binders with delightful compatibility in the state-of-art electrode process, can promote a uniform formation of the SEI on the hard carbon surface enriched in inorganic components, which can ensure long-term interfacial stability and suppresses excessive solvent decomposition and facilitates Na + transfer at the interface. Consequently, the initial Coulombic efficiency of the hard carbon anode with 70 %PMMA binder achieves 86 %, with prominent cycling stability (88 % capacity retention over 500 cycles) at a high current density of 1.2 A g −1 . When paired with high loading cathodes to assemble the pouch cell, it also demonstrates stable operational scenarios.

25 ENERGY STORAGE↗

Nanoscopic Titanium Dioxide Overlayers Improve the Durability of Porphyrin Molecular Electrocatalysts while Maintaining Molecular Structure and Redox Activity

Molecular catalysts, such as metalated porphyrins, are attractive cocatalysts for photocatalytic water splitting owing to their potential to simultaneously catalyze target reactions at their metal center, extend charge-separated-state lifetimes, and accumulate the requisite charge for product formation. However, porphyrin catalysts, like most molecular catalysts, are often limited by poor stability associated with demetalation, inactivation by undesired bonding (e.g., O2 coordination/redox/dimerization), and detachment from electrode supports or semiconducting photoabsorbers. In this study, nanoscopic titanium dioxide (TiO2) overlayers, deposited by atomic layer deposition (ALD), are demonstrated to encapsulate cobalt(III) meso-tetra(4-carboxyphenyl) porphyrin chloride (CoTCPP) molecular catalysts and thereby improve their adhesion to electrode surfaces over a wide range of electrode potentials spanning from -1.0 V vs RHE to +1.8 V vs RHE. Through analysis of Raman and ultraviolet-visible spectroscopy, it was confirmed that the metalloporphyrin structure was maintained when the surface-bound CoTCPP was encapsulated by 10 - 250 ALD cycles (~2 - 18 nm thick) of TiO2. Additional characterization of CoTCPP catalysts before and after electrochemical measurements reveals that up to 97% of the encapsulated CoTCPP remains tethered to the electrode surface after chronoamperometry tests under hydrogen evolution reaction (HER) conditions, compared to <36% for unencapsulated CoTCPP. This study also shows that encapsulated CoTCPP molecules remain partially redox active for overlayers up to 8 nm, which can also attenuate undesired redox mediator back reactions like ferricyanide reduction.

08 HYDROGEN↗

Evaluation of the interfacial bonding strength between hafnia and silica layers deposited by electron-beam evaporation

Factors contributing to the mechanical strength of multilayer optical coatings involving alternating layers of electron-beam evaporated hafnia and silica is investigated. It is observed that upon rupture resulting from nanosecond laser damage, fragments consisting of layer pairs are produced. These pairs are formed as a result of a strong asymmetry in adhesion strength between interfaces, leading to preferential delamination at interfaces where silica is deposited on hafnia, and not the reverse, despite the fact that both interface types consist of the same pair of materials. The observed disparity in adhesion strength was further studied using nanomechanical scratch tests, revealing loads at which fracture occurs, and fracture morphology, both of which are highly dependent on deposition order. Based on these measurements, along with the morphological analysis of the nanostructure of the coatings, we conclude that the surface microstructure in each coating layer affects its adhesion strength with the succeeding layer. The findings outlined here are particularly relevant to the production of large aperture, high-performance optics designed for use in next-generation lasers.

adhesion strength↗

Measurement of crack length in width tapered beam experiments

The width tapered beam method for measuring fracture toughness has been contemplated for use in measuring the adhesion of photovoltaic materials, is promoted by it being a viable method for use directly on modules rather than to engineered test specimens. However, precise determination of crack length is often difficult as failure often involves tendril formation, cavitation voids, and other plastic deformation at the crack front in addition to obfuscation by opaque materials. Because fracture energy varies as the square of crack length, imprecise crack tip length results in large measurement uncertainties. In this work, we develop a method to estimate the crack tip length using the relationship between the applied force and the displacement of the load frame. The crack tip is determined for every data point and can be defined from a calibration curve related to the amount of energy put into the beam, or from a theoretically idealized estimation. Once a calibration curve is set up and the equations programmed, the fracture energy as a function of position on the newly formed crack interface can be accurately estimated. The test additionally provides much easier analysis and insight into the joint failure through more precise knowledge of fracture toughness at each de-bonded area.

42 ENGINEERING↗