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At least 649 records · Page 36

Out-of-plane behavior of selectively stitched curved beams subjected to four-point bending

Through-the-thickness stitching can be used to provide a pathway to reduce interlaminar damage in laminated polymer composites. To decrease the amount of stitching, a selective stitching process is necessary to reduce the total manufacturing time in stitched polymer composites. In this study, L-shaped laminates are stitched in the radius section to arrest out-of-plane damage that can occur when subjected to four-point bending loads. A cohesive zone finite element model of the L-shaped laminate was developed. An embedded spring element approach was used to represent the through-the-thickness reinforcements within the finite element model. Specimens with stitches in the radius region of the L-shaped laminate were found to have greater maximum loads before failure. The through-the-thickness stitches are observed to locally reduce the radial stresses in the radius region of the L-shaped laminate, which results in delamination growth away from the radius centerline and greater load-carrying capability.

Stitched Composites↗

Acceleration Factors for Reliability Assessment of Polymer Tantalum Capacitors

Using polymer tantalum capacitors in Hi-Rel systems requires an assessment of the reliability characteristics of the parts. For this assessment, tantalum capacitors are typically subjected to reliability testing at temperatures and voltages exceeding their specified values, and the failure rate (FR) — or the probability of failure during use conditions — is calculated based on voltage and temperature acceleration factors. In this work, various types and lots of polymer tantalum capacitors have been tested at highly accelerated life test (HALT) conditions and the acceleration factors have been determined using different techniques. It has been shown that the behavior of capacitors under HALT conditions can be described based on the time-dependent dielectric breakdown (TDDB) model, which explains the presence of infant mortality (IM) and wear-out failures using the same failure mechanisms and allows for an assessment of the acceleration factors. The difference in acceleration factors obtained using exponential and power models is discussed. Analysis shows that with proper derating, screening, and qualification testing, the reliability of frameless Hi-Rel COTS polymer tantalum capacitors is adequate for space missions.

Alex Eidelman↗

Acceleration Factors for Reliability Assessment of Polymer Tantalum Capacitors

Using polymer tantalum capacitors in Hi-Rel systems requires an assessment of the reliability characteristics of the parts. For this assessment, tantalum capacitors are typically subjected to reliability testing at temperatures and voltages exceeding their specified values, and the failure rate (FR) — or the probability of failure during use conditions — is calculated based on voltage and temperature acceleration factors. In this work, various types and lots of polymer tantalum capacitors have been tested at highly accelerated life test (HALT) conditions and the acceleration factors have been determined using different techniques. It has been shown that the behavior of capacitors under HALT conditions can be described based on the time-dependent dielectric breakdown (TDDB) model, which explains the presence of infant mortality (IM) and wear-out failures using the same failure mechanisms and allows for an assessment of the acceleration factors. The difference in acceleration factors obtained using exponential and power models is discussed. Analysis shows that with proper derating, screening, and qualification testing, the reliability of frameless Hi-Rel COTS polymer tantalum capacitors is adequate for space missions.

Alex Eidelman↗

The Compressive Behavior of Isocyanate-crosslinked Silica Aerogel at High Strain Rates

Aerogels are low-density, highly nano-porous materials. Their engineering applications are limited due to their brittleness and hydrophilicity. Recently, a strong lightweight crosslinked silica aerogel has been developed by encapsulating the skeletal framework of amine-modified silica aerogels with polyureas derived by isocyanate. The mesoporous structure of the underlying silica framework is preserved through conformal polymer coating, and the thermal conductivity remains low. Characterization has been conducted on the thermal, physical properties and the mechanical properties under quasi-static loading conditions. In this paper, we present results on the dynamic compressive behavior of the crosslinked silica aerogel (CSA) using a split Hopkinson pressure bar (SHPB). A new tubing pulse shaper was employed to help reach the dynamic stress equilibrium and constant strain rate. The stress-strain relationship was determined at high strain rates within 114-4386/s. The effects of strain rate, density, specimen thickness and water absorption on the dynamic behavior of the CSA were investigated through a series of dynamic experiments. The Young's moduli (or 0.2% offset compressive yield strengths) at a strain rate approx.350/s were determined as 10.96/2.08, 159.5/6.75, 192.2/7.68, 304.6/11.46, 407.0/20.91 and 640.5/30.47 MPa for CSA with densities 0.205, 0.454, 0.492, 0.551,0.628 and 0.731 g/cu cm, respectively. The deformation and failure behaviors of a native silica aerogel with density (0.472 g/cu cm ), approximately the same as a typical CSA sample were observed with a high speed digital camera. Digital image correlation technique was used to determine the surface strains through a series of images acquired using high speed photography. The relative uniform axial deformation indicated that localized compaction did not occur at a compressive strain level of approx.17%, suggesting most likely failure mechanism at high strain rate to be different from that under quasi-static loading condition. The Poisson s ratio was determined to be 0.162 in nonlinear regime under high strain rates. CSA samples failed generally by splitting, but were much more ductile than native silica aerogels.

Luo, H.↗

LLNL FY22 Aging and Lifetimes Exit Criteria: Milestone 8119, GC#01

Polysiloxane foams utilized for stockpile applications experience changes over time induced by exposure to thermal, radiative, and mechanical stresses. The interplay of these stresses can lead to chemical and/or physical changes in the polymer, such as compression set and material degradation over time. Understanding the mechanisms of material aging and identifying material degradation prior to failure are critical in maintaining the integrity of the nuclear stockpile. Our prior work using solid-state NMR spectroscopy has shown that we can observe signatures of thermal, radiative, and mechanical aging of silicone elastomers using differences in NMR parameters such as relaxation (T1 and T2). However, most of our measurements have been on bulk samples and have only provided an average aging behavior of each sample. Here, we have used magnetic resonance imaging (MRI) to provide relaxation-weighted images that are a metric of structural heterogeneity (crosslink density) in polymers across multiple length scales. In addition, the larger sample size that can be accommodated in animal MRI scanners has the potential to make the technique adaptable to detecting heterogeneities in whole parts.

36 MATERIALS SCIENCE↗

Electrolyte–Electrocatalyst Interfacial Effects of Polymeric Materials for Tandem CO 2 Capture and Conversion Elucidated Using In Situ Electrochemical AFM

Integrating CO 2 capture and electrochemical conversion has been proposed as a strategy to reduce the net energy required for CO 2 regeneration in traditional CO 2 capture and conversion schemes and can be coupled with carbon-free renewable electricity. Polyethylenimine (PEI)-based materials have been previously studied as CO 2 capture materials and can be integrated in these reactive capture processes. PEI-based electrolytes have been found to significantly increase the CO 2 loading, and impact selectivity and rate of product formation when compared to the conventional aqueous electrolytes. However, the influence of these materials at the catalyst–electrode interface is currently not well understood. In this study, PEI-based electrolytes were prepared and their impact on the morphology of a silver electrode performing electrochemical CO 2 reduction (CO 2 R) was studied using in situ electrochemical atomic force microscopy (EC-AFM). The presence of PEI on the electrode surface could be distinguished based on nanomechanical properties (DMT modulus), and changes were observed as negative polarization was applied, revealing a reorganization of the PEI chains due to electrostatic interactions. These changes were impacted by the electrolyte composition, including the addition of supporting electrolyte KHCO 3 salt, as well as CO 2 captured by the PEI-based electrolyte, which minimized the change in surface mechanical properties and degree of PEI alignment on the electrode surface. The changes in surface mechanical properties were also dependent on the PEI polymer length, with higher molecular weight PEI showing different reconfiguration than the shorter polymer brushes. The study highlights that the choice of polymer material, the electrolyte composition, and CO 2 captured impact the nearelectrode environment, which has implications for CO 2 R, and presents EC-AFM as a new tool that can be used to probe the dynamic behavior of these interfaces during electrocatalysis.

36 MATERIALS SCIENCE↗

Exceptional Electron-Rich Heteroaromatic Pentacycle for Ultralow Band Gap Conjugated Polymers and Photothermal Therapy

Stable redox-active conjugated molecules with exceptional electron-donating abilities are key components for the design and synthesis of ultralow band gap conjugated polymers. While hallmark electron-rich examples such as pentacene derivatives have been thoroughly explored, their poor air stability has hampered their broad incorporation into conjugated polymers for practical applications. Herein, we describe the synthesis of the electron-rich, fused pentacyclic pyrazino[2,3-b:5,6-b’]diindolizine (PDIz) motif and detail its optical and redox behavior. The PDIz ring system exhibits a lower oxidation potential and a reduced optical band gap than the isoelectronic pentacene while retaining greater air stability in both solution and the solid state. The enhanced stability and electron density, together with readily installed solubilizing groups and polymerization handles, allow for the use of the PDIz motif in the synthesis of a series of conjugated polymers with band gaps as small as 0.71 eV. Importantly; the tunable absorbance throughout the biologically relevant near-infrared I and II regions enables the use of these PDIz-based polymers as efficient photothermal therapeutic reagents for laser ablation of cancer cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

InAs sidewall tunnel diodes enabled by surface states

Negative differential resistance (NDR), where the device current decreases with increasing bias voltage, is a representative phenomenon where quantum mechanics induces counterintuitive physical behavior and offers promising applications such as high-frequency oscillators, amplifiers, and multilevel logic circuits. While the NDR behavior has been extensively studied in various materials and devices, the role of surface properties in NDR, particularly in InAs-based diodes, remains underexplored. In this work, we report the observation of NDR in vertically structured InAs p + n diodes that exhibit a peak-valley current ratio of ∼6, which is suitably high for applications. Circumference-normalized current–voltage characterization revealed that the NDR originates from band-to-band tunneling between the valence band of p + -InAs and the conduction band of an n + -InAs surface, where the n + surface is due to surface states on otherwise n − -InAs. In addition, by comparing devices with various surface passivation methods (without intentional passivation, benzocyclobutene polymer, and silicon nitride), we found that the surface termination significantly affects the NDR characteristics. We present an equivalent circuit model to explain the observed device behavior. These findings offer insights into surface-enabled NDR phenomena and present new knobs for engineering NDR devices.

Circuit theorems↗

Exploring the Photophysics of N-Type Polymer N2200

The polymer interphase is a complex environment comprised of polymer chains, solvent molecules, and electrolyte ions. However, the microenvironments that these ingredients produce is both poorly-understood and difficult to investigate given the system's inherent structural heterogeneity. Nonetheless, a fundamental understanding of the structure, electrochemical behavior, and excited-state dynamics is a key prerequisite to optimizing devices based on such a system - for instance, photoelectrochemical cells for the direct, light-driven production of solar hydrogen, which may minimize efficiency losses compared to sequential light harvesting and electrochemical hydrogen production in separate but linked devices. This work combines transient absorption (TA) spectroscopy, which is a powerful tool for the observation of a variety of excited states on a femto- to microsecond timescale, with time-resolved microwave conductivity (TRMC) spectroscopy, which selectively probes the dynamics of free charge carriers (FC), of a blend of a donor polymer (PTB7-Th) and acceptor polymer (N2200) in a bulk heterojunction. Initial results indicate an extension of FC lifetime and homogenization of the microenvironment on a whole-film level, not just at the surface of the polymer; however, many questions are still under active investigation, including the changes in energy of the involved polaron states, effective conjugation length, FC mobility and migration distance, etc. Additional experiments regarding the photoinitiated behavior of the blend in different environments and on different timescales are ongoing.

charge recombination↗

High Speed Thermal Imaging on Ballistic Impact of Triaxially Braided Composites

Ballistic impact experiments were performed on triaxially braided polymer matrix composites to study the heat generated in the material due to projectile velocity and penetration damage. Quantifying the heat generation phenomenon is crucial for attaining a better understanding of composite behavior and failure under impact loading. The knowledge gained can also be used to improve physics-based models which can numerically simulate impact of composites. Triaxially braided (0/+60/-60) composite panels were manufactured with T700S standard modulus carbon fiber and two epoxy resins. The PR520 (toughened) and 3502 (untoughened) resin systems were used to make different panels to study the effects of resin properties on temperature rise. Ballistic impact tests were conducted on these composite panels using a gas gun, and different projectile velocities were applied to study the effect on the temperature results. Temperature contours were obtained from the rear surface of the panel during the test through a high speed, infrared (IR) thermal imaging system. The contours show that high temperatures were locally generated and more pronounced along the axial tows for the T700S/PR520 composite specimens; whereas, tests performed on T700S/3502 composite panels using similar impact velocities demonstrated a widespread area of lower temperature rises. Nondestructive, ultrasonic C-scan analyses were performed to observe and verify the failure patterns in the impacted panels. Overall, the impact experimentation showed temperatures exceeding 525 K (485degF) in both composites which is well above the respective glass transition temperatures for the polymer constituents. This expresses the need for further high strain rate testing and measurement of the temperature and deformation fields to fully understand the complex behavior and failure of the material in order to improve the confidence in designing aerospace components with these materials.

thermal imaging↗

Thermal/Mechanical Response of a Polymer Matrix Composite at Cryogenic Temperatures

In order for polymeric-matrix composites to be considered for use as structural materials in the next generation of space transportation systems, the mechanical behavior of these materials at cryogenic temperatures must be investigated. This paper presents experimental data on the residual mechanical properties of a carbon-fiber polymeric composite, IM7/PETI-5, both before and after aging. Both tension and compression modulus and strength were measured at room temperature, -196C, and -269 C on five different laminate configurations. One set of specimens was aged isothermally for 576 hours at -184 C in an unconstrained state. Another set of corresponding specimens was aged under constant uniaxial strain for 576 hours at -184 C. Based on the experimental data presented, it is shown that trends in stiffness and strength that result from changes in temperature are not always smooth and consistent. Moreover, it is shown that loading mode and direction are significant for both stiffness and strength, and aging at cryogenic temperature while under load can alter the mechanical properties of pristine, un-aged laminates made of IM7/PETI-5 material.

Whitley, Karen S.↗

Experimental Evaluation of Axial Crush Behavior of Woven Tubular Laminates with a Moving Support Condition

The objectives of the investigation were to measure the specific energy absorption (SEA) of the plain-weave carbon fiber reinforced polymer (CFRP) tubes, study the effect of tube length on SEA and stable crushing force, analyze the effect of using a crush trigger, and compare force-displacement data using different specimen support conditions. Dynamic crush testing of CFRP tubes was performed using the crash sled in the Impact Dynamics Laboratory at NASA Glenn Research Center.

Rudy T. Haluza↗

Discrimination of xylene isomers in a stacked coordination polymer

The separation and purification of xylene isomers is an industrially important but challenging process. Developing highly efficient adsorbents is crucial for the implementation of simulated moving bed technology for industrial separation of these isomers. Herein, we report a stacked one-dimensional coordination polymer {[Mn(dhbq)(H 2 O) 2 ], H 2 dhbq = 2,5-dihydroxy-1,4-benzoquinone} that exhibits an ideal molecular recognition and sieving of xylene isomers. Its distinct temperature-adsorbate–dependent adsorption behavior enables full separation of p -, m -, and o -xylene isomers in both vapor and liquid phases. The delicate stimuli-responsive swelling of the structure imparts this porous material with exceptionally high flexibility and stability, well-balanced adsorption capacity, high selectivity, and fast kinetics at conditions mimicking industrial settings. This study may offer an alternative approach for energy-efficient and adsorption-based industrial xylene separation and purification processes.

Science & Technology - Other Topics↗

Bacterial-Retted Hemp Fiber/PLA Composites

The push for sustainability in all facets of manufacturing has led to an increased interest in biomass as an alternative to non-renewable materials. Hemp bast fiber mats were produced from a bacterial retting process, named BFM, as the fiber reinforcement. The objective of this study was to evaluate the feasibility of laminating BFM with polylactic acid (PLA) for a composite panel product. Since both BFM and PLA are biodegradable, the resulting BFM-PLA composites will be 100% biodegradable. PLA pallets were processed into thin polymer sheets which served as the matrix. The BFM and PLA plates were laminated in five layers and compression-molded into composite panels. Experiments were conducted on the three BFM-to-PLA ratios (35/65, 45/55, and 50/50). Mechanical properties (tensile and bending properties) and physical properties (thickness swell and water absorption) were tested and compared to the currently commercial sheet molding compound (SMC) from fiber glass. The thermal behavior of the BFM/PLA composites was characterized using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The developed BFM/PLA composite product is a sustainable alternative to existing synthetical fiber-reinforced polymer (FRP) that is biodegradable in landfill at the end of life.

Smith, Lee M. (ORCID:0000000264390357)↗

Benzotriazole‐Based Nonfused Ring Acceptors for Efficient and Thermally Stable Organic Solar Cells

Abstract Nonfused ring acceptors (NFRAs) have attracted significant attention for nonfullerene organic solar cells (OSCs) owing to their chemical tunability and facile synthesis. In this study, a benzotriazole‐based NFRA with chlorinated end groups (Triazole‐4Cl) is developed to realize highly efficient and thermally stable NFRA‐based OSCs; an analogous NFRA with nonchlorinated end groups (Triazole‐H) is synthesized for comparison. Triazole‐4Cl film exhibits the high‐order packing structure and the near‐infrared absorption capability, which are advantageous in charge transport and light harvesting of the resulting OSCs. In particular, the strong crystalline behavior of Triazole‐4Cl results in enhanced self‐aggregation, leading to high charge carrier mobility. Owing to these properties, a PBDB‐T (polymer donor):Triazole‐4Cl OSC demonstrates a high short‐circuit current, fill factor, and power conversion efficiency (PCE = 10.46%), outperforming a PBDB‐T:Triazole‐H OSC (PCE = 7.65%). In addition, the thermal stability of a PBDB‐T:Triazole‐4Cl OSC at an elevated temperature of 120 °C exceeds that of a PBDB‐T:Triazole‐H OSC. This is mainly attributed to the significantly higher cold crystallization temperature of Triazole‐4Cl (205.9 °C). This work provides useful guidelines for the design of NFRAs to achieve efficient and thermally stable NFRA‐based OSCs.

Polymer Science↗

Electrochemical mechanisms of leakage‐current in photovoltaic modules

Abstract This paper analyzes the mechanisms and pathways for leakage current flow observed in Si photovoltaic modules subjected to high temperature and humidity and a large voltage bias with respect to ground. The current inside of the frame is in the form of electron motion, but in the glass and polymer, it is in at least a large part attributable to the movement of ions. When the mode of current flow changes from electronic to ionic conduction, electrochemical reactions will take place at the interface. This can include reactions that produce volatile chemical species like H 2 , CO x , and O 2 , along with ionic species such as OH − and H 3 O + . Here, we see evidence of the importance of different charge carriers with different diffusion rates and the influence of electrochemical processes involved. The application of negative voltage to the cell circuit affects the resistivity of glass producing surfaces with poor conductivity but with some increases in the electrochemical potential producing complicated interactions that are important when the voltage is changed. In the polymer, there is the development of a space charge region and a chemical gradient providing two oppositional forces to current flow, which when released create a complicated discharge process. Here, we give a basic understanding of the charge/discharge of PV cells highlighting how the specific mechanisms are important in understanding some of the degradation processes in PV modules. We find that there is evidence of multiple significant charge carrier species with different diffusion time scales. The glass/polymer interface forms a depleted region of higher resistance after prolonged exposure to current. Charge also builds up at the polymer to cell antireflective coating interface and mostly flows to the gridlines to experience electrochemical reactions. These complexities result in non‐linear behavior where the apparent resistivities of the different layers change during charge/discharging processes, making the modeling of the current flow extremely difficult.

14 SOLAR ENERGY↗

Stiff and strong, lightweight bi-material sandwich plate-lattices with enhanced energy absorption

Plate-based lattices are predicted to reach theoretical Hashin–Shtrikman and Suquet upper bounds on stiffness and strength. However, simultaneously attaining high energy absorption in these plate-lattices still remains elusive, which is critical for many structural applications such as shock wave absorber and protective devices. In this article, we present bi-material isotropic cubic + octet sandwich plate-lattices composed of carbon fiber-reinforced polymer (stiff) skins and elastomeric (soft) core. This bi-material configuration enhances their energy absorption capability while retaining stretching-dominated behavior. We investigate their mechanical properties through an analytical model and finite element simulations. Our results show that they achieve enhanced energy absorption approximately 2–2.8 times higher than their homogeneous counterparts while marginally compromising their stiffness and strength. When compared to previously reported materials, these materials achieve superior strength-energy absorption characteristics, making them an excellent candidate for stiff and strong, lightweight energy absorbing applications.

36 MATERIALS SCIENCE↗