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At least 523 records · Page 29

Microstructure and heteroatom dictate the doping mechanism and thermoelectric properties of poly(alkyl-chalcogenophenes)

Heteroatom substitution can favorably alter electronic transport in conductive polymers to improve their thermoelectric performance. Here we report the spectroscopic, structural, and thermoelectric properties of poly(3–(3',7'-dimethyloctyl) chalcogenophenes) or P3RX doped with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), where the heteroatom [X = thiophene (T), selenophene (Se), tellurophene (Te)], the doping methodology, and extent of doping are systematically varied. Spectroscopic measurements reveal that while all P3RX polymers are appreciably doped, the doping mechanism is inherently different. Poly(3-hexylthiophene) (P3HT, used as a control) and poly(3–(3',7'-dimethyloctyl)tellurophene) (P3RTe) are doped primarily via integer charge transfer (ICT), whereas poly(3–(3',7'-dimethyloctyl)selenophene) (P3RSe) and poly(3–(3',7'-dimethyloctyl)thiophene) (P3RT) are doped via charge transfer complex (CTC) mechanisms. Despite these differences, all polymers saturate with roughly the same number of F4TCNQ counterions (1 dopant per 4 to 6 heterocycles), reinforcing the idea that the extent of charge transfer varies with the doping mechanism. Grazing incidence wide-angle x-ray scattering measurements provide insight into the structural driving forces behind different doping mechanisms—P3RT and P3RSe have similar microstructures in which F4TCNQ intercalates between the π-stacked backbones resulting in CTC doping (localized carriers), while P3HT and P3RTe have microstructures in which F4TCNQ intercalates in the alkyl side chain region, giving rise to ICT doping (delocalized carriers). These structural and spectroscopic observations shed light on why P3HT and P3RTe obtain electrical conductivities ca. 3 S/cm, while P3RT and P3RSe have conductivities <10–3 S/cm under the same thin film processing conditions. Ultimately, this work quantifies the effects of heteroatom, microstructural ordering, extent of doping, and doping mechanism, thereby providing rational guidance for designing future thermoelectric polymer-dopant systems.

36 MATERIALS SCIENCE↗

A review of dynamic mechanical characterization of high temperature PMR polyimides and composites

This paper reviews the applications of dynamic mechanical characterization for high-temperature PMR polyimides and their graphite-fiber-reinforced composites. This characterization technique provides insights into the processability, performance, and structure property relationships of the polyimides and composites. The dynamic mechanical properties of various molding powders, commercially obtained prepregs, neat resins, and as-fabricated as well as aged composites are presented. Some applied aspects of the dynamic mechanical data are discussed.

Pater, Ruth H.↗

Hygrothermal aging and recycling effects on mechanical and thermal properties of recyclable thermoplastic glass fiber composites

Abstract Glass fiber‐reinforced polymer composites are widely used in marine applications, including renewable energy devices and submarines, due to their strength‐to‐weight ratios and corrosion resistance. As sustainability becomes more important, recyclable thermoplastic composites are gaining attention in marine energy applications. These materials face harsh conditions such as high chloride water, UV radiation, pressurization, and thermal cycling, which can affect their durability and recyclability. This study examines the impact of hygrothermal aging on the recyclability of an Elium glass fiber (GF) composite. Samples were mechanically ground for recycling, and mechanical and thermal properties were compared between aged and unaged samples. After seawater aging, the tensile strength and modulus of the unaged composite dropped by 25% and 13% respectively, due to water ingress along the fiber‐matrix interface. The recycled composite showed reduced flexural strength as the long fiber composite was converted into short fibers during the process. Differential scanning calorimetry (DSC) revealed no change in glass transition temperature after aging. Weight loss (25%) was attributed to the thermal stability of the glass fibers. Dynamic mechanical analysis (DMA) showed that the storage modulus increased with aging, and fracture analysis confirmed a mixed mode of failure for aged composites. Highlights Hygrothermal aging lowers mechanical performance of Elium® GF composites. Failure mechanism tends to be matrix cracking and interface bonding. Glass transition temperature is not reduced by hygrothermal aging. Fractured composite was successfully recycled via thermoforming. Flexural strength of the recycled composite is lower.

17 WIND ENERGY↗

Basic failure mechanisms in advanced composites

The fundamental failure mechanisms which result from the interaction of thermal cycling and mechanical loading of carbon-epoxy composites were studied. This work was confined to epoxy resin uniderictionally reinforced with HTS carbon fibers, and consists of first identifying local fiber, matrix and interface failure mechanisms using the model composite specimen containing a small number of fibers so that optical techniques can be used for characterization. After the local fracture process has been established for both mechanical loading and thermal cycling, engineering composite properties and gross fracture modes are then examined to determine how the local events contribute to real composite performance. Flexural strength in high fiber content specimens shows an increase in strength with increased thermal cycling. Similar behavior is noted for 25 v/o material up to 200 cycles; however, there is a drastic reduction after 200 cycles indicating a major loss of integrity probably through the accumulation of local cleavage cracks in the tensile region.

Mazzio, V. F.↗

A Numerical Solution Routine for Investigating Oxidation-Induced Strength Degradation Mechanisms in SiC/SiC Composites

The stress rupture strength of silicon carbide fiber-reinforced silicon carbide (SiCSiC) composites with a boron nitride (BN) fiber coating decreases with time within the intermediate temperature range of 700-950 C. Various theories have been proposed to explain the cause of the time dependent stress rupture strength. Some previous authors have suggested that the observed composite strength behavior is due to the inherent time dependent strength of the fibers, which is caused by the slow growth of flaws within the fibers. Flaw growth is supposedly enabled by oxidation of free carbon at the grain boundaries. The objective of this paper is to investigate the relative significance of the various theories for the time-dependent strength of SiCSiC composites. This is achieved through the development of a numerically-based progressive failure analysis routine and through the application of the routine to simulate the composite stress rupture tests. The progressive failure routine is a time marching routine with an iterative loop between a probability of fiber survival equation and a force equilibrium equation within each time step. Failure of the composite is assumed to initiate near a matrix crack and the progression of fiber failures occurs by global load sharing. The probability of survival equation is derived from consideration of the strength of ceramic fibers with randomly occurring and slow growing flaws as well as the mechanical interaction between the fibers and matrix near a matrix crack. The force equilibrium equation follows from the global load sharing presumption. The results of progressive failure analyses of the composite tests suggest that the relationship between time and stress-rupture strength is attributed almost entirely to the slow flaw growth within the fibers. Although other mechanisms may be present, they appear to have only a minor influence on the observed time dependent behavior.

degradation↗

Harnessing biomimetic cryptic bonds to form self-reinforcing gels

Cryptic sites, which lay hidden in folded biomolecules, become exposed by applied force and form new bonds that reinforce the biomaterial. While these binding interactions effectively inhibit mechanical deformation, there are few synthetic materials that harness mechano-responsive cryptic sites to forestall damage. Here, we develop a computational model to design polymer gels encompassing cryptic sites and a lower critical solution temperature (LCST). LCST gels swell with a decrease in temperature, thereby generating internal stresses within the sample. The gels also encompass loops held together by the cryptic sites, as well as dangling chains with chemically reactive ends. A decrease in temperature or an applied force causes the loops to unfold and expose the cryptic sites, which then bind to the dangling chains. We show that these binding interactions act as “struts” that reinforce the network, as indicated by a significant decrease in the volume of the gel (from 44% to 80%) and shifts in the volume phase transition temperature. Once the temperature is increased or the deformation is removed, the latter “cryptic bonds” are broken, allowing the loops to refold and the gel to return to its original state. These findings provide guidelines for designing polymer networks with reversible, mechano-responsive bonds, which allow gels to undergo a self-stiffening behavior in response to a temperature-induced internal stress or external force. When applied as a coating, these gels can prevent the underlying materials from undergoing damage and thus, extend the lifetime of the system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strengthening poly(lactic acid) composites with poly(methyl methacrylate) functionalized flax nanofibrils

Biobased reinforcements for poly(lactic acid) (PLA) are needed for more additive manufacturing applications requiring higher strength and sustainability. Flax nanofibrils (FNFs) produced through mechanical refining were explored as a lower energy alternative to cellulose nanofibril (CNF) reinforcements. To compatibilize the FNFs for the PLA matrix, a grafting-through surfactant free emulsion polymerization (SFEP) was performed to functionalize the FNF surface with poly(methyl methacrylate) (PMMA). FNFs produced using different refining energy were functionalized under varying solid contents in suspension. Polymerizations performed at 0.7 wt% FNFs in water yielded the highest degree of PMMA functionality. These optimal conditions were scaled up and the PMMA modified FNFs melt compounded into PLA yielding a 12% increase in tensile strength and 92% increase in the modulus of elasticity as compared to the original PLA. Interestingly, the FNFs with the lowest refining energy yielded the strongest composites using these methods, surpassing the higher refining energy CNF reinforcements. This increase was attributed to improved dispersion of the FNF reinforcements in the PLA matrix that was enabled by the PMMA coating on the FNF surface preventing interfibrillar adhesion and aggregation within the PLA matrix.

Mulligan, Abigail [University of Maine]↗

Test and Analysis of Composite Hat Stringer Pull-off Test Specimens

Hat stringer pull-off tests were performed to evaluate the delamination failure mechanisms in the flange region for a rod-reinforced hat stringer section. A special test fixture was used to pull the hat off the stringer while reacting the pull-off load through roller supports at both stringer flanges. Microscopic examinations of the failed specimens revealed that failure occurred at the ply termination in the flange area where the flange of the stiffener is built up by adding 45/-45 tape plies on the top surface. Test results indicated that the as-manufactured microstructure in the flange region has a strong influence on the delamination initiation and the associated pull-off loads. Finite element models were created for each specimen with a detailed mesh based on micrographs of the critical location. A fracture mechanics approach and a mixed mode delamination criterion were used to predict the onset of delamination and the pull-off load. By modeling the critical local details of each specimen from micrographs, the model was able to accurately predict the hat stringer pull-off loads and replicate the variability in the test results.

Li, Jian↗

Polymer grafted aramid nanofiber reinforces immiscible waste polypropylene/poly(ethylene terephthalate)

Polypropylene (PP) and poly(ethylene terephthalate) (PET) are plastics commonly used for packaging because of their excellent barrier and mechanical properties. The properties of these plastics are often diminished after mechanical recycling, inevitably causing down-cycling. Furthermore, this problem is exacerbated when different kinds of polymers mix. Aramid nanofibers have the potential to improve the mechanical properties of polymers due to their excellent mechanical properties but their poor dispersion in polymers is a challenge. Grafting polymers onto nanofibers can help address this challenge. In this work, different loading levels (1%, 2%, and 5%) of polymer grafted aramid nanofibers (ANFs) are blended with waste PP/PET (90/10), simulating a PP waste stream containing traces of PET contaminants. Scanning electronic microscopy, rheology, and differential scanning calorimetry results show the affinity of PP functionalized aramid nanofibers (PP_ANF) towards the PP matrix. At 1 wt% of the nanofiber, the size of the PET droplets in the PP matrix of the PP_ANF blend range from 0.2 to 2.0 μm while that of unmodified ANF and PET_ANF blends are in the range of 0.1–6.2 and 0.5–7.4 μm, respectively. In summary, polymer grafted ANFs have the tendency of improving properties of its like polymers due to similarity in the grafting polymer and the polymer matrix.

36 MATERIALS SCIENCE↗

Shape Persistent, Highly Conductive Ionogels from Ionic Liquids Reinforced with Cellulose Nanocrystal Network

Abstract Shape‐persistent, conductive ionogels where both mechanical strength and ionic conductivity are enhanced are developed using multiphase materials composed of cellulose nanocrystals and hyperbranched polymeric ionic liquids (PILs) as a mechanically strong supporting network matrix for ionic liquids with an interrupted ion‐conducting pathway. The integration of needlelike nanocrystals and PIL promotes the formation of multiple hydrogen bonding and electrostatic ionic interaction capacitance, resulting in the formation of interconnected networks capable of confining a high amount of ionic liquid (≈95 wt%) without losing its self‐sustained shape. The resulting nanoporous and robust ionogels possess outstanding mechanical strength with a high compressive elastic modulus (≈5.6 MPa), comparable to that of tough, rubbery materials. Surprisingly, these rigid materials preserve the high ionic conductivity of original ionic liquids (≈7.8 mS cm −1 ), which are distributed within and supported by the nanocrystal network‐like rigid frame. On the one hand, such stable materials possess superior ionic conductivities in comparison to traditional solid electrolytes; on the other hand, the high compression resistance and shape‐persistence allow for easy handling in comparison to traditional fluidic electrolytes. The synergistic enhancement in ion transport and solid‐like mechanical properties afforded by these ionogel materials make them intriguing candidates for sustainable electrodeless energy storage and harvesting matrices.

Lee, Hansol↗

Elucidating Abnormal Grain Growth in Thermomagnetic Processed Materials with Transfer Learning and Reinforcement Learning

The goal of this research program is to establish the mechanism governing local grain boundary motion, which is needed to design and process desirable microstructures for better performance, by identifying the relative contributions of grain boundary (GB) energy and mobility to grain growth. Classical models for grain growth assume that the primary mechanism for reducing the total interfacial energy is area reduction and that GB restructuring is not significant. This assumption implies that grain growth is locally driven by curvature. However, recent experimental observations using new non-destructive 3D x-ray diffraction microscopy techniques (3D-XRM) reveal that classic descriptors (i.e., curvature, number of neighbors, grain size) do not predict real grain growth. Instead, local GB motion appears to be governed by its energy relative to its neighbors such that low-energy boundaries replace those of higher energy. However, simulations that incorporate GB energy anisotropy still fail to reproduce these observations. These discrepancies suggest that the common assumption for grain growth theory must be re-examined to predict and, thus, control microstructure evolution in real polycrystals. A significant challenge to testing this assumption is due to anisotropic GB mobility. Mobility may cause abnormal grain growth or affect the final grain shapes or growth rate but its true contributions are unknown because it is difficult to measure. For example, observations in Fe have found that grains associated with high energy and high mobility boundaries tend to experience abnormal grain growth, whereas abnormal grain growth is associated with low energy and high mobility boundaries in alumina. As mobility and energy both control GB motion, it is challenging to isolate the local driving forces necessary to test the common assumption that the primary mechanism is area reduction. The novelty of this work is the use of machine learning tools to capture GB mobility and energy from 3D-XRM measurements in polycrystals to test the common assumption used in grain growth models. Machine learning can capture high-order correlations in dynamic systems like those found in the evolving GB topology. The PIs have developed a physics-regularized interpretable machine learning microstructure evolution (PRIMME) model that accurately replicates the grain growth behavior of its trained data set.

36 MATERIALS SCIENCE↗

Low-velocity impact damage in graphite-fiber reinforced epoxy laminates

An experimental investigation was conducted to identify the failure mechanisms and to understand damage propagation in compression-loaded composite structures. The tests were conducted on several laminates of different ply orientation with thickness that ranged from 0.56 to 0.75 cm. The panels were damaged by 1.27-cm-diameter aluminum spheres propelled normal to the specimen surface at velocities ranging from 30 m/s to 140 m/s. Results indicate that there is significant internal laminate damage due to low-velocity impact with no surface damage. The internal damage consists of delamination and intraply cracking. Three damage propagation modes were identified as causing specimen failure; which are delamination, axial load-lateral deformation coupling, and local shear failure.

Rhodes, M. D.↗

Flax fiber-reinforced fatty acid vitrimer biocomposite with enhanced chemical recyclability

Here, this study unveils a sustainable, easily recyclable biocomposite, leveraging the dynamic nature of covalently adaptive bonds in a vitrimer matrix. The fabrication involved a fatty acid-derived vitrimer as the polymer matrix and multi-layered, nonwoven flax mat as reinforcing scaffold. The incorporation of these fibers significantly improved the mechanical performance of the vitrimer matrix uniformly. The ester-based covalently adaptive network plays a crucial role in enabling exceptional fiber-matrix bonding, as well as recyclability. The vitrimer matrix dissolves in ethylene glycol through transesterification, facilitating complete material recovery and biocomposite recycling without compromising the original properties of the matrix and reinforcing fibers.

36 MATERIALS SCIENCE↗

Fiber reinforced thermoplastic resin matrix composites

Polyimide polymer composites having a combination of enhanced thermal and mechanical properties even when subjected to service temperatures as high as 700.degree. F. are described. They comprise (a) from 10 to 50 parts by weight of a thermoplastic polyimide resin prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and (b) from 90 to 50 parts by weight of continuous reinforcing fibers, the total of (a) and (b) being 100 parts by weight. Composites based on polyimide resin formed from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and pyromellitic dianhydride and continuous carbon fibers retained at least about 50% of their room temperature shear strength after exposure to 700.degree. F. for a period of 16 hours in flowing air. Preferably, the thermoplastic polyimide resin is formed in situ in the composite material by thermal imidization of a corresponding amide-acid polymer prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. It is also preferred to initially size the continuous reinforcing fibers with up to about one percent by weight of an amide-acid polymer prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. In this way imidization at a suitable elevated temperature results in the in-situ formation of a substantially homogeneous thermoplastic matrix of the polyimide resin tightly and intimately bonded to the continuous fibers. The resultant composites tend to have optimum thermo-mechanical properties.

Jones, Robert J.↗

A review of the fabrication methods and mechanical behavior of continuous thermoplastic polymer fiber–thermoplastic polymer matrix composites

Abstract Thermoplastic polymer fiber–thermoplastic polymer matrix composites (PPCs or PRFPs), often recognized as self‐reinforced or single polymer composites, are potential candidates for future advanced polymer composites because of various advantages ( e.g., recyclability, formability, low‐cost, ultra‐lightweight, environmental friendliness, etc.). The manufacturability and mechanical behavior of these composites compared to conventional carbon‐/glass‐/aramid‐fiber‐reinforced polymers is of great interest to the composites community, but there are a limited number of studies in this area. To this end, this paper reviewed fabrication methods with different processing parameters and mechanical behavior of uni‐/multi‐directional thermoplastic PPCs featuring continuous thermoplastic polymer fibers from limited data in the literature. It was shown that most specific behaviors (normalized by density) of these materials in various loading conditions (e.g., quasi‐static tension/shear/flexure, tension‐tension fatigue, and out‐of‐plane impacting, etc.) are comparable to or better than glass‐/aramid‐fiber‐reinforced polymers. Particularly, the specific ductility in the foregoing conditions outperforms all the carbon‐/glass‐/aramid‐fiber‐reinforced polymers. Thermoplastic PPCs with remarkable performance can be achieved through several uncomplicated methods (e.g., film stacking, hot compaction, powder and solution impregnations, matrix infusion and injection molding, additive manufacturing, etc.), which have some similarities to the methods used for carbon‐/glass‐/aramid‐fiber‐reinforced polymers. Moreover, several opportunities and challenging problems of thermoplastic PPCs were summarized at the end of this review paper. Efficient solutions may require countless efforts in the composites community to further strengthen the performance and understanding of thermoplastic PPCs for wide applications in various engineering fields in the future.

36 MATERIALS SCIENCE↗

Telescoping Mechanics: A New Paradigm for Composite Behavior Simulation

This report reviews the application of telescoping mechanics to composites using recursive laminate theory. The elemental scale is the fiber-matrix slice, the behavior of which propagates to laminate. The results from using applications for typical, hybrid, and smart composites and composite-enhanced reinforced concrete structures illustrate the versatility and generality of telescoping scale mechanics. Comparisons with approximate, single-cell, and two- and three-dimensional finite-element methods demonstrate the accuracy and computational effectiveness of telescoping scale mechanics for predicting complex composite behavior.

Chamis, C. C.↗

Elevated-temperature fracture resistances of monolithic and composite ceramics using chevron-notched bend tests

The quasi-static fracture behaviors of monolithic ceramics (SiC, Si3N4, MgAl2O4), self-reinforced monoliths (acicular grained Si3N4, acicular grained mullite), and ceramic matrix composites (SiC whisker/Al2O3 matrix, TiB2 particulate/SiC matrix, SiC fiber/CVI SiC matrix, Al2O3 fiber/CVI SiC matrix) were measured over the temperature range of 20 to 1400 C. The chevron notched, bend bar test geometry was essential for characterizing the elevated temperature fracture resistances of this wide range of quasi-brittle materials during stable crack growth. Fractography revealed the differences in the fracture behavior of the different materials at the various temperatures. The fracture resistances of the self-reinforced monoliths were comparable to those of the composites and the fracture mechanisms were found to be similar at room temperature. However at elevated temperatures the differences of the fracture behavior became apparent where the superior fracture resistance of the self-reinforced monoliths were attributed to the minor amounts of glassy, intergranular phases which were often more abundant in the composites and affected the fracture behavior when softened by elevated temperatures.

Ghosh, Asish↗

Recent progress in NASA Langley Research Center textile reinforced composites program

Research was conducted to explore the benefits of textile reinforced composites for transport aircraft primary structures. The objective is to develop and demonstrate the potential of affordable textile reinforced composite materials to meet design properties and damage tolerance requirements of advanced aircraft structural concepts. Some program elements include development of textile preforms, processing science, mechanics of materials, experimental characterization of materials, and development and evaluation of textile reinforced composite structural elements and subcomponents. Textile 3-D weaving, 3-D braiding, and knitting and/or stitching are being compared with conventional laminated tape processes for improved damage tolerance. Through-the-thickness reinforcements offer significant damage tolerance improvements. However, these gains must be weighted against potential loss in in-plane properties such as strength and stiffness. Analytical trade studies are underway to establish design guidelines for the application of textile material forms to meet specific loading requirements. Fabrication and testing of large structural parts are required to establish the potential of textile reinforced composite materials.

Dexter, H. Benson↗