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Tuning the chemical and physical crosslinks of poly(dimethyl siloxane)-based elastomers enables significantly enhanced puncture-resistant property with rapid self-healing capability.
The mechanical and physical properties of three neat matrix materials, i.e., PEEK (polyetheretherketone) thermoplastic, Hexcel F155 rubber-toughened epoxy and Hercules 8551-7 rubber-toughened epoxy, were experimentally determined. Twelve unidirectional carbon fiber composites, incorporating matrix materials characterized in this or earlier studies (with one exception; the PISO(sub 2)-TPI matrix itself was not characterized), were also tested. These composite systems included AS4/2220-1, AS4/2220-3, T500/R914, IM6/HX1504, T300/4901A (MDA), T700/4901A (MDA), T300/4901B (MPDA), T700/4901B (MPDA), APC2 (AS4/PEEK, ICI), APC2 (AS4/PEEK, Langley Research Center), AS4/8551-7, and AS4/PISO(sub 2)-TPI. For the neat matrix materials, the tensile, shear, fracture toughness, coefficient of thermal expansion, and coefficient of moisture expansion properties were measured as a function of both temperature and moisture content. For the unidirectional composites, axial and transverse tensile, longitudinal shear, coefficient of thermal expansion, and coefficient of moisture expansion properties were determined, at room temperature and 100 C.
Efficient separation of the plant cell wall polymers during lignocellulose processing has been historically challenging due to insolubility of the polymers and their propensity for recalcitrant reassembly. Methods, such as “lignin first” extraction techniques, have advanced efficient biomass use, but the molecular mechanisms for recalcitrance remain enigmatic. Here, we discuss how solid-state Nuclear Magnetic Resonance (NMR) approaches report on the 3D organization of cellulose, xylan, and lignin in the plant cell wall. Recent results illustrate that the organization of these polymers varies across biomass sources and sample preparation methods, with even minimal physical processing causing significant effects. These structural differences contribute to variable extraction efficiencies for bioproducts after downstream processing. We propose that solid-state NMR methods can be applied to follow biomass processing, providing an understanding of the polymer rearrangements that can lead to poor yields for the desired bioproducts. The utility of the technique is illustrated for mechanical processing using lab-scale vibratory ball milling of Sorghum bicolor .
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Additive manufacturing, or simply 3D printing (3DP), where objects are built through layer-wise material deposition, has gained significant academic and industrial attention as a result of the development of advanced and functional materials requiring rapid, customized, and flexible solutions. In the context of green manufacturing, diversifying environmentally and economically sustainable material portfolios is an essential endeavor for the success of 3DP technology that uses widely available, highly valuable, and renewable materials. Here, we used stereolithography (SLA) for processing methacrylate-based photocurable resins containing crab shell-derived chitin nanowhiskers (CNWs), which are surface-functionalized by reactive acrylate groups. Results from full spectral, thermal, structural, and topological analyses corroborate not only the surface functionalization of CNWs but also indicate the presence of these photocurable CNW (pCNW) fillers in the 3D-printed nanocomposites. Owing to the strong interfacial bond induced by the physical and chemical crosslinking between the pCNW and methacrylate (MA) polymer matrix, the internally formulated nanocomposites displayed enhanced thermomechanical properties (e.g., storage modulus and glass transition temperature) compared to those of commercially available pure SLA resins. For instance, the inclusion of 0.5 wt % pCNW improved the tensile strength and stiffness to up to 78 and 71%, respectively, without compromising the toughness and ductility of the printed material. Accordingly, this result also evidences the compatibility between the filler and resin materials. Consequently, the formation of a crosslinked network in the nanocomposite structure results in a higher thermal stability and activation energy (i.e., up to ~79%) for all the hybrid materials than the pristine MA. Finally, the high-resolution SLA print features, dimensional accuracy, and enhanced mechanical performance of our microstructure-forming functionalized chitin-based nanocomposites make them promising materials for a wide range of robust and high-performance industrial applications.
Mechanical forces can enhance the chemical depolymerization of synthetic polymers when shear flow accelerates chain scission. To quantify the extent of mechanically-accelerated scission, the effect of simple shear flow (duration and strength) with low Weissenberg and Deborah numbers was investigated by considering the impact of applied work in both simple shear and shear dominated mixed flows. Hydrogenated polyisoprene was chosen as a model linear, entangled system. The conditions (strain amplitude, frequency, and shearing time) necessary to increase chain scission were assessed in the rubbery melt. Shear flow accelerated chain scission at higher temperatures, suggesting an activated process. Isothermal scission versus work curves were superposed by applying shift factors a T,S , whose Arrhenius-like temperature dependence gave an apparent activation energy for chain scission of ~ 110 kJ/mol, which is likely a combination of the activation energy of viscosity and bond energy. This work provides a base for quantifying the impact of shear on depolymerization of polymer melts and highlight the connection between viscous dissipation and scission chemistry.
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A high-temperature linear amorphous hydrocarbon polymer synthesized cationically from 2,5-norbornadiene was studied thermomechanically with respect to physical transitions and stability in nitrogen. The glass transition temperature was determined to be 320 C (at less than 1 cps), which is probably the highest known for a linear hydrocarbon addition polymer. The thermomechanical technique of torsional braid analysis, together with thermogravimetric analysis, differential thermal analysis, infrared analysis, and solubility studies, was used to investigate the sequential events of the glass transition and degradation. The polymer is of particular interest since it is a high-temperature plastic which in the bulk form would probably need to be processed at high speeds in the vicinity of the glass transition temperature in an inert atmosphere. The presence of tertiary hydrogen atoms should render it amenable to degradation by the earth's environment.
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Donor-acceptor (DA) conjugated polymers (CPs) with narrow bandgaps and open-shell (diradical) character represent an emerging class of materials whose rich behavior emanates from their collective electronic properties and diminished electron pairing. However, the structural and electronic heterogeneities that define these materials complicate bandgap control at low energies and connections linking topology, exchange interactions, and (opto)electronic functionality remain nascent. To address these challenges, we demonstrate structurally rigid and strongly π-conjugated copolymers comprised of a solubilizing thiadiazoloquinoxaline acceptor and cyclopenta[2,1-b:3,4-b']dithiophene or dithieno[3,2-b:2',3'-d]thiophene donors. Atom-specific substitution modulates local aromatic character within the donor resulting in dramatic differences in structural, physicochemical, electronic, and magnetic properties of the polymers. These long-range π-mediated interactions facilitate control between low-spin aromatic and high-spin quinoidal forms. This work provides a strategy to understand the evolution of the electronic structure within DA CPs, control the ground state spin multiplicity, tune spin-spin interactions, and articulate the emergence of their novel properties.
Organic conjugated polymers and oligomers are key electronic materials for applications such as transistors, photovoltaics, and light emitting devices due to their potential for solution processability, mechanical flexibility, and precise structure-based tuning compared to inorganic materials. In dilute environments, the optoelectronic properties of conjugated polymers are largely governed by their constitutional structure and, to a lesser degree, their solution-state intramolecular configuration. In the solid state, intramolecular conformation and intermolecular electronic coupling impact these properties substantially, especially in relation to device performance. Therefore, an increasingly important area of research concerning conjugated materials is developing design strategies aimed at optimizing the solid-state packing for electronic applications. Programming solid-state packing arrangements through discrete non-covalent interactions is an emerging strategy within the context of conjugated polymers. This review focuses on the use of the two most prevalent discrete and directional interactions used to dictate the self-assembly of conjugated polymers and oligomers—hydrogen bonds and chalcogen bonds. Further, we also discuss how these design motifs can imbue conjugated materials with appealing physical properties while simultaneously retaining or improving electronic capabilities.
The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle–particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (K eq ) of the polymeric solvent to the particle interface. It is demonstrated that low Keq leads to shear thinning, while high K eq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in K eq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.
Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.
Suspensions of polymeric nano-and microparticles are fascinating stress-responsive material systems that, depending on their composition, can display a diverse range of flow properties under shear, such as drastic thinning, thickening, and even jamming (reversible solidification driven by shear). However, investigations to date have almost exclusively focused on nonresponsive particles, which do not allow in situ tuning of the flow properties. Polymeric materials possess rich phase transitions that can be directly tuned by their chemical structures, which has enabled researchers to engineer versatile adaptive materials that can respond to targeted external stimuli. Reported herein are suspensions of (readily prepared) micrometer-sized polymeric particles with accessible glass transition temperatures (T g ) designed to thermally control their non-Newtonian rheology. The underlying mechanical stiffness and interparticle friction between particles change dramatically near T g . Capitalizing on these properties, it is shown that, in contrast to conventional systems, a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' T g . This straightforward strategy enables the in situ turning on (or off) of the system's ability to shear jam by varying the temperature relative to T g and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.
The physical and mechanical properties of advanced composite materials as related to their use in structures on planetary surfaces are reviewed. Polymer matrix composites are recommended as the best materials in the first exploration stages. Achievement of mechanical properties, physical properties, improved processability, and ease of assembly required on planetary surfaces depends on the tailorability of composites.
Flexible, high performance polymers such as polyimides are often employed in aerospace applications. They typically find uses in areas where improved physical characteristics such as fire resistance, long term thermal stability, and solvent resistance are required. It is anticipated that such polymers could find uses in future long duration exploration missions as well. Their use would be even more advantageous if self-healing capability or mechanisms could be incorporated into these polymers. Such innovative approaches are currently being studied at the NASA Kennedy Space Center for use in high performance wiring systems or inflatable and habitation structures. Self-healing or self-sealing capability would significantly reduce maintenance requirements, and increase the safety and reliability performance of the systems into which these polymers would be incorporated. Many unique challenges need to be overcome in order to incorporate a self-healing mechanism into flexible, high performance polymers. Significant research into the incorporation of a self-healing mechanism into structural composites has been carried out over the past decade by a number of groups, notable among them being the University of I1linois [I]. Various mechanisms for the introduction of self-healing have been investigated. Examples of these are: 1) Microcapsule-based healant delivery. 2) Vascular network delivery. 3) Damage induced triggering of latent substrate properties. Successful self-healing has been demonstrated in structural epoxy systems with almost complete reestablishment of composite strength being achieved through the use of microcapsulation technology. However, the incorporation of a self-healing mechanism into a system in which the material is flexible, or a thin film, is much more challenging. In the case of using microencapsulation, healant core content must be small enough to reside in films less than 0.1 millimeters thick, and must overcome significant capillary and surface tension forces to flow, mix and react to achieve healing. Vascular networks small enough to fit into such films must also overcome these same flow limitations. Self-healing has also been demonstrated in ionomeric substrates such as Surlyn , wherein the heat generated by a projectile impact triggers the latent ability of this substrate to flow back to its original shape. Recent work using Diels-Alder reactions have shown promise in bringing about actual reforming of broken chemical bonds to achieve self-healing [2]. All self-healing mechanisms that rely on the use of inherent latent substrate properties require some degree of polymer chain flow to achieve any significant level of healing.
Understanding how solvent properties influence the solution-to-film assembly of conjugated polymers remains a critical challenge due to the complex and intertwined nature of polymer–solvent interactions. In this study, we integrate a data-driven framework with experimental validation to identify key parameters influencing the assembly and performance of poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] (DPP-DTT) in organic field-effect transistors (OFETs). A machine learning (ML) approach identified the normalized Reichardt polarity parameter (E T N ) as a significant descriptor correlated with DPP-DTT hole mobility (μ). Systematic DPP-DTT devices fabricated using solvents across a wide E T N range revealed that higher E T N solvents yield enhanced μ. To elucidate the structural origins of high μ, we conducted comprehensive analyses using UV–vis–NIR spectroscopy and grazing incidence wide angle X-ray scattering (GIWAXS) measurements. The results revealed that films processed from high E T N solvents exhibit reduced paracrystallinity. By analyzing the solution-state behavior using optical microscopy and solution WAXS, we revealed polymer solubility differences in the various solvents and associated distinct polymer assembly pathways, elucidating why the high E T N solvent produces long-range ordered films. Notably, the high E T N solvent shows a pronounced preference for liquid-crystal (LC)-mediated assembly, providing a mechanistic explanation for the enhanced structural order. Therefore, these results demonstrate that solvent polarity, as evaluated by E T N , serves as an important parameter that plays a significant role in the DPP-DTT assembly pathway and resultant solid-state morphology. This work provides a strategy for integrating data science with experiments to identify critical parameters associated with complex polymer systems and helps guide rational process design for high-performance organic electronics.
Here, we develop off-lattice simulations of semiflexible polymer chains subjected to applied mechanical forces by using Markov Chain Monte Carlo. Our approach models the polymer as a chain of fixed length bonds, with configurations updated through adaptive nonlocal Monte Carlo moves. This proposed method enables precise calculation of a polymer’s response to a wide range of mechanical forces, which traditional on-lattice models cannot achieve. Our approach has shown excellent agreement with theoretical predictions of persistence length and end-to-end distance in quiescent states as well as stretching distances under tension. Moreover, our model eliminates the orientational bias present in on-lattice models, which significantly impacts calculations such as the scattering function, a crucial technique for revealing the polymer conformation.