Restoration of Strength in Polyamide Woven Glass Fiber Organosheets by Hot Pressing: Case Study of Impact and Compression after Impact.

Thermoplastic composite organosheets (OSs) are increasingly recognized as a viable solution for automotive and aerospace structures, offering a range of benefits including cost-effectiveness through high-rate production, lightweight design, impact resistance, formability, and recyclability. This study examines the impact response, post-impact strength evaluation, and hot-pressing repair effectiveness of woven glass fiber nylon composite OSs across varying impact energy levels. Experimental investigations involved subjecting composite specimens to impact at varying energy levels using a drop-tower test rig, followed by compression-after-impact (CAI) tests. The results underscore the exceptional damage tolerance and improved residual compressive strength of the OSs compared to traditional thermoset composites. This enhancement was primarily attributed to the matrix's ductility, which mitigated transverse crack propagation and significantly increased the amount of absorbed energy. To mitigate impact-induced damage, a localized hot-pressing repair approach was developed. This allowed to restore the post-impact strength of the OSs to pristine levels for impact energies below 40 J and by 83.6% for higher impact energies, when OS perforation was observed. The measured levels of post-repair strength demonstrate a successful restoration of OS strength over a wide range of impact energies, and despite limitations in achieving complete strength recovery above 40 J, hot-pressing repair emerges as a promising strategy for ensuring the longevity of thermoplastic composites through repairability.

Effect of Post-Cured through Thickness Reinforcement on Disbonding Behavior in Skin-Stringer Configuration.

An experimental investigation of interlaminar toughness for post-cured through-thickness reinforcement (PTTR) skin-stringer sub-element is presented. The improvement in the crack resistance capability of skin-stringer samples was shown through experimental testing and finite element analysis (FEA) modeling. The performance of PTTR was evaluated on a pristine and initial-disbond of the skin-stringer specimen. A macro-scale pin-spring modeling approach was employed in FEA using a non-linear spring to capture the pin failure under the mixed-mode load. The experimental results showed a 15.5% and 20.9% increase in strength for the pristine-PTTR and initial-disbond PTTR specimens, respectively. The modeling approach accurately represents the overall structural response of PTTR laminate, including stiffness, adhesive strength, crack extension scenarios and progressive pin failure modes. This modeling approach can be beneficial for designing damage-tolerant structures by exploring various PTTR arrangements for achieving improved structural responses.

Mechanics of Pure Bending and Eccentric Buckling in High-Strain Composite Structures.

To maximize the capabilities of nano- and micro-class satellites, which are limited by their size, weight, and power, advancements in deployable mechanisms with a high deployable surface area to packaging volume ratio are necessary. Without progress in understanding the mechanics of high-strain materials and structures, the development of compact deployable mechanisms for this class of satellites would be difficult. This paper presents fabrication, experimental testing, and progressive failure modeling to study the deformation of an ultra-thin composite beam. The research study examines the deformation modes of a post-deployed boom under repetitive pure bending loads using a four-point bending setup and bending collapse failure under eccentric buckling. The material and fabrication challenges for ultra-thin, high-stiffness (UTHS) composite boom are discussed in detail. The continuum damage mechanics (CDM) model for the beam is calibrated using experimental coupon testing and was used for a finite element explicit analysis of the boom. It is shown that UTHS can sustain a bending radius of 14 mm without significant fiber and matrix damage. The finite element model accurately predicts the localized transverse fiber damage under eccentric buckling and buckling stiffness of 15.6 N/mm. The results of the bending simulation were found to closely match the experimental results, indicating that the simulation accurately shows deformation stages and predicts damage to the material. The findings of this research provide a better understanding of the structure characteristics with the progressive damage model of the UTHS boom, which can be used for designing a complex deployable payload for nano-micro-class satellites.

Effect of Resin Bleed Out on Compaction Behavior of the Fiber Tow Gap Region during Automated Fiber Placement Manufacturing.

Automated fiber placement is a state-of-the-art manufacturing method which allows for precise control over layup design. However, AFP results in irregular morphology due to fiber tow deposition induced features such as tow gaps and overlaps. Factors such as the squeeze flow and resin bleed out, combined with large non-linear deformation, lead to morphological variability. To understand these complex interacting phenomena, a coupled multiphysics finite element framework was developed to simulate the compaction behavior around fiber tow gap regions, which consists of coupled chemo-rheological and flow-compaction analysis. The compaction analysis incorporated a visco-hyperelastic constitutive model with anisotropic tensorial prepreg viscosity, which depends on the resin degree of cure and local fiber orientation and volume fraction. The proposed methodology was validated using the compaction of unidirectional tows and layup with a fiber tow gap. The proposed approach considered the effect of resin bleed out into the gap region, leading to the formation of a resin-rich pocket with a complex non-uniform morphology.

Off-Set Interactions of Ruthenium-bda Type Catalysts for Promoting Water-Splitting Performance.

O-O bond formation with Ru(bda)L2 -type catalysts is well-known to proceed through a bimolecular reaction pathway, limiting the potential application of these catalysts at low concentrations. Herein, we achieved high efficiencies with mononuclear catalysts, with TOFs of 460±32 s-1 at high catalyst loading and 31±3 s-1 at only 1 µM catalyst concentration, by simple structural considerations on the axial ligands. Kinetic and DFT studies show that introduction of an off-set in the interaction between the two catalytic units reduces the kinetic barrier of the second-order O-O bond formation, maintaining high catalytic activity even at low catalyst concentrations. The results herein furthermore suggest that π-π interactions may only play a minor role in the observed catalytic activity, and that asymmetry can also rationalize high activity observed for Ru(bda)(isoq)2 type catalysts and offer inspiration to overcome the limitations of 2nd order catalysis.

Electronic Influence of the 2,2'-Bipyridine-6,6'-dicarboxylate Ligand in Ru-Based Molecular Water Oxidation Catalysts.

Water provides an ideal source for the production of protons and electrons required for generation of renewable fuels. Among the most-prominent electrocatalysts capable of water oxidation at low overpotentials are Ru(bda)L2-type catalysts. Although many studies were dedicated to the investigation of the influence of structural variations, the true implication of the bda backbone on catalysis remains mostly unclarified. In this work, we further investigated if electronic effects are contributing to catalysis by Ru(bda)(pic)2 or if the intrinsic catalytic activity mainly originates from the structural features of the ligand. Through introduction of pyrazines in the bda backbone, forming Ru(N1-bda)(pic)2 and Ru(N2-bda)(pic)2, electronic differences were maximized while minimizing changes in the geometry and other intermolecular interactions. Through a combination of electrochemical analysis, chemical oxygen evolution, and density functional theory calculations, we reveal that the catalytic activity is unaffected by the electronic features of the backbone and that the unique bimolecular reactivity of the Ru(bda)L2 family of catalysts thus purely depends on the spatial geometry of the ligand.

Configurational and Constitutional Dynamics of Enamine Molecular Switches.

Dual configurational and constitutional dynamics in systems based on enamine molecular switches has been systematically studied. pH-responsive moieties, such as 2-pyridyl and 2-quinolinyl units, were required on the "stator" part, also providing enamine stability through intramolecular hydrogen-bonding (IMHB) effects. Upon protonation or deprotonation, forward and backward switching could be rapidly achieved. Extension of the stator π-system in the 2-quinolinyl derivative provided a higher E-isomeric equilibrium ratio under neutral conditions, pointing to a means to achieve quantitative forward/backward isomerization processes. The "rotor" part of the enamine switches exhibited constitutional exchange ability with primary amines. Interestingly, considerably higher exchange rates were observed with amines containing ester groups, indicating potential stabilization of the transition state through IMHB. Acids, particularly BiIII , were found to efficiently catalyze the constitutional dynamic processes. In contrast, the enamine and the formed dynamic enamine system showed excellent stability under basic conditions. This coupled configurational and constitutional dynamics expands the scope of dynamic C-C and C-N bonds and potentiates further studies and applications in the fields of molecular machinery and systems chemistry.

A Robotics-Inspired Screening Algorithm for Molecular Caging Prediction.

We define a molecular caging complex as a pair of molecules in which one molecule (the "host" or "cage") possesses a cavity that can encapsulate the other molecule (the "guest") and prevent it from escaping. Molecular caging complexes can be useful in applications such as molecular shape sorting, drug delivery, and molecular immobilization in materials science, to name just a few. However, the design and computational discovery of new caging complexes is a challenging task, as it is hard to predict whether one molecule can encapsulate another because their shapes can be quite complex. In this paper, we propose a computational screening method that predicts whether a given pair of molecules form a caging complex. Our method is based on a caging verification algorithm that was designed by our group for applications in robotic manipulation. We tested our algorithm on three pairs of molecules that were previously described in a pioneering work on molecular caging complexes and found that our results are fully consistent with the previously reported ones. Furthermore, we performed a screening experiment on a data set consisting of 46 hosts and four guests and used our algorithm to predict which pairs are likely to form caging complexes. Our method is computationally efficient and can be integrated into a screening pipeline to complement experimental techniques.

Formation and Out-of-Equilibrium, High/Low State Switching of a Nitroaldol Dynamer in Neutral Aqueous Media.

The nitroaldol reaction is demonstrated as an efficient dynamic covalent reaction in phosphate buffers at neutral pH. Rapid equilibration was recorded with pyridine-based aldehydes, and dynamic oligomerization could be achieved, leading to nitroaldol dynamers of up to 17 repeating units. The dynamers were applied in a coherent stimuli-responsive molecular system in which larger dynamers transiently existed out-of-equilibrium in a neutral aqueous system rich in formaldehyde, controlled by nitromethane.

Modeling compressive behavior of open-cell polymerized high internal phase emulsions: effects of density and morphology.

The compressive behavior of poly(HIPE) foams was studied using the developed micromechanics based computational model. The model allowed identifying the morphological parameters governing the foam compressive behavior. These parameters comprise: (i) foam density, (ii) Sauter mean diameter of voids calculated from the morphological analysis of the polydispersed microstructure of poly(HIPE), and (iii) polymer/strut characteristic size identified as the height of the curvilinear triangular cross-section. The model prediction compared closely with the experiments and considered both the linear and plateau regions of the compressive poly(HIPE) behavior. The computational model allows the prediction of structure-property relationships for poly(HIPE) foams with various relative densities and open cell microstructure using the input parameters obtained from the morphology characterization of the poly(HIPE). The simulations provide a pathway for understanding how tuning the manufacturing process can enable the optimal foam morphology for targeted mechanical properties.

Effect of Curing Rate on the Microstructure and Macroscopic Properties of Epoxy Fiberglass Composites.

Curing rates of an epoxy amine system were varied via different curing cycles, and glass-fiber epoxy composites were prepared using the same protocol, with the aim of investigating the correlation between microstructure and composite properties. It was found that the fast curing cycle resulted in a non-homogenous network, with a larger percentage of a softer phase. Homogenized composite properties, namely storage modulus and quasi-static intra-laminar shear strength, remained unaffected by the change in resin microstructure. However, fatigue tests revealed a significant reduction in fatigue life for composites cured at fast curing rates, while composites with curing cycles that allowed a pre-cure until the critical gel point, were unaffected by the rate of reaction. This result was explained by the increased role of epoxy microstructure on damage initiation and propagation in the matrix during fatigue life. Therefore, local non-homogeneities in the epoxy matrix, corresponding to regions with variable crosslink density, can play a significant role in limiting the fatigue life of composites and must be considered in the manufacturing of large scale components, where temperature gradients and significant exotherms are expected.