Mechanical Properties and Synergistic Interfacial Interactions of ZnO Nanorod-Reinforced Polyamide–Imide Composites
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Dallas Kesler↗
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Electrochemical CO2 Reduction by 2,2' Bipyridine-5,5'-Biscarboxylic Acid Derived-Rhenium Coordination Polyamides
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Materials science, Energy - Synthetic fuels, Chemi↗
Influence of Fiber Orientation on Deformation of Additive Manufactured Composites
Anisotropy caused by flow-induced fiber orientation of discontinuous fibers within the extrudate in the Extrusion Deposition Additive Manufacturing (EDAM) process gives rise to anisotropic shrinkage in printed parts and thereby, final part deformations. Three fiber orientation states, described by the second-order orientation tensor, were investigated to determine their influence upon final geometry. Two material systems were investigated including a short glass fiber-reinforced polyamide and a short carbon fiber-reinforced polyamide. A curvilinear geometry was modeled and printed virtually in the thermo-mechanical simulation, ADDITIVE3D©. The scale of the printed geometry was in the range of 300–400 mm and contained three semicircular geometry regions connected to linear regions, thereby inducing significant magnification of the spring-in deformation. The predicted deformation of the printed geometry for the three fiber orientation states and two material systems were compared. The deformation predicted for glass fiber-filled polyamide and carbon fiber-filled polyamide of the same fiber orientation states showed comparable deformations. In conclusion, the largest residual deformation was shown to correspond to the orientation tensor with the greatest degree of anisotropy.
36 MATERIALS SCIENCE↗
Non-equilibrium simulations of hydraulic permeation: Role of mechanical boundary conditions in dense membranes
Understanding the mechanisms of water transport in reverse osmosis membranes is critical for improving membrane performance and guiding material design. While classical models describe transport as either solution-diffusion (SD)—involving concentration-driven diffusion through a homogeneous medium—or pore-flow (PF)—involving pressure-driven convection through percolated water channels—their applicability to crosslinked polyamide membranes remains debated. Here, using non-equilibrium molecular dynamics simulations, we investigate the impact of mechanical support conditions on pressure-driven water transport in polyamide membranes across varying crosslink densities and pressure differentials (1000–5000 bar). Two support conditions are considered: graphene-restrained, representing experimentally relevant supported membranes, and freeze-restrained, mimicking a self-supported structure. In graphene-restrained systems, water concentration gradients and constant pressure profiles emerge, consistent with SD theory and incompatible with PF assumptions due to the absence of percolated pores and sub-nanometer voids. In contrast, freeze-restrained systems display uniform water concentration and linearly decreasing pressure at 1000 bar, and exhibit compressibility-induced water gradients and partial percolation at 5000 bar, resembling PF-like behavior. However, the underlying assumptions of PF theory—continuous solvent pathways and pressure transmission through water-filled pores—are not met under most conditions. Our results demonstrate that accurate modeling of reverse osmosis membranes must incorporate realistic mechanical boundary conditions to distinguish between transport mechanisms. For dense polyamide membranes supported by porous substrates, graphene-restrained simulations best reflect experimental setups and support the SD model as the dominant mechanism of water permeation.
molecular dynamics↗
RNA polymerase II trapped on a molecular treadmill: Structural basis of persistent transcriptional arrest by a minor groove DNA binder
Elongating RNA polymerase II (Pol II) can be paused or arrested by a variety of obstacles. These obstacles include DNA lesions, DNA-binding proteins, and small molecules. Hairpin pyrrole-imidazole (Py-Im) polyamides bind to the minor groove of DNA in a sequence-specific manner and induce strong transcriptional arrest. Remarkably, this Py-Im–induced Pol II transcriptional arrest is persistent and cannot be rescued by transcription factor TFIIS. In contrast, TFIIS can effectively rescue the transcriptional arrest induced by a nucleosome barrier. The structural basis of Py-Im–induced transcriptional arrest and why TFIIS cannot rescue this arrest remain elusive. Here we determined the X-ray crystal structures of four distinct Pol II elongation complexes (Pol II ECs) in complex with hairpin Py-Im polyamides as well as of the hairpin Py-Im polyamides–dsDNA complex. We observed that the Py-Im oligomer directly interacts with RNA Pol II residues, introduces compression of the downstream DNA duplex, prevents Pol II forward translocation, and induces Pol II backtracking. These results, together with biochemical studies, provide structural insight into the molecular mechanism by which Py-Im blocks transcription. Our structural study reveals why TFIIS fails to promote Pol II bypass of Py-Im–induced transcriptional arrest.
59 BASIC BIOLOGICAL SCIENCES↗
Accumulation of microplastics in soil after long-term application of biosolids and atmospheric deposition
Land-applied biosolids can be a considerable source of microplastics in soils. Previous studies reported microplastics accumulation in soils from biosolid application, however, little is known about the contribution of atmospherically deposited microplastics to agricultural soils. In this study, we quantified and characterized microplastics in soils that have been amended with biosolids over the past 23 years. We also collected atmospheric deposition samples to determine the amount and type of plastics added to soils through atmospheric input over a period of about 2 years. Soil samples were taken from a replicated field trial where biosolids have been applied at rates of 0, 4.8, 6.9, and 9.0 t/ha every second crop. The biosolids were anaerobically digested and dewatered, and were applied by spreading onto the soil surface. Soil and atmospheric samples were extracted for microplastics by Fenton's reaction to remove organic matter followed by flotation in a zinc chloride solution to separate plastic from soil particles. Samples were analyzed for microplastics by optical microscopy and Laser Direct Infrared Imaging Analysis (LDIR). The mean number of microplastics identified from biosolids samples was 12,000 particles/kg dry biosolids. The long-term applications of biosolids to the soil led to mean plastics concentrations of 383, 500, and 361 particles/kg dry soil in the 0–10 cm depth for low, medium, and high biosolids application rates, respectively. These plastic concentrations were not significantly different from each other, but significantly higher than those found in non biosolids-amended soil (117 particles/kg dry soil). The dominant plastic types by number found in biosolids were polyurethane, followed by polyethylene, and polyamide. The most abundant plastics in soil samples were polyurethane, polyethylene terephthalate, polyamide, and polyethylene. Atmospheric deposition contributed to 15 particles/kg dry soil per year and was mainly composed of polyamide fibers. In conclusion, this study shows that long-term application of biosolids led to an accumulation of microplastics in soil, but that atmospheric deposition also contributes a considerable input of microplastics.
54 ENVIRONMENTAL SCIENCES↗
Thermomechanical and sequential stress performance of photovoltaic backsheets
Photovoltaic backsheet technology is utilized to protect the interior components of solar modules from environmental stress as well as provide electrical insulation to the module. The growing demand for solar energy and longer module service life requirements have brought backsheet performance into focus. Despite being a protective packaging material, many backsheets have exhibited failure in the field, limiting the performance and service life of entire modules. Most backsheets consist of multiple polymeric layers laminated together using adhesives. A new backsheet, with a high performance polyamide structure, has been developed as the solution to module failure. Primarily, it contains a unique polyamide-ionomer alloy targeted at improved weather resistance. In this study, several photovoltaic industry standard backsheets, and the novel polyamide compositions of multilayered backsheets fabricated from the coextrusion process, were examined using thermomechanical analysis (TMA). The coefficient of thermal expansion (CTE) for entire backsheets and their constituent layers was used to model the thermomechanical behavior of various backsheet constructions. Subsequently, thermal cycling was performed in the TMA to examine the intrinsic thermal behavior of the backsheets. Thermal cycling in the TMA indicates the resilience and dimensional stability in the coextruded structures as opposed to the laminated structures. Lastly, results from a Module Accelerated Sequential Testing (MAST), are included to show the mechanical integrity of these backsheets after sequential exposure to stressors including damp heat, ultra-violet (UV) light radiation, and thermal cycling. The laminate backsheets deteriorated extensively after sequential exposure to these stressors, while the novel coextruded structures retained their physical properties.
14 SOLAR ENERGY↗
Ductile Glassy Polymer Networks Capable of Large Plastic Deformation and Heat-Induced Elastic Recovery
Many thermoplastic polymers are ductile by combining strength and large deformations. These deformations are irreversible - known as plastic deformation. Elastomers can deform reversibly but have low strength. To this end, we developed glassy and ductile polyamide networks capable of large plastic deformation (>200% strain) and high strength (~50 MPa tensile strength and ~1500 MPa Young’s modulus), similar to those of polyolefins and Nylon-66. We discovered that hydrogen bonding between meta-phthalamide groups was essential to the ductility. Since these polyamide networks are covalently bonded, we demonstrated their unique durability by repeatable elastic recovery at elevated temperatures, exhibiting indifferent tensile properties in each cycle. Furthermore, when we fixed the strain during the elastic recovery, these polyamide networks actuated stresses of 9–18 MPa, among the highest reported in shape-memory polymer actuators. Here, we envision these ductile, glassy polymer networks as promising alternatives to ductile thermoplastics, given the combined benefit of ductility and durability.
36 MATERIALS SCIENCE↗
Enzymatic Nylon Deconstruction: Enzyme Discovery, Engineering, and Opportunities
Nylons are widely used synthetic polyamides valued for their strength, versatility, and durability across diverse applications. However, their petrochemical origin and energy-intensive production underscore the need for efficient, circular solutions. Conventional recycling methods remain limited by incomplete recovery, material degradation, and costly sorting requirements. Enzymatic depolymerization offers a selective, low-energy alternative capable of processing mixed waste streams under mild conditions. While significant progress has been achieved for polyesters, enzymatic degradation of polyamides is still at an early stage. The discovery of nylon hydrolases demonstrated the potential of biological systems to evolve catalysts for synthetic polyamides, yet reported depolymerization yields remain low. These limitations reflect both the structural complexity of nylons and the need for improved enzyme discovery and engineering. In conclusion, this review highlights recent advances, key challenges, and future directions for enzymatic nylon recycling, outlining its potential role enabling mixed polymer waste to be used as a green feedstock for remanufacturing.
Amides↗
Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability
Aliphatic polyamides, or nylons, are typically highly crystalline and thermally robust polymers used in high-performance applications. Nylon 6, a high-ceiling-temperature (HCT) polyamide from e-caprolactam, lacks expedient chemical recyclability, while low-ceiling temperature (LCT) nylon 4 from pyrrolidone exhibits complete chemical recyclability, but it is thermally unstable and not melt-processable. Here, we introduce a hybrid nylon, nylon 4/6, based on a bicyclic lactam composed of both HCT ..epsilon..-caprolactam and LCT pyrrolidone motifs in a hybridized offspring structure. Hybrid nylon 4/6 overcomes trade-offs in (de)polymerizability and performance properties of the parent nylons, exhibiting both excellent polymerization and facile depolymerization characteristics. This stereoregular polyamide forms nanocrystalline domains, allowing optical clarity and high thermal stability, however, without displaying a melting transition before decomposition. Of a series of statistical copolymers comprising nylon 4/6 and nylon 4, a 50/50 copolymer achieves the greatest synergy in both reactivity and polymer properties of each homopolymer, offering an amorphous nylon with favorable properties, including optical clarity, a high glass transition temperature, melt processability, and full chemical recyclability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Beyond nothingness in the formation and functional relevance of voids in polymer films
Abstract Voids—the nothingness—broadly exist within nanomaterials and impact properties ranging from catalysis to mechanical response. However, understanding nanovoids is challenging due to lack of imaging methods with the needed penetration depth and spatial resolution. Here, we integrate electron tomography, morphometry, graph theory and coarse-grained molecular dynamics simulation to study the formation of interconnected nanovoids in polymer films and their impacts on permeance and nanomechanical behaviour. Using polyamide membranes for molecular separation as a representative system, three-dimensional electron tomography at nanometre resolution reveals nanovoid formation from coalescence of oligomers, supported by coarse-grained molecular dynamics simulations. Void analysis provides otherwise inaccessible inputs for accurate fittings of methanol permeance for polyamide membranes. Three-dimensional structural graphs accounting for the tortuous nanovoids within, measure higher apparent moduli with polyamide membranes of higher graph rigidity. Our study elucidates the significance of nanovoids beyond the nothingness, impacting the synthesis‒morphology‒function relationships of complex nanomaterials.
36 MATERIALS SCIENCE↗
Flame and acid resistant polymide fibers
Economical process improves flame resistance and resistance to acids of polyamide fibers, without modifying colors of mechanical properties. Process improves general safety of garments and other items made from polyamide fibers and makes them suitable for applications requiring exposure to oxygen-rich atmosphere or corrosive acids. Halo-olefins are added to surface of fibers by photoadditon in sealed chamber. Process could be used with films and other forms of polyamide.
Stringham, R. S.↗
Synthesis of aromatic secondary diamines
A series of N-methyl substituted aromatic polyamides derived from the secondary aromatic diamines, 4,4'-bis(methylamino)diphenylmethane, 3,3'-bis(methylamino) diphenylmethane, 4,4'-bis(methylamino)benzophenone or 3,3'-bis(methylamino)benzophenone and isophthaloyl dichloride, terphthaloyl dichloride or 3,3'diphenylmethane dicarboxylic acid dichloride was prepared by high temperature solution polymerization in s-tetrachloroethane. Compared to analogous unsubstituted and partially N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures, reduced crystallinity, improved thermal stability and good solubility in chlorinated solvents.
Wolfe, J. F.↗
Heat resistant protective hand covering
The heat resistant, protective glove is made up of first and second shell sections which define a palm side and a backside, respectively. The first shell section is made of a twill wave fabric of a temperature-resistant aromatic polyamide fiber. The second shell section is made of a knitted fabric of a temperature-resistant aromatic polyamide fiber. The first and second shell sections are secured to one another, e.g., by sewing, to provide the desired glove configuration and an opening for insertion of the wearer's hand. The protective glove also includes a first liner section which is secured to and overlies the inner surface of the first shell section and is made of a felt fabric of a temperature-resistant aromatic polyamide fiber and has a flame resistant, elastomenic coating on the surface facing and overlying the inner surface of the first shell section.
Sidman, K. R.↗
Polyimide/metal composite films via in situ decomposition of inorganic additives - Soluble polyimide versus polyimide precursor
Polyimide-metal oxide (Co3O4 or CuO) composite films have been prepared via in situ thermal decomposition of cobalt (II) chloride or bis(trifluoroacetylacetonato)copper(II). A soluble polyimide (XU-218) and its corresponding prepolymer (polyamide acid) were individually employed as the reaction matrix. The resulting composites exhibited a greater metal oxide concentration at the air interface with polyamide acid as the reaction matrix. The water of imidization that is released during the concurrent polyamide acid cure and additive decomposition is believed to promote metal migration and oxide formation. In contrast, XU-218 doped with either HAuCl4.3H2O or AgNO3 yields surface gold or silver when thermolyzed (300 C).
Rancourt, J. D.↗
Development of Polyimides-Based NLO Materials for Electrooptical Applications
Development of thermally stable optical materials for nonlinear optics have recently focused on the covalent incorporation of NLO chromophores into high performance polymers, especially thermally stable and processable polyamides. One key aspect for the incorporation of robust NLO chromophores into high Tg polymers is to sustain poling induced order. Other advantages include high loading level of chromophores, and elimination of possible phase separation as well as chromophore sublimation at processing or working temperature. We have prepared several polyimide based polymers which are covalently linked with thermally stable chromophores that we have developed, since polyamides generally exhibit high Tg and good film transparency. Here, we report the development and subsequent incorporation of indoline based chromophores into polyamides, leading to thermally stable NLO polymers.
Rutherford, Jacqueline↗
Linking water quality, fouling layer composition, and performance of reverse osmosis membranes
Fouling of polyamide membranes during reverse osmosis (RO) is a major challenge for adopting membrane technologies to treat highly contaminated waters, especially those containing organic foulants (e.g., natural organic matter (NOM), polysaccharides) and dominant cations (e.g., sodium, magnesium, calcium). Here, this work combines bench-scale membrane fouling experiments with detailed characterization of feedwater chemistry and fouling layer composition/morphology to reveal fundamental mechanisms of (in)organic fouling during RO. Divalent cations are shown to promote fouling by hydrophobic NOM containing aromatic and carboxyl groups, while NOM fouling in the presence of a monovalent cation, sodium, occurs by smaller fulvic acids containing larger fractions of carboxyl groups and other oxygen-rich moieties. Calcium-carboxyl bridging occurs in solution and near the membrane surface to induce NOM aggregation on nanometer length scales. In complex waters containing foulant mixtures, co-fouling by calcium-carboxyl bridging and CaCO 3 precipitation influence membrane performance at longer timeframes. However, the flux decline observed for the co-fouling mechanism was less significant than the sum of its parts, suggesting both synergistic and antagonistic fouling mechanisms should be considered in membrane design/operation. These results encourage the design of pretreatment processes to reduce concentrations of multivalent ions and hydrophobic NOM in RO feedwaters, and of membrane materials to limit attachment/deposition of aggregates to/on polyamide surfaces.
42 ENGINEERING↗
Toward a sustainable circular economy of multilayer plastic films: Life cycle and techno-economic assessment with a focus on end-of-life treatment and multiple recovery cycles
This study presents a life cycle assessment (LCA) and techno-economic analysis (TEA) of end-of-life technologies for treating polyethylene–polyamide barrier film waste, focusing on quality degradation across recovery cycles. Novel treatment methods are experimentally validated, while others are drawn from literature and industry consultations. A displacement approach, assuming no quality loss, is first applied. Results show that solvent-based recycling via the solvent-targeted recovery and precipitation (STRAP) process outperforms alternatives across environmental indicators, reducing global warming potential (GWP) by 40% compared to landfilling. Incineration performs worst in most categories, particularly eutrophication (80% higher than landfilling), due to nitrogen emissions. Experimentally validated downcycling (pelletizing) proves more economically viable. The assumption of infinite recoverability is overly optimistic. To address this, we propose a mathematical framework accounting for a finite number of recovery cycles. This refined model shows reduced GWP and cost savings for solvent recovery, making its benefits less pronounced than initially estimated. Sensitivity and uncertainty analyses reveal strong dependence on recovered material quality and solvent recovery efficiency, underscoring the need for optimized process design. Finally, hotspot analysis identifies greenhouse gas emissions from the polyamide supply chain as the dominant GWP contributor. In conclusion, the results underscore potential trade-offs across pathways and show that solvent-based recovery’s sustainability depends heavily on process conditions.
36 MATERIALS SCIENCE↗