Polymer Network Research Articles

Stereoscopic Polymer Network for Developing Mechanically Robust Flexible Perovskite Solar Cells with an Efficiency Approaching 25.

Flexible perovskite solar cells (pero-SCs) have the potential to overturn the application scenario of silicon photovoltaic technology. However, their mechanical instability severely impedes their practical applicability, and the corresponding intrinsic degradation mechanism remains unclear. In this study, we systematically analyzed the degradation behavior of flexible pero-SCs under mechanical stress and observed that the structural failure firstly occurs in the polycrystal perovskite film, then extend to interfaces. To suppress the structural failure, we employed pentaerythritol triacrylate, a crosslinked molecule with three stereoscopic crosslink sites, to establish a three-dimensional polymer network in both the interface and bulk perovskite. This network reduced the Young's modulus of the perovskite and simultaneously enhanced the interfacial toughness. As a result, the formation of cracks and delamination, which occur under a high mechanical stress, was significantly suppressed in the flexible pero-SC, which consequently retained 92% of its initial power conversion efficiency (PCE) after 20000 bending cycles. Notably, the flexible device also showed a record PCE of 24.9% (certified 24.48%). This article is protected by copyright. All rights reserved.

Swelling Behaviors of Natural Rubber/Solvent Systems Based on the Extended Modified Double Lattice Model

AbstractSwelling experiments are conducted on nonfiller natural rubber using four solvents (toluene, cyclohexane, tetrahydrofuran (THF), and methylethylketone (MEK)) over temperatures from 10 to 70 °C. Toluene, cyclohexane, and THF, classified as effective solvents, show swelling ratios between 3 and 7, influenced by the crosslink density of the rubber. MEK, however, has a lower ratio of 1.5 to 2. Temperature has a minor impact on swelling compared to the crosslink density. The study evaluates the Extended Modified Double Lattice (EMDL) model for its mixing contribution in polymer network swelling, aiming to improve the Flory–Hüggins (FH) model. The superiority of EMDL above FH is in the boundary condition at the unvulcanized state, the former aligning its interaction energy with values from solvent activities in primary linear polymer/solvent solutions, unlike the FH model. The EMDL model also accounts for oriented interactions in polar solvents through a secondary lattice, linking specific interaction energy with solvent dipole moments. The study observes a nonlinear correlation between crosslinking density and sulfur amount, proposing a nonrandom mixing at lower sulfur concentrations. This model shows strong alignment with experimental data, suggesting that replacing the FH model's mixing contribution with the EMDL model could improve results with minimal additional complexity.

Nested non-covalent interactions expand the functions of supramolecular polymer networks

Supramolecular polymer networks contain non-covalent cross-links that enable access to broadly tunable mechanical properties and stimuli-responsive behaviors; the incorporation of multiple unique non-covalent cross-links within such materials further expands their mechanical responses and functionality. To date, however, the design of such materials has been accomplished through discrete combinations of distinct interaction types in series, limiting materials design logic. Here we introduce the concept of leveraging “nested” supramolecular crosslinks, wherein two distinct types of non-covalent interactions exist in parallel, to control bulk material functions. To demonstrate this concept, we use polymer-linked Pd2L4 metal–organic cage (polyMOC) gels that form hollow metal–organic cage junctions through metal–ligand coordination and can exhibit well-defined host-guest binding within their cavity. In these “nested” supramolecular network junctions, the thermodynamics of host-guest interactions within the junctions affect the metal–ligand interactions that form those junctions, ultimately translating to substantial guest-dependent changes in bulk material properties that could not be achieved in traditional supramolecular networks with multiple interactions in series.

Polymerized Network-Based Artificial Peroxisome Reprogramming Macrophages for Photoacoustic Imaging-Guided Treatment of Rheumatoid Arthritis.

Artificial peroxisomes (AP) with enzyme-mimetic catalytic activity and recruitment ability have drawn a great deal of attention in fabricating protocell systems for scavenging reactive oxygen species (ROS), modulating the inflammatory microenvironment, and reprogramming macrophages, which is of great potential in treating inflammatory diseases such as rheumatoid arthritis (RA). Herein, a macrophage membrane-cloaked Cu-coordinated polyphthalocyanine-based AP (CuAP) is prepared with a macrocyclic conjugated polymerized network and embedded Cu-single atomic active center, which mimics the catalytic activity and coordination environment of natural superoxide dismutase and catalase, possesses the inflammatory recruitment ability of macrophages, and performs photoacoustic imaging (PAI)-guided treatment. The results of both in vitro cellular and in vivo animal experiments demonstrated that the CuAP under ultrasound and microbubbles could efficiently scavenge excess ROS in cells and tissues, modulate microenvironmental inflammatory cytokines such as interleukin-1β, tumor necrosis factor-α, and arginase-1, and reprogram macrophages by polarization of M1 (proinflammatory phenotype) to M2 (anti-inflammatory phenotype). We believe this study offers a proof of concept for engineering multifaceted AP and a promising approach for a PAI-guided treatment platform for RA.

Multifunctional coating films of gelatin/d-glucose/agarose reinforced by Piper L. leaf extract: Physicochemical properties and mandarin preservation

Eco-friendly, active, non-toxic coatings have recently been considered as a feasible approach for enhancing the storability of post-harvest produce, which deal with global problem from environmental pollutions of chemical uses and petro-based plastics. In this interest, the present work is to the development of multifunctional coating films through blending gelatin, agarose, d-glucose, and Piper betle L. extract before being applied for preserving ‘Duong’ mandarin. As compared to single addition of agarose, the co-supplement of agarose and d-glucose was considered to be more efficient in revitalizing the mechanical strength and surface hydrophobicity of the neat gelatin, which highlighted a vital role of d-glucose in the polymeric network. Interestingly, gelatin/d-glucose/agarose formulated with Piper betle L. extract showed greater mechanical strength, flexibility, UV-shielding, solubility, antibacterial and antioxidant activities than gelatin/d-glucose/agarose coating films. Considerably, the antibacterial property of such active films/coatings was found to even better after being aged for 30 days at the room temperature (25 °C). Based on initial screening, the gelatin/agarose/d-glucose coating formulation included with 2 % (w/w) Piper betle L. extract presenting the best mechanical strength (2.46 MPa), flexibility (31.03 %), and antioxidant activity (IC50 = 37.45 μg/mL) along with the adequate tested bacterial inhibition, was applied for ready-to-eat mandarin preservation. The significant improvement in visual appearance and peel color was recorded for the mandarin coated with gelatin/agarose/d-glucose/Piper betle L. extract (2 %, w/w) after 17-d storage at 20 °C and 64 %RH, which exhibited the lowest mass loss and total soluble solids.

Deciphering the factors influencing electric field mediated polymerization and depolymerization at the solution–solid interface

Strong and oriented electric fields are known to influence structure as well as reactivity. The strong electric field (EF) between the tip of a scanning tunneling microscope (STM) and graphite has been used to modulate two-dimensional (2D) polymerization of aryl boronic acids where switching the polarity of the substrate bias enabled reversible transition between self-assembled molecular networks of monomers and crystalline 2D polymer (2DP) domains. Here, we untangle the different factors influencing the EF-mediated (de)polymerization of a boroxine-based 2DP on graphite. The influence of the solvent was systematically studied by varying the nature from polar protic to polar aprotic to non-polar. The effect of monomer concentration was also investigated in detail with a special focus on the time-dependence of the transition. Our experimental observations indicate that while the nucleation of 2DP domains is not initiated by the applied electric field, their depolymerization and subsequent desorption, are a consequence of the change in the polarity of the substrate bias within the area scanned by the STM tip. We conclude that the reversible transition is intimately linked to the bias-induced adsorption and desorption of the monomers, which, in turn, could drive changes in the local concentration of the monomers.

Synthesis of PDMS Chain Structure with Introduced Dynamic Covalent Bonding for High‐Performance Rehealable Tactile Sensor Application

AbstractIn addressing the increasing demand for wearable sensing systems, the performance and lifespan of such devices must be improved by enhancing their sensitivity and healing capabilities. The present work introduces an innovative method for synthesizing a healable disulfide bond contained in a polydimethylsiloxane network (PDMS−SS) that incorporates ionic salts, which is designed to serve as a highly effective dielectric layer for capacitive tactile sensors. Within the polymer network structure, the cross‐linking agent pentaerythritol tetrakis 3‐mercaptopropionate (PTKPM) forms reversible disulfide bonds while simultaneously increasing polymer softness and the dielectric constant. The incorporation of dioctyl sulfosuccinate sodium salt (DOSS) significantly improves the capacitance and sensing properties by forming an electrical double‐layer through interactions between the electrode charge and salt ions at the contact interface. The developed polymer material‐based tactile sensor shows a strong response signal at low pressure (0.1 kPa) and maintains high sensitivity (0.175 kPa−1) over a wide pressure range (0.1–10 kPa). It also maintains the same sensitivity over 10 000 repeated applications of external pressure and is easily self‐healed against mechanical deformation due to the dynamic disulfide covalent bonding, restoring ≈95% of its detection capacity.

Rugged Island-Bridge Inorganic Electronics Mounted on Locally Strain-Isolated Substrates.

Various strain isolation strategies that combine rigid and stretchable regions for stretchable electronics were recently proposed, but the vulnerability of inorganic materials to mechanical stress has emerged as a major impediment to their performance. We report a strain-isolation system that combines heteropolymers with different elastic moduli (i.e., hybrid stretchable polymers) and utilize it to construct a rugged island-bridge inorganic electronics system. Two types of prepolymers were simultaneously cross-linked to form an interpenetrating polymer network at the rigid-stretchable interface, resulting in a hybrid stretchable polymer that exhibited efficient strain isolation and mechanical stability. The system, including stretchable micro-LEDs and microheaters, demonstrated consistent operation under external strain, suggesting that the rugged island-bridge inorganic electronics mounted on a locally strain-isolated substrate offer a promising solution for replacing conventional stretchable electronics, enabling devices with a variety of form factors.

A Rational Design of Bio-Derived Disulfide CANs for Wearable Capacitive Pressure Sensor.

Classic approaches to integrate flexible capacitive sensor performance are to on-demand microstructing dielectric layers and to adjust dielectric material compositions via the introduction of insoluble carbon additives (to increase sensitivity) or dynamic interactions (to achieve self-healing). However, the sensor's enhanced performances often come with the increased material complexity, discouraging its circular economy. Herein, we introduce a new intrinsic self-healable, closed-loop recyclable dielectric layer material, a fully nature-derived dynamic covalent poly(disulfide) decorated with rich H bonding and metal-catechol complexations. The polymer network possesses a mechanically ductile character with an Arrhenius-like dependent viscoelasticity. The assembled capacitive pressure sensor is able to achieve a sensitivity up to 9.26 kPa-1, fast response/recovery times of 32/24ms, and could deliver consistent signals of continuous consecutive cycles even after being self-healed or closed-loop recycled for real-time detection of human motions. This is expected to be of high interest for current capacitive sensing research to move towards a life-like, high performance and circular economy direction. This article is protected by copyright. All rights reserved.

Bulk transparent supramolecular glass enabled by host–guest molecular recognition

Supramolecular glass is a non-covalently cross-linked amorphous material that exhibits excellent optical properties and unique intrinsic structural features. Compared with artificial inorganic/organic glass, which has been extensively developed, supramolecular glass is still in the infancy stage, and itself is rarely recognized and studied thus far. Herein, we present the development of the host–guest molecular recognition motifs between methyl-β-cyclodextrin and para-hydroxybenzoic acid as the building blocks of supramolecular glass. Non-covalent polymerization resulting from the host–guest complexation and hydrogen bonding formation enables high transparency and bulk state to supramolecular glass. Various advantages, including recyclability, compatibility, and thermal processability, are associated with dynamic assembly pattern. Short-range order (host–guest complexation) and long-range disorder (three dimensional polymeric network) structures are identified simultaneously, thus demonstrating the typical structural characteristics of glass. This work provides a supramolecular strategy for constructing transparent materials from organic components.

Functional Soft Materials with Resistance to Liquid Leakage for Thermal Energy Storage

AbstractFunctional soft materials have great potential commercial applications in thermal energy storage, which are required to have a long life, good flexibility, and resistance to liquid leakage. Herein, a composite hydrogel with thermal storage properties is prepared through coupling molecular self‐assembly and in situ polymerization. Hydrophobic stearic acid (SA), as a thermal storage phase change material (PCM), is dispersed in polyacrylamide (PAM) hydrogel network in the form of oil–water emulsion (O/W). The PAM polymer network with good flexibility physically limits high‐frequency collision between SA PCM droplets. This unique design avoids demulsification in phase change emulsion so that the as‐prepared hydrogel composite can resist liquid leakage. The PAM hydrogel network plays the role of heterogeneous nucleation, resulting in the super‐cooling of SA emulsion at only 0.3 °C. On the other hand, SA PCM droplets in as‐prepared soft material do not directly contact with liquid water, so melting/crystallization process is independent of water. As a result, the soft material exhibits a thermal storage density of up to 99.3 J g−1. The present study is an important step toward designing soft energy storage materials.

Effect of Cross-Link Homogeneity on the High-Strain Behavior of Elastic Polymer Networks

Effect of Cross-Link Homogeneity on the High-Strain Behavior of Elastic Polymer Networks

Unleashing the potential of Cajanus cajun biochar polymer composite for Cu (II) removal: mechanism, modification, and application.

This study introduces a cost-effective approach to fabricating a porous and ionically surface-modified biochar-based alginate polymer networks composite (SBPC) through air drying. The study critically analyzes the role and concentrations of various components in the success of SBPC. Characterization techniques were employed to evaluate the microstructure and adsorption mechanism, confirming the ability of the adsorbent's carboxyl and hydroxyl groups to eliminate various heavy metal ions in water simultaneously. The SBPC demonstrated high copper binding capacities (937.4mg/g and 823.2mg/g) through response surface methodology (RSM) and column studies. It was also influential in single and natural systems, exhibiting competitive behavior and efficient removal of Cu2+. The Langmuir isotherm and pseudo-second-order kinetics strongly correlate with experimental data, with R2 values of 0.98 and 0.99, respectively. SBPC showed remarkable stability, up to 10 desorption cycles, and achieved 98% Cu2+ adsorption efficiency and 91.0% desorption. Finally, the cost analysis showed a cost of 125.68 INR/kg or 1.51 USD/kg, which is very low compared to the literature. These results highlight the potential of SPBC and show that it provides an efficient and cost-effective solution for removing Cu2+ from a real system.

Advanced Pyrene Copolymer/rGO Hydrogels for Efficient Congo Red Removal from Aqueous Systems

AbstractThis study investigates the use of hydrogel semi‐interpenetrating polymer networks (semi IPN) as efficient adsorbents for removing the dye congo red (CR) from aqueous solutions. Specifically, three hydrogel semi IPN, namely AH0–AH2, were synthesized through redox polymerization of acrylamide, polyethylenimine, polyhydroxylethylmethacrylate and (pyren‐1‐yl)methyl methacrylate/2‐acrylamido‐2‐methylpropane‐1‐sulfonic acid copolymer (pyrene−AMPS) using a reduced graphene oxide (RGO)‐N,N’‐methylene‐bis(acrylamide) (MBA)‐based crosslinker (GABC). Results indicated that these hydrogels were efficient in removing CR at pH 6.73, with the adsorption behaviour conforming to the Langmuir isotherm. This suggests a monolayer adsorption pattern, indicating a chemical nature. Thermodynamic analysis supports the practical feasibility of this process. The negative Gibbs free energy of adsorption (ΔG̊) indicates that adsorption is spontaneous and favorable. Conversely, the positive standard entropy of adsorption (ΔS̊) suggests an increase in molecular randomness during the process. Additionally, the standard enthalpy change (ΔH̊) suggests an endothermic activation energy for the binding process. Response Surface Methodology (RSM), utilizing four variables was employed to optimize the removal of CR. The model demonstrated high R2‐values and strong agreement between experimental and projected results, affirming its reliability. AH1 and AH2 showed significant efficacy in removing CR dye from aqueous solutions, underscoring their potential application in wastewater remediation.

A Lithium‐Affinitive Covalent Organic Polymer Network Functionalized Separator for Dendrite‐Free and High‐Durability Lithium–Sulfur Batteries under Harsh Conditions

AbstractLithium–Sulfur (Li─S) batteries are renowned for their high theoretical specific capacity and cost‐effectiveness. Nevertheless, their performance could be impeded by obstacles including lithium dendrite growth and lithium polysulfide (LiPS) shuttle, particularly under harsh conditions. Herein, an economical strategy is reported for modifying polyolefin separators (PP) with covalent organic polymer networks (TPE) to alter Li solvent structure, enhance lithium‐ion transport, and suppress shuttle effects. Combining in situ/ex situ characterization and theoretical calculations, it is demonstrated that the lithiophilic groups (‐C═N‐) in the TPE@PP separator form strong interaction with lithium, facilitating the dissociation of Li─Solvent/LiPS‐solvent to release freer lithium ion and shape a stable solid electrolyte interface rich in LiF and Li3N. The polymer network serves as a “highway” that accelerates Li transport and promotes uniform nucleation behavior. Therefore, the Li|TPE@PP|CNT/S cell enables 60% capacity retention after 2000 cycles at 1.0 C and exhibits stable cycling performance of 100 cycles from ‐40 to 80 °C. Moreover, the pouch cell maintains a capacity of more than 600 mA h g−1 after 30 cycles at 0 °C. This study provides a promising avenue for the application of high‐performance batteries in harsh environment from the perspective of separator engineering.

Combination of NIR and UV‐LEDs Enables Physical and Chemical Drying of Aqueous Coating Dispersions as New Green Technology

AbstractHeptamethine based cyanines, namely 1,3,‐trimethyl‐2‐(2‐2[2‐phenylsulfanyl‐3‐[2‐(1,3,3‐trimethyl‐1,3,3‐trithyl‐1,3‐dihydro‐indol‐2‐ylidene)‐ethylidene]cyclohex‐1‐enyl]vinyl)‐3H‐indolium chloride (S1) and 2‐[2‐(2‐chloro‐[2‐[1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1,3‐dihydro‐benzo[e]indol‐2‐ylidene]‐ethylidene]cyclopent‐1‐enyl]vinyl]‐1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1Hbenzo[e]indolium hydroxide, inner salt, triethylammonium salt (S2), efficiently result in physical drying of an aqueous dispersion comprising a polyurethane binder. S2 possesses a water solubility of 40 g/L. A high‐intensity NIR‐LED emitting at 820 nm with an intensity of 1 W/cm2 served as light source. The cyanine converted the light absorbed into heat by internal conversion needing less drying time compared to conventional drying. Water content after film formation showed less then 1%. In the second step, UV exposure with a LED emitting at 395 nm resulted in formation of semi‐interpenetrating polymer networks by crosslinking of the multifunctional (meth)acrylate operating as reactive diluent. TPO‐L served as effective UV‐photoinitiator. Furthermore, the UV‐exposure together with Norrish Type I and Type II photoinitator systems results in a very efficient bleaching of the green physical dried film. This contribution shows for the first time a new photonic hybrid technique describing successful replacement of an oven‐based process by a photonic based step that generates heat needed for drying.This article is protected by copyright. All rights reserved.

Real and In Silico Microgels Show Comparable Bulk Moduli Below and Above the Volume Phase Transition.

The compressibility of soft colloids influences their phase behavior and flow properties, especially in concentrated suspensions. Particle compressibility, which is proportional to the reciprocal of the bulk modulus K, is a key parameter for soft polymer-based particles that can be compressed in crowded environments. Here, microgels with different degrees of cross-linking, i.e.,softness, are investigated below and above their volume phase transition temperature (VPTT). By combining molecular dynamics simulations with small-angle neutron scattering with contrast variation, a change in the particle bulk moduli of two orders of magnitude is observed. The degree of cross-linking has a significant impact on the bulk modulus of the swollen microgel, while above the VPTT the values of K are almost independent of the cross-linking density. The excellent agreement between experimental results and simulations also highlight that the model microgels from computer simulationspossess both the internal architecture and the elastic properties of real polymeric networks. This paves the way to a systematic use of simulations to investigate the behavior of dense microgelsuspensions below and above their VPTT.

Recent Trends of Recycling and Upcycling of Polymers and Composites: A Comprehensive Review

This review article gathers the most recent recycling technologies for thermoset and thermoplastic polymers. Results about existing experimental procedures and their effectiveness are presented. For thermoset polymers, the review focuses mainly on fibre-reinforced polymer composites, with an emphasis on epoxy-based systems and carbon/glass fibres as reinforcement, due to the environmental concerns of their end-of-life management. Thermal processes (fluidised bed, pyrolysis) and chemical processes (different types of solvolysis) are discussed. The most recent combined processes (microwave, steam, and ultrasonic assisted techniques) and extraordinary recycling attempts (electrochemical, biological, and with ionic liquids) are analysed. Mechanical recycling that leads to the downgrading of materials is excluded. Insights are also given for the upcycling methodologies that have been implemented until now for the reuse of fibres. As for thermoplastic polymers, the most state-of-the-art recycling approach for the most common polymer matrices is presented, together with the appropriate additivation for matrix upcycling. Mechanical, chemical, and enzymatic recycling processes are described, among others. The use of fibre-reinforced thermoplastic composites is quite new, and thus, the most recent achievements are presented. With all of the above information, this extensive review can serve as a guide for educational purposes, targeting students and technicians in polymers recycling.

Improved Mechanical Strength without Sacrificing Li-Ion Transport in Polymer Electrolytes.

Next-generation batteries demand solid polymer electrolytes (SPEs) with rapid ion transport and robust mechanical properties. However, many SPEs with liquid-like Li+ transport mechanisms suffer a fundamental trade-off between conductivity and strength. Dynamic polymer networks can improve bulk mechanics with minimal impact to segmental relaxation or ionic conductivity. This study demonstrates a system where a single polymer-bound ligand simultaneously dissociates Li+ and forms long-lived Ni2+ networks. The polymer comprises an ethylene oxide backbone and imidazole (Im) ligands, blended with Li+ and Ni2+ salts. Ni2+-Im dynamic cross-links result in the formation of a rubbery plateau resulting in, consequently, storage modulus improvement by a factor of 133× with the introduction of Ni2+ at rNi = 0.08, from 0.014 to 1.907 MPa. Even with Ni2+ loading, the high Li+ conductivity of 3.7 × 10-6 S/cm is retained at 90 °C. This work demonstrates that decoupling of ion transport and bulk mechanics can be readily achieved by the addition of multivalent metal cations to polymers with chelating ligands.

Understanding the Mechanochemistry of Mechano-Radicals in Self-Growth Materials by Single-Molecule Force Spectroscopy.

Recent research on mechano-radicals has provided valuable insights into self-growth and adaptive responsive materials. Typically, mechanophores must remain inert in the absence of force but respond quickly to external tension before other linkages within the polymer network. Azo compounds exhibit promising combinations of mechanical stability and force-triggered reactivity, making them widely used as mechano-radicals in force-responsive materials. However, the activation conditions and behavior of azo compounds have yet to be quantitatively explored. In this study, we investigated the mechanical strength of three azo compounds using single-molecule force spectroscopy. Our results revealed that these compounds exhibit rupture forces ranging from ~500 to 1000 pN, at a loading rate of 3×104 pN s-1. Importantly, these mechanophores demonstrate distinct kinetic properties. Their unique mechanical attributes enable azo bond scission and free radical generation before causing major polymer backbone damage of entire material during polymer network deformation. This fundamental understanding of mechanophores holds significant promise for the development of self-growth materials and their related applications.