Tough Polymer Research Articles

Mechanically Interlocked Polymers with Dense Mechanical Bonds.

ConspectusMechanically interlocked polymers (MIPs) such as polyrotaxanes and polycatenanes are polymer architectures that incorporate mechanical bonds, which represent a compelling frontier in polymer science. MIPs with cross-linked structures are known as mechanically interlocked networks (MINs) and are widely utilized in materials science. Leveraging the motion of mechanical bonds, MINs hold the potential for achieving a combination of robustness and dynamicity. Currently, the reported MINs predominantly consist of networks with discrete mechanical bonds as cross-linking points, exemplified by well-known slide-ring materials and rotaxane/catenane cross-linked polymers. The motion of these mechanically interlocked cross-linking points facilitates the redistribution of tension throughout the network, effectively preventing stress concentration and thereby enhancing material toughness. In these instances, the impact of mechanical bonds can be likened to the adage "small things can make a big difference", whereby a limited number of mechanical bonds substantially elevate the mechanical performance of conventional polymers. In addition to MINs cross-linked by mechanical bonds, there is another type of MIN in which their principal parts are polymer chains composed of dense mechanical bonds. Within these MINs, mechanical bonds generally serve as repeating units, and their unique properties stem from integrating and amplifying the function of a large amount of mechanical bonds. Consequently, MINs with dense mechanical bonds tend to reflect the intrinsic properties of mechanical interlocked polymers, making their exploration critical for a comprehensive understanding of MIPs. Nevertheless, investigations into MINs featuring dense mechanical bonds remain relatively scarce.This Account presents a comprehensive overview of our investigation and insights into MINs featuring dense mechanical bonds. First, we delve into the synthetic strategies employed to effectively prepare MINs with dense mechanical bonds, while critically evaluating their advantages and limitations. Through meticulous control of the core interlocking step, three distinct strategies have emerged: mechanical interlocking followed by polymerization, supramolecular polymerization followed by mechanical interlocking, and dynamic interlocking. Furthermore, we underscore the structure-property relationships of MINs with dense mechanical bonds. The macroscopic properties of MINs originate from integrating and amplifying countless microscopic motions of mechanical bonds, a phenomenon we define as an integration and amplification mechanism. Our investigation has revealed detailed motion characteristics of mechanical bonds in bulk mechanically interlocked materials, encompassing the quantification of motion activation energy, discrimination of varying motion distances, and elucidation of the recovery process. Additionally, we have elucidated their influence on the mechanical performance of the respective materials. Moreover, we have explored potential applications of MINs, leveraging their exceptional mechanical properties and dynamicity. These applications include enhancing the toughness of conventional polymers, engineering mechanically adaptive and multifunctional aerogels, and mitigating Li protrusion as interfacial layers in lithium-ion batteries. Finally, we offer our personal perspectives on the promises, opportunities, and key challenges in the future development of MINs with dense mechanical bonds, underscoring the potential for transformative advancements in this burgeoning field.

Closed-loop recycling of carbon-fiber-reinforced polymers

A new process allows full recovery of starting materials from tough polymer composites.

Highly Stretchable and Self-Healable Tough Polymer Elastomer through Dy3+ and Cu2+ Coordination Cross-Linking

Highly Stretchable and Self-Healable Tough Polymer Elastomer through Dy³⁺ and Cu²⁺ Coordination Cross-Linking

Synthesis of Tough and Fluorescent Self-Healing Elastomers by Scandium-Catalyzed Terpolymerization of Pyrenylethenylstyrene, Ethylene, and Anisylpropylene.

The synthesis of fluorescent self-healing polymers by the incorporation of a fluorophore-containing olefin into a polyolefin backbone through catalyst-controlled multicomponent copolymerization is of fundamental interest and practical importance, but such an approach has remained unexplored to date. Herein, we report for the first time the synthesis of tough and fluorescent self-healing polymers by sequence-controlled terpolymerization of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP) using a sterically demanding half-sandwich scandium catalyst. The resulting terpolymers consisted of relatively long alternating E-alt-AP sequences, isolated Pyr units, and short E-E blocks, which exhibited excellent tensile strength, remarkable self-healability, and high fluorescence quantum yield. The excellent mechanical and self-healing properties could be attributed to the nanophase separation of the crystalline E-E segments and the hard Pyr aggregates from a flexible E-alt-AP segment matrix, in which the Pyr units not only served as an efficient fluorophore but also played an important role in forming nanodomains and enhancing the polymer mobility. Furthermore, the styrenyl C═C bond of the Pyr unit in the terpolymers could undergo [2 + 2] cycloaddition under photoirradiation, which thus enabled the fabrication of a self-healable fluorescent two-dimensional image on a terpolymer film through photolithography. This work offers an unprecedented efficient protocol for the synthesis of a brand-new family of fluorescent self-healing materials, showcasing the high potential of catalyst-controlled sequence-regular copolymerization of different olefins for the creation of novel functional polymers.

Enhancing the Toughness and Strength of Polymers Using Mechanically Interlocked Hydrogen Bonds.

The energy dissipative features of hydrogen bonds under conditions of mechanical strain have provided an ongoing incentive to explore hydrogen bonding units for the purpose of controlling and customizing the mechanical properties of polymeric materials. However, there remains a need for hydrogen bond units that (1) possess directionality, (2) provide selectivity, (3) dissipate energy effectively, and (4) can be incorporated readily into polymeric materials to regulate their mechanical properties. Here, we report mechanically interlocked hydrogen bond units that incorporate multiple hydrogen bonds within a [2]catenane structure. The conformational flexibility and associated spatial folding characteristics of the [2]catenane units allow for molecular scale motion under external stress, while the interlocked structure serves as a pivot that maintains the directionality and selectivity of the resultant hydrogen bonding units. When incorporated into polymers, these interlocked hydrogen bond motifs serve to strengthen and toughen the resulting materials. This study not only presents a novel hydrogen bond unit for creating polymeric materials with improved mechanical properties but also underscores the unique opportunities that mechanically interlocked hydrogen bond structures may provide across a diverse range of applications.

Tailored Catalysis Inducing Exceptionally Fire-Safe and Mechanically Reinforced Epoxy at An Ultralow Loading.

An unconventional P/N/Si-free fire safety of epoxy at an ultralow loading with a significantly improved mechanical robustness and toughness via a mere nanocomposite technique is a great challenge. To achieve the goal, a proof of concept is proposed associated with a hierarchical manipulation of catalysis-tailored FexSy ultrathin nanosheets on organic-layered double hydroxide (LDH-DBS@FexSy) toward the formation of porous piling structure via a self-sacrificing conversion of metal-organic framework. A sufficient characterization certified the targeted architecture and composition. A P/N/Si-free ultralow loading of 2 wt % LDH-DBS@FexSy (i.e., 0.6 wt % FexSy) imparted epoxy with UL-94 V-0 rating, a 36.1% reduction of peak heat release rate, as well as a pronounced fire-protection feature. A systematic contrastive investigation evidenced a time-dependent fire-shielding effect induced by a featured catalysis-tailored ultrafast charring behavior at the interface of epoxy and LDH nanosheets. Intriguingly, the tensile strength, impact strength, and flexural strength were simultaneously enhanced by 62.2, 185.4, and 62.9%, respectively, with a 0.6 wt % incorporation of FexSy hierarchy on the basis of a "root-soil"-inspired interfacial "interlocking" structure. In perspective, an integrated manipulation of an interface catalysis-tailored ultrafast charring and hierarchical "interlocking" construction offer an effective balance of the fire safety, mechanical robustness, and toughness of polymers.

Virtual Fatigue Behaviour Analysis of Coir Fibre-Reinforced PVC Composites

PVC (polyvinyl chloride) is a tough polymer used in applications, including plumbing and construction materials. As natural fibre-reinforced composites have more advantages over conventional synthetic composites, this paper focuses on the fatigue analysis of PVC composite which is reinforced with coir fibre. The influences of three input parameters, namely, the size of the coir fibre, coir fibre content, and the chemicals that are used in the treatment of coir fibre on the fatigue life of the composite are examined. In the response surface model (RSM), Box-Behnken designs (BBD) are employed for the preparation/analysis/optimization of the samples. ANSYS software is used to perform the fatigue analysis of different samples containing various combinations of the parameters. To determine the effects of various input parameters on the fatigue behaviour of composites, ANOVA is employed to determine their optimal levels. Regression equations are established to determine the fatigue limit. When treated with triethoxy(ethyl)silane, coir with a concentration of 6 wt.% and a particle size of 75 μm exhibits a maximum fatigue limit of 2.819 MPa.

Anomalous scaling law of strength and toughness in polymers with strong interfacial secondary bonds

In materials design, the increase of toughness usually leads to the decrease of strength, which is a long-standing challenge. Polymeric materials with strong interfacial secondary bonds have recently emerged as promising solutions due to their remarkable capabilities to increase toughness and strength simultaneously. Nevertheless, a quantitative understanding on how toughness increases with strength is unavailable, posing challenges for deeper understanding and on-demand design for stronger and tougher advanced materials. In this work, we reveal a quadratic scaling law of simultaneously increased strength and toughness that unifies multiscale evidences from theories, computations and experiments across multiple material systems, where the deformation mechanisms are dominated by breaking and reforming of interfacial secondary bonds. Our results highlight the significance of interfacial secondary bonding combined with topology design to enable a wide range of strong and tough advanced materials.

Thermomechanical study on toughened PVC with an impact modifier based on the acrylonitrile-styrene-acrylate core-shell particles

Development of impact modifiers with the core-shell structure for enhancing toughness of rigid polymers have attracted a great deal of interest. In this study, poly (butyl acrylate) (PBA) as the core was prepared via emulsion polymerization and subsequently grafted with styrene and acrylonitrile (SAN) to construct the shell layer through seeded emulsion polymerization and to produce ASA particles. Then, ASA particles containing 40, 50, and 60 wt% of PBA core and those with non-crosslinked shell were compounded with PVC through melt-blending technique in different compositions. DLS, SEM and TEM analyses revealed uniform spherical core-shell morphologies with average particle size of 170–190 nm. Cross-sectional SEM images exhibited a well-distribution and dispersion of ASA particles in PVC matrix relative to the non-crosslinked one. This can be attributed to the formation and grafting of the rigid thermoplastic SAN layer on the PBA core. Impact results of the prepared compounds showed an increasing trend with the increase in core content and also amount of ASA. The highest impact strength (135 kJ/m2) was found for the compound containing 15 wt% of ASA (with 60 wt% of PBA core) particles, which was 26 times higher than the neat PVC (5 kJ/m2). A comparative study between PVC compounds demonstrated higher heat deformation temperature, elastic modulus, and impact strength for those containing ASA with the crosslinked shell. Remarkable compatibility with PVC matrix and enhancement in thermomechanical properties for the prepared core-shell ASA particles revealed their promising potential for toughening of PVC.

Strain-induced crystallization and phase separation used for fabricating a tough and stiff slide-ring solid polymer electrolyte.

The demand for mechanically robust polymer-based electrolytes is increasing for applications to wearable devices. Young's modulus and breaking energy are essential parameters for describing the mechanical reliability of electrolytes. The former plays a vital role in suppressing the short circuit during charge-discharge, while the latter indicates crack propagation resistance. However, polymer electrolytes with high Young's moduli are generally brittle. In this study, a tough slide-ring solid polymer electrolyte (SR-SPE) breaking through this trade-off between stiffness and toughness is designed on the basis of strain-induced crystallization (SIC) and phase separation. SIC makes the material highly tough (breaking energy, 80 to 100 megajoules per cubic meter). Phase separation in the polymer enhanced stiffness (Young's modulus, 10 to 70 megapascals). The combined effect of phase separation and SIC made SR-SPE tough and stiff, while these mechanisms do not impair ionic conductivity. This SIC strategy could be combined with other toughening mechanisms to design tough polymer gel materials.

Resilient and Tough Conductive Polymer Hydrogel for a Low-Hysteresis Strain Sensor.

Conductive polymer hydrogels are vital in strain sensors, yet achieving high resilience and toughness is a challenge. This study employs a prestretch method to engineer a tough conductive polymer hydrogel with sufficient resilience. Initially, a blend film of polyvinylalcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH) is prepared through solution casting, followed by a swelling process to form a PVA-EVOH hydrogel. This hydrogel, with PVA crystallites as crosslinking points, exhibits high toughness. The hydrogel is then immersed in pyrrole and ferric chloride solutions for in-situ polymerization of polypyrrole (PPy), creating a conductive PPy/PVA-EVOH hydrogel. Finally, a 200% prestretch is applied, breaking short chains within the network, eliminating energy dissipation at low strains. This results in a hydrogel with a 100% elastic deformation range, while maintaining high fracture toughness (1700Jm-2 ). The prestretched PPy/PVA-EVOH hydrogel functions as a strain sensor with low hysteresis, providing consistent strain measurements during loading and unloading. This outperforms the non-prestretched sample, which shows inconsistent responses between stretching and releasing.

Hierarchical MXene@PBA nanohybrids towards high-efficiency flame retardancy and smoke suppression of robust yet tough polymer nanocomposites at ultra-low additions

Developing efficient flame-retardant MXene-based polymeric materials with enhanced mechanical properties has been a huge challenge. Herein, Prussian blue analogues (PBAs) were used to modify the surface of MXene nanosheets via an electrostatic self-assembly method to construct hierarchical MXene-based nanohybrids (MXene@PBA). Then, MXene@PBA was incorporated into the epoxy matrix to fabricate high-performance epoxy nanocomposites (EP-MXene@PBA). The study indicates that hierarchical MXene@PBA exhibits excellent dispersion performance in the epoxy matrix. Notably, MXene@PBA results in high-efficiency flame retardancy and smoke suppression for epoxy nanocomposites at ultra-low additions. What is very surprising is that only 1.0 wt% MXene@PBA can easily enhance the UL-94 rating of EP-1.0%MXene@PBA to V0. Meanwhile, the peak heat release rate (pHRR), total smoke production (TSP), and peak CO production rate (pCO) are remarkably reduced by 36.70%, 34.28%, and 43.48%, compared to those of the pristine epoxy resin, respectively. Furthermore, the 1.0 wt% MXene@PBA nanohybrids can enhance the flexural and impact strengths of EP-1.0%MXene@PBA. This work provides a feasible strategy for the creation of multifunctional MXene derivatives and their polymeric nanocomposites and holds great promise for many industrial applications.

Sacrificial Mechanical Bond is as Effective as a Sacrificial Covalent Bond in Increasing Cross-Linked Polymer Toughness.

Sacrificial chemical bonds have been used effectively to increase the toughness of elastomers because such bonds dissociate at forces significantly below the fracture limit of the primary load-bearing bonds, thereby dissipating local stress. This approach owes much of its success to the ability to adjust the threshold force at which the sacrificial bonds fail at the desired rate, for example, by selecting either covalent or noncovalent sacrificial bonds. Here, we report experimental and computational evidence that a mechanical bond, responsible for the structural integrity of a rotaxane or a catenane, increases the elastomer's fracture strain, stress, and energy as much as a covalent bond of comparable mechanochemical dissociation kinetics. We synthesized and studied 6 polyacrylates cross-linked by either difluorenylsuccinonitrile (DFSN), which is an established sacrificial mechanochromic moiety; a [2]rotaxane, whose stopper allows its wheel to dethread on the same subsecond time scale as DFSN dissociates when either is under tensile force of 1.5-2 nN; a structurally homologous [2]rotaxane with a much bulkier stopper that is stable at force >5.5 nN; similarly stoppered [3]rotaxanes containing DFSN in their axles; and a control polymer with aliphatic nonsacrificial cross-links. Our data suggest that mechanochemical dethreading of a rotaxane without failure of any covalent bonds may be an important, hitherto unrecognized, contributor to the toughness of some rotaxane-cross-linked polymers and that sacrificial mechanical bonds provide a mechanism to control material fracture behavior independently of the mechanochemical response of the covalent networks, due to their distinct relationships between structure and mechanochemical reactivity.

Modified poly(phenylene oxide)/(CaSr)TiO3 composites with ultrahigh permittivity and low loss for microwave substrates

Polymer/ceramic composites used as microwave dielectric combine the excellent dielectric properties of ceramic with the toughness of polymer. The properties of composites are not only determined by the properties of components but also influenced by the polymer-ceramic interface. In this work, we conducted experiments and simulations on the dielectric properties and thermal conductivity of modified poly(phenylene oxide)/(CaSr)TiO3 (mPPO/CST) composites. A comparison of composites filled with different sizes (2.5, 11, and 20 µm) of CST fillers demonstrates that smaller particle (more filler-matrix interface) is beneficial to mechanical properties but detrimental to dielectric properties and heat transfer. The finite element simulation results are in good agreement with the experimental values, which is of significance for guiding future experiments. The composite filled with 80 wt. % CST20 has a high relative density of 97%, an ultrahigh εr of ∼20, and a low tan δ of 0.0019 at 10 GHz. Meanwhile, the mPPO/CST composites are eco-friendly and suitable for mass production and are promising candidates for automotive and aerospace applications.

A facile strategy to improve the strength and toughness of high-performance polymers and recycling by dynamic Ni-coordination crosslinking

It is of great significance to enhance mechanical properties and thermal stability of high-performance polymers. A new coordination polymer film (Ni/PPy) with high tensile strength and excellent heat resistance has been successfully prepared via a palladium-catalyzed C-C coupling reaction. For newly synthesized polymer film, bipyridine is incorporated into polymer chains during the synthesis process and subsequently crosslinked by nickel acetate. More importantly, Ni-coordination can be removed by external pyrophosphate to recover the linear polymer, which endows the polymer with recyclability. This strategy is expected to be an effective means for increasing the mechanical properties and recyclability of high-performance polymer materials.

Insights into nanomechanical behavior of B. mori silk fibroin-hydroxyapatite bio-nanocomposite using MD simulations: Role of varying hydroxyapatite content

Nanocomposite material composed of Bombyx mori Silk Fibroin and hydroxyapatite (B. mori SF-HA) is a potential biomaterial for bone tissue engineering. Here, Bombyx mori Silk Fibroin (B. mori SF) is a flexible and tough organic, polymer phase, and hydroxyapatite (HA) is hard and stiff mineral phase. Knowledge about mechanical deformation behavior together with governing mechanisms, and the role of the two phases (SF and HA phase) and interfacial interactions between them, in B. mori SF-HA biomaterial, at fundamental level is an important factor to consider while developing the tissue grafts. Such nanometer scale behavior is often preferably investigated using molecular dynamics method. Present study aims at understanding the mechanical deformation behavior and associated physical mechanisms in B. mori SF-HA bio-nanocomposite, at nanoscale. For this purpose, computational atomistic models of B. mori SF-HA bio-nanocomposite are developed with varying HA content. Mechanical behavior analysis of these composite models under tensile loading were performed using Molecular Dynamics (MD) simulations. Elastic modulus and tensile strength values in the range of 7–20 GPa and 200–700 MPa, respectively, are obtained for B. mori SF-HA composite, in case of different HA contents, wherein, increased mechanical properties are observed with increase in HA content. Analyses of the deformation trajectories show that the deformation flow behavior in B. mori SF-HA bio-nanocomposites is mainly defined by the soft SF phase. However, energetics analyses show that, the HA phase and SF-HA interfacial interactions also play a considerable role in mechanical performance of B. mori SF-HA bio-nanocomposite. Additionally, interfacial shear strength values in B. mori SF-HA bio-nanocomposite, for different HA contents, have also been obtained. The observations made and insights gained in present work has contribution and impact in gaining an insight into the mechanistic interactions occurring at nanoscale between SF and HA phases in B. mori SF-HA bio-composite.

Interweaving Elastic and Hydrogen Bond-Forming Polymers into Highly Tough and Stress-Relaxable Binders for High-Performance Silicon Anode in Lithium-Ion Batteries.

A central challenge in practically using high-capacity silicon (Si) as anode materials for lithium-ion batteries is alleviating significant volume change of Si during cycling. One key to resolving the failure issues of Si is exploiting carefully designed polymer binders exhibiting mechanical robustness to retain the structural integrity of Si electrodes, while concurrently displaying elasticity and toughness to effectively dissipate external stresses exerted by the volume changes of Si. Herein, a highly elastic and tough polymer binder is proposed by interweaving polyacrylic acid (PAA) with poly(urea-urethane) (PUU) elastomer for Si anodes. By systematically tuning molecular parameters, including molecular weights of hard/soft segments and structures of hard segment components, it is demonstrated that the mechanical properties of polymer binders, such as elasticity, toughness, and stress relaxation ability, strongly affect the cycling performance of Si electrodes. This study provides new insight into the rational design of polymer binders capable of accommodating the volume changes of Si, primarily by judicious modulation of the mechanical properties of polymer binders.

All-polymer nanocomposites having superior strength, toughness and ultralow energy dissipation

Toughening polymers has attracted significant interest. Traditionally, polymer toughness is enhanced by constructing polymer networks or introducing sacrificial bonds into the chains between crosslink points. These strategies, though, introduce pronounced energy dissipation and associated heat, both of which are undesirable under long-term cyclic loading, for example at the interface of implants in the human body. By incorporating single-chain nanoparticles (SCNPs) into linear polymer chains to generate all-polymer nanocomposites (APNCs), we have been able to achieve high strength, high toughness with low energy dissipation. Using a combination of simulation and experimental results, we are advancing a “SCNPs effect” where tightly cross-linked SCNPs produce a modulus contrast to achieve strengthening and toughening. Benefitting from the soft interface, the penetrable and deformable SCNPs cause the surrounding polymer chains to move in concert, significantly reducing the interfacial friction to achieve low energy dissipation. The intramolecular cross-linking of the SCNPs and adhesion between the SCNPs and polymer matrix are critical for realizing such high-performance systems. Based on a Gaussian regression model and back propagation (BP) neural network, the mechanical strength can be predicted and is supported by simulations. The APNC concept described can be applied to elastomers and gels, broadening its utilization in high-cycle and low-dissipation applications, like soft robots, flexible sensors and cartilage replacements, and artificial heart valves.

Toughening self-healing elastomer crosslinked by metal–ligand coordination through mixed counter anion dynamics

Mechanically tough and self-healable polymeric materials have found widespread applications in a sustainable future. However, coherent strategies for mechanically tough self-healing polymers are still lacking due to a trade-off relationship between mechanical robustness and viscoelasticity. Here, we disclose a toughening strategy for self-healing elastomers crosslinked by metal–ligand coordination. Emphasis was placed on the effects of counter anions on the dynamic mechanical behaviors of polymer networks. As the coordinating ability of the counter anion increases, the binding of the anion leads to slower dynamics, thus limiting the stretchability and increasing the stiffness. Additionally, multimodal anions that can have diverse coordination modes provide unexpected dynamicity. By simply mixing multimodal and non-coordinating anions, we found a significant synergistic effect on mechanical toughness ( > 3 fold) and self-healing efficiency, which provides new insights into the design of coordination-based tough self-healing polymers.

Tough citric acid-modified cellulose-containing polymer composites with three components consisting of movable cross-links and hydrogen bonds

Tough citric acid-modified cellulose-containing polymer composites with three components consisting of movable cross-links and hydrogen bonds