Polymeric Materials Research Articles

Positioning dynamic polymeric materials within the modern polymer economy: From application to recycling and circularity

AbstractInnovations in dynamic polymeric materials offer prospects to improve the circularity and lower the environmental impact of the modern polymer economy. These materials are also beginning to blur the distinction between re‐use and recycling methods since the bulk material properties of the material may be rationally changed after applying a stimulus or performing a controlled chemical reaction. In this Perspective, we propose that dynamic polymers denote a unique class of versatile post‐consumer polymer waste, which shares similarities to emergent upcycling approaches while also offering additional opportunities within more classical recycling schemes. A brief overview of stimuli‐responsive polymers is presented where illustrative examples are discussed within the context of developing practical materials. Dynamic covalent polymeric materials are then highlighted, along with emerging techniques such as polymer editing, with a focus on recent reports demonstrating rational manipulation of bulk material properties. Finally, we discuss these examples alongside modern recycling methods and explore how dynamic polymers could perform in this sphere.

Mechanochromic Polymer Film with High Sensitivity toward Tensile Strain by the Post-Curing Ring-Closure Induced Pre-Stretching.

Mechanochromic materials has received broad research interests recently, owing to its ability to monitor the in-situ stress/strain in polymer materials in a straight forward way. However, one major setback that hinder the practical application of these materials is their low sensitivity toward tensile strain. Here we show a new strategy for pre-stretching of the mechanochromic agent in a polymer film on the molecular scale, which can effectively enhance the mechanochromic sensitivity of a polymer film toward tensile strain. In-situ fluorescent measurement during tensile test showed an early activation of the mechanochromic agent at tensile strain as low as 50%. The pre-stretching effect is realized by firstly inducing ring-opening of the mechanochromic agent by molecular functionalization, and then compelling the ring-closure process in the cured film by elevated temperature. This post-curing ring-closure process will result in pre-stretched mechanochromic agent in a crosslinked network. The mechanism for mechanochromic activation of polymer films with different composition was elaborated by visco-elastic measurements, and the effect of pre-stretching was further confirmed by polymer films with other compositions. Combined with the simplicity of the method developed, we believe this work will offer an alternative strategy to enhance the sensitivity of different mechanochromic agents toward tensile strain. This article is protected by copyright. All rights reserved.

Architectural Editing of Polyesters and Polyurethanes via Palladium(II)-Catalyzed [3,3]-Sigmatropic Oxo-Rearrangements.

Architecture underlies the thermomechanical properties of polymers. Yet, few strategies are available to tune a polymer's architecture after it is prepared without altering its chemical composition. The ability to edit the architecture of a polymer would dramatically expand the accessible architecture-property space of polymeric materials. Herein, we disclose a backbone rearrangement approach to tune the short-chain branching of polymers. Specifically, we demonstrate that palladium(II)-catalyzed [3,3]-sigmatropic oxo-rearrangements can transform branched polyesters and polyurethanes to their linear counterparts. While the effects on materials properties are generally subtle in the case of polyesters, more dramatic changes are observed in the case of polyurethanes: two polyurethanes undergo a soluble-to-insoluble transition, and one exhibits a dramatic increase in both strain at break and toughness after rearrangement. Additionally, the incorporation of alkenes in the polymer backbone through the rearrangement enables facile deconstruction via ethenolysis. In all, we disclose a powerful and broad-scope strategy to edit the architecture of polymer backbones and thereby tune their physical and chemical properties.

Synergies and applications of polyimides featured low permittivity and high thermal conductivity

The continuous upgrading of electronic technology has facilitated the integration and miniaturization of electronic and electrical equipment, as well as putting great pressure on the multifunctional demand for internal materials. Developing insulating materials with both low permittivity and high thermal conductivity has become imperative. This perspective focuses on polyimide (PI), which is the top material of the polymer material pyramid, discusses the characteristic parameters that affect its dielectric property and thermal conductivity. A series of basic schemes to regulate the dielectric/thermal properties of PI are summarized, revealing the bottlenecks and drawbacks of the current research. Future development trends of PIs featured low permittivity-high thermal conductivity are anticipated, and novel ideas are proposed for the development of new generation of multifunctional PIs.

Biodegradable Alkali-Swellable Emulsion Polymers: Industrial and Commercial Thickeners.

Sustainability and circularity are key issues facing the global polymer industry. The search for biodegradable and environmentally-friendly polymers that can replace conventional materials is a difficult challenge that has been met with limited success. Alternatives must be cost-effective, scalable, and provide equivalent performance. We report that latexes made by the conventional emulsion polymerization of vinyl acetate and functional vinyl ester monomers are efficient thickeners for consumer products and biodegrade in wastewater. This approach uses readily-available starting materials and polymerization is carried out in water at room temperature, in one pot, and generates negligible waste. Moreover, the knowledge that poly(vinyl ester)s are biodegradable will lead to the design of new green polymer materials.

Coarse graining with control points: a cubic-Bézier based approach to modeling athermal fibrous materials

Fibrous materials continue to be of central importance to modern life, including traditional materials, such as textiles and paper, modern materials, such as polymeric materials and glass fiber, and emerging materials, such as carbon nanotube yarns. Developing constitutive laws for the mechanical behavior of such materials can be challenging owing to the often non-periodic microstructure, resulting in fairly large and computationally intractable representative volume elements. Therefore, it is imperative to design novel coarse-grained models that can bridge the computational gap and capture accurate physics associated with the mechanical behavior of fibrous materials. In this work, cubic-Béziers are used to represent fiber-segments, allowing for up to C 2(curvature)-continuous representation of curved fibers. Equations of motion are derived in terms of the control points, which allow for minimization and time integration strategies with the Lagrangian and Hamiltonian formalism. This coarse-grained model promises faster and more accurate computational performance compared to discrete approaches.

Modular Synthesis of Conjugated Aromatic Boronate Esters by Radical Xanthate Addition

AbstractConjugated aromatic boronate esters serve as crucial intermediates in the synthesis of pharmaceuticals and polymer materials. Traditional methods for their synthesis typically involve organoboration of aromatic ring compounds, where pre-constructions of aromatic rings are required. Here, we present a general strategy for the synthesis of diverse conjugated aromatic boronate esters based on the radical addition of xanthates. Through this method, we synthesized various boronate ester xanthates that could be utilized as a platform to furnish conjugated aromatic building blocks, including thiophenes, pyrroles, tetralones, naphthols, and naphthylamines. This cost-effective strategy holds promise as a viable method for the industrial-scale production of (hetero)aromatic boronate esters.

Physicochemical characteristics and oil sorption behaviours of novel polymeric materials based on modifications of water hyacinth (Eichhornia crassipes) fibres

Physicochemical characteristics and oil sorption behaviours of novel polymeric materials based on modifications of water hyacinth (Eichhornia crassipes) fibres

Upgrading event driven Monte Carlo simulations for molecule‐based morphological control for battery and sensor applications

AbstractMultiphase polymeric materials and applications play a prominent role in our society. One of the key challenges is the design and modification of their macromolecules so that the composition and structuring of the phases as well as the interactions between them can be controlled from the molecular scale onwards. In the present contribution, it is highlighted that more recently developed event driven (kinetic) Monte Carlo models provide an interesting framework to grasp molecular variations over various length scales. The strength lies in the tracking of individual molecules per phase of interest so that interphase transfer events can be sampled based on the distributed nature of the (macro)molecules present. Hence, the micro‐scale of local concentrations and temperatures can be connected to the meso‐scale defining interphase transport and morphological variations, with an additional connection to the macro‐ or application scale within reach by adding macro‐scale transfer events to the overall sampling scheme. Starting from a benchmark coupled matrix based Monte Carlo (CMMC) study on the multiphase formation of engineering composites which explicitly acknowledges the type of (macro)molecules present in each phase, it is showcased that the CMMC framework can support the general field of energy and electronics applications. This is highlighted through (i) a case study devoted to the design of polymer electrolytes for batteries, and (ii) a case study on blend design for the regulated stretching of piezoresistive sensors.

Radical Homopolymerization of Linear α‐Olefins Enabled by 1,4‐Cyano Group Migration

Abstractα‐Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small‐molecule or polymeric products. Despite numerous advantages of radical polymerization, it has been well‐documented as textbook knowledge that α‐olefins and their functionalized derivatives cannot be radically homopolymerized because of the degradative chain transfer side reactions. Herein, we report our studies on the homopolymerization of thiocyanate functionalized α‐olefins enabled by 1,4‐cyano group migration under radical conditions. By this approach, a library of ABC sequence‐controlled polymers with high molecular weights can be prepared. We can also extend this strategy to the homopolymerization of α‐substituted styrenic and acylate monomers which are known to be challenging to achieve. Overall, the demonstrated functional group migration radical polymerization could provide new possibilities to synthesize polymers with unprecedented main chain sequences and structures. These polymers are promising candidates for novel polymeric materials.

Radical Homopolymerization of Linear α-Olefins Enabled by 1,4-Cyano Group Migration.

α-Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small-molecule or polymeric products. Despite numerous advantages of radical polymerization, it has been well-documented as textbook knowledge that α-olefins and their functionalized derivatives cannot be radically homopolymerized because of the degradative chain transfer side reactions. Herein, we report our studies on the homopolymerization of thiocyanate functionalized α-olefins enabled by 1,4-cyano group migration under radical conditions. By this approach, a library of ABC sequence-controlled polymers with high molecular weights can be prepared. We can also extend this strategy to the homopolymerization of α-substituted styrenic and acylate monomers which are known to be challenging to achieve. Overall, the demonstrated functional group migration radical polymerization could provide new possibilities to synthesize polymers with unprecedented main chain sequences and structures. These polymers are promising candidates for novel polymeric materials.

Depth-resolved elemental and molecular analysis of polymeric multilayers with EI-MS and ICP-OES using chemometric evaluation

Polymeric composite materials with layered structures have increasingly gained importance as, for specific applications, the required properties cannot be achieved with one single material; thus, for example, multi-layer polymers or special surface coatings are employed.None of the conventionally available techniques enables a comprehensive characterization of composite materials, including depth-resolved information about their organic and elemental constituents.In this work, a previously introduced approach enabling the direct characterization of the organic and inorganic constituents of solid polymer samples was further developed and optimized for depth profiling analysis of stacked layer polymers. For this purpose, the ablation chamber’s washout behavior and transfer line’s transport efficiency were improved. Chemometric methods were applied for the data analysis to gain greater insight and enable more precise differentiation, comparison and classification.The work investigates the feasibility of the developed approach by analyzing a multi-layer stacked polymer sample created from nail polishes and using cluster analysis on the data collected with the bimodal detection. The layers of the sample could be differentiated by their organic and elemental constituents’ fingerprints, achieving a depth resolution of 7 µm.

Modified xanthan gum (natural polymeric material) and its derivative for wastewater treatment: A review

AbstractNaturally occurring xanthan gum (XG) has much commercial importance because of its excellent physicochemical, eco‐friendly, and non‐toxic properties. It is used in various applications like protein extraction, wastewater treatment, tissue engineering, drug delivery, food packaging, and so forth. XG is a natural material, and it has some limitations related to the mechanical stress, thermal stability, and hydration. To overcome the limitation, XG can be modified by adding third component or modification of operation for specific applications. XG can be modified by physical, genetically, enzymatically, or chemical processes. Revamped XG also enhances the efficiency toward adsorbing toxic metal ions and organics from synthetic or industrial effluents. The emphasis of present review article is to address the structural characteristics along with the focus on the developing chemically modified XG like grafted, cross‐linked, nanocomposites, and functionally modified biopolymer. However, this review commences thorough discussion on numerous ways of modifications, which can be attempted in XG structure, expanding its applications for heavy metal ion along with dye removal.

Rigid polyurethane foams from commercial castor oil resins

Rigid polyurethane foams (RPUFs) are among the most used polymeric materials due to their tailorable properties. Greener and biobased polyol sources for synthesising RPUFs have been recently prototyped because of the ever-growing demand for more sustainable materials solutions. Castor Oil has also rapidly become one of the most successful alternatives to replace polyurethane fossil-based components. This study extensively investigates three types of RPUFs developed from commercially available Castor Oil-based resins, correlating their properties across different length scales. In particular, X-ray diffraction identified a characteristic peak whose intensity correlated with the apparent foam density, morphology (obtained from computed tomography scans) and mechanical properties. Furthermore, quasi-static compression and vibration transmissibility tests revealed distinctive anisotropic mechanical responses among the foams, with one type of RPUF consistently outperforming the others due to its lower porosity, reaching 13.3 MPa of compressive modulus. These findings demonstrate the possibility of tuning the mechanical properties of foams via compositional control.

A novel method for air assisted nanosecond pulsed fiber laser beam transmission micro-channelling on thick PMMA material

The demand for scaling up polymeric materials for mass production or scaling down for microscale applications is at its peak in the modern era. Laser beam technology enables the formation of micro-channels on polymers, specifically polymethyl methacrylate (PMMA). This study examines the viability and cost-effectiveness of employing the diode pump fiber laser transmission technique to create micro-channels on thick, transparent PMMA under air-assisted circumstances for biomedical engineering and micro-fluidics applications. The analysis has included process variables such as pulse frequency, power, and cutting speed, as well as machining parameters including depth of cut, kerf width, and heat-affected zone (HAZ) width. The results of multi-objective optimization indicate that the following parameters—a pulse frequency of 51.30 kHz, a working power of 13 % of 50 W, and a cutting speed of 0.60 mm/s—contribute to the desired microfluidics response values: 12.54 µm depth of cut, 24.05 µm kerf width, and 5.98 µm HAZ width.

UV-Irradiation Effects on the Structural, Optical and Electrical Characteristics of Soft Blended Polymeric Materials Loaded with Multi-Walled Carbon Nanotubes (MWCNTs)

Undoped and doped polyvinylpyrrolidone/carboxy-methyl cellulose/zinc sulfide/nickel oxide (PVP/CMC/ZnS/NiO) nanocomposite blends with multi-walled carbon nanotubes (MWCNTs) were prepared using sol-gel and solid-state reactions and casting techniques. Various blends were formed and their composition and morphologies were characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. The structures of the nano-fillers were examined using the XRD technique. The influence of the concentrations of MWCNTs on the linear and nonlinear optical parameters of PVP/CMC/ZnS/NiO nanocomposite blends was examined. The optical band gap energies were decreased from (direct, indirect: 5.31, 5.06) eV for undoped blends to 4.38 and 3.34 eV for the blends doped with the highest concentration of MWCNTs (0.15 wt%). The refractive indices of the various blends were calculated based on the obtained optical band gap energies using various models. The effect of MWCNTs concentrations on the dielectric constants, energy density, electric modulus and ac conductivity at room temperature of the PVP/CMC/0.5ZnS-0.5NiO/x wt% MWCNTs samples were explored using an Inductance, L, Capacitance, C, and Resistance, R (LCR) meter bridge.

Interface engineering of multi-component core-shell flame retardant towards enhancing fire safety of thermoplastic polyurethane and mechanism investigation

Polymeric materials usually present substantial hazards to human health and the environment as a consequence of their flammability which leads to the emission of a great deal of heat and toxic fumes. To address this issue, it is imperative to urgently enhance the flame retardancy of polymer materials. This study focuses on the synthesis of a novel gel-silica/polydopamine double-layer microencapsulated cobalt ions (Co2+) modified ammonium polyphosphate (APP-Co@PDA@Si) and its utilization in thermoplastic polyurethane (TPU) composites. The resulting TPU composite, containing 10.0 wt% APP-Co@PDA@Si, exhibited excellent flame-retardant properties, i.e. achieving a limiting oxygen index of 30.0 % and the V-0 grade in the UL-94 test. Furthermore, peak heat release rate, total heat release, peak smoke production rate, and total smoke release of the TPU composite were decreased by 88.51 %, 66.06 %, 61.73 %, and 74.01 %, respectively, in comparison to those of pure TPU. The enhanced fire safety of the TPU composite was attributed to the synergistic effect among Co2+ catalytic carbonization, the free radicals capture effect of APP, and the flame-retardant functions of PDA and silane. This innovative strategy proposed in this work holds great promise for improving the fire-resistance of TPU.

The Air Permeability and the Porosity of Polymer Materials Based on 3D-Printed Hybrid Non-Woven Needle-Punched Fabrics.

The possibility of controlling the porosity and, as a result, the permeability of fibrous non-woven fabrics was studied. Modification of experimental samples was performed on equipment with adjustable heating and compression. It was found that the modification regimes affected the formation of the porous structure. We found that there was a relationship between the permeability coefficient and the porosity coefficient of the materials when the modification speed and temperature were varied. A model is proposed for predicting the permeability for modified material with a given porosity. As the result, a new hybrid composite material with reversible dynamic color characteristics that changed under the influence of ultraviolet and/or thermal exposure was produced. The developed technology consists of: manufacture of the non-woven needle-punched fabrics, surface structuring, material extrusion, additive manufacturing (FFF technology) and the stencil technique of ink-layer adding. In our investigation, we (a) obtained fibrous polymer materials with a porosity gradient in thickness, (b) determined the dependence of the material's porosity coefficient on the speed and temperature of the modification and (c) developed a model for calculating the porosity coefficient of the materials with specified technological parameters.

Supramolecularly Connected Armor-like Nanostructure Enables Mechanically Robust Radiative Cooling Materials.

Passive daytime radiative cooling (PDRC) is a promising practice to realize sustainable thermal management with no energy and resources consumption. However, there remains a challenge of simultaneously integrating desired solar reflectivity, environmental durability, and mechanical robustness for polymeric composites with nanophotonic structures. Herein, inspired by a classical armor shell of a pangolin, we adopt a generic design strategy that harnesses supramolecular bonds between the TiO2-decorated mica microplates and cellulose nanofibers to collectively produce strong interfacial interactions for fabricating interlayer nanostructured PDRC materials. Owing to the strong light scattering excited by hierarchical nanophotonic structures, the bioinspired film demonstrates a desired reflectivity (92%) and emissivity (91%) and an excellent temperature drop of 10 °C under direct sunlight. Notably, the film guarantees high strength (41.7 MPa), toughness (10.4 MJ m-3), and excellent environmental durability. This strategy provides possibilities in designing polymeric PDRC materials, further establishing a blueprint for other functional applications like soft robots, wearable devices, etc.

Ultrasonic welding of Cork Wood/PLA composites: effect of welding factors on lap shear strength performance

Ultrasonic welding of Cork Wood/PLA composites: effect of welding factors on lap shear strength performance