Polymer Hybrid Materials Research Articles

Fabrication of heteroatom-doped graphene-porous organic polymer hybrid materials via femtosecond laser writing and their application in VOCs sensing

Graphene, a two-dimensional material featuring densely packed sp2-hybridized carbon atoms arranged in a honeycomb lattice, has revolutionized material science. Laser-induced graphene (LIG) represents a breakthrough method for producing graphene from both commercial and natural precursors via direct laser writing, offering advantages such as simplicity, efficiency, and cost-effectiveness. This study demonstrates a novel approach to synthesize a composite material exclusively from a porous organic polymer (POP) by direct femtosecond laser writing on a compressed imide-linked porous organic polymer substrate. The formation of the LIG on the substrate was identified using X-ray diffractometry (XRD) and Raman analysis, where the variation of the 2D peaks of the LIG was obtained. The resulting heterostructure, termed LIG@NI-POP, consists of a few-layered porous and conductive graphene engraved onto the surface of microporous polyimide. X-ray Photoemission Spectroscopy (XPS) confirmed the formation of a hierarchical porous hybrid material with high nitrogen (N) and oxygen (O) self-doping in the graphene. Leveraging its porosity, surface and bulk chemistry, and electrical properties, LIG@NI-POP was tested for sensing volatile organic compounds (VOCs) as a proof-of-concept application. The composite material exhibited dual functionality as a sensor and adsorbent for VOCs, demonstrating significant sensitivity and selectivity towards acetone over ethanol due to enhanced intermolecular interactions. This approach broadens the scope of laser direct writing to include various porous polymers, facilitating the fabrication of hybrid materials that integrate the unique properties of both graphene and porous polymers, thereby enhancing their potential applications in areas that leverage these synergistic properties.

Synthesis, Dynamic Mechanical Properties of Poly(Styrene-co-Acrylonitrile) Grafting Silica Nanocomposites

A series of styrene–acrylonitrile (SAN) copolymer nanoparticles were prepared by grafting styrene–acrylonitrile from both aggregated silica and colloidally dispersed silica nanoparticles using atom-transfer radical polymerisation (ATRP). Cross-linking and macroscopic gelation were minimised by using a miniemulsion system. The thermal and mechanical behavior of composites were made from PSAN aggregated silica nanoparticles or colloidally dispersed silica has been examined by Differential scanning calorimetry (DSC) and Dynamic mechanical thermal analysis (DMTA). The filler particles increased the rubbery modulus above the Tg of PSAN considerably and led to a temperature-independent plateau of the modulus between 130 and 240 °C similar to that normally observed for crosslinked amorphous polymers. Covalent attachment of PSAN to the silica nanoparticles, by grafting the polymer from the surface of the silica using atom-transfer radical polymerization (ATRP), gave rise to hybrid materials with a comparable elastic plateau. While neat PSAN started to flow and deform irreversibly above 120 °C, the new silica nanoparticle–polymer hybrid materials proved stable up to 240 °C, which was more than 120 °C above the Tg of the polymer. Aggregated silica nanoparticles displayed more affect compared to colloidally dispersed silica.

A comprehensive experimental study of eco-friendly hybrid polymer composites using pistachio shell powder and Aquilaria agallocha Roxb

This study investigates the effects of incorporating pistachio shell powder and a mixture of Aquilaria agallocha Roxb (AAR) resin with epoxy on the mechanical, dynamic mechanical, thermal, and biodegradability properties of an epoxy composite. Filler loadings ranged from 10 to 35% by volume, in 5% increments. Scanning electron microscopy (SEM) revealed a uniform distribution of the hybrid polymer materials, particularly at 30% natural resin content, enhancing the load-bearing capacity of the composites. The addition of pistachio shell powder and AAR resin significantly improved the flexural modulus and strength of the composites. At a filler volume of 35%, the hybrid polymer exhibited a maximum impact resistance of 2,718 J/m2, demonstrating increased energy absorption. Moreover, the hybrid system enhanced the damping factor by up to 30%, suggesting superior dynamic mechanical performance. Thermogravimetric analysis (TGA) indicated that the hybrid composites displayed better thermal stability compared to pure epoxy resin. These findings suggest that the combination of pistachio shell powder and AAR natural resin offers a sustainable approach to reinforcing epoxy-based composites, providing improved mechanical and thermal performance for potential industrial applications.

Unraveling the Electrochemical Insights of Cobalt Oxide/Conducting Polymer Hybrid Materials for Supercapacitor, Battery, and Supercapattery Applications.

This review article focuses on the potential of cobalt oxide composites with conducting polymers, particularly polypyrrole (PPy) and polyaniline (PANI), as advanced electrode materials for supercapacitors, batteries, and supercapatteries. Cobalt oxide, known for its high theoretical capacitance, is limited by poor conductivity and structural degradation during cycling. However, the integration of PPy and PANI has been proven to enhance the electrochemical performance through improved conductivity, increased pseudocapacitive effects, and enhanced structural integrity. This synergistic combination facilitates efficient charge transport and ion diffusion, resulting in improved cycling stability and energy storage capacity. Despite significant progress in synthesis techniques and composite design, challenges such as maintaining structural stability during prolonged cycling and scalability for mass production remain. This review highlights the synthesis methods, latest advancements, and electrochemical performance in cobalt oxide/PPy and cobalt oxide/PANI composites, emphasizing their potential to contribute to the development of next-generation energy storage devices. Further exploration into their application, especially in battery systems, is necessary to fully harness their capabilities and meet the increasing demands of energy storage technologies.

Enhanced Antimicrobial Properties of Polymeric Denture Materials Modified with Zein-Coated Inorganic Nanoparticles.

Polymeric denture materials can be susceptible to colonization by oral microorganisms. Zein-coated magnesium oxide nanoparticles (zMgO NPs) demonstrate antimicrobial activity. The aim of this study was to investigate the antimicrobial effect and adherence of different oral microorganisms on hybrid polymeric denture materials incorporated with zMgO NPs. Five types of polymeric denture materials were used. A total of 480 disc-shaped specimens were divided by material type (n=96/grp), then subdivided by zMgO NPs concentration: control with no nanoparticles and other groups with zMgO NPs concentrations of 0.3%, 0.5% and 1% by weight. Characterization of the polymeric denture materials incorporating zMgO NPs was done, and the antimicrobial activity of all groups was tested against four types of microorganisms: 1) Streptococcus mutans, 2) Staphylococcus aureus, 3) Enterococcus faecalis and 4) Candida albicans. The samples underwent an adherence test and an agar diffusion test. Experiments were done in triplicates. The characterization of the hybrid samples revealed variation in the molecular composition, as well as a uniform distribution of the zMgO NPs in the polymeric denture materials. All hybrid polymeric denture materials groups induced a statistically significant antimicrobial activity, while the control groups showed the least antimicrobial activity. The agar diffusion test revealed no release of the zMgO NPs from the hybrid samples, indicating the NPs did not seep out of the matrix. The zMgO NPs were effective in reducing the adherence of the tested microorganisms and enhancing the antimicrobial activity of the polymeric denture materials. This antimicrobial effect with the polymeric dentures could aid in resisting microbial issues such as denture stomatitis.

Gold Nanoparticles Modulate Excimer and Exciplex Dynamics of PDDCP-Conjugated Polymers.

How plasmonic nanostructures modulate the behavior of exciplexes and excimers within materials remains unclear. Thus, advanced knowledge is essential to bridge this gap for the development of optoelectronic devices that leverage the interplay between plasmonic and conjugated polymer hybrid materials. Herein, this work aims to explore the role of gold nanoparticles (AuNPs) in modulating exciplex and excimer states within the conjugated polymer poly(2,5-di(3,7-dimethyloctyloxy) cyanoterephthalylidene) (PDDCP), known for its photoluminescent and semi-conductive properties, aiming to create innovative composite materials with tailored optical features. The spectral analysis was conducted to investigate the effects of AuNPs on the PDDCP, varying AuNP volume percentages to measure changes in the absorption profile, molar extinction coefficient (ε), absorption cross-section (σa), and optical bandgap (Eg). Fluorescence spectra of the mixture at different volume ratios were also examined to assess exciplex formation, while amplified spontaneous emission (ASE) profiles were analyzed to study the behavior and photochemical stability of the polymer-NP hybrid material. Increasing AuNP volume induced both blue and red shifts in the absorption profile of the PDDCP. Higher AuNPs concentrations correlated with decreased ε and σa, inversely impacting Eg. The emission spectra obtained at varied AuNP volume ratios indicated significantly enhanced exciplex and excimer formations. The ASE profiles remained consistent but showed reduced intensity with increasing AuNPs concentrations, indicating their influence on hybrid material behavior and stability. The findings suggest that AuNPs affect PDDCP's optical characteristics, altering the absorption profile, bandgap, and fluorescence spectra. Furthermore, the observed reduction in ASE intensity highlights their influence on the behavior and photochemical stability of the hybrid material. These results contribute to a better understanding of the versatile applications of plasmonic-conjugated hybrid polymers.

Combining Injection Molding and 3D Printing for Tailoring Polymer Material Properties

AbstractModern polymer‐based technical components not only have to fulfill demanding mechanical‐structural properties but need to integrate different functions to yield hybrid systems for complex operations. Typically, neither materials nor processing technologies are fully compatible with each other. The aim of the work is to combine the advantages of seemingly incompatible manufacturing processes such as high‐volume injection molding (IM) and precision additive manufacturing to produce functional and customized hybrid materials. IM is widely used for polymer processing but stands against high investment costs for tailor‐made molds with high‐resolution features. They focus on overprinting of injection‐molded parts made of thermoplastic polyurethane (TPU) with microstructures via projection‐microstereolithography (PµSL) to generate hybrid polymer materials with spatially tailored stiffness, enabling selective reinforcement, resulting in an E modulus increase of 195% compared to mere IM‐processed TPU. With that, the hybridization of processing methods is showcased to extend the product properties of polymer materials obtained via either IM or PµSL printing that have, prospectively, a maximum degree of individualization as well as a multitude of structural and functional features at the same time. To achieve optimum interfacial adhesion, the influence of surface roughness is studied, and reinforcement effects of different overprinted microstructure types are evaluated.

Evaluation of optical and self-healing properties of Titania/ionic liquid/poly(butyl methacrylate) hybrid material based on thermally reversible Diels–Alder chemistry

ABSTRACT In this study, we report the development of a hybrid polymer material comprising poly(butyl methacrylate) and titania, which exhibits the three key elements of visible-light transparency, UV shielding, and self-healing. Nanodispersion of titania in the polymers was achieved using the sol – gel method using titanium propoxide as the raw material. Furthermore, by adding tetrabutylphosphonium chloride, an ionic liquid, we suppressed visible light absorption due to charge transfer between poly(butyl methacrylate) and titania, resulting in enhanced visible light transmittance. An approach involving crosslinking points comprising Diels – Alder functional groups was used to heal scratches in the hybrid material at 75°C for 30 min. Dynamic viscoelastic measurements and microscopic observations were conducted to investigate the self-healing mechanism. These findings suggested that this phenomenon occurred through the fluidization of the polymer matrix and the recombination reaction of the crosslinking points, which comprise Diels – Alder and titania. The development of intelligent materials with combined transparency, UV protection, and self-healing capabilities provides potential avenues for future research to enhance and broaden their versatile characteristics for widespread applications.

Silica based on inorganic–polymer hybrid materials for removing toxic ions from wastewater

As a result of the adsorption of copolymer 5-(4-nitro)phenylazo-8-methacryloxyquinoline with methyl methacrylate on the surface of mesoporous silica gel, a new polymer-inorganic composite material was obtained. Based on the comparison of the sorption capacity of the synthesized composite and the composite based on silica gel with in situ immobilized poly-5-(4-nitro)phenylazo-8-methacryloxyquinoline, it was concluded that the method of in situ immobilization of complex-forming polymers on the surface of silica gel is more effective compared to their physical adsorption.

Polyethersulfone Polymer for Biomedical Applications and Biotechnology.

Polymers stand out as promising materials extensively employed in biomedicine and biotechnology. Their versatile applications owe much to the field of tissue engineering, which seamlessly integrates materials engineering with medical science. In medicine, biomaterials serve as prototypes for organ development and as implants or scaffolds to facilitate body regeneration. With the growing demand for innovative solutions, synthetic and hybrid polymer materials, such as polyethersulfone, are gaining traction. This article offers a concise characterization of polyethersulfone followed by an exploration of its diverse applications in medical and biotechnological realms. It concludes by summarizing the significant roles of polyethersulfone in advancing both medicine and biotechnology, as outlined in the accompanying table.

Near-infrared Y-branch polymer splitters realized with compact MMI structures for efficient power splitting

Optical splitters are promising photonic devices for next-generation photonic integrated circuits, which enable signal distribution and routing between the different components, facilitating complex optical functionalities on a single chip. This research introduces what we believe is a novel numerical technique for enhancing optical network efficiency by incorporating a taper-based step-index (SI) Y-branch multimode interference (MMI) splitter with organic-inorganic hybrid polymer materials. The proposed device comprises a core width of 5 µm for the input and output waveguides to satisfy the single-mode conditions. We designed and optimized the MMI splitter using the beam propagation method (BPM). The splitter demonstrates the power splitting property with an efficiency of 86%. The excess losses for the MMI splitter are 0.52 dB and 0.50 dB for TE and TM modes, respectively, at 1.55 µm. The polarization dependence loss (PDL) and propagation loss (PL) are 0.015 dB and 0.00019 dB/µm, respectively.

Identification of Hybrid Polymer Material STERED and Basic Material Properties Used in Road Substructures or Pavements.

Modern road construction uses a large number of polymer-based materials. Material composition depends on their roles. Among the most important functions of road body materials is to transfer all loads safely to the subgrade. A thorough understanding of material properties in various climates is crucial for this purpose. In the automotive industry, polymer residues from recycling can be used to make innovative materials, such as STERED, a hybrid polymer composite. Drawing on the porous nature of this material, this paper investigates its mechanical behavior. For road construction, the compressive properties of the material are most important. The paper presents the results of a detailed analysis and experimental research of the STERED material from in-lab tests. Successful research will lead to the inclusion of the material in road body compositions with excellent retention properties, vibration damping, and potential in circular economy.

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids.

Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride-trifluoroethylene), Poly(VDF-co-TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico-chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm-1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology-vertical or planar-the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K-1. Based on the obtained maximum power density of 4.9 µW m-2, these materials are suitable for a new generation of TE devices.

Polarization manipulation on step-index composite polymer beam splitters for photonics circuitry

This paper presents composite beam splitters realized with polymer materials for developing photonic integrated circuits. We used organic-inorganic hybrid polymer materials to form this composite beam splitter realized with step-index (SI) core profiles. We used the alternating direction implicit technique of the Rsoft CAD BeamPROP solver to design and analyze these beam splitters. We successfully examined and manipulated the beam splitter’s polarization dependency to obtain a 99% output efficiency with a 50:50 splitting ratio. The SI beam splitter exhibits an excess loss of 0.014 dB. When we apply polarized light in this beam splitter, the excess loss increases to 2 dB, and this loss gradually decreases as the angle of incident light increases. The excess loss reduces to 0.05 dB at the 31-degree angles of the incident polarized light. We also investigated the crosstalk of this beam splitter by varying the wavelength, and it is evident that the lowest crosstalk is −19.77 dB at the polarized angle of 31°.

High N-containing porphyrinic C3N4 hybrid polymeric material as efficient photocatalyst for selective CO2 reduction

A new porphyrinic-C3N4 material was successfully synthesized using a new method and was characterized at each stage of the process using a range of spectroscopic techniques, including FT-IR and NMR. The XPS, SEM, and EDX studies of the material were also carried out which showed only one dominant morphology and the existence of C and N in the compound which confirm the formation of Por-C3N4. The material was loaded with Co2+ ions by mixing and stirring methanolic solution of Co(O2CH3).4H2O with DMF solution of por-C3N4 for 24 h and the resulting dried compound was subjected to carbonization. The PXRD pattern proved that Co-por-C3N4 did not degrade into oxide, hydroxide, or any other form of Co. The photocatalyst exhibited a higher selectivity for CO production of 11 μmol g−1 (at pH = 11) compared to 6.7 μmol g−1 (at pH = 8) from CO2. The result indicates the possibility of integrating the porphyrin component into C3N4 units via covalent attachment to create a 3D hybrid polymer which was described in the result and discussion section. This polymer shows promise in efficiently transforming CO2 into CO under visible light exposure, offering promising prospects for solar-driven CO production from CO2.

Fabrication of green polymeric hybrid materials for batch and column adsorption study of Blue-XGRRL dye

Fabrication of green polymeric hybrid materials for batch and column adsorption study of Blue-XGRRL dye

A Critical Review on Tribological and Mechanical Characteristics of Hybrid Polymer Composite Materials

AbstractThis review paper presents tribological and mechanical characteristics of hybrid polymer composite materials that exhibit low friction and low wear. Polymer fiber reinforced materials possess low weight and high specific quality along with high specific stiffness. This study targets a critical review of wear and frictional characteristics of hybrid polymer composite materials. Tribological properties have been evaluated by various researchers using a rotating pin‐on‐disc tribometer and reciprocating wear testing machine. Most likely filler materials are carbon, graphite, nano silica, bronze, glass fibers, MoS2, and polytetrafluoroethylene (PTFE) added in the polyether ether ketone (PEEK), polyamide 66, thermoses polymer, etc. It improves mechanical and tribological properties of hybrid composite materials. This review paper aims to highlights the comparative study of various fillers added in PEEK, Polyamide 66, and thermoses polymer hybrid materials. Recently hybrid composites are used in wide range of applications since it has light weight and high strength.

Directional-Freezing-Enabled MXene Orientation toward Anisotropic PVDF/MXene Aerogels: Orientation-Dependent Properties of Hybrid Aerogels.

Polymer hybrid materials that contain reinforcements with a preferred orientation have received growing attention because of their unique properties and promising applications in multifunctional fields. Herein, anisotropic poly(vinylidene fluoride) (PVDF)/MXene hybrid aerogels with highly ordered delaminated MXene nanosheets and anisotropic porous structures were successfully fabricated by unidirectional freezing of thermoreversible gels followed by a freeze-drying process. The strong interfacial interactions between PVDF chains and abundant functional groups on the surface of MXene enabled the orientation of MXene nanosheets at the boundaries of ice crystals as the semicrystalline PVDF and delaminated MXene nanosheets are squeezed along the freezing direction. These aerogels display distinct properties along the freezing and perpendicular to the freezing (transverse) directions. These anisotropic aerogels are flexible and flame-retardant and possess an anisotropic compression performance, heat transfer, electrical conductivity, and electromagnetic interference (EMI) shielding. Further, by increasing the MXene loadings, the electrical conductivity and EMI shielding performances of hybrid aerogels were significantly improved. The PVDF aerogel showed sticky hydrophobicity with a contact angle of 139°, whereas the contact angle increased significantly in hybrid aerogels (153°) with low water adhesion, making them suitable as self-cleaning materials. The combination of the above characteristics makes these hybrid aerogels potential candidates for a wide range of electronic applications.

Holmium-Containing Metal-Organic Frameworks as Modifiers for PEBA-Based Membranes.

Recently, there has been an active search for new modifiers to create hybrid polymeric materials for various applications, in particular, membrane technology. One of the topical modifiers is metal-organic frameworks (MOFs), which can significantly alter the characteristics of obtained mixed matrix membranes (MMMs). In this work, new holmium-based MOFs (Ho-MOFs) were synthesized for polyether block amide (PEBA) modification to develop novel MMMs with improved properties. The study of Ho-MOFs, polymers and membranes was carried out by methods of X-ray phase analysis, scanning electron and atomic force microscopies, Fourier transform infrared spectroscopy, low-temperature nitrogen adsorption, dynamic and kinematic viscosity, static and dynamic light scattering, gel permeation chromatography, thermogravimetric analysis and contact angle measurements. Synthesized Ho-MOFs had different X-ray structures, particle forms and sizes depending on the ligand used. To study the effect of Ho-MOF modifier on membrane transport properties, PEBA/Ho-MOFs membrane retention capacity was evaluated in vacuum fourth-stage filtration for dye removal (Congo Red, Fuchsin, Glycine thymol blue, Methylene blue, Eriochrome Black T). Modified membranes demonstrated improved flux and rejection coefficients for dyes containing amino groups: Congo Red, Fuchsin (PEBA/Ho-1,3,5-H3btc membrane possessed optimal properties: 81% and 68% rejection coefficients for Congo Red and Fuchsin filtration, respectively, and 0.7 L/(m2s) flux).

Role of imperfect coordination of amorphous metal oxide in its chemical reaction with epoxy resin in metal − polymer hybrid material

The chemical bonding between laser − induced metal oxide and polymer highly determines the interfacial bonding performance of metal − polymer hybrid materials. To achieve reliable interfacial chemical bonding, it is crucial to gain a molecular/atomic level understanding of the chemical reaction mechanism between the metal oxide and epoxy resin (main components of epoxy polymer). Previous research has demonstrated that laser ablation induces the formation of amorphous aluminium oxide on aluminium alloy surfaces. Our solid − state nuclear magnetic resonance (ssNMR) investigation reveals that this amorphous aluminium oxide is consisted mainly of 4 − fold and 5 − fold coordinated Al sites. Through an innovative combination of ssNMR and density functional theory calculations, this aluminium oxide was confirmed to form Al − O − C bonds with epoxy resin, preferentially at imperfectly coordinated Al sites due to active donor − acceptor interactions. It is clarified that imperfect coordination of amorphous aluminium oxide plays a more critical role than its amorphous nature in forming stable adsorption structure with epoxy resin. Furthermore, compared to on crystalline surface, 5 − fold coordinated Al site on amorphous surface exhibits higher reactivity, and the origin of activity is revealed through distortion/interaction analysis. This study provides a research guidance for further regulation and optimization of interfacial reactivity and bonding characteristics of metal − polymer hybrid materials.