Polymer Hybrid Materials Research Articles

Strategy for Selective Printing of Gate Insulators Customized for Practical Application in Organic Integrated Devices.

Direct drawing techniques have contributed to the ease of patterning soft electronic materials, which are the building blocks of analog and digital integrated circuits. In parallel with the printing of semiconductors and electrodes, selective deposition of gate insulators (GI) is an equally important factor in simplifying the fabrication of integrated devices, such as NAND and NOR gates, and memory devices. This study demonstrates the fabrication of six types of printed GI layers (high/low-k polymer and organic-inorganic hybrid material), which are utilized as GIs in organic field-effect transistors (OFETs), using the electrostatic-force-assisted dispensing printing technique. The selective printing of GIs on the gate electrodes enables us to develop practical integrated devices that go beyond unit OFET devices, exhibiting robust switching performances, non-destructive operations, and high gain values. Moreover, the flexible integrated devices fabricated using this technique exhibit excellent operational behavior. Therefore, this facile fabrication technique can pave a new path for the production of practical integrated device arrays for next-generation devices.

Poly(ethylene Terephthalate) Carbon-Based Nanocomposites: A Crystallization and Molecular Orientation Study.

Hybrid polymeric materials incorporating carbon nanostructures or inorganic constituents stand as a promising class of materials exhibiting distinct but also complementary features. Carbon nanotubes have been proposed as unique candidates for polymer reinforcement; however, sustained efforts are further needed in order to make full use of their potential. The final properties of the reinforced polymer are controlled in part by the morphology and the eventual molecular orientation of the polymer matrix. In the present study, multiwall carbon nanotubes (MWCNTs) were utilized in order to reinforce polyethylene terephthalate (PET) composites. The effect of CNTs on the crystallization and the orientation of the structurally hybridized polymeric material has been investigated from the perspective of assessing their impact on the final properties of a relevant nanocomposite product. Functionalized MWCNTs were used to achieve their optimal dispersion in the polymer matrix. The physical properties of the composites (i.e., crystallinity and orientation) were characterized via differential scanning calorimetry, X-ray diffraction, and polarized Raman microscopy. The addition of well-dispersed CNTs acted as a nucleation agent, increasing the crystallization of the polyethylene terephthalate matrix and differentiating the orientation of both CNTs and macromolecular chains.

Design of Ionic-Liquid-Based Hybrid Polymer Materials with a Magnetoactive and Electroactive Multifunctional Response.

Multifunctional materials with sensor and actuator capabilities play an increasing role in modern technology. In this scope, hybrid materials with magnetic sensing and an electromechanical actuator response based on magnetic ionic liquids (MILs) and the polymer poly(vinylidene fluoride) (PVDF) have been developed. MILs comprising different cation alkyl chain lengths [Cnmim]+ and sharing the same anion [FeCl4]- were incorporated at 20 wt % into the PVDF matrix and the morphological, physical, chemical, and functional properties of the materials were evaluated. An increasing IL alkyl chain length leads to the formation of a porous structure, together with an increase in the electroactive PVDF β-phase content of the polymer and a decrease in the crystallinity degree and thermal stability. The magnetic susceptibility of the [Cnmim][FeCl4]/PVDF films reveals a paramagnetic behavior. The multifunctional response is characterized by a magnetoionic response that decreases with increasing IL alkyl chain length, the highest magnetoionic coefficient (1.06 ± 0.015 V cm-1 Oe-1) being observed for [C2mim][FeCl4]/PVDF. The electromechanical actuator response is characterized by a highest displacement of 1.1 mm for the [C4mim][FeCl4]/PVDF film by applying a voltage of 4 V at a frequency of 100 mHz. Further, their solution processing makes these multiresponsive materials compatible with additive manufacturing technologies.

Comparative Study on the Influence of Noble Metal Nanoparticles (Ag, Au, Pd) on the Photocatalytic Activity of ZnO NPs Embedded in Renewable Castor Oil Polymer Matrices.

Hybrid polymeric materials, due to the unique combination of properties that can be obtained by the convenient variation of organic and inorganic components, represent an attractive alternative for many applications, especially photocatalysis. Herein, we report the preparation of nanocomposite films containing functionalized ZnO nanoparticles, as well as in situ photogenerated noble metal nanoparticles (Ag, Au, Pd), for the achieving of materials with enhanced photocatalytic activity under visible light. The flexible free-standing nanocomposite films were synthesized by photopolymerization of a monomer mixture (silane castor oil urethane dimethacrylate and polypropylene oxide urethane dimethacrylate) in the presence of a Irgacure 819 photoinitiator. The efficiency of ZnO NPs functionalization was established by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis, while the polymer composites were characterized by UV-Vis spectroscopy, X-ray diffraction, transmission electron microscopy and scanning electron microscopy to evidence the formation, size and distribution of the nanoparticles inside the photocrosslinked matrix. To establish the photocatalytic capacity of nanocomposite films, the decomposition of various pollutants (methyl orange, phenol, metronidazole) was monitored under visible light irradiation, the best results being obtained for Au/ZnO film. Also, the advantage of immobilizing the catalysts in a polymeric support and its recycling ability without a significant decrease in photocatalytic efficiency was analysed.

Corrosion protection performance of titania nanoparticles filled poly(4-methyl-5-vinylthiazole) applied on mild steel in 3.5% sodium chloride solution

Mild steel materials have wide applications in marine construction, because they are low cost, available and easy to handle. However, they have to be protected from corrosive media by coating with polymer hybrid materials. This paper focuses on the anticorrosive properties of poly(4-methyl-5-vinylthiazole) PVTZ coatings on mild steel. Further the coating resistance is enhanced by incorporating Titania Nano particles (TiO2NPs). The nanoparticles were evaluated using X-ray diffraction studies (XRD) and transmission electron microscopy (TEM). PVTZ and its TiO2 nanocomposite were coated on mild steel. Their anticorrosive behavior was analyzed by potentiodynamic polarization and electrochemical impedance spectroscopy in 3.5% (w/v) NaCl.

Viscoelasticity of Nanosheet-Filled Polymer Composites: Three Regimes in the Enhancement of Moduli.

We employed nonequilibrium molecular dynamics simulations to elucidate the viscoelastic properties of nanosheet (NS)-filled polymer composites. The effects of NS loadings and NS-polymer interaction on viscoelasticity were examined. The simulation results show that the NS-filled polymer composites exhibit an enhanced storage modulus and loss modulus as the NSs are loaded. There are three regimes of the enhanced process based on the NS loadings. At lower NS loadings, the motion of polymers slows down owing to the interaction between NSs and polymers, and the polymer chains generally follow the Rouse dynamics. As the NS loadings increase, the polymer chains are confined between NSs, leading to a substantial increment in dynamic moduli. At higher NS loadings, a transient network is formed, which strengthens the dynamic moduli further. In addition, the attractive NS-polymer interaction can improve the dispersion of NSs and increase the storage and loss moduli. The present work could provide essential information for designing high-performance hybrid polymeric materials.

Effect of metal oxide additives on the structural and barrier properties of a hybrid organosilicon sol-gel coating in 3.5% NaCl medium

Hybrid sol-gel materials provide a favorable alternative to the use of toxic phosphate and chromate conversion coating to protect metal substrates from corrosion attack. Herein, a systematic study was performed to investigate the effect of metal oxide additives i.e niobium(V) oxide), titanium(IV) ethoxide, and zirconium(IV) propoxide on the structural and corrosion protection properties of novel hybrid sol-gel coatings applied on a mild steel (MS) surface. Nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) analyses revealed the introduction of structural changes on the parent hybrid polymer upon loading it with the metal oxide additives. Moreover, the gel permeation chromatography (GPC) studies of the functionalized hybrid polymeric materials proved higher polymerization extent in these materials in comparison with the parent polymer. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests have shown that the metal oxide additives displayed; to various extents, an enhancement in the barrier properties of the base hybrid coating for a MS substrate in a 3.5 wt.% NaCl medium. Zirconium(IV) propoxide additive showed the highest corrosion resistance as compared to parent sol-gel coating or other metal oxide additives. Scanning electron microscope (SEM) analyses indicate an excellent homogeneous coverage of the functionalized coatings on the MS surface with no signs of defects, delamination, or micro cracks behaviors. The present study gains deeper insights into the interactions nature between the oxide additive and the host polymer matrix.

Boron nitride nanotube clusters and their hybrid nanofibers with polycaprolacton: Thermo-pH sensitive drug delivery functional materials

Electrospinning-electrospraying is a promising technique in synthesis of hybrid polymeric materials for many applications, especially for drug delivery purposes. Since one of the most worrisome adverse effects of anticancer drugs such as doxorubicin (Dox), cisplatin and Fluorouracil (5FU) is cardiotoxicity, finding a possible novel strategy to prevent or manage this lethal side effect should be considered as one of the most important issues for investigation. In this study, we fabricated a fibrous scaffold containing encapsulated Dox to prevent Dox-induced cardiomyopathy with limited clinical use and improve clinical outcomes of chemotherapy in cancer patients. Simultaneous electrospinning-electrospraying was used to produce hybrid nanofibers intended to be used for controlled releases of doxorubicin. Boron nitride nanotubes (BNNTs) clusters were synthesized and employed for encapsulation of Dox and then they were subjected to electrospraying. Electrospinning of polycaprolactone (PCL) solution was performed simultaneously to provide a nanofiber network substrate for BNNT/Dox nanocapsules. Polycaprolactone nanofibers with average diameters at the range of 240 ± 55–450 ± 50 nm were synthesized depending on various electrospinning conditions. BNNTs/Dox homogenous solution in methanol/acetone (50/50 V/V) was prepared and electrosprayed on the surface of the nanofibers. Different properties of the produced electrospun mats such as morphology, thermal characteristics and in vitro drug releases were investigated. The results revealed the excellent thermo-pH sensitivity of the prepared BNNTs/PCL functional nano-mats.

Hybrid polymer composite materials. Part 2. Preparation technology

The main methods (pressing and winding) of the processing of hybrid polymer composites to obtain items were examined. Advantages and disadvantages of the methods were noted. Good combinations of different-module fibers (carbon, glass, boron, organic) in hybrid polymer materials are described, which allow one to prepare materials with high compression strength on the one hand, and to increase fracture energy of samples and impact toughness on the other hand.

Design, synthesis, and characterization of novel organic–inorganic hybrid polymeric materials for electroluminescence applications

Design and syntheses of two electroluminescent metallopolymers from a novel, multidentate, redox active, and di-anionic organic building block.

A perspective on polyoxometalates as versatile synthons for precisely hybridized polymer materials

AbstractWe summarize the emerging advances of polyoxometalate (POM)–polymer hybrid materials in the last decade and chart the future possibilities in this field. The discussion is mainly focused on two critical roles of POMs: the structural synthon for fabricating well‐defined macromolecular architectures, and the functional synthon for advanced hybrid polymer materials in energy‐ and health‐related applications. The precise structures, modular synthesis and task‐directed functional design to overcome the current societal challenges are proposed to be a developing trend in POM–polymer hybrid materials. © 2019 Society of Chemical Industry

Polyoxometalate-Polymer Hybrid Materials as Proton Exchange Membranes for Fuel Cell Applications.

As one of the most efficient pathways to provide clean energy, fuel cells have attracted great attention in both academic and industrial communities. Proton exchange membranes (PEMs) or proton-conducting electrolytes are the key components in fuel cell devices, which require the characteristics of high proton conductivity as well as high mechanical, chemical and thermal stabilities. Organic–inorganic hybrid PEMs can provide a fantastic platform to combine both advantages of two components to meet these demands. Due to their extremely high proton conductivity, good thermal stability and chemical adjustability, polyoxometalates (POMs) are regarded as promising building blocks for hybrid PEMs. In this review, we summarize a number of research works on the progress of POM–polymer hybrid materials and related applications in PEMs. Firstly, a brief background of POMs and their proton-conducting properties are introduced; then, the hybridization strategies of POMs with polymer moieties are discussed from the aspects of both noncovalent and covalent concepts; and finally, we focus on the performance of these hybrid materials in PEMs, especially the advances in the last five years. This review will provide a better understanding of the challenges and perspectives of POM–polymer hybrid PEMs for future fuel cell applications.

Polymer network of graphene oxide with covalently attached 2-(4′-Hydroxyphenyl)fulleropyrrolidine and Palladium: Synthesis, properties and theoretical studies

A new single layer graphene oxide hybrid polymeric material was fabricated in which the fullerene moieties covalently attached to the edges of surface of SLGO sheets were coordinated to palladium atom in an η2-fasion, SLGO-php-C60/Pd. The polymer was characterized by SEM, TEM, FT-IR and Raman techniques. The newly formed material exhibited reversible electrochemical activity in the negative potential range due to the reduction of fullerene cages with an overall electrochemical behavior resembling that of typical organic conducting polymers. The electron density of states calculated using DFT method clearly confirmed the fullerene cage reduction via electron transfer from the low-lying SLGO states. Therefore, coordination polymers of fullerene moieties bonded to the graphene sheets are easier to reduce in comparison to the coordination polymers of pristine C60. In addition, the spectroscopic and electrochemical properties of SLGO-php-C60/Pd hybrid polymeric material were also compared with php-C60/Pd polymer and SLGO-php-C60 hybrid films to seek film morphology-property relations. The present study extends the application of graphene oxide providing electrically conducting, redox-active polymer material for different applications.

Hybrid materials – a review on co-dispersion, processing, patterning, and properties

ABSTRACT Inorganic and organic hybrids are a class of new materials that are purposely designed and arranged at individual species levels (often at nanoscale) to provide new morphological attributes and properties. This review is intended to offer a systematic discussion and understanding of nanoparticle–polymer hybrid materials. First, integration of nanoparticles and organic matrices is explained from two aspects: mixing of nanoparticles and organic matrix materials and in-situ formation of hybrids; the latter includes both in-situ nanoparticle formation and in-situ polymerisation. Traditional processing techniques for hybrids, such as spin coating and casting, are briefly reviewed followed by more detailed discussion on patterning through self-organisation, laser-induced patterning, and nanoimprint lithographic moulding. The extraordinary potentials of hybrids in existing property improvement and new property creation, including mechanical property, electronic property, optical property, catalytic property, magnetic property, and sensing property are presented. Lastly, opportunities and challenges for future hybrid material development are provided.

Composites of hydrophilic polymers and organic nanocrystals enable enhanced robustness

We describe a new family of composite materials, polymer/organic nanocrystal (ONC) hybrids. These were prepared from soluble ONCs based on perylene diimides (PDI) and water‐soluble polymers (sodium alginate and polyvinyl alcohol). Polymer/ONC films were characterized by optical spectroscopy, electron microscopy, and tensile strength studies. The films show enhanced chemical and mechanical stability due to synergy between the constituents. The hybrid films are stable in both water and organic solvents, unlike the individual components. The ONCs we employed possess nonlinear optical activity (second harmonic generation, SHG); they showed improved photostability (stable SHG under laser light) in the hybrids. Tensile strength enhancement (as high as twofold in the film having just 2.4% ONCs by weight) was observed as revealed by mechanical measurements. Hybrids with aligned ONCs were also prepared using simple extrusion via syringe needle followed by gelation. Employing ONCs in polymeric hybrid materials enables facile fabrication in aqueous media, synergy, chemical, mechanical, and photostability as well as useful photofunction (SHG), introducing a versatile class of composite materials.

Surfactant modulated structural modification of hybrid poly(p-phenylenediamine)/titanium dioxide composites and investigation of their functional behaviour

Hybrid polymer materials obtained by combining functional polymers with metal oxides are important functional materials having significant technological implications. Herein, we have described surfactant modulated structural manipulation of hybrid poly(p-phenylenediamine)/\(\hbox {TiO}_{2}\) composites using oleic acid as the surfactant molecule and investigated functional utility of the polymer composites. Hybrid polymer composites were synthesized by an oxidative polymerization technique using \(\hbox {H}_{2}\hbox {O}_{2}\) as the oxidant and chloroglycinato(1,10-phenanthroline) copper(II) monohydrate as the catalyst. Structural characterization was performed by using conventional techniques like Fourier-transform infrared, ultraviolet–visible spectroscopy, photoluminescence, X-ray diffraction and thermogravimetric analysis. The effect of structural modification on the functional behaviour of the hybrid polymer composites was investigated and important observations were noted. Structural modification of the hybrid polymer composites significantly improved the mechanical and thermal characteristics. Conductivity values obtained from I–V measurement and band gap calculation indicate that there is scope for using such materials as wide band gap semiconductor materials and also as insulator materials.

Novel terpolymers containing carbazole, coumarin and Alq3 complexes

Abstract In this paper, the synthesis of terpolymers bearing carbazole, coumarin and 8-hydroxyquinoline moiety as pendant groups with content of coumarin and 8-hydroxyquinoline between 0.5 and 4 mol% was elaborated. Then the terpolymers underwent complexation reactions with aluminum bis(8-hydroxyquinoline)isopropoxylate (Alq2ispr) to form polymeric hybrid materials with aluminum tris(8-hydroxyquinoline) (Alq3) as side groups. The presence of carbazole, coumarin (MK) and 8-hydroxyquinoline (QM) as well as Alq3 in the terpolymers was confirmed by NMR, UV, photoluminescence, and size exclusion chromatography. The results indicates that these hybrid polymers have moderate molecular weights and solubility in common organic solvents. For photoluminescence spectra, an evidence for energy transfer from carbazole to coumarin and Alq3 groups was observed and highest relative fluorescence intensity was exhibited by solutions of the terpolymers containing the lowest content of MK, QM and Alq3.

Composite Materials: Excellent Nanofiber Adhesion for Hybrid Polymer Materials with High Toughness Based on Matrix Interdiffusion During Chemical Conversion (Adv. Funct. Mater. 8/2019)

Composite Materials: Excellent Nanofiber Adhesion for Hybrid Polymer Materials with High Toughness Based on Matrix Interdiffusion During Chemical Conversion (Adv. Funct. Mater. 8/2019)

Improvement of the transparency, mechanical, and shape memory properties of polymethylmethacrylate/titania hybrid films using tetrabutylphosphonium chloride

The crosslink density adjustment strategy based on tetrabutylphosphonium chloride allows for the design of multifunctional hybrid polymer materials that are optically clear and combine excellent mechanical and shape memory properties.

Excellent Nanofiber Adhesion for Hybrid Polymer Materials with High Toughness Based on Matrix Interdiffusion During Chemical Conversion

AbstractOne of the challenges for multiphase materials is the improvement of the interconnectivity of their separate phases. A promising route toward excellent adhesion is molecular interdiffusion, in which molecules are transferred to enable physical interaction. In the present work, a novel straightforward and direct method is developed to tune the adhesion between electrospun nanofibers and their matrix, starting from fundamental insights on molecular diffusion and considering in situ chemical formation of one of the polymer phases to effectively regulate interdiffusion. Proof‐of‐concept is provided for the adhesion of a thermoplastic phase (poly(ε‐caprolactone)) to a thermoset matrix (epoxy) during the cured‐induced formation of the latter. For isothermal curing, only an intermediate temperature (50 °C) allows the production of nanofiber hybrid materials with good adhesion between the constituents and preservation of the nanomorphology. Moreover, excellent adhesion properties are obtained in case a two‐step curing (25 °C/80 °C), or coaxial electrospinning (polyamide 6/poly(ε‐caprolactone)) toward core–shell nanomorphologies is applied. Improvements in toughness of the optimized interdiffused materials with G values over 600 J m−2 (up to 65% improvement) are recorded due to excellent bonding of the thermoplastic nanofibers with the matrix.