Effective permittivity of nanocomposites from 3D charge transport simulations

The effective permittivity and stored energy in nanocomposites incorporating dielectric and conducting nanofillers are computed by simulating bipolar charge injection, transport, attachment, and recombination through amorphous polymer using a self‐consistent 3D particle‐in‐cell model with nanofillers treated as extensions to the classical electrical double layer. Effective permittivities computed using an energy conserving scheme is shown to have excellent agreement with the Lichtenecker, Bruggeman, and Maxwell‐Garnett mixing rules especially at low volume fraction, low permittivity contrast, and small Clausius‐Mossotti factor, and lie well within the Wiener bounds. The energy conserving scheme with Maxwell‐Garnett E field interpolation combines the best of the Maxwell‐Garnett and fundamental Lichtenecker rules and results in broad validity over the entire volume fraction range. Computed stored energies show monotonic increase with dielectric fillers and a peak at 25 vol % for conducting fillers, attributed to the competing effects of higher energy with increasing E field modification and lower energy with decreasing binder volume. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43300.     

Design and preparation of cross‐linked α‐methylstyrene acrylonitrile copolymer nanoparticles and their interfacial investigation with rubber

Cross‐linked α‐methylstyrene and acrylonitrile (MStAN) copolymer particles in a latex form were synthesized by free radical emulsion polymerization. The particles showed a narrow size distribution and an average diameter of 65 nm. The amount of the vinyl groups at the surface of the (MStAN) copolymer particles resulted from varied amount of the initiator (APS) and the cross‐linking agent (DVB) was detected by iodine titration method. When filled into ethylene propylene rubber (EPR), the MStAN nano‐particles exhibited excellent reinforcing capabilities, and with the increase of the vinyl groups at the surface of MStAN particles, the tensile stress of MStAN/EPR increased. Results demonstrated that the vinyl groups at the surface of the (MStAN) copolymer particles provided certain chemical interactions between the filler particles and the macromolecular chains of rubber matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41914.     

Properties and nanoscale structure of polypropylene‐layered double hydroxide composites prepared by compatibilizer‐free way

Polypropylene (PP) is the second most widespread commodity polyolefin. Even a small quantity of inorganic component is sufficient to achieve significant improvement of stiffness, strength, thermal stability, biodegradability, etc. The major drawback of inorgano‐organic composite materials is insufficient compatibility of the PP matrix with inorganic filler. A suitable choice of the layered double hydroxide‐modifying anion opens a possibility to obtain PP‐inorganic nanocomposites without a need to use compatibilizers like maleic anhydride grafted PP. The nanocomposites were prepared by melt blending in a twin‐screw mini‐extruder and characterized by dynamic mechanical thermal analysis, and electron microscopy. Nonpolar PP matrix mix uniformly with clay organophilized with functionalized surfactant acids, giving rise to composites with improved thermo‐mechanical properties. Influences of the anionic modifier and the filler content (2 or 5% w/w) on mechanical properties and nanoscale structure of the composites are discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2429–2438, 2013     

Low‐cost,environmentally friendly route to produce glass fiber‐reinforced polymer composites with microfibrillated cellulose interphase

In this article, an easy, effective, and eco‐friendly method to improve the mechanical performance of glass fiber‐reinforced polymer composites is proposed, which involves the coating of unsized glass fiber fabric layers by simple immersion in an aqueous suspension containing sugarcane bagasse microfibrillated cellulose (MFC), followed by vacuum‐assisted liquid resin infusion as the processing method. From atomic force microscopy, a 250 nm MFC‐rich interphase was found, revealing its ability to build micro‐ and nanobridges acting as bulk epoxy matrix and GF linker. The interlaminar shear strength, quasi‐static tensile, and flexural tests, as well as the morphological and fractographic inspection of test coupons containing the secondary substructure, broadly supported the assumption of the efficient role on the interfacial level of this nano reinforcement by enhancing the load transference and distribution from the polymer matrix to the main reinforcing fiber system compared to baseline unsized fiber‐reinforced epoxy laminates. This finding permits this class of composite materials to be considered as having great potential to achieve products with excellent performance/cost ratios. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44183.     

Development of simplified Tandon‐Weng solutions of Mori‐Tanaka theory for Young's modulus of polymer nanocomposites considering the interphase

The known Tandon‐Weng model originated from Mori–Tanaka theory commonly underestimates the Young's modulus of polymer nanocomposites containing spherical nanofillers. This phenomenon is attributed to disregarding the nanoscale interfacial interaction between polymer and nanoparticles, which forms a different phase as interphase in polymer nanocomposites. In this paper, the simplified Tandon‐Weng model is developed assuming interphase and the predictions of the developed model are compared with the experimental data. The calculations of the developed model completely agree with the experimental results at reasonable levels of interphase properties. Additionally, the effects of main material and interphase properties on the predictions of modulus are evaluated. The developed model predicts that a high‐content, thick, and strong interphase creates a high modulus in polymer nanocomposites. These logical observations demonstrate the correctness of the developed model for Young's modulus of polymer nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43816.     

Poly(p‐phenylene sulfide) nanofibers prepared by CO2 laser supersonic drawing

Poly(p‐phenylene sulfide) (PPS) nanofibers are prepared by irradiating a PPS fiber with a carbon dioxide (CO₂) laser while drawing it at supersonic speeds. A supersonic jet is generated by blowing air into a vacuum chamber through the fiber injection orifice. Nanofibers obtained at a laser power of 30 W and chamber pressure of 10 kPa exhibit an average diameter of 600 nm and a draw ratio of 110,000. Scanning electron microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction analyses are employed to investigate the relationships among the chamber pressure, fiber morphology, and crystallization behavior. The nanofibers exhibit two melting temperatures (T_m): approximately 280°C and 320°C. The endothermic peak at T_m = 280°C is ascribable to lamellar crystals and that at T_m = 320°C to the highly complete crystals, since the polymer molecular chain is highly oriented. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40922.     

Poly(vinyl alcohol)/CaCO3‐diacid nanocomposite: Investigation of physical and wetting properties and application in heavy metal adsorption

Poly(vinyl alcohol) (PVA) nanocomposite and modified CaCO₃ nanoparticles (NPs) were fabricated by ultrasound agitation method with particle content altering from 3, 5, and 8 wt %. The CaCO₃ surface was successfully treated by 10 wt % of bioactive dicarboxylic acid (DA). The influences of loading modified NPs on the thermal, mechanical, adsorption, contact angle, and physical properties of the poly(vinyl alcohol) nanocomposite films were thoroughly studied. The results showed that incorporation of modified CaCO₃ into the PVA matrix had better performance than the pure PVA. Meanwhile, tensile strength, Young's modulus, and thermal stability are enhanced from 33.36 MPa, 1.26 GPs, and 242.918C (neat PVA) to 81.7 MPa, 4.81 GPa, and 312.95 °C (PVA/CaCO₃‐DA NC 5 wt %), respectively. Also, the adsorption capacity of the PVA/CaCO₃‐DA NCs 5 and 8 wt % revealed that the NC films could act as an appropriate absorbent for the removal of Cd(II) ions with maximum adsorption capacity of about 20.70 and 25.19 mg g^?1 for Cd(II), respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45414.     

Influence of a sorbitol‐based nucleating agent modified with silsesquioxanes on the non‐isothermal crystallization of isotactic polypropylene

This article investigates the effect of modifying the polypropylene (iPP) α‐phase nucleating agent 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) with tetrasilanolphenyl silsesquioxane (phPOSS). It has been proven that an increasing amount of silsesquioxane leads to differences in the crystallization behavior. What is more, it has been observed that the nucleation effect that results from the addition of sorbitol derivatives is suppressed by phPOSS activity. To understand the influence of phPOSS addition on the crystallization kinetics of PP/DMDBS/phPOSS composites that have been prepared by melt processing in a twin screw extruder, differential scanning calorimetry, rotational rheometry and Fourier transform infrared spectroscopy are performed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40131.     

Preparation of a polymer containing indole groups by RAFT polymerization and one‐phase synthesis of AuNPs‐polymer nanocomposites

A one‐phase synthesis of AuNPs‐polymer nanocomposites using HAuCl₄ as the precursor is reported in this article. A flexible polymer, poly(2‐(4‐(di(1H‐indol‐3‐yl)methyl)phenoxy) ethyl methacrylate) (PMPEM), containing indole groups on the side chain was utilized as both a reducing reagent and soft template in the system. The PMPEM‐Au nanocomposites with three different sizes of AuNPs (25–50, 2, and 5 nm) were obtained just through choosing different solvents such as toluene, tetrahydrofuran (THF), and N,N‐dimethylformamide, respectively. Nanocomposites including the size of 25–50 and 2 nm AuNPs showed strong NLO absorption and refraction behaviors. The nonlinear refractive index n₂ of PMPEM‐Au nanocomposites prepared in toluene and THF were 9.35 × 10^?11 and 1.85 × 10^?10 m²/W, third‐order susceptibility χ⁽³⁾ were 2.55 × 10^?11 and 4.26 × 10^?11 esu, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Antibacterial activity and cytotoxicity of hydrogel–nanosilver composites based on copolymers from 2‐acrylamido‐2‐methylpropanesulfonate sodium

In this research, we contributed to the search for potential hydrogel–silver dressings by generating hydrogel–silver nanoparticles (AgNPs) composites prepared by the dipping of the crosslinked hydrogel poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium) (1:1) and poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium) (1:1) into an aqueous suspension of citrate‐stabilized AgNPs. The composites obtained were evaluated by an antibacterial activity assay on Staphylococcus aureus and Escherichia coli and subjected to an in vitro cytotoxicity assay for human fibroblasts. The composite formed from the hydrogel poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium) with 3 mol % N,N‐methylene bisacrylamide showed the highest antibacterial activity and the least cytotoxicity among the composites tested; this makes it an excellent alternative as a potential dressing for the treatment of deep and exudative wounds. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39644.     

Development of highly reinforced maleated natural rubber nanocomposites based on sol–gel‐derived nano alumina

In the present study, sol–gel synthesized alumina (Al₂O₃) nanoparticles were characterized by Fourier transform infrared spectra, X‐ray diffraction, field‐emission scanning electron microscopy. Then, Al₂O₃ nanoparticles were employed to improve cure, mechanical, and thermal properties of maleated natural rubber (MNR) nanocomposites. The MNR nanocomposite with 2 phr nano Al₂O₃ exhibited excellent value of cure rate index and exceptionally high value of mechanical properties like modulus and tensile strength in comparison to unfilled MNR compound. Thermogravimetric analysis indicated that nano Al₂O₃ was able to improve the thermal stability of MNR composites to some extent. Additionally, the present study revealed that the interfacial interaction between MNR and nano Al₂O₃ was far better than that between NR and nano Al₂O₃ as confirmed from crosslinking degree measurement and morphological analysis. The present article offers a fresh approach to prepare high performance nano Al₂O₃‐based MNR compounds for future industrial application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46248.     

Preparation of highly emissive,thermally stable,UV‐cured polysilsesquioxane/ZnO nanoparticle composites

A high molecular weight polysilsesquioxane (LPMSQ)/ZnO nanocomposite was prepared by blending a methacryl‐substituted polysilsesquioxane and PMMA‐coated ZnO nanoparticle (NP) followed by UV‐curing process. These LPMSQ/ZnO nanocomposites gave high thermal and mechanical stabilities originated from the rigid ladder structured siloxane backbone of LPMSQ. The polysilsesquioxane and surface‐modified ZnO nanoparticles showed excellent compatibility between MMA groups in LPMSQ‐ and PMMA‐capped ZnO nanoparticles to give well‐dispersed LPMSQ/ZnO nanocomposites. Mechanically pliant and flexible free standing films were obtained, and the photo and optical properties of these hybrid nanocomposites were examined. The high photoluminescent properties were maintained even after severe thermal treatments exceeding 400°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42333.     

Preparation of 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 with tunable morphologies via polyacrylonitrile as a template and applications in lithium‐ion batteries

Samples of 0.4Li₂MnO₃·0.6LiNi_1/3Co_1/3Mn_1/3O₂ (LMO) with tunable morphologies were synthesized via polyacrylonitrile (PAN) as a template. The starting PAN/N,N‐dimethylformamide (DMF) ratios, including 1:9, 1:10, 1:12, and 1:14, were optimized for the fiber morphologies and electrochemical performance. Through electrospinning, metal salts were well dispersed in the PAN fibers. The crystal structure and morphologies of the PAN/LMO fibers were characterized by X‐ray diffraction, scanning electron microscopy, and thermal analysis. Along with the decrease in the concentration of PAN in the precursor, the diameters of the PAN/LMO fibers decreased. On the other hand, at the highest and lowest concentrations, 1:9 and 1:14, of PAN with DMF, micrometer PAN fibers were electrospun, whereas ratios of PAN to DMF of 1:10 and 1:12 resulted in the electrospinning of millimeter‐long fibers of PAN. In the interface of PAN and metal salts, LMOs were grown and accompanied the decomposition of PAN, and the crystal morphologies of LMO quite depended on the diameter and length of the PAN/LMO nanofibers. During heat treatment, the morphologies of the PAN fibers controlled the removal of small molecules and the crystal morphologies of LMOs. The charge/discharge results indicate that LMO with a tubular structure delivered a capacity of 262.3 mAh/g at a cutoff voltage of 2.5–4.8 V at a 0.1 C rate. Benefitting from a unique hollow and nanocrystalline architecture, it also exhibited good rate and cycling performances. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43022.     

Synthesis of Fe3O4@SiO2@MPS@P4VP nanoparticles for nitrate removal from aqueous solutions

In this study, synthesis of Fe₃O₄@SiO₂@MPS@poly(4‐vinylpyridine) core‐shell‐shell structure was investigated as an efficient adsorbent for removal of nitrate ions from aqueous solutions. Fe₃O₄ nanoparticles were initially prepared by co‐precipitation method, then the surface of Fe₃O₄ was coated with SiO₂ through a modified St öber method. Finally, the Fe₃O₄@SiO₂ nanoparticles were modified by 3‐(trimethoxysilyl) propyl methacrylate followed by emulsion polymerization of 4‐vinylpyridine. The resultant material was acidified in HCl solution to be effective for nitrate removal. The synthesized sample was characterized by X‐ray diffraction, transmission electron microscopy, field‐emission scanning electron microscopy, Fourier‐transform infrared spectra, thermogravimetric analysis (TGA), and vibrating sample magnetometer. The removal efficiency was optimized for some experimental parameters such as pH, contact time, and amount of sorbent loading. The maximum predictable adsorption capacity was 80.6 (mg nitrate/g sorbent) at optimum conditions. Also, regeneration of the nitrate adsorbed particles was possible with NaOH solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44330.     

Role of silk fibroin and rice starch on some physical properties of hydroxyapatite‐based composites

The role of organic blends of silk fibroin (SF) and rice starch (RS) in bone composites based on inorganic hydroxyapatite (HA) is studied. The physical property of HA‐based composites prepared by using the sol–gel method from Ca(OH)₂ and H₃PO₄ in ethanol and water solvent (4 : 1 volume ratio) could be improved by adding SF and RS (1 : 2 weight ratio) to HA (7 : 3 weight ratio). The Fourier transform infrared spectrometer spectrum shows that the SF and RS organic phases are blended homogeneously into the HA crystal structure. Addition of SF increases the pore size and surface area of the composites, as measured by Brunauer–Emmett–Teller method, but their pore volume is slightly decreased. The values of lattice parameters, crystallinity, and crystallite size, as determined from the field‐emission scanning electron microscope, transmission electron microscope, and X‐ray diffractometer results, increase after adding RS. The results are agreeable with the increase of their compressive strength and Young's modulus. Thus, the improved physical property of the prepared HA–SF/RS composites is better suited as bone‐filling material than the standard HA or HA‐based composites with either SF or RS only. Therefore, due to its low cost, biocompatibility, and nontoxicity, this innovative solution could be worth taken under consideration by the restorative dental and orthopedic implants industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42722.     

Mechanical properties study of micro‐ and nano‐hydroxyapatite reinforced ultrahigh molecular weight polyethylene composites

This is a comparative study between ultrahigh molecular weight polyethylene (UHMWPE) reinforced with micro‐ and nano‐hydroxyapatite (HA) under different filler content. The micro‐ and nano‐HA/UHMWPE composites were prepared by hot‐pressing method, and then compression strength, ball indentation hardness, creep resistance, friction, and wear properties were investigated. To explore mechanisms of these properties, differential scanning calorimetry, infrared spectrum, wettability, and scanning electron microscopy with energy dispersive spectrometry analysis were carried out on the samples. The results demonstrated that UHMWPE reinforced with micro‐ and nano‐HA would improve the ball indentation hardness, compression strength, creep resistance, wettability, and wear behavior. The mechanical properties for both micro‐ and nano‐HA/UHMWPE composites were comparable with pure UHMWPE. The mechanical properties of nano‐HA/UHMWPE composites are better compared with micro‐HA/UHMWPE composites and pure UHMWPE. The optimum filler quantity of micro‐ and nano‐HA/UHMWPE composites is found to be at 15 wt % and 10 wt %, separately. The micro‐ and nano‐HA/UHMWPE composites exhibit a low friction coefficient and good wear resistance at this content. The worn surface of HA/UHMWPE composites shows the wear mechanisms changed from furrow and scratch to surface rupture and delamination when the weight percent of micro‐ and nano‐HA exceed 15 wt % and 10 wt %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42869.     

Enhanced thermal conductivity of PLA‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid

Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp² network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46397.     

Annealing‐promoted unidirectional migration of organic‐modified nanoparticles embedded two‐dimensionally in polymer thin films

The spatial structures of oleic acid‐modified CeO₂ nanoparticles in polystyrene (PS) thin films spin‐coated on silicon substrates were observed by transmission electron microscopy, when the films underwent thermal annealing above the glass‐transition temperature of PS. Before annealing, the nanoparticles have segregated to the surface of the films, and formed two‐dimensional spatial structures in the PS films. Then, the nanoparticles migrated away from the film surface to the substrate/film interface during thermal annealing, maintaining the two‐dimensional spatial structures. In addition, we demonstrated that such unidirectional migration of nanoparticles across the PS film occurs regardless of the characteristics of the substrate surface, the concentration of nanoparticles, and the thickness of the films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42760.     

Investigations on the surface structure and properties of silica‐polyamine composites on the nanoscales and microscales

The structure and properties of silica polyamine composites (SPC) made from microparticles of amorphous silica gel (300–600 microns) and silica nanoparticles (10–20 nm) modified with aminopropyltrimethoxysilane (APTMS), poly(allylamine) (PAA) or poly(ethyleneimine) (PEI) have been studied. The APTMS nano‐hybrids showed batch capacities for copper equal to or better than the corresponding polymer‐based micro‐hybrids. Loading of the PEI on the nanoparticles was independent of molecular weight of the polymer. Dynamic light scattering measurements showed that the SiO₂ nanoparticles and the composites made from them aggregate in water and the degree of aggregation is dependent on the surface modification. All of the amine‐modified materials were catalysts for the Knoevenagel reaction but interestingly, the microparticles modified with APTMS were better catalysts than the corresponding nanoparticles or the polyamine modified composites. Solid‐state ¹⁹Si NMR has been used to elucidate the surface structure of the various composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42271.     

Preparation and characterization of poly(ϵ‐caprolactone‐co‐p‐dioxanone)–poly(ethylene glycol)–poly(ϵ‐caprolactone‐co‐p‐dioxanone)/bioactive inorganic particle nanocomposites

With an aim to develop injectable hydrogel with improved solution stability and enhanced bone repair function, thermogelling poly(ε‐caprolactone‐co‐p‐dioxanone)‐poly(ethylene glycol)‐poly(ε‐caprolactone–co‐p‐dioxanone) (PECP)/bioactive inorganic particle nanocomposites were successfully prepared by blending the triblock copolymer (PECP) with nano‐hydroxyapatite (n‐HA) or nano‐calcium carbonate (n‐CaCO₃). The hydrogel nanocomposites underwent clear sol–gel transitions with increasing temperature from 0 to 50°C. The obtained hydrogel nanocomposites were investigated by ¹H NMR, FT‐IR, TEM, and DSC. It was found that the incorporation of inorganic nanoparticles into PECP matrix would lead to the critical gelation temperature (CGT) shifting to lower values compared with the pure PECP hydrogel. The CGT of the hydrogel nanocomposites could be effectively controlled by adjusting PECP concentration or the content of inorganic nanoparticles. The SEM results showed that the interconnected porous structures of hydrogel nanocomposites were potentially useful as injectable scaffolds. In addition, due to the relatively low crystallinity of PECP triblock copolymer, the aqueous solutions of the nanocomposites could be stored at low temperature (5°C) without crystallization for several days, which would facilitate the practical applications. The PECP/bioactive inorganic particle hydrogel nanocomposites are expected to be promising injectable tissue engineering materials for bone repair applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013