In situ poly(sodium acrylate)‐based nanocomposite formation by redox‐initiated solution polymerization

Polymer‐based nanocomposites have been widely investigated as a potential method to modify polymer and biopolymer properties. Poly(sodium acrylate) (PNaA)/nanosilver nanocomposites with 0.5, 1, 2, and 3 wt% nanofiller were prepared by in situ polymerization. The free radical, redox‐initiated, aqueous solution polymerization of NaOH‐neutralized acrylic acid was conducted in the presence of nanosilver. The progress of the polymerization was monitored using gravimetric conversion measurements. The addition of 0.5 wt% nanosilver to the polymerization resulted in a significant decrease in rate of polymerization The effect on rate was noticeably reduced when the experiment was repeated with nanoclay, a nonmetallic nanofiller, in lieu of nanosilver. POLYM. ENG. SCI., 55:1230–1236, 2015. © 2015 Society of Plastics Engineers     

Effect of nanosilver on the photodegradation of poly(lactic acid)

The poly(lactic acid), PLA, mixed with nanosilver in solution easily forms nanocomposite in solid state (after solvent evaporation), which was proved by UV–Vis spectroscopy. This work focuses on photodegradation occurring in PLA films doped with nanosilver. The changes in chemical structure of photodegraded PLA has been determined using FTIR spectroscopy. Differential scanning calorimetry of UV‐irradiated PLA samples provided information on polymer glass transition and crystallization/melting processes. It was found that PLA alone is more sensitive to photodegradation than PLA/silver nanocomposites. The mechanism of nanocomposite photodegradation and effect of nanosilver was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40144.     

Remote actuation of hydrogel nanocomposites: Heating analysis,modeling, and simulations

Recently, there has been increasing interest in remote heating of polymer nanocomposites for applications such as actuators, microfluidic valves, drug delivery devices, and hyperthermia treatment of cancer. In this study, magnetic hydrogel nanocomposites of poly(ethylene glycol) (PEG) with varying amounts of iron oxide nanoparticle loadings were synthesized. The nanocomposites were remotely heated using an alternating magnetic field (AMF) at three different AMF amplitudes, and the resultant temperatures were recorded. The rate of the temperature rise and the steady state temperatures were analyzed with a heat transfer model, and a correlation of heat generation per unit mass with the nanoparticle loadings was established for different AMF amplitudes. The temperature rise data of a PEG system with different swelling properties were found to be accurately predicted by the model. Furthermore, the correlations were used to simulate the temperatures of the nanocomposite and the surrounding tissue for potential hyperthermia cancer treatment applications. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Eco‐friendly produced lightweight structural graphene/polyamide 12 nanocomposite: Mechanical performance and the controlling microstructural mechanisms

The present study explores the potential use of graphene nanoplatelets (GL‐GNPs), synthesized from glucose through a new chemical approach that is facile, economical, and eco‐friendly alternative to the conventional Hummer's method, as a nanoreinforcement in polymers for the production of light‐weight structural polymer nanocomposites. Understanding the interface character of GL‐GNPs/Polyamide 12 (PA12) nanocomposites with various nanofiller loadings and how this affects their tensile behavior, are focal points of interest. Results reveal that enhancements in polymer stiffness and strength are superior at low GL‐GNPs content than higher contents. This is attributed to higher degree of GL‐GNPs exfoliation and increased polymer phase crystallinity. Interestingly, abundant small/imperfect PA12 crystallites have grown on the GL‐GNPs surface, strongly interlinking thus the polymer and graphene phases within nanocomposites. The intensity of such crystallites in interface region is the determinant of the nanocomposites' Young's modulus, assessed at small applied tensile stress. While the GL‐GNPs‐PA12 interfacial bonding is the determinant of yield and ultimate strengths, estimated at medium and high stress levels. Overall, the 1 wt% GL‐GNPs/PA12 nanocomposite is considered the optimum. Its low density and good mechanical performance among the previously developed graphene/Polyamide nanocomposites, propose promising future for GL‐GNPs‐based nanocomposites as ecofriendly and cost‐effective lightweight structural material. POLYM. ENG. SCI., 58:1201–1212, 2018. © 2017 Society of Plastics Engineers     

Ultrasound assisted twin screw extrusion of polymer-nanocomposites containing carbon nanotubes

The unique morphology and strong intertube attraction between carbon nanotubes (CNTs) make the dispersion of CNTs challenging and hence limit its effective use. A novel method for the continuous dispersion of multi-walled carbon nanotubes (MWNTs) in a polymer matrix for manufacturing high performance nanocomposites was developed using an ultrasonically assisted twin screw extrusion process. Reduction of the die pressure and variation of the ultrasonic power consumption as a function of amplitude were measured at various MWNT loadings. The effect of ultrasound on rheological, electrical, morphological and mechanical properties of polyetherimide (PEI) matrix and PEI-filled with 1-10 wt% MWNTs was studied. In the treated nanocomposites, the complex viscosity, storage and loss moduli were increased and damping characteristics were decreased as compared to untreated ones. Rheological and electrical percolations were found to be between 1 and 2 wt% MWNT loading. Ultrasonic treatment does not affect the electrical conductivity of nanocomposites. Mechanical properties such as Young's modulus and tensile strength were significantly increased with MWNT loading but moderately with ultrasonic treatment at high loadings and certain ultrasonic amplitudes. The morphology and state of dispersion of MWNTs were investigated by means of HRSEM. In the ultrasonically treated nanocomposites, the obtained micrographs showed excellent dispersion of MWNTs in PEI matrix.     

Studies on physico-mechanical properties and thermal characteristics of polypropylene/layered silicate nanocomposites

Polypropylene/layered silicate nanocomposites were prepared from base polymer (10 MFI) and octadecylamine modified montmorillonite (1.30P nanomer), melt compounded with and without compatibilizer, i.e., maleic anhydride grafted polypropylene (Epolene-G3015). Physico-mechanical properties of the virgin PP and nanocomposites with different nanomer percentages and compatibilizer loadings were studied and compared. Thermal characteristics of nanocomposites were also compared with those of the virgin polymer. TEM analysis of the nanocomposites was carried out to study the dispersion of nanomer in the resulting hybrids. The nanocomposites showed improved mechanical properties over those of the virgin polymer with a marginal increase in specific gravity. Addition of compatibilizer further enhanced the mechanical properties of nanocomposites because of the compatibilization of the clay and host polymer interface. The uncompatibilized nanocomposites showed an increase in thermal stability and a higher melting point. However, the compatibilized nanocomposites showed delayed crystallization due to the presence of an oligomeric fraction of the added Epolene. Polym. Compos. 25:646–652, 2004. © 2004 Society of Plastics Engineers.     

Remarkable change in the broadband electrical behavior of poly(vinylidene fluoride)–multiwalled carbon nanotube nanocomposites with the use of different processing routes

Poly(vinylidene fluoride) (PVDF) nanocomposites have plenty of applications in the electronic realm. In this study, we produced nanocomposites based on PVDF and multiwalled carbon nanotubes (MWCNTs), with various MWCNT loadings, using three different processing routes: solution mixing, melt mixing, and electrospinning. The broadband electrical behavior of these nanocomposites was studied and compared via impedance spectroscopy. The morphologies of the nanocomposites were characterized by transmission electron microscopy and scanning electron microscopy. The results reveal that the electrical behaviors of the samples were completely different according to the processing route used. Solution mixing was the most suitable method for producing nanocomposites with the highest conductivities, at low MWCNT loadings, whereas electrospinning was the most suitable method for producing nanocomposites with the lowest dielectric permittivity. These differences were attributed to the different arrangements of the MWCNTs caused by the different processes. Although the solution-mixed samples exhibited long and twisted MWCNTs, the melt-mixed samples had shorter MWCNTs, and the electrospun samples had MWCNTs embedded and aligned inside the insulating polymer nanofibers. Thus, these results project a vast horizon for tailoring the structure and thereby the broadband electrical behavior of PVDF–MWCNT nanocomposites for different types of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47409.     

Reinforcement in melt-processed polymer–graphene composites at extremely low graphene loading level

We have prepared polymer nanocomposites reinforced with exfoliated graphene layers solely via melt blending. For this study polyethylene terephthalate (PET) was chosen as the polymer matrix due to its myriad of current and potential applications. PET and PET/graphene nanocomposites were melt compounded on an internal mixer and the resulting materials were compression molded into films. Transmission electron microscopy and scanning electron microscopy revealed that the graphene flakes were randomly orientated and well dispersed inside the polymer matrix. The PET/graphene nanocomposites were found to be characterized by superior mechanical properties as opposed to the neat PET. Thus, at a nanofiller load as low as 0.07 wt%, the novel materials presented an increase in the elastic modulus higher than 10% and an enhancement in the tensile strength of more than 40% compared to pristine PET. The improvements in the tensile strength were directly correlated to changes in elongation at break and indirectly correlated to the fracture initiation area. The enhancements observed in the mechanical properties of polymer/graphene nanocomposites achieved at low exfoliated graphene loadings and manufactured exclusively via melt mixing may open the door to industrial manufacturing of economical novel materials with superior stiffness, strength and ductility.     

High-density polyethylene reinforced by low loadings of electrochemically exfoliated graphene via melt recirculation approach

The purpose of the paper is to demonstrate the effectiveness of high-aspect ratio electrochemically exfoliated graphene (EEG) as a filler in high-density polyethylene (HDPE); we use an industrially viable polymer processing technique (melt blending with melt recirculation) to ensure excellent dispersion and reinforcement at low loadings. The effects of nanofiller loading were evaluated for two different HDPE grades with two different melt flow indices (MFI) based on crystallization, tensile, and rheological properties. The findings indicate improvements in mechanical properties (tensile modulus and tensile strength) for all HDPE/EEG nanocomposite samples; however, the reinforcement was more pronounced at 0.2 wt% loading, indicating a transition from excellent dispersion at lower loadings to aggregated at higher loadings. The low and high MFI HDPE/EEG nanocomposites at 0.2 wt% EEG loading displayed an improvement of 31% and 40% in tensile modulus and 19% and 33% in tensile strength, respectively. The improved mechanical response with higher MFI nanocomposites is likely due to enhanced dispersion associated with the lower melt viscosity. Similarly, the rheological results also showed maximum increase in storage and loss modulus at a loading of 0.2 wt% EEG. In conclusion, EEG can be an effective filler if proper dispersion is achieved, which is challenging at high loadings.     

Effect of nanoclay on the morphology and properties of acrylonitrile butadiene styrene toughened polyoxymethylene (POM)/clay nanocomposites

Here, we report the morphology and properties of melt‐blended poly(acrylonitrile‐butadiene‐styrene) (ABS) toughened polyoxymethylene (POM)/clay nanocomposites at different clay loadings (2.5 and 5 phr). The number average domain diameter (D_n) of the ABS droplets in the (75/25 w/w) POM/ABS blend was gradually decreased with increase in clay loading. The X‐ray diffraction (XRD) study and transmission electron microscopic (TEM) analysis of the (75/25 w/w) POM/ABS/clay nanocomposites revealed that, the major amount of clay silicates was dispersed selectively in the POM phase of the blend with an exfoliated morphology. The thermal stability of the (75/25 w/w) POM/ABS blend was increased with the increase in clay loadings. Differential scanning calorimetry (DSC) study suggested the enhancement in the non‐isothermal crystallization temperature of the matrix polymer in the blend/clay nanocomposites. The rheological study revealed a shear thinning behavior in the nanocomposites indicating good processability of the nanocomposites. The solvent uptake property of the blend was decreased in the presence of small amount of the clay in the nanocomposites. The tensile strength and Young modulus of the (75/25 w/w) POM/ABS blend were increased, whereas, percent elongation of the blend was decreased with increasing the clay content. The toughening effect of the ABS was prominent in the POM/ABS/clay nanocomposites compared to the pristine polymer. POLYM. COMPOS., 35:273–282, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of EVA/clay Nanocomposites with improved barrier performance

Poly (ethylene‐co‐vinyl acetate) (EVA)/clay nanocomposites containing two different organoclays with different clay loadings were prepared. The transport of gases (oxygen and nitrogen) through the composite membranes was investigated and the results were compared. These studies revealed that the incorporation of nanoclays in the polymer increased the efficiency of the membranes toward barrier properties. It was also found that the barrier properties of the membranes decreased with clay loadings. This is mainly due to the aggregation of clay at higher loadings. The morphology of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy and X‐ray scattering. Small angle X‐ray scattering results showed significant intercalation of the polymer chains between the organo‐modified silicate layers in all cases. Better dispersed silicate layer stacking and more homogeneous membranes were obtained for Cloisite® 25A based nanocomposites compared with Cloisite® 20A samples. Microscopic observations (SEM and TEM) were coherent with those results. The dispersion of clay platelets seemed to be maximized for 3 wt % of clay and agglomeration increased with higher clay loading. Wide angle X‐ray scattering results showed no significant modifications in the crystalline structure of the EVA matrix because of the presence of the clays. The effect of free volume on the transport behavior was studied using positron annihilation spectroscopy. The permeability results have been correlated with various permeation models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt-spinning of LDH/HDPE nanocomposites

Melt-spinning of layered double hydroxide (LDH)/high density polyethylene (HDPE) nanocomposites was reported for the first time. Initially LDH/HDPE nanocomposites were prepared by melt-mixing, in which clay loadings were up to 3 wt% while compatibilizer to clay ratio was kept to be 2:1. LDHs were hydrophobically modified by hexadienoic acid, tetradecanoic acid, and octadecanoic acid to overcome the incompatibility between matrix polymer and LDH. The organomodified LDH showed different interlayer arrangements. Both the modifications and the processing conditions affected the properties of melt-spun fibers. Nanocomposites were rheologically characterized by using a classical semi-quantitative method and additionally by a rather new method, which is an interpretation of Carreau–Yasuda model. Tetradecanoic acid modified LDH at 1 wt% filler loading was found to give most notable results.     

Impact of titanium and silica/titanium fumed oxide nanofillers on the elastic properties and thermal decomposition of a polyester resin

The impact of nanoparticles of titanium (rutile) and silica–titanium fumed oxide (STO) on both the acoustic properties and thermal decomposition of a styrene‐crosslinked unsaturated polyester resin were studied with the methods of ultrasonic probing and thermal decomposition mass spectrometry at filler loadings ranging from 0.5 to 5.0%. It was shown that the elastic modulus, Poisson's ratio, and thermal resistivity in the titanium‐filled nanocomposites increased at small loadings of about 0.5%, whereas in the STO‐filled nanoparticles, the decreases in the parameters at loadings of up to 1.5% was replaced by some increases at higher loadings of up to 5.0%. Distinctions in the concentration dependences of the elastic parameters and the thermal decomposition intensity for both fillers could be explained by the features of the polymer–particle interactions because of the differences in both the number of active sites located on the particle's surface and the polymer structure within interface regions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42010.     

Influence of organic modification on mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites

The influence of organic modifiers on intercalation extent, structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)–clay nanocomposites were studied. Two different organic modifiers with varying hydrophobicity (single tallow versus ditallow) were investigated. The nanocomposites were prepared from melt processing method and characterized using wide angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. Mechanical properties such as tensile modulus (E), break stress (σ_brk), and % break strain (ε_brk) were determined for nanocomposites at various clay loadings. Extent of PMMA intercalation is sufficient and in the range 9–15 Å depending on organoclay and filler loading. Overall thermal stability of nanocomposites increases by 16–30°C. The enhancement in T_g of nanocomposite is merely by 2–4°C. With increase in clay loading, tensile modulus increases linearly while % break strain decreases. Break stress is found to increase till 4 wt % and further decreases at higher clay loadings. The overall improvement in thermal and mechanical properties was higher for the organoclay containing organic modifier with lower hydrophobicity and single tallow amine chemical structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheological behavior of new melt compounded copolyamide nanocomposites

In this paper the rheological behavior of new polyamide-based nanocomposites produced by melt compounding using three different silicate loadings and screw speeds was investigated. The thermoplastic matrices selected were a polyamide 6 and its statistical copolymer having partially aromatic structure, whereas the clay was a commercial organo-modified montmorillonite. Hybrid systems were prepared by means of a laboratory-scale twin screw extruder and were submitted to rheological and structural investigations. The rheological experiments (dynamic frequency sweep, steady rate sweep and stress relaxation tests) were performed to evaluate the effect of both system composition (kind of matrix and clay content) and extrusion rate on the flow behavior of the nanocomposites. Rheology, that is highly sensitive to the nanoscale structure of the materials, put out a pseudo-solid like flow behavior at long times in the hybrids with silicate content higher than 6 wt% and produced with high extrusion rate; this response was related to the formation of an extended structural network across the polymer matrix due to strong polymer-silicate interactions that slow the relaxation times of the macromolecules. Corresponding to this behavior, TEM micrographs have shown a quite uniform dispersion of clay particles on micron-scale and a fair level of silicate exfoliation on nanoscale with a macroscopic preferential orientation of the layers in samples. The rheological measurements also reveal that this flow response is more marked for nanocomposites based on the copolyamide matrix, suggesting that this resin may have a higher silicate affinity respect to polyamide 6 homopolymer.     

Ultrasound–assisted synthesis and characterization of polymethyl methacrylate/reduced graphene oxide nanocomposites

This article reports ultrasound–assisted synthesis of polymethyl methacrylate (PMMA)/reduced graphene oxide (RGO) nanocomposites by in situ emulsion polymerization coupled with in situ reduction of graphene oxide. The thermal degradation kinetics of the nanocomposites was also assessed with Criado and Coats‐Redfern methods. Intense microconvection generated by ultrasound and cavitation results in uniform dispersion of RGO in the polymer matrix, which imparts markedly higher physical properties to resulting nanocomposites at low (≤1.0 wt %) RGO loadings, as compared to nanocomposites synthesized with mechanical stirring. Some important properties of the PMMA/RGO nanocomposites synthesized with sonication (with various RGO loadings) are: glass transition temperature (0.4 wt %) = 124.5°C, tensile strength (0.4 wt %) = 40.4 MPa, electrical conductivity (1.0 wt %) = 2 × 10^?7 S/cm, electromagnetic interference shielding effectiveness (1.0 wt %) = 3.3 dB. Predominant thermal degradation mechanism of nanocomposites (1.0 wt % RGO) is 1D diffusion with activation energy of 111.3 kJ/mol. © 2017 American Institute of Chemical Engineers AIChE J, 64: 673–687, 2018     

Mass‐produced graphene—HDPE nanocomposites: Thermal,rheological, electrical,and mechanical properties

Economically viable high‐density polyethylene (HDPE)/graphene nanocomposites were produced using mass produced graphene powder and an industrial twin‐screw melt‐compounding machine. Rheological and electrical properties were investigated and scanning electron microscopy was carried out to investigate graphene dispersion and its network formation in the matrix. Mechanical properties of the nanocomposites were evaluated using tensile, flexural and impact tests. Differential scanning calorimetry analysis indicated that the crystalline structure of the polymer might be affected by high loadings of graphene. SEM evaluation revealed reasonable graphene dispersion in the matrix. In addition, the amount of graphene required to form a percolated network was similar for both rheological and electrical networks. The nanocomposites exhibited a significant increase in Young's and flexural moduli without a notable reduction in impact strength up to 14 wt% graphene loading. In these experiments, compounding graphene powder with HDPE produced a clear and distinct improvement in mechanical properties at an industrially suitable low cost. POLYM. ENG. SCI., 59:675–682, 2019. © 2018 Society of Plastics Engineers     

Formation of polypropylene/functional graphene oxide nanocomposites with Different FGs loading in elongation flow condition

Aggregation of nanofiller in polymer matrix is the key barrier to enhance the mechanical and thermal properties of polymer nanocomposites. Here, we report a novel vane mixer based on elongation flow processing, which is facial to achieve the homogeneous dispersion of functional graphene oxide sheets (FGs) in isotactic polypropylene (iPP). Scanning electron microscopy reveals that FGs in iPP matrix are fully exfoliated and uniformly dispersed. The crystallization behavior, mechanical properties and thermal stability of the nanocomposites with different FGs loadings are investigated by differential scanning calorimetry, dynamic thermomechanical analysis, and thermogravimetric analysis, respectively. The results illustrate that the mechanical and thermal stability of the iPP/FGs composites has enhancement obviously at low FGs loadings. POLYM. ENG. SCI., 59:830–837, 2019. © 2018 Society of Plastics Engineers     

Chemical Grafting of Crosslinked Polypyrrole and Poly(vinyl Chloride) onto Modified Graphite: Fabrication,Characterization, and Material Properties

ABSTRACT

Conjugated polymer/graphite nanocomposites have been known as high performance materials owing to improve the physicochemical properties relative to conventional once. Multilayered polymer nanocomposites based on polypyrrole (PPy), polyvinylchloride (PVC) as matrices and p-phenylene diamine (PDA) as linker were prepared via chemical in situ polymerization process and subsequently investigated the physical characteristics of fabricated nanocomposites at various loadings. The structural characterization and morphology of prepared nanocomposites were inspected by Fourier transform infrared spectroscopy (FTIR), X-ray photon spectroscopy (XPS), energy dispersive X-ray spectroscope (EDX), field emission scanning electron microscope (FESEM), respectively. The composite III showed higher thermal stability at 10 wt% loading of PPy. According to differential scanning calorimetry (DSC), the glass transition temperature (T_g), melting temperature T_m, and crystallization temperature (T_c) of nanocomposites increases with PPy loading (2–10 wt%) owing to crosslinking and chain rigidity. Moreover, higher surface area was displayed by the multilayered PPy/PVC/PDA@FG nanocomposites. Remarkably, electrical conductivity of ultimate nanocomposites was also found to be a function of PPy loading.     

Studies on conducting polymer intercalated layered double hydroxide nanocomposites: Antituberculosis drug delivery agents

The synthesis of layered double hydroxide (LDH) was carried out using different ratios of Mg:Al. The intercalation of polypyrrole (Ppy) within interlayer space of LDH was carried out via ultrasonication using different loadings of the conducting polymer. Fourier transform infrared (FTIR) spectra and XRD analysis showed successful intercalation of Ppy in LDH while UV-visible spectra confirmed polaronic state of the conducting polymer within the LDH. Scanning electron microscopy and transmission electron microscopy studies showed successful incorporation of Ppy and loading of the drug was also established. The concentration of Rifampicin, an antituberculosis drug in LDH/Ppy, was confirmed by Langmuir adsorption isotherm. The in vitro release characteristics showed sustained release behaviour at pH 7.4 for a period of 180 hours. The nanocomposites exhibited immense potential for their application as Rifampicin drug carriers.