Description of mechanical properties of particulate-filled nanostructured polymer composites using fractal analysis

A number of the main mechanical characteristics (yield strength, impact toughness, microhardness) of particulate-filled polymer nanocomposites are quantitatively described using fractal analysis. The approach is used to study the main mechanical behavior features of these materials. The influence of the initial particle size of nanofiller and the degree of particle aggregation on the mechanical properties of nanocomposites is shown.     

Structural Interpretation of Variation in Properties of Polymer/Carbon Nanotube Nanocomposites near the Nanofiller Percolation Threshold

Technical Physics - The structure of the nanofiller in the polymer matrix of polymer/carbon nanotube nanocomposites can be characterized by the dimension of the nanofiller network, which is a...     

Structural model for the reinforcement of polymethyl methacrylate/carbon nanotube nanocomposites at an ultralow nanofiller content

The structural basis of the anomalously high reinforcement of polymer/carbon nanotube nanocomposites at an ultralow nanofiller content is studied. This effect is shown to be caused by the absence of interaction between carbon nanotubes and the related sharp increase in the interphase adhesion. From the standpoint of a nanofiller structure, the effect disappears when three critical points related to the structure of carbon nanotubes in a polymer matrix are reached. These points are a percolation threshold, an aggregative nanofiller stability threshold, and the beginning of formation of closed circular carbon nanotube structures.     

Comparing the Effect of Micro- and Nano-Scale Silica on the Rheological,Dynamic Mechanical Properties and Flame Resistance of Nylon 6,6

Nylon 6,6 micro- and nano-silica composites were prepared by melt processing using a twin-screw extruder. Three nanocomposites containing 4, 8, and 12 wt.% of nanosilica were prepared. In order to compare the effect of size, a microcomposite containing 4 wt.% of micron-size silica was also prepared. The effects of particle type (micro- and nano-size) on the dynamic thermomechanical and rheological properties, morphology, and flame resistance of the composites were examined. The dynamic thermomechanical properties (DMTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic rheometry, thermogravimetry analysis (TGA), and limiting oxygen index (LOI) data are reported. The particles were observed to be dispersed uniformly, but with a different level of coalescence, by means of SEM and TEM. The DMTA results showed that the damping factor peak positions of the nanocomposites at low content of nanofiller shifted more to higher temperature compared to those of nanocomposites containing high concentrations of nanofiller. Dynamic rheometry, using a parallel plate rheometer, showed that the rheological moduli of the nanocomposites increased with increase in nanofiller concentration; however, this increase was greater in the high-frequency region. These results showed that increasing the concentration of nanofiller, and the consequent coalescence effect within the nanocomposites, led to rheological moduli values similar to those of the microcomposite. The TGA and LOI results of the microcomposite and nanocomposite containing 4wt.% of nanosilica showed that nanosilica had a more significant effect to enhance the heat and flame resistance of nylon 6,6 compared to that of micron-sized silica.     

Organic–inorganic nanocomposite films made from polyurethane dispersions and colloidal silica particles

Polyurethane/silica nanocomposites were prepared by solution blending of polyurethane water dispersion (PUD) based on polycarbonate macrodiol with colloidal silica aqueous sol LUDOX TMA. Because of mixing PUDs made from linear polyurethane with the nanofiller, only physical polymer/filler type of interface formed by hydrogen bonds was obtained. As a result the materials were possible to reuse after dissolution in acetone followed by dispersion in water. The effect of colloidal silica content on mechanical, thermal, morphological, and swelling properties of obtained films was tested by tensile test, dynamic mechanical thermal analysis, thermogravimertic analysis, scanning electron microscopy, atomic force microscopy, and swelling analyses. The nanocomposites were classified in three groups differing in the internal structure and functional properties: organic matrix filled with inorganic nanofiller (up to 10 wt% of silica), bicontinous systems (25 and 32 wt% of silica) and inorganic matrix filled with polyurethane (50 and 60 wt% of silica). Only small amount of colloidal silica (up to 10 wt%) improves thermo-mechanical properties, smoothes the materials, and suppresses extent of swelling without changing of the films transparency.     

Description of the degree of reinforcement of polymer/carbon nanotube nanocomposites in the framework of percolation models

A radically new percolation model for describing the extremal dependence of the degree of reinforcement of polymer/carbon nanotube nanocomposites on the nanofiller content has been proposed. It has been shown that, for this nanofiller, the percolation threshold almost coincides with the aggregation threshold on the concentration scale. From the structural point of view, the extremum of this dependence is caused by the change in the type of the reinforcing component (from interphase regions to the skeleton of carbon nanotubes). From the mathematical point of view, the behavior of the degree of reinforcement is described by the general percolation relationship with replacement of the critical exponents near the percolation threshold. Neither the functionalization of the nanofiller nor the preliminary ultrasound treatment qualitatively change the dependence under study.     

Preparation and Rheology of Isocyanate Functionalized Graphene Oxide/Thermoplastic Polyurethane Elastomer Nanocomposites

Using monomer-functionalized nanofiller to prepare polymeric nanocomposites is a promising strategy toward achieving enhanced performance. In this study toluene-2,4-diisocyanate (TDI), one of the monomers used for synthesizing polyurethane, was covalently functionalized on graphene oxide (GO) and then the functionalized GO (TDI-GO) was polymerized with polycaprolactone diol (PCL) via in-situ polymerization, leading to chemically linked polyurethane nanocomposites through the covalent bonds between the isocyanate groups on GO and the hydroxyl-terminated PCL. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and dispersion experiments of the nanofillers demonstrated that the TDI was successfully grafted onto the GO. The rheological properties were investigated to establish the structure-property relationships of the nanocomposites. The storage moduli (G’), loss moduli (G”) and complex viscosity (η*) of the samples increased monotonically with TDI-GO content, which is attributed to the strong polymer-filler interactions and the effective dispersion of the nanofillers. Additionally, the tan δ variation with frequency, the intersection of G’ and G”, Han plots, van Gurp-Palmen plots and Cole-Cole plots all showed that the incorporation of TDI-GO decreased the degree of microphase separation and improved the elastic properties of the nanocomposites. We suggest this is related to the enhanced interactions between the polymer and nanofillers, which strongly restricted the mobility and relaxation of the polymer chains.     

Gradient of molecular dynamics at the glass transition of PETg-Montmorillonite nanocomposites

Temperature Modulated Differential Scanning Calorimetry (TMDSC) is used to estimate Cooperative Rearranging Region (CRR) average sizes for polymer/clay nanocomposites, obtained by mixing polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol (PETg) filled and organically modified nanoclay (C15A) following a master-batch process. Two different basal distances are obtained. It is shown that the greater the basal distance and the nanofiller content, the lower the heat capacity step at the glass transition temperature ΔCp(T_g), and the lower the CRR volume. It is also shown that the evolution of the CRR volume is consistent with the evolution of the fragility index obtained by DSC and Broadband Dielectric Spectroscopy (BDS) when the nanofiller content changes. The fragility index and the CRR size decreases can be correlated to nanofiller presence, hindering the molecular movements. From the Vollenberg and Heikens [34] approach, this behaviour can also be interpreted through the existence of an interfacial bilayer. This interfacial bilayer is composed by a zone, which is next to the nanofiller, with a density higher than the matrix one, followed by a more expanded zone with a density lower than the matrix one.     

Molecular mechanisms of failure in polymer nanocomposites

Molecular dynamics simulations of polymers reinforced with nanoscopic filler particles reveal the mechanisms by which nanofillers improve the toughness of the material. We find that the mobility of the nanofiller particle, rather than its surface area, controls its ability to dissipate energy. Our results show similarities between the toughening mechanisms observed in polymer nanocomposites and those postulated for biological structural materials such as spider silk and abalone adhesive.     

固态高分子体系多尺度分子运动的核磁共振研究

固体核磁共振技术是研究固态高分子材料中结构和分子动力学的一种非常重要和有效的手段. 该技术的一个重要特点是可以通过合理的实验方法,实现对研究体系中从低频(Hz)到中频(kHz)乃至高频(MHz)范围内分子运动的观测. 因此,固体核磁共振技术非常适合研究高分子体系中各类不同尺度分子运动. 该文首先简要介绍核磁共振研究分子运动的基本原理和方法,以及固态高分子体系的结构和分子动力学特点,然后结合固态高分子体系中的一些例子对核磁共振在固态高分子多尺度分子运动方面的一些研究成果展开讨论.     

Fullerene–epoxy nanocomposites-enhanced mechanical properties at low nanofiller loading

In this study, we characterized the mechanical properties of fullerence (C₆₀) epoxy nanocomposites at various weight fractions of fullerene additives in the epoxy matrix. The mechanical properties measured were the Young’s modulus, ultimate tensile strength, fracture toughness, fracture energy, and the material’s resistance to fatigue crack propagation. All of the above properties of the epoxy polymer were significantly enhanced by the fullerene additives at relatively low nanofiller loading fractions (~0.1 to 1% of the epoxy matrix weight). By contrast, other forms of nanoparticle fillers such as silica, alumina, and titania nanoparticles require up to an order of magnitude higher weight fraction to achieve comparable enhancement in properties.     

Effect of modifiers on mechanical properties of polymer-based composite materials

In this paper, we present the experimental results on the study of mechanical properties of polymer-based nanocomposite materials with carbon nanotube or ultradisperse diamond inclusions. Tests are performed by nanoindentation methods. The results obtained for nanocomposites and a polymer used as a matrix in nanocomposites are compared.     

Nucleation of electroactive β-phase poly(vinilidene fluoride) with CoFe2O4 and NiFe2O4 nanofillers: a new method for the preparation of multiferroic nanocomposites

Multiferroic and magnetoelectric materials show enormous potential for technological developments. Multiferroic composites are more attractive for applications due to their enhanced properties with respect to single-phase multiferroic materials. In this paper we report on the nucleation of the electroactive β-phase of poly(vinylidene fluoride), PVDF, by the addition of CoFe₂O₄ and NiFe₂O₄ nanoparticles in order to prepare poly(vinylidene fluoride)/ferrite nanocomposite for multiferroic and magnetoelectric applications,. The dispersed ferrite nanofiller particles strongly enhance the nucleation of the β-phase of the polymer matrix. In this way, magnetoelectric polymer nanocomposites can be processed avoiding the usual α- to β-phase transformation by stretching of the polymer matrix.     

Damage Mechanisms of Hierarchical Composites: Computational Modelling

Computational studies of damage mechanisms in hierarchical composites, including biocomposites, nanoparticle reinforced polymer composites and other materials are discussed. Different methods of the analysis of hierarchical effects in the multiscale composites are demonstrated, among them, hierarchical fiber bundle model, 3D multiscale finite element models, analytical studies. Considering wood as a gradient, cellular material with layered composite cell walls, one analyzed the effect of wood structure on damage resistance of wood. The influence of nanoparticles distribution in unidirectional polymer matrix composites with secondary nanoreinforcement on the strength and damage resistance of the composites is demonstrated. The concept of nanostructuring of interfaces and grain boundaries as an important reserve of the improvement of the materials properties is formulated.     

Structure and Mechanical Properties of Melt Intercalated Po1lypropylene–Organomontmorillonite Nanocomposites

The preparation and properties of polymer nanocomposites, obtained by melt-compounding of polypropylene (PP) and organomontmorillonite (OMMT) modified by different alkyl ammonium salts, are described. A copolymer of maleic anhydride and PP was used as a compatibilizing additive. Nanocomposites with OMMT content of 1, 5 and 10 wt% were prepared and tested. The influence of OMMT content on the tensile stress–strain curves, elastic modulus, yield and tensile strength, and ultimate elongation of the nanocomposites is determined. The results of measuring the microhardness and impact strength of polymer nanocomposites are presented. Long-term creep tests were performed to predict the long-term deformation behavior of nanocomposites. The crystallinity of nanocomposites was analyzed by means of differential scanning calorimetry and optical microscopy, while the structural features were studied by X-ray diffraction and scanning electron microscopy methods.     

Fractal description of significant nano-effects in polymer composites with nanosized fillers. Aggregation,phase interaction,and reinforcement

The paper analyzes experimental data obtained on physical and mechanical properties of nanostructured particle-reinforced composites with elastomer matrices and nano- and microsized carbon-containing particles by scanning probe microscopy and nanoindentation with specialized 3D computer processing. The nano-effects observed in the elastomer matrices are described using the fractal approach. A fractal model of nanoparticle aggregation in a polymer matrix is proposed. Phase interactions in the nanostructured polymer materials are described and fractal relations that predict the reinforcing effect of this type of media are presented. It is shown that interphase regions in the nanostructured composites are the same reinforcing elements as a nanofiller for the medium. It is found that reinforcement of elastomer composites by nanosized particles is a true nano-effect.     

Improved Biodegradation and Thermal Properties of Poly(lactic acid)/Layered Silicate Nanocomposites

Poly(lactic acid) (PLA)/layered silicate nanocomposites have successfully been prepared using the solution route. Two types of organically modified nanoclays, namely, MEE and MAE have been used. The nanostructure, as observed from wide angle X-ray diffraction, indicates an intercalated hybrid for both PLA–MEE and PLA–MAE, and depends on the type of organic modifier used. Intercalation is higher in PLA–MEE as compared to PLA–MAE system. Crystallite dimensions of nanoclays and nanocomposites have been calculated from the Scherrer equation. Crystallite size of nanocomposites is higher than that of pure nanoclay, which in turn affects the properties of the nanocomposites. Wide angle X-ray diffraction patterns also suggest that PLA and its nanocomposites are predominantly amorphous before annealing but, after annealing, PLA and its nanocomposites are fairly crystalline. The crystallinity of the nanocomposites has decreased in comparison to neat polymer suggesting some sort of interaction between organically modified nanoclay and polymer. The nanohybrids show significant improvement in the thermal properties of the matrix as compared to pristine polymer. The nature of interaction between nanoparticles and polymer is higher in PLA–MEE against PLA–MAE, as evident from the lower value of the heat of fusion in the case of PLA–MEE. The nanoparticles act as nucleating agent, and thereby, control the spherulite dimension of the matrix. The comparison of biodegradation of PLA and its nanocomposites has been studied in several media. Biodegradability of PLA has significantly been enhanced in the presence of nanoclays which has been explained on the basis of amorphous content in the polymer matrix. Finally, the regulated biodegradation has been discussed.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.     

Comparative Analysis of the Reinforcement of Polymers with 2D-Nanofillers: Organoclay and Boron Nitride

Using the percolation reinforcement model, it has been shown that the main factor governing the degree of reinforcement of polymer/2D-nanofiller composites is the ability of a nanofiller to generate interfacial regions. This parameter is interrelated with two fundamental structural characteristics of a nanocomposite, i.e., the fractal dimension of its structure and the content of polymer matrix/nanofiller interfacial surfaces. The negative effect of high nanofiller anisotropy on the elasticity modulus of a nanocomposite is demonstrated.     

Fabrication and Characterization of Polyethylene Nanocomposite Films Containing Zinc Oxide (ZnO) Nanoparticles Synthesized by a Cost-Effective and Safe Method

ZnO nanoparticles were synthesized through a cost-effective and safe method followed by fabrication and characterization of polyethylene/ZnO nanocomposite films and investigation of their properties. The morphology and size of the synthesized nanoparticles were evaluated by field emission scanning electron microscopy (FE-SEM). It was found that nanoparticles with a plate-like morphology with an average thickness of 50-70?nm were synthesized. The nanocomposites were characterized by using Fourier transform infrared analysis (FTIR) and ultraviolet–visible spectroscopy (UV-VIS). In addition, the effects of the amount of zinc oxide nanoparticles (ZnO-NPs) on the mechanical properties of the films and particles and their antibacterial properties against a gram-negative bacterium (Escherichia coli) and gram-positive bacteria (Staphylococcus aureus) were investigated. In the case of nanoparticles, one more gram-positive bacterium (Staphylococcus aureus) was studied. The results demonstrated an inhibition of growth of all bacteria in a broth medium for both the nanoparticles and nanocomposites. The FE-SEM micrographs revealed that by increasing the nanofiller content an inferior quality of dispersion was obtained which was reflected in the lower tensile strength of the nanocomposites compared to the pure PE. It was demonstrated that the addition of poly ethylene graft maleic anhydride (PE-g-MA), as compatibiliser, improved the dispersion state of the nanoparticles and, consequently, the ultimate mechanical properties. In addition, it was shown that the fabricated nanocomposites exhibited considerable UV-shielding properties.