Structural and mechanical properties of advanced polymer gels with rigid side-chains using coarse-grained molecular dynamics

Computational modeling was utilized to design complex polymer networks and gels which display enhanced and tunable mechanical properties. Our approach focuses on overcoming traditional design limitations often encountered in the formulation of simple, single polymer networks. Here, we use a coarse-grained model to study an end-linked flexible polymer network diluted with branched polymer solvent chains, where the latter chains are composed of rigid side-chains or “spikes” attached to a flexible backbone. In order to reduce the entropy penalty of the flexible polymer chains these rigid “spikes” will aggregate into clusters, but the extent of aggregation was shown to depend on the size and distribution of the rigid side-chains. When the “spikes” are short, we observe a lower degree of aggregation, while long “spikes” will aggregate to form an additional secondary network. As a result, the tensile relaxation modulus of the latter system is considerably greater than the modulus of conventional gels and is approximately constant, forming an equilibrium zone for a broad range of time. In this system, the attached long “spikes” create a continuous phase that contributes to a simultaneous increase in tensile stress, relaxation modulus and fracture resistance. Elastic properties and deformation mechanisms of these branched polymers were also studied under tensile deformation at various strain rates. Through this study we show that the architecture of this branched polymer can be optimized and thus the elastic properties of these advanced polymer networks can be tuned for specific applications.     

Effect of sample thickness on the mechanical properties of injection-molded polyamide-6 and polyamide-6 clay nanocomposites

The effect of the thickness on the mechanical properties of injection-molded specimens of pure polyamide-6 (PA6) and polyamide-6 clay nanocomposites (PA6-NC) with 5 wt% of layered silicates was investigated. Plates of 0.5, 0.75, 1 and 2 mm thickness were characterized in the injection direction using Dynamic Mechanical Analysis under torsion and tension respectively, and tensile tests. The fracture surfaces were analyzed by Scanning Electron Microscopy. In contrast with PA6, PA6-NC showed thickness effect and clear differences in the mechanical and thermomechanical properties between skin and core, especially in the 2 mm thick samples. Increasing thickness in PA6-NC led to a reduction of tensile modulus and yield stress. In the fracture surface of the thicker tensile specimens the formation of a sheet-like structure was observed. Multiple voiding in the core causing initial failure in this region and a stiffer skin with a better orientation of the layered silicates in the injection direction are two important elements of a micromechanical model proposed in this paper to explain the fracture mechanism in PA6-NC.     

Calculating barrier properties of polymer/clay nanocomposites: Effects of clay layers

We analyzed the effects of clay layers on the barrier properties of polymer/clay nanocomposites containing impermeable and oriented clay layers. Using the relative permeability theory in combination with the detour theory, we obtained new relative permeability expressions that allow us to investigate the relative permeability R_p as a function of lateral separation b, layer thickness w, gallery height H, layer length L, and layer volume fraction Φ_s. It was found that intercalated and/or incomplete exfoliated structures and dispersed tactoids with several layers can effectively enhance the barrier properties of the materials. Furthermore, we developed the chain-segment immobility factor to briefly discuss the chain confinement from clay layers. The results showed that the chain confinement enhanced the barrier properties of the intercalated nanocomposites. Our model is better consistent with the experiments when Φ_s>0.01. The findings provide guidelines for tailoring clay layer length, volume fraction and dispersion for fabricating polymer-clay nanocomposite with the unique barrier properties.     

Predictions of micromechanics models for interfacial/interphase parameters in polymer/metal nanocomposites

In this paper, the polymer-metal interfacial/interphase parameters (PMIP) in polymer/metal nanocomposites are studied by modeling the mechanical properties. In this regard, the experimental results of yield strength, Young's modulus and elongation at break can be compared with the micromechanical models to evaluate the PMIP. The good agreement obtained between the experimental data of samples and the predictions confirms the applicability of models for polymer/metal nanocomposites. Many calculated parameters show the existence of a strong interphase in the reported samples. It is concluded that the fine morphology of nanoparticles and the strong interaction/adhesion at the polymer-metal interface can produce the significant PMIP in the polymer/metal nanocomposites.     

Multiscale micromechanical modeling of polymer/clay nanocomposites and the effective clay particle

Polymer/clay nanocomposites have been observed to exhibit enhanced mechanical properties at low weight fractions (W_c) of clay. Continuum-based composite modeling reveals that the enhanced properties are strongly dependent on particular features of the second-phase ‘particles’; in particular, the particle volume fraction (f_p), the particle aspect ratio (L/t), and the ratio of particle mechanical properties to those of the matrix. These important aspects of as-processed nanoclay composites require consistent and accurate definition. A multiscale modeling strategy is employed to account for the hierarchical morphology of the nanocomposite: at a lengthscale of thousands of microns, the structure is one of high aspect ratio particles within a matrix; at the lengthscale of microns, the clay particle structure is either (a) exfoliated clay sheets of nanometer level thickness or (b) stacks of parallel clay sheets separated from one another by interlayer galleries of nanometer level height, and the matrix, if semi-crystalline, consists of fine lamella, oriented with respect to the polymer/nanoclay interfaces. Here, quantitative structural parameters extracted from XRD patterns and TEM micrographs (the number of silicate sheets in a clay stack, N, and the silicate sheet layer spacing, d₍₀₀₁₎) are used to determine geometric features of the as-processed clay ‘particles’, including L/t and the ratio of f_p to W_c. These geometric features, together with estimates of silica lamina stiffness obtained from molecular dynamics simulations, provide a basis for modeling effective mechanical properties of the clay particle. In the case of the semi-crystalline matrices (e.g. nylon 6), the transcrystallization behavior induced by the nanoclay is taken into account by modeling a layer of matrix surrounding the particle to be highly textured and therefore mechanically anisotropic. Micromechanical models (numerical as well as analytical) based on the ‘effective clay particle’ were employed to calculate the overall elastic modulus of the amorphous and semi-crystalline polymer-clay nanocomposites and to compute their dependence on the matrix and clay properties as well as internal clay structural parameters. The proposed modeling technique captures the strong modulus enhancements observed in elastomer/clay nanocomposites as compared with the moderate enhancements observed in glassy and semi-crystalline polymer/clay nanocomposites. For the case where the matrix is semi-crystalline, the proposed approach captures the effect of transcrystallized matrix layers in terms of composite modulus enhancement, however, this effect is found to be surprisingly minor in comparison with the ‘composite’-level effects of stiff particles in a matrix. The elastic moduli for MXD6-clay and nylon 6-clay nanocomposites predicted by the micromechanical models are in excellent agreement with experimental data. When the nanocomposite experiences a morphological transition from intercalated to completely exfoliated, only a moderate increase in the overall composite modulus, as opposed to the expected abrupt jump, was predicted.     

Insight into molecular interactions between constituents in polymer clay nanocomposites

The mechanisms responsible for the enhancement of physical properties of polymer clay nanocomposites (PCN) over pristine polymers are not well understood. This knowledge is important for obtaining a better control over the physical properties of PCN and designing PCN with tailored properties. The interactions among the different constituents of PCN may be a key factor for controlling physical properties of PCN. The interaction energy is an important measure of the interactions among different constituents of composites. Molecular dynamics (MD) is a useful tool for studying the nature and quantitative analysis of interaction energies of a molecular system. In this work, the interaction energies among different components of intercalated organically modified montmorillonite (OMMT) and PCN have been investigated. Here, the interaction of polymer or organic modifier with clay and polymer and modifier is studied. Also, the nature and quantitative contributions arising from functional groups or backbone chain have been assessed. This investigation provides important insight into the mechanism of intercalation, and specific information about the interactions of different constituents in the nanocomposites system. In this current work using MD, for the first time, we have provided a detailed quantitative picture of interactions among the different components of OMMT and PCN.     

Formation of nanoparticle aggregates and agglomerates in polymer nanocomposites and their distinct impacts on the mechanical properties

In this study, the different effects of nanoparticle aggregates and agglomerates on the mechanical properties of polymer nanocomposites are comprehensively investigated. To this end, a specific strategy, based on the equilibrium between the dispersion and cohesion energies in the mixing stage, is proposed using which the content and size of aggregates/agglomerates can be defined. The aggregated/agglomerated networks are considered to place in constrained volumes (CVs), having co-continuous morphology. An equivalent box model (EBM), corresponding to the system, is used to predict the tensile modulus of the nanocomposite. Different test results of HDPE nanocomposite samples, containing 1–3 wt.% of surface-modified silica nanoparticles, prepared by a semi-industrial single screw extruder, are applied to validate the model. Moreover, other data from the literature are also used to further evaluate the accuracy and capability of the proposed analytical method.     

TPO based nanocomposites. Part 1. Morphology and mechanical properties

The relationship between morphology and the mechanical properties of thermoplastic olefin (TPO) materials that are reinforced with organoclay fillers and prepared by melt processing is reported. Nanocomposites based on blends of polypropylene and elastomer and using an organoclay masterbatch were prepared in a twin-screw extruder. Transmission electron microscopy, atomic force microscopy and wide-angle X-ray scattering were employed to carry out a detailed particle analysis of the morphology of the dispersed clay and elastomer phases for these nanocomposites. The improvement in mechanical properties, e.g. stiffness enhancement as evaluated by stress-strain analysis and impact strength obtained from notched Izod impact tests, were successfully explained in terms of morphological changes induced by the presence of the clay and elastomer particles. Quantitative analyses of TEM micrographs and AFM images revealed a decrease in the aspect ratio of the clay particles and a reduction in the size of elastomer particles with increasing clay content. In addition, WAXD scans indicated a skin-core effect for the injection molded specimens in terms of both polypropylene crystal orientation and clay filler orientation. This information is essential for the understanding of the mechanism of mechanical property enhancement in nanocomposite materials.     

Large deformation mechanical behavior of flexible nanofiber filled polymer nanocomposites

In the present work, the large deformation behavior of high aspect ratio flexible nanofiber reinforced polymer composites is investigated. Simple or successive tensile tests are performed at room temperature, i.e. in the rubbery state. By studying two different types of fibers, namely cellulose nanofibrils and carbon nanotubes, with two processing routes, the role of entanglements and of interactions existing between fibers—within the nanofiber network that can be formed in the material—on the composite properties is highlighted. For cellulosic nanofillers, strong hydrogen bonds between fibers lead to a spectacular reinforcement effect combined with a decrease of the composite ultimate strain and an irreversible damage of composite properties after first deformation (rigid network). When such strong interactions between fillers are limited (soft entangled network or simple contacts between non-entangled fibers) the resulted reinforcement is less important and no decrease of the deformation at break is observed. For carbon nanotube fillers, the evolution of the filler network during tensile test is finally highlighted by in situ electrical measurements.     

Effect of Ti particle size on mechanical and tribological properties of TiCN coatings prepared by reactive plasma spraying

Titanium carbonitride (TiCN) coatings were successfully fabricated by reactive plasma spraying (RPS) from agglomerated Ti-graphite feedstock. The effect of Ti particle size on the microstructure and phase composition of plasma sprayed TiCN coatings was investigated. The Vickers microhardness of coatings was measured by a Microhardness Test and the corresponding Weibull distribution were also analyzed. In addition, a pin-on-disk tribometer was employed to determine the trobological properties of coatings. Results show that all the coatings consist of TiC_xN_1−x (0 ≤ x ≤1) and minor Ti₂O phases, and the amount of Ti₂O increases with the increase of Ti particle size. The Weibull distribution of Vickers microhardness of all the coatings shows apparent scattering, while the coating sprayed with Ti particle size of 28 µm exhibits a relatively even distribution. Compared with the coating sprayed with Ti particle size of 14 µm or 48 µm, the coating sprayed with Ti particle size of 28 µm exhibits improved mechanical and tribological properties, which are attributed to the high microhardness and strong bonding strength.     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

Effect of modified carbon nanotube on the properties of aromatic polyester nanocomposites

Aromatic polyester nanocomposites based on poly(ethylene 2,6-naphthalate) (PEN) and carbon nanotube (CNT) were prepared by melt blending using a twin-screw extruder. Modification of CNT to introduce carboxylic acid groups on the surface was performed to enhance intermolecular interactions between CNT and the PEN matrix through hydrogen bonding formation. Morphological observations revealed that the modified CNT was uniformly dispersed in the PEN matrix and increased interfacial adhesion between the nanotubes and the PEN, as compared to the untreated CNT. Furthermore, a very small quantity of the modified CNT substantially improved thermal stability and tensile strength/modulus of the PEN nanocomposites. This study demonstrates that the thermal, mechanical, and rheological properties of the PEN nanocomposites are strongly dependent on the uniform dispersion of CNT and the interactions between CNT and PEN, which can be enhanced by slight chemical modification of CNT, providing a design guide of CNT-reinforced PEN nanocomposites with a great potential for industrial uses.     

Effects of particle type on thermal and mechanical properties of polyoxymethylene nanocomposites

The effects of particle size of titanium dioxide (TiO₂) on mechanical, thermal, and morphological properties of pure polyoxymethylene (POM) and POM/TiO₂ nanocomposites were investigated and compared with the results for nanoparticle ZnO in the same matrix, reported in a previous paper. POM/TiO₂ nanocomposites with varying concentration of TiO₂ were prepared by the melt mixing technique in a twin screw extruder, the same method that used for blending the homogeneous ZnO nanocomposites. The dispersion of TiO₂ particles in POM nanocomposites was studied by scanning electron microscopy (SEM). The agglomeration, as observed by the mechanical properties of TiO₂ particles in the polymer matrix, increased with increasing TiO₂ content, a result not found for ZnO even at lower particle sizes. Increasing the filler content of POM/TD32.4 and POM/TD130 (130 nm) nanocomposites resulted in a decrease in tensile strength. The Young modulus, stress at break and impact strength of TiO₂ nanocomposite did not improve with increasing filler contents, in opposition to the better agglomeration conditions of ZnO nanocomposite even at lower particle sizes. Because of agglomeration, the POM/TD32.4 nanocomposites had lower mechanical properties and lower degradation temperature than the POM/TD130 ones. The sizes of nanoparticles determined the agglomeration, but however, the agglomeration also depended on the type of nanoparticles, even when using the same matrix (POM) and the same mixing method. TiO₂ nanoparticles were more difficult to mix and were more agglomerated in the POM matrix as compared to ZnO nanoparticles, regardless of the size of the nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of particle size on the mechanical properties of polystyrene and poly(butyl acrylate) core/shell polymers

The effects of particle size and polymer location (core or shell) on the mechanical properties of core/shell materials composed of polystyrene (PST) and poly(butyl acrylate) (PBA) made by a two-stage emulsion or microemulsion polymerization process are reported. Low-seed content (LSC) latexes were made by batch polymerization in microemulsions stabilized with DTAB in the presence of an organic salt (dibutyl phosphite). High-seed content (HSC) latexes were produced by microemulsion or emulsion polymerization in semi-continuous process. These latexes were subsequently used to form core/shell particles of PST/PBA or PBA/PST and their mechanical properties were examined and compared. Our results indicate that core/shell particle size and the location of the polymers have important effects on the mechanical properties.     

Effect of morphology on the permeability,mechanical and thermal properties of polypropylene/SiO2 nanocomposites

Spherical silica nanoparticles with 20 and 100 nm diameters and organic‐template layered silica nanoparticles synthesized by the sol‐gel method were melt blended with a polypropylene (PP) matrix in order to study and quantify their effect on the oxygen and water vapor permeability and mechanical and thermal behavior. With regard to barrier properties, the spherical nanoparticles barely increased the oxygen permeability at low loads (≤10 wt%); meanwhile the layered nanoparticles dramatically increased it even at low loading (<5 wt%) probably due to the percolation effect. The changes in water vapor permeability were similar to those in oxygen permeability. The repulsive interaction between nanoparticles and PP forms interconnecting voids where the gas permeates. Tensile stress–strain tests showed that the composites present up to a 56% increase in the elastic modulus with spherical nanoparticles at 20 wt%, while layered nanoparticles show a decrease probably due to agglomerations and voids. Thermogravimetric analysis under inert conditions showed that the nanoparticles improved the PP thermal degradation process through the adsorption of volatile compounds on their surface, where the smaller spherical nanoparticles show the greatest stabilization. © 2015 Society of Chemical Industry     

Effect of vanadium pentoxide on the mechanical,thermal, and electrical properties of poly(vinyl alcohol)/vanadium pentoxide nanocomposites

In this study, we examined the effect of vanadium pentoxide (V₂O₅) on the mechanical, thermal, and morphological properties of poly(vinyl alcohol) (PVA)/V₂O₅ nanocomposites. The PVA/V₂O₅ nanocomposites were prepared by solution mixing, followed by film casting. The results show that the Young's moduli of the resulting nanocomposites films were higher than the pure PVA modulus with increasing V₂O₅ content, and it reached a maximum point at about 0.4 wt % V₂O₅ content at 8.55 GPa. The tensile strength and stress at break increased with increasing V₂O₅ content. The addition of V₂O₅ did not affect the melting temperature. The crystallization temperatures of PVA were significantly changed with increasing V₂O₅ content. The 5% weight loss degradation temperature of the nanocomposites was measured by thermogravimetric analysis. The degradation temperatures of the V₂O₅ nanocomposites increased with increasing filler content and were higher than the degradation temperature of pure PVA; this showed a lower thermal stability compared to those of the nanocomposites. The results show that the thermal stability increased with the incorporation of V₂O₅ nanoparticles. The dielectric constant of PVA had a tendency to improve when the dispersion of particles was effective. The morphology of the surfaces the nanocomposites was examined by scanning electron microscopy. We observed that the dispersion of the V₂O₅ nanoparticles was relatively good; only few aggregations existed after the addition of the V₂O₅ nanoparticles at greater than 0.4 wt %. In perspective, the addition of 0.4 wt % V₂O₅ nanoparticles into PVA maximized the mechanical, thermal, and electrical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mapping the real micro/nanostructures for the prediction of elastic moduli of polypropylene/clay nanocomposites

An understanding of the overall nanocomposite behaviour is developed through the combination of real data from micro/nanostructures and the fundamental material characteristics of the constitutive phases. Captured morphological images, using either scanning electron microscopy (SEM) or transmission electron microscopy (TEM), are utilised to generate the geometric information regarding mapping the micro/nanostructures. The material properties, on the other hand, are obtained from conducted tests and previous literature. The numerical results predicting the elastic moduli of polypropylene (PP)/clay nanocomposites are compared with the experimental data and available composites theoretical models. Very good agreement has been shown, establishing the viability of this kind of morphology-based numerical approach.     

Effect of glass fiber surface chemistry on the mechanical properties of glass fiber reinforced, rubber-toughened nylon 6

The mechanical properties of nylon 6 and its blends with maleated ethylene-propylene rubber (EPR-g-MA) plus glass fibers were examined as a function of the chemical functionality of the silane surface treatment applied to the glass fibers. Three reactive silane coupling agents, with anhydride, epoxy, or amine functionality, were used and found to have little effect on the mechanical properties when no EPR-g-MA is present. When 20 wt% EPR-g-MA is used as a rubber toughener, however, the yield strength and Izod impact strength were lowest for the amine functional silane and highest for the anhydride silane, while the epoxy silane fell in-between. These results were attributed to the differences in reactivity of the three reactive silanes. An unreactive silane (octyl groups) was used as a release agent on the glass fibers and compared with the anhydride functional silane. The octyl silane did not improve the ductility of the composite, as may have been speculated, and had poor yield strength and impact resistance when compared to the anhydride silane. Both octyl and anhydride treated glass fibers improve the heat distortion temperature such that most of the high temperature stiffness that is lost on addition of EPR-g-MA is regained by adding glass fibers.     

Morphology and mechanical properties of polymer nanocomposites with a poly(hydroxy ether of bisphenol A) matrix

The poly(hydroxy ether of bisphenol A) (phenoxy (Ph)) has been revealed as a polymeric matrix able to intercalate in, and partially exfoliate a commercial organically modified montmorillonite. Dispersion was attributed to chemical interactions between the Ph and the inorganic clay. A significant increase in the modulus of elasticity (33% with 3.8% montmorillonite (MMT) addition) was observed, together with an unusual increase in ductility attributed to surfactant migration, that should allow tailoring of the processing conditions to widen exfoliation. Ph‐based nanocomposites could be used as a nanostructured masterbatch for producing new polymer nanocomposites by mixing the masterbatch with the polymeric matrices that either miscibilize or are compatible with Ph. Copyright © 2006 Society of Chemical Industry     

Network model for the viscoelastic behavior of polymer nanocomposites

A theoretical network model reproducing some significant features of the viscoelastic behavior of unentangled polymer melts reinforced with well dispersed non-agglomerated nanoparticles is presented. Nanocomposites with low filler volume fraction (∼10%) and strong polymer-filler interactions are considered. The model is calibrated based on results obtained from discrete simulations of the equilibrium molecular structure of the material. This analysis provides the statistics of the network of chains connecting fillers, of dangling strands having one end adsorbed onto fillers, and that of the population of loops surrounding each nanoparticle. The network kinetics depends on the attachment-detachment dynamics of grafted chains of various types and is modeled by using a set of convection equations for the probability distribution functions. The overall viscoelastic response depends strongly on the lifetime of the polymer-filler junctions. The largest reinforcement is observed at low strain rates and low frequency oscillations. A solid like behavior is predicted for systems in which the polymer molecules interact strongly with the nanoparticles, effect which is associated with the behavior of the network of bridging segments.