Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.
SBS nanocomposites based on a SBS triblock copolymer containing different weight fractions of a commercial Cloisite 20A organoclay were prepared by melt‐processing. Extensive electron microscopy as well as WAXS and static tensile and tensile creep tests were used to evaluate the resulting morphological and mechanical properties of the nanocomposites. The nanocomposite morphology is characterized by a combination of intercalated and partly exfoliated clay platelets with occasional clay aggregates present at higher clay contents; nanocomposite features that are reflected by the results of both the static tensile as well as the tensile creep tests at room temperature. For this particular thermoplastic elastomer nanocomposite system, well dispersed nanoclays lead to an enhanced stiffness and ductility; effects that induce promising improvements in nanocomposite creep performance.
This paper investigates the effect of both the clay loading and the monomer feed rate on the morphology and properties of poly(styrene‐co‐butyl acrylate)‐clay nanocomposites prepared in emulsion polymerization. Analysis by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) of the nanocomposites prepared by batch polymerization showed that the polymer clay nanocomposites (PCNs) with 1–3 wt.‐% clay loading resulted in intercalated structures, while exfoliated structures were obtained at 10 wt.‐% clay loading. The polymerization was also carried out with semi‐batch polymerization. The morphology, thermal stability, and mechanical properties of nanocomposites obtained were found to be more strongly dependent on the clay/polymer ratio than the monomer feed rate.
The aim of the present contribution is to understand how ionic strength, brought by the addition of salt to laponite/PEO nanocomposite dispersions, influences the texture and adhesion characteristics at nano‐ and microscales in multilayered nanocomposite films prepared from such dispersions. At the nano‐scale, SAXS and XRD measurements indicated that the clay platelets orient parallel to the film plane and that the polymer chains intercalate the clay platelets regardless of salt addition. A gradual transition from an agglomerated structure, containing polymer‐rich and clay‐rich domains, to a fine‐balanced structure with smaller distinct details without excess PEO was observed, via AFM, on the exposed edges of cryo‐microtomed films with increasing ionic strength.
Bio‐stereo nanocomposite polylactides are prepared by polymerization followed by stereocomplexation in scCO2/dichloromethane through in situ polymerization and master batch processes. The bio‐stereo nanocomposite polylactides show intercalated‐exfoliated and fully exfoliated nanoscale clay distribution in a perfect stereocomplex polylactide matrix. In situ polymerization proves better strategy to produce well‐exfoliated silicate layers in the stereocomplex matrix compared to the MB route that increases the melting temperature by up to ≈64 °C. The thermal properties of these materials maintain both stereocomplex and nanocomposite features simultaneously. The results open a new and versatile way to develop polylactide‐based materials.
Organoclay–polyolefin nanocomposites have been shown to exhibit slightly increased thermal stability and decreased flammability, compared to unfilled polyolefins. In contrast, we find that when the clay has not been organically modified, the resulting polyolefin nanocomposites are less thermally stable and, unexpectedly, also much less flammable. In this contribution, we investigate the mechanistic origins of these effects. Clay–polyolefin nanocomposites were prepared by in situ polymerization of ethylene or propylene, using a catalyst adsorbed onto the clay. Decreased thermal stability is attributed to clay‐catalyzed polymer decomposition, while decreased flammability arises in part from clay‐catalyzed formation of a polyaromatic char from olefins trapped in the material by the dispersed nanofiller.
Acrylonitrile‐butadiene‐styrene (ABS)/clay nanocomposites have been prepared using two types of ABS with different AN contents and a chemically modified clay, Cloisite 20A. The composites were prepared by melt mixing in a twin‐screw extruder. Their morphological properties were characterized by XRD and TEM. The thermal stability of the polymer nanocomposites was studied using TGA and flammability tests. The results were analyzed in terms of the effect of the clay content and the type of ABS used on the clay dispersion and the thermal stability of the nanocomposites. Experimental results confirmed that better dispersion and intercalation and/or exfoliation can be obtained when using an ABS with a higher AN content. The study using TGA and flammability tests showed that the nanodispersed layers of silicate enhanced the thermal stability of the ABS matrix, and that an ABS with higher AN content was more effective in providing fire retardancy. This suggests that when using higher AN contents, more polar groups are present within the polymer matrix, allowing a more homogeneous dispersion and intercalation of the chain polymers into the organomodified montmorillonite clay (MMT), and even some exfoliation of the nanoclay.
PA6 nanocomposite films with different nanoclay dispersion degrees are prepared by melt compounding and cast extrusion. The dispersion of the MMT platelets (homogeneity and degree of exfoliation) is evaluated qualitatively by TEM and quantitatively by rheology and NMR; it ranges from microcomposites to highly exfoliated nanocomposites. Compared to neat PA6, the optical properties (clarity, gloss, haze) are worse for the microcomposites and better for the nanocomposites. The mechanical properties depend strongly on the exfoliation level. Better exfoliation leads to higher stiffness. The strain at break decreases compared to neat PA6 films even in the case of highly exfoliated nanocomposites films. At low MMT content, the microcomposite has a higher ductility than well exfoliated nanocomposites films.
Thermo‐mechanical degradation of LDPE‐based nanocomposites was studied by mainly investigating the rheological properties. For all of the investigated processing conditions, the viscosity of the nanocomposites was higher than that of the pure‐LDPE matrix, but on increasing the severity of the mixing conditions, the difference between the viscosity of the nano‐filled polymer and that of the pure LDPE decreased. The X‐ray traces of the nanocomposites suggest that intercalation has been achieved during the melt, when less‐severe processing conditions were used. At severe processing conditions (longer mixing time, high temperature and shear stress) the thermo‐mechanical degradation was accelerated, possibly due to the loss of mass from the organoclay galleries. The variations of the viscosity in the presence of two organo‐modified montmorillonite (MMt) clays were compared to the ones observed with a MMt clay at different processing conditions.
Novel fluoroalkyl end‐capped oligomer/hydroxyapatite nanocomposites have been easily prepared by the reaction of disodium hydrogenphosphate and calcium chloride in the presence of self‐assembled molecular aggregates formed by fluoroalkyl end‐capped oligomers in aqueous media. The fluorinated hydroxyapatite nanocomposites thus obtained were found to exhibit a good dispersibility in a variety of media, and were applied to the surface modification of glass.
The efficiency of melamine cyanurate and a clay filler for improving the flame retardancy and other physical properties of polyamide 6 was examined. Partially intercalated‐exfoliated morphologies were obtained. Nanocomposites suffered from polymer degradation during compounding, while the molecular weight was enhanced in the case of the flame retarded samples. Silicates were shown to restrain crystallization, whereas melamine cyanurate induced heterogeneous nucleation. Both additives positively influenced the tensile modulus of the prepared samples, decreasing their ability to elongate. With respect to the UL94 flammability test, melamine cyanurate was proved to be not sufficiently capable of increasing the tendency of nanocomposites to drip, negatively affecting flammability.
The selective positioning of clay platelets at the polymer/polymer interface in a blend with drop/matrix morphology has a contrasting effect: on the one hand, it promotes a refinement of the morphology during the intense flows which occur during melt compounding; on the other hand, it induces coarsening in the course of prolonged slow flows experienced during rheological analysis. Rather than to a usual coalescence process, the increase of the average sizes of the dispersed phase is primarily due to a clustering mechanism of clay‐coated droplets, which keep their individuality inside the clusters because of the elastic connotation of the layered interface.
A simple, easily accessible solvent‐free method for the dispersion of MWCNTs into PET is proposed, based on the preparation of a microparticulate polymer/nanotube masterbatch via cryogenic impact‐milling and its subsequent melt blending with the bulk polymer. Thermal and mechanical properties of nanocomposites prepared using this method were evaluated as a function of nanotube concentration. Thermal stability was improved, and superior crystallization behavior of PET in the nanocomposites was observed. Significant improvements of around 25% in tensile strength and tensile modulus of the nanocomposites was achieved using this strategy, with only 0.25 wt.‐% MWCNT, compared to previous literature data where 1 wt.‐% MWCNT was employed.
The influence of size and surface area of two different types of clay on the structure and characteristics of PEO/clay nanocomposites in the form of multilayered films is discussed. To search for new synergistic properties and/or improve the properties of nanocomposite films already known, we study polymer nanocomposites that have laponite as well as montmorillonite incorporated. While DSC measurements showed that higher laponite amounts gradually suppress the crystallinity of PEO in the nanocomposite, XRD measurements provided evidence that higher montmorillonite amounts ensure an improved final orientation of the clay platelets, parallel to the plane of the multilayered film.
PSU/MMT nanocomposites are prepared by dispersing MMT nanolayers in a PSU matrix via in situ photoinduced crosslinking polymerization. Intercalated methacrylate‐functionalized MMT and polysulfone dimethacrylate macromonomer are synthesized independently by esterification. In situ photoinduced crosslinking of the intercalated monomer and the PSU macromonomer in the silicate layers leads to nanocomposites that are formed by individually dispersing inorganic silica nanolayers in the polymer matrix. The morphology of the nanocomposites is investigated by XRD and TEM, which suggests the random dispersion of silicate layers in the PSU matrix. TGA results confirm that the thermal stability and char yield of PSU/MMT nanocomposites increases with the increase of clay loading.
Novel silver/polymer composites based on thiol‐ene chemistry are prepared by an in situ bottom‐up approach. The in situ synthesis of silver particles inside the polymer matrix is achieved in one pot by photoreduction reaction in presence of a silver precursor and the concurrent crosslinking reaction. XPS analysis confirms the formation of silver particles; TEM morphological investigation shows a very good dispersion and distribution of the nanometric silver particles within the thiol‐ene network. Antimicrobial properties of the photocured hybrids are also evaluated.
Next to the intended increase of the impact toughness, impact modification of polycarbonate generally results in an unwanted decrease in yield stress and time‐to‐failure under constant stress. It is demonstrated that this loss in strength can be fully compensated for by an annealing treatment, or by increasing the mold temperature. The influence of impact modification on the short‐ and long‐term strengths of glassy polymers is predicted by the extension of existing models with a scaling rule based on the filler volume percentage. Introduction of this scaling rule in the evolution of yield stress during physical aging even allows for the direct prediction of yield stress on the basis of processing conditions.
This report highlights the importance of nanocomposite formation and dispersion upon improvements in properties for high performance epoxy based layered silicate nanocomposites. This is achieved through the preparation of epoxy nanocomposites with varying clay concentrations using ultrasonic and solvent based fabrication and standard shear mixing procedures. Ultrasonication (combined with a solvent), in comparison to shear mixing methods, produces superior nanoscale dispersion according to SEM and TEM. As a result of the improvements in nanoscale dispersion, the corresponding improvements in fracture toughness, strength, strain to failure (compressive and flexural) and char stability are presented. TGA shows that while the initial thermal decomposition process is not affected, the stability of the char layer formed during decomposition increases with improved nanoscale dispersion as well as increasing concentration. The effect of moisture upon the dynamic mechanical thermal analysis of the epoxy nanocomposites displays some dependence upon the clay dispersion with a modest increase in plasticisation for the sonicated samples. Overall, this work shows that for a high performance epoxy anhydride resin system, significant improvements in key properties can be achieved at low levels of addition if appropriate sonicated dispersion methods can be utilised.
The preparation of new rubber based nanocomposites by using properly modified organophilic clays is described. A commercial organophilic montmorillonite containing a hydroxylated ammonium ion is reacted with LPBs. The reaction causes a decrease of the polarity of the clay and a great increase of the interlayer distance. The modified organoclays are successfully dispersed into rubber matrices (SBR or BR) by melt blending in an internal batch mixer. SAXS analyses and TEM micrographs revealed the formation of highly exfoliated nanocomposites containing intercalated stacks made of few lamellae.
Nanocomposites of poly(ethylene terephthalate) and two different montmorillonite‐based organoclays were prepared by a co‐rotating twin screw extruder. Dispersion of nanoclays in the polymer matrix was examined by TEM and XRD. Nanocomposites with lower content of organoclay showed exfoliated morphology while by increasing the amount of organoclay the intercalated morphology was more prevalent. Both organoclays had a good intercalation with PET and were uniformly dispersed within the polymer. Oxygen permeability of thin films of nanocomposites showed that the nanocomposites had better oxygen barrier properties than the neat PET. Tensile and impact properties of the nanocomposites also were measured.
