Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.
The intercalation of cationic copolymer into a smectic clay, montmorillonite, has been used to produce polymerically modified organoclays. The organoclays of different lamellar morphology and content of quaternary ammonium groups have been prepared by altering the clay/polymer ratio. The organoclays prepared have been explored in the design of antimicrobial materials based on clay/polymer nanotechnology. Polyamide nanocomposites containing organoclays with incorporated cationic polymer showed an antimicrobial activity and improved mechanical properties. The antimicrobial efficiency and the mechanical properties of the nanocomposites were controlled by the variation of the content of the cationic polymer incorporated into the organoclay and organoclay loading.
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.
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.
Polymer/clay composite hydrogels were prepared based on PVA hydrogels containing 3–10 wt.‐% MOM. Their microstructure and morphology were studied by FT‐IR, WAXS and SEM, whereas the interactions between MOM and PVA were evaluated by thermal analyses. The swelling ratios for the PVA/MOM hydrogels decrease with increasing MOM content. WAXS results indicate that MOM was intercalates, and DSC results show a strong interaction between PVA and MOM. This interaction results in a stable network, which is confirmed by the elastic modulus and the thermal decomposition behavior of the hydrogels. Therefore, MOM acts as a co‐crosslinker, improving the stability of the network.
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.
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.
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.
PCL‐based nanoclay (layered silicate) nanocomposites are prepared using a small scale intermeshing co‐rotating twin‐screw extruder. Improving the level of nanoclay dispersion in PCL nanocomposites is obtained by changing the extrusion parameters. Increasing the screw speed and decreasing the throughput leads to an improved dispersion quality, as observed from the improved mechanical properties of the nanocomposites as well as from their clearly affected rheological and crystallization behavior. Furthermore, a commercially available software that simulates the twin‐screw extrusion process (LUDOVIC) is used to asses the processing parameters applied for making the nanocomposites.
Sunflower oil‐based HBTPU/Ag and LTPU/Ag nanocomposites have been prepared by in situ catalytic reduction of a silver salt. The virgin polymer and their nanocomposites are soluble in various polar organic solvents and amenable for both solution‐casting and hot pressing. XRD, TEM, and UV spectroscopic analyses ascertained well‐dispersed, narrow‐sized Ag nanoparticles. Tensile testing, dynamic mechanical, thermogravimetric, and DSC analyses showed desirable mechanical and thermal features with improvement upon incorporation of Ag nanoparticles and the presence of a hyperbranched component in the nanocomposites. RSM has been used to evaluate the catalytic efficacy of the nanocomposites.
A high degree of exfoliation of MMT in NR is achieved by using the so‐called “propping‐open approach” in which a stepwise expansion of the interlayer spacing of MMT takes place. The nanostructure is characterized by WAXD and TEM which indicate different extents of clay dispersion depending on the fatty‐acid chain length. Curing kinetics of different nanocomposites is studied and interestingly low activation energies of the vulcanization process are observed in the case of NR/EMMT nanocomposites. The incorporation of EMMT dramatically affects composite properties whereas DMA indicates significant reduction of tan δ peak height and the tensile strength approximately doubles from 14 to 30 MPa with only 5 phr EMMT.
A set of isotactic propylene copolymers with either 1‐hexene or 1‐octadecene were synthesized using a metallocene catalyst, and their nanocomposites with 5 wt.‐% of clay and 15 wt.‐% of compatibilizer were prepared and characterized. Clay intercalation and dispertion depend on the comonomer content in the matrix which improves at high short‐chain‐branching levels. The presence of both clay and compatibilizer increased the crystallization temperature of the matrix. A strong correlation between the elastic modulus of the matrix and its relative increase in the nanocomposite was observed. By adding clay and compatibilizer to the copolymer, the modulus can be increased by a factor of two. The results open new perspectives in the understanding of the effect of polyolefin topology on nanocomposites properties.
The effect of wood species on the TVOC emission factor and the physico‐mechanical properties of GPBs is investigated. Of the two wood species, the water absorption was higher for the GPBs made using Eucalyptus sp. than for those using Pinus massoniana. The Eucalyptus sp. GPBs pressed at room temperature, 40 and 60 °C all demonstrated higher moisture absorption than commercial GPBs. The TVOC emission factor decreased with increasing press temperature, especially for Eucalyptus sp. but remained under ‘excellent’ grade as defined by the KACA. From these results, GPB with higher content of wood particles should be considered for the replacement of wood‐based panels such as particleboard and medium density fiberboard (MDF).
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.
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.
A reactive organic montmorillonite clay (VMMT), modified with (4‐vinylbenzyl) triethylammonium cations, has been prepared and used as a nanofiller to reinforce a corn‐oil‐based polymer resin. The polymer resin was prepared by the cationic polymerization of conjugated corn oil, styrene and divinylbenzene, using boron trifluoride diethyl etherate modified with Norway fish oil as the initiator. The results indicate that the VMMT is intercalated in the corn‐oil‐based polymer resins. When compared with the pure polymers, these novel nanocomposites reinforced with 2 to 3 wt.‐% VMMT exhibit significant improvements in modulus, strength, strain and toughness. Furthermore, incorporating VMMT into the corn‐oil‐based polymer matrix also leads to improved thermal stability of the nanocomposites over the pure resins of up to 400 °C.
The traditional PA 6.6 production route, i.e. solution melt polymerization followed by extrusion, is applied to the in situ intercalation of PA 6.6/clay nanocomposites. Organoclays of different types are tested and the derived nanocomposites are thoroughly characterized in terms of molecular weight, thermal properties and morphology. Reaction acceleration is found in the presence of fully exchanged organoclays, which is attributed to a chain extension mechanism based on clay SiOH groups. Analysis of the nanocomposites' nanostructure indicates that the applied solution melt polymerization process results in some flocculation of the tested organoclays, which is improved in some cases after extrusion and leads to partially exfoliated nanocomposites.
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.
EVA copolymer/organoclay nanocomposites were prepared using melt‐compounding. Organoclays were obtained using wet and semi‐wet modification methods. These methods enable us to obtain organoclays with adequate modifier incorporation, but organoclays with a homogeneous and narrow agglomeration size distribution were obtained only with the wet method. TS and EB were higher for nanocomposites obtained with organoclays prepared using the wet method. Analysis of Limiting Oxygen Index, UL94 test and Cone Calorimeter test showed that the retardant properties of nanocomposites were also influenced by the kind of modifiers and the modification method.
pCBT/MWCNT nanocomposites were prepared by in situ polymerization of CBT after solid‐phase HEBM of the polymerization catalyst containing CBT with MWCNT. The crystallinity and crystallization behavior of the pCBT nanocomposites were studied by WAXS and DSC. The MWCNTs did not affect the crystallinity of the isothermally produced pCBT significantly, but acted as nucleation agents during the crystallization of pCBT from its melt. pCBT/MWCNT nanocomposites were subjected to DMTA, static flexure, and dynamic Charpy impact tests. The flexural modulus, strength, and impact strength from these tests all went through a maximum as a function of the MWCNT content. Optimum properties were found in the MWCNT range of 0.25–0.5 wt.‐%.
