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.
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.
PET/PE blends are prepared with and without different types of organo‐modified montmorillonites (OMMT) using a extrusion process. The droplet size of PE dispersed phase decreases upon organoclays addition, however without any direct dependence on the organoclay initial surface tension. To assess the effect of the organomodifier without MMT, PET/PE blends are then compounded adding solely the surfactants (similar to those used to modify the various organoclays). Whatever the chemical nature of the surfactant, a refinement of the PE droplets is observed, interestingly similar to those previously observed in presence of clay. This shows unambiguously that the key factor for organoclay compatibilization efficiency, in the case of PET/PE blends, is the surfactant modifier itself and not the MMT platelets.
This work aims at improving the interfacial bonding between polyamide‐12 and CNFs. CNFs were oxidized and dispersed in polyamide‐12 giving rise to polymer nanocomposites. The oxidation caused an increase in the specific surface area and structural defects of the fibers, as indicated by surface area and Fourier‐transform Raman spectroscopy. The nanocomposites exhibited improved thermal and thermo‐oxidative stabilities. The oxidized nanofibers had marginal effect on the crystallinity and crystallization of the polyamide‐12. An over‐proportional enhancement of stiffness due to the fibers could be achieved. In spite of these improvements the fiber/polymer adhesion should be further improved.
A novel zirconia polyester nanocomposite is prepared using an in situ approach. Surface‐functionalized zirconia nanoparticles are obtained by attaching 3‐phosphonopropionic acid to the metal oxide. Neat and surface‐covered metal oxide particles are incorporated at the beginning of the polyesterification reaction of isophthalic acid and neopentyl glycol resulting in zirconia/poly(neopentyl isophthalate) (PNI) nanocomposites. TEM shows that the dispersibility of the inorganic filler is improved by covering the zirconia surface with carboxylic acid groups. These results are verified by SAXS. Rheological measurements reveal that the viscosities are increasing compared to pristine PNI at particle loads of 10 wt% (neat zirconia) and 5 wt% (phosphonic‐acid‐capped zirconia), respectively.
Polyurethanes with narrow‐disperse (ND) and polydisperse (PD) hard segment (HS) distributions were prepared in a two‐step process. First, a poly(propylene oxide) end‐capped with MDI (4,4′methylenebis(phenyl isocyanate) was synthesized. To this prepolymer either a diamine–diamide was added to form ND HSs or a mixture of a diamine–diamide and additional MDI to form PD HSs in the copolymers. The polyurethanes displayed a ribbon‐like crystalline morphology, and it was found that the copolymers with ND HSs were more crystalline, had a higher modulus, a less temperature‐dependant modulus, and a higher melting temperature than their PD counterparts. Overall, the polyurethanes with the narrow‐dispersed HSs displayed superior properties.
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.
Graphene nanocomposites are prepared by chemical reduction of graphite oxide (GO) dispersion with vitamin C in the presence of SAN latex followed by melt compounding. In this process, GO is well dispersed in an aqueous SAN emulsion before reduction. During reduction the SAN latex is adsorbed on the graphene sheets of the chemically reduced GO (CRGO). After melt compounding of such hybrid particles with SAN, the nanocomposites show uniform dispersion of CRGO in SAN resulting in improved stiffness with respect to SAN/graphite. The reduction of GO in the presence of polymer latex represents a versatile route to graphene masterbatches and does not require either drying of GO or thermal GO expansion at high temperatures.
Nanocomposites of linear low‐density polyethylene (LLDPE), with three different amounts of polyhedral oligomeric silsesquioxanes (POSS), were prepared through melt‐mixing in a batch‐mixer at 150 °C. The structure of the prepared nanocomposites was studied by X‐ray scattering and optical microscopy. The surface morphology of the nanocomposites was investigated through field‐emission SEM. The thermal properties of the pure LLDPE and nanocomposites were studied by differential scanning calorimeter (DSC). Thermomechanical properties were assessed on a Paar‐Physics MCR501 rheometer using a solid‐state rectangular fixture. Results exhibited a significant improvement in both the storage and loss moduli of the neat LLDPE upon the incorporation of the POSS particles. A substantial improvement in thermal stability was also observed in the high‐temperature region.
The fabrication of nanocomposites by organic modification of clay during mixing into NR is reported. NR/OMMT nanocomposites show more intercalation and exfoliation at higher modifier content, increasing the tensile modulus primarily by improved filler reinforcement. Comparison with nominally identical pre‐modified OMMT shows similar microstructures and physical properties. No effect of mixing duration is observed, indicating that modification is rapid. Unlike montmorillonite, unmodified sepiolite disperses well in NR, so organo‐modification improves compatibility but does not affect the nanocomposite microstructure. This means that organo‐sepiolite offers relatively small improvements over sepiolite as a filler for NR.
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.
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.
A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.
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 based on an amorphous copolyester (PCTG) were obtained by melt mixing, changing the screw speed and the nature of the surfactant, which differed in polarity and molecular volume. Using Young's modulus as a measure of the dispersion level, a less‐polar nature and a higher molecular volume of the surfactant appeared as positive structural factors for dispersion of the clay in the less‐polar PCTG. The Cloisite 20A, which led to the highest modulus (widest dispersion), was mixed at different contents with PCTG at the observed optimum screw speed (200 rpm). Intercalated structures were observed by WAXD and TEM. The dispersion was wide, as observed by TEM, and led to a large (77%) modulus increase after 7% organoclay addition and to important increases in both tensile yield stress and dimensional stability in creep.
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.
A new class of polymer materials is reviewed, the SPCs, in which the matrix and the reinforcement share the same chemical composition. In addition to their milder environmental impact as compared to traditional polymer composites, they show superior mechanical performance mainly due to the improved adhesion between matrix and reinforcement. Another advantage of SPCs is the missing dispersion step in their production, thus contrasting the common polymer nanocomposites. Definition, manufacturing, classification, and the application opportunities of SPCs are described. Special attention is paid on the very new members of the SPC family, the micro‐ and nanofibrillar SPCs, including the techniques for preparation of their starting neat micro‐ and nanofibrils using bulk polymers.
This paper reports the properties of highly oriented nanocomposite tapes based on isotactic PP and needle‐like sepiolite nanoclay, obtained by a solid state drawing process. The intrinsic 1D character of sepiolite allows its exploitation in 1D objects, such as oriented polymer fibres and tapes, where it can be uniaxially oriented upon drawing. A synergistic increase in mechanical properties is presented for highly drawn tapes (λ ≤ 20) and low filler loadings (≤2.5 wt.‐%), which can not be simply explained by micromechanical composite models. Instead, mechanical properties are intimately related to the dispersion state of the nanoclays in PP, the rheological properties of the nanocomposites and the polymer morphology.
Soft coatings are widely used to tailor the surface chemistry of materials without altering their bulk properties. However, the strength of adhesion between the coating and the substrate must be high enough for long‐term applications. This has become a major challenge in the medical field, especially for polymer‐coated stents, mainly due to several coating failures reported after mechanical expansion during clinical implantation. In this work, the applicability of current polymer‐metal adhesion tests to polymer‐coated stents is discussed. The small punch test was proposed as an adhesion test that allows fundamental studies on the adhesion and coating properties. This adhesion test was applied to thin fluorocarbon coatings deposited by plasma on 316L stainless steel.
A diacrylate polysulfone oligomer is synthesized and used as the acrylic oligomer for the in situ synthesis of noble metal/PSU nanocomposites through UV‐induced simultaneous radical polymerization of acrylic functionalities and NP formation by reduction of their precursors. Thus, silver or gold NPs are formed in situ during polymer network formation. FESEM analysis of the morphology of the cured systems demonstrates that the nanoparticles of the noble metals are homogeneously distributed in the network without macroscopic agglomeration.
