D.L. Hunter

Effect of melt processing conditions on the extent of exfoliation in organoclay-based nanocomposites

Polymer layered silicate nanocomposites have been studied for nearly 50 years, but few references deal with the importance of how the organoclay was processed into the plastic of choice. Many articles focus on the importance of the chemistry used to modify the surface of the clay, usually montmorillonite, without including the role of processing. This paper demonstrates the importance of both the chemistry of the clay surface and how the clay was melt processed into the thermoplastic. Two different clay treatments were added to polyamide 6 using four different types of extruders with multiple screw designs. The mixtures of organoclay and polyamide 6 were characterized by X-ray diffraction, transmission electron microscopy, and mechanical property tests. The degree of dispersion is interpreted in terms of the residence time distribution in the extruder and the intensity of shear. A model for organoclay delamination in a polymer melt is proposed that envisions the role of both shear and time.

Effect of organoclay structure on nylon 6 nanocomposite morphology and properties

Abstract A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress–strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.

Polycarbonate nanocomposites. Part 1. Effect of organoclay structure on morphology and properties

Abstract Polycarbonate nanocomposites were prepared by melt processing from a series of organoclays based on sodium montmorillonite exchanged with various amine surfactants. To explore the effects of matrix molecular weight on dispersion, an organoclay was melt-mixed with a medium molecular weight polycarbonate (MMW-PC) and a high molecular weight polycarbonate (HMW-PC) using a twin screw extruder. The effects of surfactant chemical structure on the morphology and physical properties were explored for nanocomposites formed from HMW-PC. Wide angle X-ray scattering, transmission electron microscopy, and stress–strain behavior were employed to investigate the nanocomposite morphology and physical properties. The modulus enhancement is greater for nanocomposites formed from HMW-PC than MMW-PC. This trend is attributed to the higher shear stress generated during melt processing. A surfactant having both polyoxyethylene and octadecyl tails shows the most significant improvement in modulus with some of the clay platelets fully exfoliated. However, the nanocomposites formed from a range of other organoclays contained both intercalated tactoids and collapsed clay particles with few, if any, exfoliated platelets.

Polycarbonate nanocomposites: Part 2. Degradation and color formation

Abstract Polycarbonate nanocomposites were prepared using two different twin screw extruders from a series of organoclays based on sodium montmorillonite, with somewhat high iron content, exchanged with various amine surfactants. It seems that a longer residence time and/or broader residence time distribution are more effective for dispersing the organoclay. The effects of organoclay structure on color formation during melt processing were quantified using colorimeter and UV–Vis spectroscopy techniques. Color formation in the PC nanocomposites depends on the type of organoclay and the type of pristine clay employed. Double bonds in the hydrocarbon tail of the surfactants lead to more darkly colored materials than saturated surfactants. The most severe color was observed when using a surfactant containing hydroxy-ethyl groups and a hydrocarbon tail derived from tallow. Molecular weight degradation of the PC matrix during melt processing produces phenolic end groups which were tracked by UV–Vis spectroscopy. Greater dispersion of the clay generally led to higher reduction in molecular weight due to the increased surface area of clay exposed; however, for color, the situation is far more complex. Hydroxy-ethyl groups and tallow unit on the surfactant lead to more degradation. A selected series of organoclays based on synthetic clay Laponite® and calcium montmorillonite from Texas (TX-MMT) were also prepared to explore the effects of the clay structure. Laponite® and TX-MMT produce less color formation in PC nanocomposites than montmorillonite probably due to lower content of iron. Dynamic rheological properties support the trends of molecular weight degradation and dispersion of clay.