Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants

The thermal stability of seven organically modified montmorillonites (‘organoclays’) has been investigated using differential thermal analysis, differential scanning calorimetry, and thermogravimetry in conjunction with X-ray diffractometry. Six organoclays were synthesised by replacing the interlayer inorganic cations, initially present, with quaternary phosphonium and ammonium surfactant cations. The samples modified with tetrabutylphosphonium (TBP), and butyltriphenylphosphonium (BTPP) ions have an appreciably higher thermal stability than the octadecyltrimethylammonium (ODTMA)-modified clays. Thus, in the case of TBP- and BTPP-modified montmorillonites, the onset temperature of decomposition is close to 300 °C. Samples modified with hexadecyltributylphosphonium (HDTBP) ions have a lower onset temperature of decomposition of 225 °C. In comparison, the onset temperature for ODTMA-montmorillonites (obtained at different concentrations of ODTMA-bromide) ranges from 158 to 222 °C, being highest where the concentration of intercalated surfactant is lowest. The onset temperature for a commercial alkylsilane-treated quaternary ammonium-modified organoclay (S-BEN N-400FP) is 207 °C. The basal spacing of the TBP- and BTPP-modified clays is 1.7–1.8 nm, indicating a monolayer arrangement of quaternary phosphonium ions in the interlayer space, while the value of 2.5 nm for HDTBP-montmorillonite indicates a more open structure. The ODTMA-modified samples have basal spacings ranging from 1.9 to 2.1 nm, indicative of a bilayer to pseudo-trilayer arrangement. The exceptionally high basal spacing of 3.4 nm for the S-BEN N-400FP organoclay might be due to interlayer penetration of organosilane hydrolysis products during synthesis. The thermal properties of organoclays are apparently related to the nature of the surfactants and their arrangement in the interlayer space of montmorillonite.     

A straightforward preparation and characterization of novel poly(vinyl alcohol)/organoclay/silver tricomponent nanocomposite films

In the present investigation, novel poly(vinyl alcohol)/organoclay/silver (PVA/OMMT/Ag) tricomponent nanocomposite (NC) films with different compositions were prepared by solution intercalation method under ultrasonic irradiation process. The NC films were obtained by mixing a colloidal solution consisting of Ag nanoparticles (NPs) (3, 5, 7 and 9 wt%) with a water solution of PVA and OMMT (10 wt%) via solution casting method. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis (TGA) were utilized to characterize the morphology and properties of the PVA/OMMT/Ag NC films. TGA confirmed that the heat stability of the nanocomposite was improved. The enhancement in the thermal properties of the hybrid materials was due to strong hydrogen bonding between OH groups of PVA, free acid functionalized groups of OMMT, and the Ag NPs. SEM and TEM results also showed that the OMMT and Ag NPs were dispersed homogeneously in the PVA matrix on nanoscale.     

Insertion of novel optically active poly(amide-imide) chains containing pyromellitoyl-bis-l-phenylalanine linkages into the nanolayered silicates modified with l-tyrosine through solution intercalation

In the present investigation, for the first time, functional optically active poly(amide-imide) (PAI)/organonanosilica bionanocomposite films were successfully fabricated through solution intercalation technique. At the start, Cloisite Na⁺ and protonated form of l-tyrosine amino acid were used for the preparation of the novel chiral organoclay via ion-exchange reaction. Then, PAI containing phenylalanine amino acid was synthesized via solution polycondensation of N,N’-(pyromellitoyl)-bis-phenylalanine diacid chloride (5) with 4,4′-diaminodiphenylsulfone (6). This polymer was end-capped with amine end groups near the completion of the reaction to interact chemically with organoclay. Finally, PAI/organ-nanosilica bionanocomposites films containing 5, 10 and 15% of organoclay were prepared via solution intercalation method through blending of organoclay with the PAI solution. The nanostructures and properties of the PAI/organoclay hybrids were investigated using Fourier transform infrared spectroscopy, X-ray diffraction (XRD), scanning electron microscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and thermogravimetry analysis (TGA) techniques. XRD, FE-SEM and TEM results revealed the formation of exfoliated and intercalated organoclay platelets in the PAI matrix. TGA results indicated that the addition of organoclay into the PAI matrix increases in the thermal decomposition temperatures of the resulted bionanocomposites. The transparency of the nanocomposite films decreased gradually by the addition of organoclay, and the films became semitransparent as well as brittle at high loading of organoclay. Mechanical data indicated improvement in the tensile strength and modulus with organoclay loading. The film containing a 10 wt.%. of organoclay had a tensile strength of the order of 85.24 MPa relative to the 67.52 MPa of the pure PAI.     

Modified smectitic Tunisian clays used in the formulation of high performance lubricating greases

Two smectitic Tunisian clays were organically modified by exchange reaction with dioctadecyl dimethylammonium chloride (DODMA) and hexadecyl benzyl dimethylammonium chloride (HBDMA). The resulting organoclays were used in the formulation of lubricating greases. The results of the performance tests applied to the obtained greases showed that their physicochemical and mechanical characteristics are in conformity with the extreme-pressure (EP) greases specifications. The obtained greases present good EP properties with only 0.5% EP additives. The smectitic clays used could constitute a raw material in the formulation of high performance lubricating greases.     

Crystallization Behavior of Nanocomposites Synthesized from the Poly (L-lactide)-poly (Propylene Glycol) and Organoclay

This study explored the thermal behavior of PLLA–PPG nanocomposite with added organoclay. The modified clay was evenly dispersed into the matrix of LPG1000 to synthesize the nanoscale polymer. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal properties of the PLLA–PPG copolymers. Wide-angle X-ray diffraction was used to identify the crystal structure of PLLA–PPG copolymer. The crystal growth of PLLA–PPG copolymer with various proportions of added clay was observed by using polarized optical microscopy and transmission electron microscopy. The results show that adding clay could enhance the thermal stability of LPG1000 and significantly change its crystal property.     

Poly(lactic acid) nanocomposites: comparison of their properties with montmorillonite and synthetic mica (II)

Our study was to clarify the intercalation of polymer chains to organoclays and to improve the thermo-mechanical properties. Two organoclays were synthesized. One was a montmorillonite modified with hexadecylamine (C₁₆-MMT); the other was a fluorinated-mica modified with hexadecylamine (C₁₆-Mica). Dispersions of organoclays with poly(lactic acid) (PLA) were by using the solution intercalation method at different organoclay contents to produce nano-scale composites. The maximum ultimate tensile strength was observed for blends containing 4 wt% of either of the two organoclays and decreased with further increases in the organoclay content. The initial modulus increased with increasing organoclay content up to 4 wt% for C₁₆-MMT. When the C₁₆-MMT content was greater than this critical wt%, the modulus of the hybrids started to decrease. In contrast, the initial modulus of the hybrids using C₁₆-Mica increased continually with increasing clay content from 2 to 8 wt%. The tensile properties of the C₁₆-Mica hybrids were higher than those of the hybrids containing C₁₆-MMT. The optical translucency was not affected by the organoclay content up to 6 wt%; however, the films containing 8 wt% organoclays were slightly more cloudy.     

Transport properties of organic vapours in silicone/clay nanocomposites

Poly(dimethylsiloxane) (PDMS)/clay nanocomposites have been synthesized using a novel ω-ammonium functionalized oligo-PDMS surfactant (PDMS-N⁺(CH₃)₃) and processed in membrane form. In order to relate the clay morphological structure to the degree of dispersion and physical properties of the membrane, the clay ion-exchanged by PDMS-N⁺(CH₃)₃ has been compared to a non-exchanged sodium MMT and to two organoclays organo-modified by using either non-functional alkyl ammonium cations (C₃₈H₈₀N⁺) or hydroxyalkyl ammonium (C₂₂H₄₈ON⁺) cations. Morphological analysis and transport properties (sorption, diffusion and permeability) have been investigated using two penetrants: acetone and n-hexane. The mechanical and rheological properties of the PDMS nanocomposite membranes have also been studied. It has been found a significant effect of the clay organo-modifier on the morphology, physical and barrier properties of the systems.     

Polymer-clay nanocomposites prepared via in situ emulsion polymerization

A series of novel polystyrene and poly(butyl methacrylate) montmorillonites (MMT-Na) nanocomposite latexes have been successfully prepared by emulsion polymerization. First of all, chemical modification of MMT-Na with a reactive coupling agent (MMT-QS) has been employed for the synthesis of hybrids. Subsequently, in situ seeded emulsion polymerization of hydrophobic vinyl monomers, such as butyl methacrylate and styrene, using sodium dodecyl sulfate (SDS) and ammonium persulfate (APS) as surfactant and initiator, respectively, were used for nanocomposite preparation. This technique allowed preparing of stable nanocomposite latexes with high (30–45 wt.%) solids contents and with loading of inorganic particles up to 5 wt.%. The prepared wet dispersions were subsequently characterized by light scattering method. In order to characterize the microstructure of the clay layers, and that of the organoclay in polystyrene and poly(butyl methacrylate) nanocomposites, wide and small angle X-ray analyses (WAXS, SAXS) and transmission electron microscopy (TEM) techniques were used.