Effect of Surfactant Concentration on Thermal and Mechanical Properties of Poly(Butylene Succinate)/Organoclay Composites

Composite materials consisting of poly(butylene succinate) (PBS) and montmorillonite (MMT), modified to various extents using trihexyltetradecylphosphonium chloride (THTDP) cations, were prepared using a simple melt intercalation technique. The surfactant contents were varied, i.e. 0.4, 0.6, 0.8, 1.0, and 1.2 times the cation exchange capacity (CEC) of the MMT. The intercalation of the surfactant molecules into MMT layers, confirmed by the increase in interlayer spacing and significant changes in the morphology of the modified MMT, facilitated the dispersion of the clay in the PBS matrix. The properties of the PBS-based composites were changed with increasing surfactant content. The melting and crystallization temperatures increased and the degree of crystallinity (χ_c) decreased. The storage modulus was significantly enhanced below the glass transition temperature (Tg), and Tg shifted to a higher temperature, with a maximum at a surfactant loading of 0.6 CEC. The mechanical properties, including tensile strength, flexural strength, flexural modulus and impact strength, increased and then decreased with surfactant loading, with the maximum observed also at a surfactant loading of 0.6 CEC. In conclusion, an ideal balance between thermal and mechanical properties can be obtained at a surfactant quantity equivalent to 0.6 times the clay CEC. Moreover, all the composites exhibited obvious improvement in thermal and mechanical properties as compared to those of neat PBS.     

Preparation and Rheological Characteristics of Ethylene‐Vinyl Acetate Copolymer/Organoclay Nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) with 40 wt.% vinyl acetate content (EVA40)/organoclay nanocomposites were prepared using a melt intercalation method with several different clay concentrations (2.5, 5.0, 7.5, and 10.0 wt.%). X‐ray diffraction confirmed the formation of exfoliated nanocomposite in all cases with disappearance of the characteristic peak corresponding to the d‐spacing of the pristine organoclay. Transmission electron microscopy studies also showed an exfoliated morphology of the nanocomposites. Morphology and thermal properties of the nanocomposites were further examined by means of scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA), respectively. Rheological properties of the EVA40/organoclay nanocomposites were investigated using a rotational rheometer with parallel‐plate geometry in both steady shear and dynamic modes, demonstrating remarkable differences with the clay contents in comparison to that of pure EVA40 copolymer.     

Effects of Modifier Concentration on Structure and Viscoelastic Properties of Copolyester/Clay Nanocomposites

Abstract

Poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate)(PETG)/clay nanocomposites were prepared via melt intercalation technique. The effects of concentration of the organic modifier in the clay on the properties of the nanocomposites were studied. Three clays modified using the same alkyl ammonium modifier, but differing in modifier concentration, are used for this purpose. The nanocomposites are characterized using wide‐angle x‐ray diffraction for their structure. Dynamic mechanical analysis of these nanocomposites is also studied to investigate their viscoelastic behaviors. The x‐ray diffraction study shows an increase in the interlayer spacing of organically modified clays as compared to that of Na⁺ clay. The extent of increase in the interlayer spacing is dependent on the concentration of organic modifier used to modify the montmorillonite. The presence of well‐defined diffraction peaks and the observed increase in the interlayer spacing in the nanocomposites imply the formation of an intercalated hybrid. Dynamic mechanical properties show an increase in the storage modulus of the nanocomposite over the entire temperature range studied, as compared to the pristine polymer. Investigation of the rubbery plateau modulus confirms the reinforcing effect of organically modified clay. The observed enhancement in the modulus was greater for the clay with the lowest content of the organic modifier. These results indicate that in nanocomposites, apart from the compatibility of the organic modifier with the polymer, its concentration in the interlayer also plays a critical role in the structure development and thus in the enhancement of the properties. The nanocomposites showed reduced damping, which was governed by the modifier concentration in the clay.     

Polymer–Clay Nanocomposites Based on Blends of Various Types of Polyethylenes and PE-g-MA: Morphology,Thermal Properties,Microhardness, and Transparency

Polymer–clay nanocomposites have been prepared by melt blending of commercial organoclay Cloisite 15A with blends of polyethylenes (PE) and maleic-anhydride-grafted PE (PE/PE-g-MA) with wide range of composition. Three types of PE/PE-g-MA blends with different molecular structure, namely blends of high-density PE (HD) with HD-g-MA (HDMA), blends of low-density PE (LD) with LD-g-MA (LDMA), and blends of linear low-density PE (LL) with LL-g-MA (LLMA) were used. The influence of the molecular structure of the PE matrixes and the compatibility between the blend components on the morphology of the nanocomposites was studied. The thermal properties, microhardness, and transparency of the nanocomposites were investigated. The influence of the degree of exfoliation/intercalation on the materials characteristics is discussed.     

Preparation and characterization of chitosan-clay nanocomposites with antimicrobial activity

Chitosan-montmorillonite nanocomposites were prepared by an ion exchange reaction between water soluble oligomeric chitosan and a Na⁺-montmorillonite. The chitosan-montmorillonite nanocomposites were rapidly prepared within 1 h due to the high affinity between the chitosan and the montmorillonite clay host. The basal spacings of the composites were in a range of 14.5-19.6 Å depending on the mixing ratio of chitosan to clay. According to the thermogravimetric analysis (TG) and powder X-ray diffraction analysis the thermal stability of chitosan was remarkably improved in the interlayer space due to the strong electrostatic interaction of cationic chitosan molecules with anionic silicate layers. From the antimicrobial activity test it was found that the nanocomposites showed a synergistic effect in the antimicrobial activity against to Escherichia coli and Staphylococcus aureus.     

Polystyrene‐b‐Poly(Ethylene‐r‐butylene)‐b‐Polystyrene Triblock Copolymer/Organoclay Nanocomposites and Their Phase Characteristics

Abstract

Intercalated polymer/clay nanocomposites were prepared using a polystyrene‐b‐poly(ethylene‐r‐butylene)‐b‐polystyrene (SEBS) cylindrical triblock copolymer. Dynamic rheological measurements, x‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry analysis (TGA) were conducted to investigate the internal structure and physical and phase characteristics of the nanocomposites. The XRD data confirmed that the interlayer distance between the anisotropic silicates increased due to the intercalation of SEBS into the clay interlayers. As the clay loading increased, the onset points of the order–disorder transition (ODT) and order–order transition (OOT) were found to decrease, whereas the thermal decomposition temperatures, monitored by TGA, increased with the clay loading.     

Structure and Thermal Stability of Polystyrene/Layered Silicate Nanocomposites

Polystyrene/layered silicates nanocomposites were prepared by intercalation in solution method, using CHCl₃ and CCl₄ as solvents. The clay used was organically modified by hexadecyltrimethyl–ammonium bromide (CTAB) at various surfactant loadings. It was found that intercalated nanocomposite structure was obtained using CHCl₃ as solvent while exfoliated or partially exfoliated was the predominant form in the case of CCl₄. X-ray diffraction and thermogravimetric analysis were used to characterize the nanocomposite morphology and thermal stability, respectively. Enhancement in thermal stability was observed for PS-nanocomposites compared to that of pristine polymer as indicated by TGA measurements. This increment was more prevalent for exfoliated nanocomposites prepared with carbon tetrachloride as solvent.     

高压下制备的累托石/酚醛树脂复合材料微结构和热性能研究

 采用物理方法在高压下制备了酚醛树脂（PF）/累托石（REC）纳米复合材料,用X射线衍射（XRD）、透射电子显微镜（TEM）及热分析（DSC/TGA）等方法,研究了复合材料的物相、显微结构以及热学性能。结果表明,不通过层间高分子聚合反应,不预先对累托石进行有机化处理,在高压下,由聚合物分子插入粘土层间,可以形成剥离型树脂/粘土纳米复合材料,并且其热学性能发生了较大的改变。     

Thermal and Mechanical Properties of Ultra High Molecular Weight Polyethylene Fiber Reinforced High-Density Polyethylene Homocomposites: Effect of Processing Condition and Nanoclay Addition

A new method to prepare single-polymer high-density (HDPE)-ultra high molecular weight polyethylene (UHMWPE) fiber (PE-PE homocomposites) composed and also PE-PE homocomposites containing HDPE organo montmorillonite clay (OMMT) nanocomposites as a matrix (PE nanohomocomposites) was used. Owing to the major importance of fiber impregnation by the matrix and its effect on the adhesion of matrix/fiber and, consequently, the mechanical properties of the composite, a combination of powder impregnation and film stacking methods, utilizing compression molding, were used for manufacturing the PE-PE homocomposites and PE nanohomocomposites. In addition, PE nanohomocomposites with the matrix containing different amounts of nanoclay were prepared to investigate the effect of the clay on the interfacial and mechanical properties of the PE-PE nanohomocomposites. Several different processing conditions were examined to determine the best conditions for manufacturing of the PE-PE homocomposite and PE nanohomocomposites and it was concluded that 40 bar and 10 min of compression molding resulted in the highest overall mechanical properties. The PE-PE homocomposites and PE-PE nanohomocomposites showed identical trends for the relationship between the effects of processing conditions and mechanical properties. Mechanical results demonstrated that clay platelets could increase the interfacial strength by improving physical entanglements between fiber and matrix through better cocrystallization.     

Gallate-Zn-Al-layered double hydroxide as an intercalated compound with new controlled release formulation of anticarcinogenic agent

A new organic-clay material, in which the organic moiety is intercalated into the inorganic interlayer, was prepared using gallate anion (GA) as a guest, and Zn-Al-layered double hydroxide, as clay host. The ion-exchange technique was found to be effective for the intercalation process in the formation of the compound. Although the basal spacings of the LDH and its intercalated product were fairly similar, FTIR, CHNS and TGA/DTG results indicated that the GA was actually intercalated into the interlayer of the host in parallel orientation. The resulting nanostructure material possessed a well ordered layered structure with 42.2% GA loading (w/w). The release of the anion from the interlayer of the intercalated compound was found to be of controlled manner, governed by the first order kinetic and it was also concentration dependent. The material has potential as a nano-storage of anticarcenogenic agent with controlled delivery capability.     

Improved photostability of hydrophobic natural dye incorporated in organo-modified hydrotalcite

β-carotene and annatto extract are typical carotenoids used as safe colorants for foods. However, the instability against irradiation limits their wide use. The improvement of stability was investigated by the intercalation of dye into the interlayer space of the anion-exchangeable clay, hydrotalcite. A hydrophobic environment was constructed in the interlayer space of the hydrotalcite by its modification with anionic surfactants (dodecyl sulfate and dodecylbenzene sulfonate). The lipophilic β-carotene and annatto dye were successfully incorporated into the organo-modified hydrotalcite, and the incorporated dyes exhibited improved photostability under visible irradiation from a 100 W halogen lamp (190 klux) in the air. The effect of the stabilization on the anionic annatto dye was higher by the incorporation in the modified hydrotalcite than that in the modified cation exchangeable clay, suggesting that the polarity of the clay sheet had some influence on the stabilization of the incorporated dye. The stabilization effect of β-carotene was not so significant as that of the annatto dye, because sufficient intercalation of non-polar β-carotene might require stronger hydrophobic environment. The π–π interaction between the β-carotene and the benzene ring of dodecylbenzene sulfonate was found to contribute to the stability enhancement.     

X-ray diffraction studies of intercalation compounds prepared from aniline salts and montmorillonite by a mechanochemical processing

Inorganic-organic intercalation compounds comprised of montmorillonite (MMT) and aniline salts with different counter anions were prepared by a mechanochemical processing. The intercalation process and the formed structure of intercalation compounds were investigated via X-ray diffraction analysis. The amounts of intercalated species were very likely dependent on the types of counter anions and increased with decreasing the size of counter anions during the mechanochemical processing. Very interestingly, much larger interlayer expansions of 1.51 nm was observed for aniline hydrofluoride AnF- and aniline hydrochloride AnCl-MMT systems in higher intercalates loading levels, suggesting that neutral guest molecules also introduce within the interlayer regions together with anilinium cations by van der Waals interactions. Judging from the larger interlayer expansions and the size of guest molecules, intercalated species are expected to prefer a tri-molecular layer arrangement with their aromatic rings perpendicular to the silicate sheets. In contrast, for aniline hydrobromide AnBr-MMT, the interlayer expansion was ca. 0.52 nm, which reveals that only anilinium cations are introduced by ion exchange and they probably adopt a vertical orientation in the interlayers. It is inferred that aniline hydroiodide AnI-MMT compounds have a heterogeneous structure containing both anilinium and sodium cations in the interlayers. Different intercalation behaviors during the mechanochemical processing strongly suggest the smaller the size of counter anions, the more guest molecules can be intercalated into the confined clay interlayers in highly ordered arrangements.     

Characterization and transport properties of intercalated polypyrrole-vanadium pentoxide xerogel nanocomposite

Layered vanadium pentoxide (V₂O₅) xerogel is used as host material for the synthesis of conducting polypyrrole intercalated nanocomposites. Powder X-ray diffraction spectra show the increase of interlayer space of V₂O₅ xerogel indicating the formation of polypyrrole in the interlayer space of the host. Thermal stability of intercalated polypyrrole is superior compared to bulk polypyrrole. Dc conductivity of the xerogel follows Arrhenius type temperature dependence while the nanocomposites exhibit Mott's three-dimensional variable range hopping. Optical band gap decreases with intercalation of polypyrrole.     

Preparation of polyacrylamide and gamma-zirconium phosphate nanocomposites by intercalative polymerization

A new inorganic-organic nanocomposite of polyacrylamide (PAM) and gamma-zirconium phosphate (gamma-ZrP) was prepared by intercalative polymerization. Intercalation of acrylamide (AM) monomer in gamma-ZrP was investigated by sonochemical and refluxing methods. High-intensity ultrasound does not induce the polymerization of AM but enhances greatly the intercalation rate. On the other hand, ultrasound also enhanced hydrolyzation of -CONH2 and shrinkage of PAM gel. The interlayer distance of AM-intercalated gamma-ZrP is 16.4 A. The polymerization and intercalation of AM occurred nearly at the same time by refluxing method. The same gamma-ZrP/PAM nanocomposites were obtained with (NH4)2S2O8 treatment.     

High CEC generation and surface modification in mica and vermiculite minerals

Montmorillonite layered silicate has been commonly used to reinforce polymer matrices. Due to its swelling in water, organic modification of the mineral surface is easily achieved which makes the surface compatible with polymers. Other minerals like mica and vermiculite though can also lead to high aspect ratio platelets in nanocomposites, but they do not swell in water owing to much stronger electrostatic forces of attraction holding their platelets together (layer charge density >0.5?eq?·?mol^?1 in comparison with 0.25–0.5?eq?·?mol^?1 for montmorillonite). In current study, milling, delamination and cation exchange processing of mica and vermiculite minerals has been reported to explore their potential as reinforcement materials. Wet grinding and subsequent sieving of the coarse minerals led to fine-sized particles suitable to perform chemical delamination in water. The delamination process resulted in Li-mica and Na-vermiculite with enhanced access to the interlayer cations, thus, higher CEC. Successful surface modification of the delaminated minerals with alkyl ammonium ions could be achieved which resulted in significant enhancements in their basal plane spacing. Peak degradation temperatures of 260°C were measured for C18 and 2C18 modified vermiculite, whereas 300°C and 275°C were observed respectively for C18 and 2C18 modified mica minerals which make them suitable for compounding with polymers at high temperature.     

过氧化氢和连二亚硫酸钠-柠檬酸钠-碳酸氢钠处理对红土中黏土矿物的影响

过氧化氢(H₂O₂)和连二亚硫酸钠-柠檬酸钠-碳酸氢钠(DCB)作为土壤沉积物前处理的经典方法,对土壤沉积物中黏土矿物的富集有着举足轻重的作用,但关于二者对黏土矿物的影响研究较少。运用X射线衍射作为检测技术,对比研究H₂O₂和DCB两种前处理方法对红土中黏土矿物的影响。结果表明,H₂O₂或DCB处理均可促进土壤矿物颗粒的充分分散,有效地将石英等杂质分离,进而提取到很纯的黏土矿物。同时发现,DCB处理由于其Na+与黏土矿物层间阳离子交换导致数据失真,而H₂O₂处理可以保证数据的真实性。结果表明：采用H₂O₂进行前处理能获取较为准确的黏土矿物学信息。     

Effect of High-Density Polyethylene Nanocomposite Compatibilizer Type on the Interfacial Adhesion and Mechanical Properties of Polyethylene Nano-Homocomposites

In this paper, the effect of nanocomposite compatibilizer type on the interfacial adhesion and mechanical properties of new class of polyethylene (PE) homocomposites, comprising PE/clay nanocomposites as matrix and ultra high molecular weight polyethylene (UHMWPE) fibers as reinforcement, was investigated. These were manufactured by a combination of powder impregnation and film stacking methods, introduced in previous research. Three types of high-density polyethylene (HDPE) Nanocomposites were prepared based on the various compatibilizers used: (i) nanocomposites containing HDPE-grafted maleic anhydride (HDPE-g-MA) as compatibilizer of clay and HDPE matrix, (ii) linear low-density polyethylene-grafted maleic anhydride (LLDPE-g-MA) used as compatibilizer, and (iii) nanocomposites without any compatibilizer. The effects of the presence and compatibilizer type on the quality of clay dispersion, and also the interface features of HDPE-nanocomposite and UHMWPE fibers were investigated and compared with each other. The results demonstrated that the kind of compatibilizer was an important factor determining the dispersion state of clay platelets, and influenced the UHMWPE fiber–PE matrix interface adhesion and the mechanical properties of the PE nano-homocomposites.     

Synthesis of modified vermiculite by interaction with aromatic heterocyclic amines

Vermiculite of general formula [Si_6.85Al_1.15][Mg_4.68Al_0.51Fe_0.63]O₂₀(OH)₄Ca_0.128Na_0.032K_0.094 reacted with heteroaromatic amines α-, β-, and γ-picolines from aqueous solution. The products were characterized by elemental analysis, infrared spectroscopy, and X-ray diffraction. The intercalated nanocompounds maintained the crystallinity and changed the original interlayer distance of 1422 pm to 1474, 1456, and 1474 pm, for the sequence of the guest picoline molecules. Natural and intercalated vermiculite can remove copper at the solid/liquid interface; removal 0.40 mmol g⁻¹ was obtained for the original matrix, and 1.10, 0.92, and 1.33 mmol g⁻¹ for the intercalated forms. These values are near the capacity of cation exchange (CEC) of this clay mineral, which can be possibly used as source of copper removal from aqueous solution.     

Effects of surfactants on microwave-assisted solid-state intercalation of poly(carbazole) in Bentonite

The present preliminary investigation reports, for the first time, the effects of typical cationic and anionic surfactants on the microwave-assisted solid-state intercalation and polymerization of carbazole (Cz) in the basal spacings of Bentonite. The intercalation of cetyl pyridinium chloride (CPCl), a cationic surfactant, and naphthalene sulfonic acid (NSA), an anionic surfactant, in Bentonite was carried out at two loadings—25 and 50 wt%—using microwave irradiation. The in situ polymerization of Cz was successfully carried out into the surfactant-modified galleries of Bentonite. This was confirmed by Gel permeation chromatography (GPC). The intercalation of poly(carbazole) (PCz) was confirmed by FT-IR, UV–Visible, and XRD analyses. Although polymerization was carried out in the solid-state, the UV–Visible spectra revealed the doped state of PCz and the presence of a charge carrier tail. The XRD studies showed that the increase in the height of the galleries was higher in case of Bentonite/CPCl/PCz nanocomposites as compared to Bentonite/NSA/PCz nanocomposites. It also revealed different orientations of the two surfactants in the galleries of the clay. The average particle size of Bentonite/CPCl/PCz (1:0.25:0.25) and (1:0.5:0.5) nanocomposites was found to be in the range of 25–35 and 50–60 nm, respectively. The Bentonite/NSA/PCz (1:0.25:0.25) and (1:0.5:0.5) nanocomposites showed the average particle size in the range of 20–30 nm and 40–50 nm, respectively. The results revealed that both cationic and anionic surfactants strongly influenced the morphology of Bentonite/PCz nanocomposites. The difference in the mechanisms of solid-state intercalation of PCz in the presence of these surfactants has been proposed.     

Morphology and properties of poly(methyl methacrylate)/clay nanocomposites by in-situ solution polymerization

Poly(methyl metacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by in-situ solution polymerization of methyl methacrylate monomer in the presence of the organic modified MMT-clay. After the organic modification by ionic exchanging with amine salts, the organoclay becomes more hydrophobic and compatible then pristine clay with methyl methacrylate monomer. The modified clays are characterized by wide angle X-ray diffraction (WAXRD). The powdered X-ray diffraction and transmission electron microscopy (TEM) techniques were employed to study the morphology of the PMMA/clay nanocomposites which indicate that the modified clays are dispersed in PMMA matrix to form both exfoliated and intercalated PMMA/modified clay nanocomposites. The thermo-mechanical properties were measured by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC). Gas permeability analyzer (GPA) shows the excellent gas barrier property of the PMMA nanocomposites which is in good agreement with the morphology. The optical property was measured by UV-vis spectroscopy which shows that these materials have good optical clarity, and UV resistance.