Preparation and characterization of precipitated zinc silicates

The study aimed to obtain highly dispersed particles of zinc silicate, a potential filler of polymers or a paint pigment, by precipitation from solutions of sodium metasilicate and of zinc salts. The technique of silicate precipitation was worked out, and the conditions causing precipitation were optimized. The temperature, sodium metasilicate solution flow rate and concentration of zinc salts were selected so as to obtain silicates of the lowest possible bulk density, and which had low water‐absorbing capacity and high paraffin oil‐absorbing capacity. In the study, the effects of precipitation parameters were examined on the principal physicochemical properties of the silicates, the structure and uniform character of silicate particles, particle size distribution, and the surface morphology. Particular attention was devoted to the particle size distribution and the tendency to form primary agglomerates (aggregates) and secondary agglomerates, using dynamic light scattering (DLS). Studies were undertaken to develop a technique which could prevent formation of silicate particle agglomerates. With this aim, the silicates' surface was modified either during their precipitation or by the so‐called dry technique. For the modification, silane coupling agents were applied. The extent of silicate surface hydrophobicity was examined by estimation of the enthalpies of immersion of the modified silicate surface. The silicates obtained were tested as fillers of rubber mixtures (in butadiene–styrene rubber). © 2003 Society of Chemical Industry     

Effect of organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of exfoliated acrylonitrile-butadiene-styrene copolymer (ABS) clay nanocomposites: role of clay as a colloidal stabilizer

Acrylonitrile-butadiene-styrene copolymer (ABS) clay nanocomposites were synthesized using two clays (sodium montmorillonite, laponite). Both colloidal stability and mechanical properties of the nanocomposites were dependant on aspect ratios of clays. Laponite, a low aspect ratio clay, reduced particle sizes of ABS clay nanocomposite latexes, enhanced colloidal stabilities, and increased viscosity of the latexes. The colloidal stability of ABS clay latexes may result from four factors. Firstly, the electrostatic repulsion forces originated from surface charges of clays and anionic surfactant contribute to colloidal stability. Secondly, laponite layers separate sodium montmorillonite layers and polybudadiene latex particles preventing the coagulation. Thirdly, the laponite layers adsorbed on latexes act like steric barriers against coagulation. Fourthly, increased viscosity reduces latex mobility, lowering collision possibility among latex particles. Resultant ABS clay nanocomposites showed exfoliated structures, and their mechanical properties related to the relative weight ratio of sodium montmorillonite to laponite: as portions of sodium montmorillonite increased, dynamic moduli of the nanocomposites increased, because sodium montmorillonite has higher aspect (length/thickness) ratio than laponite.     

Mechanical and rheological properties of the maleated polypropylene–layered silicate nanocomposites with different morphology

Three types of maleated polypropylene–layered silicate nanocomposites with different dispersion states of layered silicate (deintercalated, intercalated, and exfoliated states) are prepared from two kinds of polypropylenes with different molecular weights, organically modified layered silicate and pristine montmorillonite to investigate the effect of the final morphology of the nanocomposite on the rheological and mechanical properties. Maleated polypropylene with high molecular weight intercalates slowly and the other with low molecular weight exfoliates fast into the organophilic layered silicates. Rheological properties such as oscillatory storage modulus, nonterminal behavior, and relative viscosity has close relationship with the dispersion state of layered silicates. The exfoliated nanocomposite shows the largest increase and the deintercalated nanocomposite shows almost no change in relative shear and complex viscosities with the clay content. The exfoliated nanocomposite shows the largest drop in complex viscosity due to shear alignment of clay layers in the shear flow. In addition, the final dispersion state of layered silicates intimately relates to the mechanical property. The dynamic storage moduli of nanocomposites show the same behavior as the relative shear and complex viscosities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1526–1535, 2003     

Water uptake behavior of layered silicate/starch–polycaprolactone blend nanocomposites

The water uptake behavior of biodegradable layered silicate/starch–polycaprolactone blend nanocomposites was evaluated. Three different commercial layered silicates (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement nanofillers. Tests were carried out in two different environments: 60 and 90% relative humidity using glycerol solutions. The clay/starch–polycaprolactone blend nanocomposites were obtained by melt intercalation and characterized by gravimetric measurements and tensile tests. The intercalated structure (determined by wide‐angle X‐ray diffraction) showed a decrease in water absorption as a function of clay content probably due to the decrease of the mean free path of water molecules. The diffusion coefficient decreased with clay incorporation but a further increase in the clay content did not show an important effect on this parameter. Elongation at break increased with exposure showing matrix plasticization. Mechanical properties of the nanocomposites deteriorated after exposure whereas they remained almost constant in the case of the neat matrix. Copyright © 2007 Society of Chemical Industry     

Novel biodegradable flame retardant,poly(butyl methacrylate)/sodium silicate/Mg(OH)2 nanocomposite

Flame retardant poly(butyl methacrylate)/sodium silicate/Mg(OH)₂ (MH) nanocomposite has been prepared via in situ emulsion polymerization of BMA, benzoyl peroxide, layered silicate, and conventional fire retardant additive, MH. The morphology, thermal stability, and flammability properties of the nanocomposite were characterized by IR, XRD, TEM, TGA, cone calorimetry, and limiting oxygen index. The thermal stability and the flame retardant properties of the polymer‐silicate‐MH showed significant improvements in the decomposition temperature and the lower heat release rates due to the formation of nanocomposites with layered silicates. Biodegradation testing by Bacillus cereus (gram‐positive) revealed the ecofriendly nature of the nanocomposite. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Effects of layered silicate structure on the mechanical properties and structures of protein‐based bionanocomposites

In this work, a nonconventional protein source of pea protein isolate (PPI) was filled with montmorillonite (MMT) and rectorite (REC) by solution intercalation respectively, and then the reinforced PPI‐based nanocomposites were produced by hot press. The structure and interaction in the nanocomposites were investigated by FTIR, XRD, DSC, DMA, and pH and Zeta‐potential tests whereas the reinforcing effect was verified by tensile test. Furthermore, the origin of enhancing mechanical performances and the effects of layered silicate structure were explored. Although the MMT with lower negative‐charge surface and smaller apparent size of crude particles was easier to be exfoliated completely, the exfoliated REC nanoplatelets with more negative‐charge could form stronger electrostatic interaction with positive‐charge‐rich domains of PPI molecules, and hence produced the highest strength in two series of nanocomposites. In this case, the newly formed hydrogen bonds and electrostatic interaction on the surface of silicate lamellas guaranteed the transferring of the stress to rigid layered silicates. The cooperative effect of newly formed physical interaction between layered silicates and PPI molecules as well as the spatial occupancy of intercalated agglomerates of layered silicates destroyed the original microphase structure of PPI matrix and cleaved the entanglements among PPI molecules. It was not in favor of enhancing the elongation and strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

EPDM/silicone blend layered silicate nanocomposite by solution intercalation method: Morphology and properties

Ethylene–propylene–diene terpolymer (EPDM)/silicone blend nanocomposites are prepared by solution method for the first time. EPDM and silicone rubber in their 50:50 (by weight) blend is intercalated within the silicate sheets of organically modified montmorillonite. Organic modification to the pristine sodium montmorillonite (Na‐MMT) surfaces is carried out by ion‐exchange reaction using hexadecyl ammonium chloride. The incorporation of such organic functional group makes Na‐MMT hydrophobic and expands the interlayer spacing between silicate sheets. The intercalated structure of EPDM/silicone blend nanocomposites is characterized by the X‐ray diffraction. Transmission electron microscopic characterization visualized the presence of both exfoliated and intercalated layered silicate in the polymer nanocomposites. The mechanical properties of the nanocomposites show a maximum improvement in tensile strength and elongation at break of 23 and 68%, respectively, compared with EPDM/silicone blend. The dielectric measurement demonstrates the increase in relative permittivity for the nanocomposite than the pure blend. The increase in the onset temperature of the thermal degradation of nanocomposites (∼52°C) corresponding to 1 wt% decomposition indicates the enhancement of thermal stability of (EPDM)/silicone blend due to interaction with silicates. POLYM. COMPOS., 35:1834–1841, 2014. © 2014 Society of Plastics Engineers     

A Comparative Study of Polystyrene/Layered Silicate Nanocomposites,Synthesized by Emulsion and Bulk Polymerization Methods

Polystyrene/clay (PS/clay) nanocomposites were synthesized by insitu emulsion and bulk polymerization methods. Sodium montmorillonite (Na-MMT) and two organically modified clays (Cloisite 30B and Cloisite 15A) were employed. The effect of clay swelling method and sonication on the d-spacing of silicate layers was also investigated. The surface morphology of pure PS and PS/clay nanocomposites were comparatively investigated using scanning electron microscopy (SEM). Thermogravimetric analysis (TGA) of PS and PS/clay nanocomposites revealed the improved thermal stability of PS/clay nanocomposites compared to pure PS. Results of optical transparency tests showed the better transparency of nanocomposite films compared to the pure PS film.     

Preparation and properties of polysulfone–clay composite membranes

Porous membranes and dense films were prepared from polysulfone solutions in N‐methyl‐2‐pyrrolidone (NMP) containing different types and amounts of clay. Commercial clays supplied by Southern Clay, either unmodified (Cloisite Na) or organically modified (Cloisite 30B and Cloisite 93A), were used. The clay behavior in the organic solvent was dependent on the presence and type of the organic compatibilizer: Cloisite containing Na ions did not swell in NMP, whereas those with the organic compatibilizer swelled, though to a different degree. Electron microscopy observations were made to examine the clay dispersion in the membrane structure. At variance with Cloisite Na and Cloisite 93A formed microaggregates, Cloisite 30B yielded nanostructures composed of both single sheets and well‐ordered multilayer silicate clusters, which were characterized by an interlayer distance higher than that of the neat clay. The increase in the distance between the layers of Cloisite 30B was related to the formation of intercalated nanocomposites, whereas the presence of single sheets well distributed in the polymer matrix supported the occurrence of delaminated nanocomposites. The intercalation of the polymer into clay layers was confirmed with wide‐angle X‐ray diffractometry. The addition of Cloisite 30B to the casting solution influenced the phase‐separation process in the coagulation bath. Therefore, by the variation of the layered‐silicate concentration in the casting solution, membranes with different morphological structures and ultrafiltration properties were obtained. Cloisite 30B was also found to improve the wettability and mechanical properties of dense films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3637–3644, 2007     

Flammability and thermal stability studies of ABS/Montmorillonite nanocomposite

Acrylonitrile–butadiene–styrene (ABS)/montmorillonite nanocomposites have been prepared using a direct melt intercalation technique by blending ABS and organophilic clay of two different particle sizes: OMTa (5 µm) and OMTb (38 µm). Their structure and flammability properties were characterized by X‐ray diffraction, high resolution electronic microscopy (HREM), thermogravimetric analysis (TGA) and cone calorimeter experiments. The results of HREM showed that ABS/5 wt% OMTa nanocomposite was a kind of intercalated–delaminated structure, while ABS/5 wt% OMTb nanocomposite was mainly an intercalated structure. The nanocomposites showed a lower heat release rate peak and higher thermal stability than the original ABS by TGA and cone calorimeter experiments. Also, the intercalated nanocomposite was more effective than an exfoliated–intercalated nanocomposite in fire retardancy. Copyright © 2003 Society of Chemical Industry     

Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Using maleic anhydride grafted poly(lactic acid) as a compatibilizer in poly(lactic acid)/layered‐silicate nanocomposites

The goal of this work was to prepare exfoliated poly(lactic acid) (PLA)/layered‐silicate nanocomposites with maleic anhydride grafted poly(lactic acid) (PLA–MA) as a compatibilizer. Two different layered silicates were used in the study: bentonite and hectorite. The nanocomposites were prepared by the incorporation of each layered silicate (5 wt %) into PLA via solution casting. X‐ray diffraction of the prepared nanocomposites indicated exfoliation of the silicates. However, micrographs from transmission electron microscopy showed the presence of intercalated and partially exfoliated areas. Tensile testing showed improvements in both the tensile modulus and yield strength for all the prepared nanocomposites. The results from the dynamic mechanical thermal analysis showed an improvement in the storage modulus over the entire temperature range for both layered silicates together with a shift in the tan δ peak to higher temperatures. The effect of using PLA–MA differed between the two layered silicates because of a difference in the organic treatment. The bentonite layered silicate showed a more distinct improvement in exfoliation and an increase in the mechanical properties because of the addition of PLA–MA in comparison with the hectorite layered silicate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1852–1862, 2006     

Layered silicates with a montmorillonite structure: Preparation and prospects for the use in polymer nanocomposites

Layered silicate nanostructures corresponding to the general formula of the natural mineral montmorillonite are prepared under hydrothermal conditions. It is demonstrated that the phase and chemical compositions of layered silicates and the sizes of their particles can be controlled by varying the hydrothermal synthesis conditions. The possibility of controlling the characteristics of synthetic layered silicates makes them promising as materials for use in the preparation of polymer-inorganic nanocomposites with specified properties.     

Study on the dynamic self‐organization of montmorillonite in two phases

Polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) polymer alloy/montmorillonite (MMT) and nylon 6 (PA6)/ABS polymer alloy/MMT nanocomposites were prepared using the direct melt intercalation technique. Their structures were characterized by XRD and TEM. The results of TEM show that the silicate layers dispersed differently in two phases. In the PC/ABS/MMT nanocomposite, the silicate layers were self‐organized in the ABS phase, whereas in the PA6/ABS/MMT nanocomposite, the silicate layers were dispersed in both phases but mainly in the PA6 phase. Furthermore, the PC/MMT nanocomposite was melt‐mixed with pure ABS, and the changed morphology of the hybrid with the change of melt‐mixing time was characterized by XRD and TEM, to study the dynamic self‐assembly of clay layers in two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1457–1462, 2004     

Polyamide nanocomposites with improved toughness

Polymer nanocomposites containing several percent of exfoliated layered silicates are materials with a unique weight/performance ratio. The only parameter that is not enhanced, but even decreased, is toughness. This work focused on the toughness enhancement of these advanced systems with polyamide matrix prepared via melt‐mixing (i.e., by a conventional method of polymer processing having an advantage of easy simultaneous addition of other components). Analogously to ternary polyamide blends with improved mechanical behavior, containing finely and separately dispersed elastomer and rigid polymer, elastomer particles with an average size of 60 nm were incorporated in the nanocomposite. The very low particle size was achieved by in situ reactive compatibilization by using suitably functionalized elastomers. The simultaneously increasing viscosity of the system enhanced exfoliation of the silicate. Melt exfoliated nanocomposites containing 3 wt % of clay and 5 wt % of elastomer particles exhibit increased toughness without significant loss of other properties. Elastomer particles increase toughness by both acting as stress concentrators (by initiating energy absorbing microdeformations) and influencing the clay‐induced matrix crystalline structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 288–293, 2005     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Effect of different preparation routes on the structure and properties of rigid polyurethane‐layered silicate nanocomposites

To identify the effect of reactive preparation on the structure and properties of rigid polyurethane (PU)‐layered silicate nanocomposite, a range of nanocomposites were prepared by combining the various precursors in different sequences. The morphology of the samples was characterized by XRD and TEM. Tensile properties and dynamic mechanical thermal properties were measured. The reactions between the layered silicates and PU precursors were monitored via FTIR to gain an understanding of the participation of nanofiller in the polymerization reaction, and the impact of this on system stoichiometry. The XRD and TEM results provided evidence that morphology can differ significantly if different synthesis methods are used. However, the mechanical properties are dominated by the stoichiometry imbalance induced by the addition of the layered silicates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2894–2903, 2006     

Reduced copper diffusion in layered silicate/fluorinated polyimide (6FDA‐ODA) nanocomposites

The copper diffusion barrier properties of layered silicate/fluorinated polyimide nanocomposites were analyzed by transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS). It was found that the particles of copper are effectively retarded from penetrating into the polyimide matrix by layered silicates. The diffusion coefficients of layered silicate/polyimide nanocomposites are lower than that of the pure polyimide. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1422–1425, 2004     

Flame retardant properties of EVA‐nanocomposites and improvements by combination of nanofillers with aluminium trihydrate

Flame retardant nanocomposites are synthesized by melt‐blending ethylene–vinyl acetate copolymers (EVA) with modified layered silicates (montmorillonites). Thermogravimetric analysis performed under different atmospheres (nitrogen and air) demonstrated a clear increase in the thermal stability of the layered silicate‐based nanocomposites. The use of the cone calorimeter to investigate the fire properties of the materials indicated that the nanocomposites caused a large decrease in heat release. The char‐formation is the main factor important for improvement and its function is outlined. Further improvements of the flame retardancy by combinations of nanofillers and traditional FR‐additives on the basis of metal hydroxides were also studied. Copyright © 2002 John Wiley & Sons, Ltd.