Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of electrospun fibers of polyhydroxybutyrate filled with different organoclays on morphology,biodegradation, and thermal stability of poly(ε‐caprolattone)

The properties of nanocomposites of poly(ε‐caprolattone) (PCL) were studied, the pristine PCL was implemented with the introduction of electrospun fibers of polyhydroxybutyrate (PHB), containing a cationic (Cloisite) or an anionic (Perkalite) clay. These multicomponent composites containing a very low amount of clay confined in fibers are different from usual nanocomposite materials containing clay dispersed in the polymer matrix, which are produced by solvent casting or melt extrusion. To analyze the influence of the different fillers on the final composite, a preliminary study on PHB cast films and fibers prepared from the same solution was carried out, and then a thorough analysis was accomplished of the behavior of these particular nanocomposites PCL/PHB fibers/clay to elucidate the effects of the filled electrospun fibers on the PCL matrix. The structure and morphology of the samples were characterized by wide‐angle X‐ray diffraction and small angle X‐ray scattering; differential scanning calorimetry and thermogravimetric analysis were used to understand the influence of the fillers on the thermal behavior and stability; mechanical properties were evaluated and biodegradation studies were carried out. The PHB electrospun fibers and the fractured surface of the final composites were examined by scanning electron microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42342.     

Influence of granulometry and organic treatment of a Brazilian montmorillonite on the properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites prepared by miniemulsion polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene‐co‐butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 μm to colloidal size were selected. The size of the clay particles was evaluated by specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clay distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X‐ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical‐mechanical analysis, thermogravimetry, and small amplitude oscillatory shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na‐MMT resulted in materials with intercalated structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of organoclay‐networks modified low‐temperature hydrogenated nitrile butadiene rubber composites

The low‐temperature grade hydrogenated nitrile butadiene rubber (LTG‐HNBR) composites with organoclays were successfully prepared for the purpose of using the clay‐networks to improve bulk properties. In order to construct different clay‐networks, three montmorillonite (MMT) modified by surfactants were added and then their dispersions and affinities in the rubber were compared. Transmission electron microscope and small‐angle X‐ray scattering results showed that 10 phr organoclays form partially exfoliated and intercalated structures in the matrix despite of modifier types. FTIR and particle analysis data display that increasing the number of alkyl tails of modifier molecules decreases the affinities of clays and their extent of intercalation in rubber whereas the special modifier with coupling agent enhances their compatibility with the bulk. The mechanical, oil resistance, and thermal properties of the composites are greatly reinforced by clay‐networks which parallel their interactions. Importantly, the addition of clays barely changes glassy temperature (T_g) of rubber bulk, but it improves its low‐temperature elasticity. Therefore, it is stressed that organoclay hybrid networks are very useful to modify low‐temperature rubber. We believe that LTG‐HNBR composites with organoclays may serve some applications of oil‐sealing products. POLYM. COMPOS., 35:1306–1317, 2014. © 2013 Society of Plastics Engineers     

Thermal and dynamic mechanical behavior of ethylene/norbornene copolymers with medium norbornene contents

A range of ethylene/norbornene copolymers were synthesized using the commercially available rac‐Et(Ind)₂ZrCl₂ metallocene catalyst. A large window of norbornene contents, between 30 and 55 mol % was used to facilitate the interpretation of the results. The polymers were characterized by means of wide‐angle X‐ray scattering, differential scanning calorimetry, and dynamic mechanical thermal analysis. The X‐ray diffractograms showed two amorphous halos, the low‐angle one increasing in the intensity with norbornene content. Calorimetric and dynamic mechanical results led to a linear relation between the glass transition temperature and the norbornene content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2159–2165, 2001     

Green composites of poly(3‐hydroxybutyrate) and curaua fibers: Morphology and physical,thermal, and mechanical properties

In this article, we report the morphology and thermal, mechanical and physical properties of poly(3‐hydroxybutyrate) (PHB)/curaua composites containing triethyl citrate (TEC) as the plasticizer. The composites were prepared by mechanical mixing using pristine and chemically treated fibers (10 wt %) and TEC (30 wt %) and characterized by differential scanning calorimetry, dynamic mechanical analysis, X‐ray diffraction, small angle X‐ray scattering, polarized optical microscopy, scanning electron microscopy, tensile tests, impact resistance test, thermodilatometry, and thermal conductivity measurements. The curaua fibers acted as nucleating agent and strongly influenced the morphology of the crystalline phase of PHB, increasing the lamella thickness, decreasing the crystal size and inducing spherulite–axialite transition. These characteristics of the PHB crystalline phase determined all the properties of the composites. The tensile properties of the composites were comparable with those of neat PHB, while the impact resistance of composites was comparable with that of plasticized PHB. The higher heat capacity and thermal expansion coefficient and the lower thermal conductivity of the composites compared with neat PHB reflect the morphological changes in the PHB crystalline phase. The strategy of developing a green polymeric material from ecofriendly components exhibiting a good balance of properties by combining curaua fibers, TEC, and PHB was successful. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44676.     

Epoxy composites based on amino‐silylated MMT: The role of interfaces and clay morphology

Epoxy‐based composites containing sodium montmorillonite (MMT) modified by silylation reaction with 3‐aminopropyltriethoxysilane (A1100) and N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (A1120) were prepared. The effect of MMT chemical functionalization, as well as inorganic content and dispersion method (i.e., sonication or combination of sonication and ball‐milling) on the morphology and mechanical and thermal properties of composites was thoroughly investigated by X‐ray diffraction analysis, dynamic mechanical and tensile static analysis, nanoindentation measurements and cone calorimeter tests. Morphological characterization showed that the MMT particles are only slightly intercalated by epoxy molecules. Tensile stress, elongation at failure, and toughness of the epoxy composites based on silylated MMT were found to be improved. The presence of 1 and 3% wt/wt of A1100 and A1120 silylated MMT clays allowed the tensile elastic modulus to increase respectively, of about 10 and 15% with respect to the pristine epoxy matrix. The overall results showed that (1) the silylation of MMT clays is a valuable method to improve the interfacial interaction between filler and epoxy matrix and (2) the interfacial interaction plays a role more significant than the clay morphology (i.e., the extent of clay intercalation/exfoliation) over the composite properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure,nanomechanics, and dynamics of dispersed surfactant‐free clay nanocomposite films

The current work presents a new approach to achieve high quality dispersion of surfactant‐free nanoclay tactoid particles in sub‐micron thin films despite the absence of organic modifier. Natural Montmorillonite particles, Cloisite, were dispersed in thin films of polycaprolactone (PCL) through a flow coating technique assisted by ultra‐sonication. Wide‐angle X‐ray scattering (WAXS), grazing‐incidence wide‐angle X‐ray scattering (GI‐WAXS), and transmission electron microscopy (TEM) were used to confirm the level of natural clay dispersion down to the level of tactoids (sub‐micron scale stacks of clay sheets). These characterization techniques were carried out in conjunction with an analysis of nanomechanical properties via strain‐induced buckling instability for modulus measurements (SIEBIMM), a high‐throughput technique to characterize thin film mechanical properties. The buckling patterns indicate that the natural clay tactoids separate buckling‐enhancing (high‐modulus) crystalline regions and interconnect buckling‐suppressing amorphous (low‐modulus) regions. Due to the tactoid length scale, the glass transition behavior of the composites as characterized by broadband dielectric relaxation spectroscopy was unmodified by the clay. Likewise, the glass transition temperature, T_g, and fragility (slope of relaxation time behavior approaching T_g), remain unaffected, indicating that these dispersed tactoids do not induce pronounced confinement effects on dynamics. POLYM. ENG. SCI., 58:1285–1295, 2018. © 2018 Society of Plastics Engineers     

Microstructure and mechanical properties of a polyethylene/polydimethylsiloxane composite prepared using supercritical carbon dioxide

A polymer composite of polyethylene (PE) and polydimethylsiloxane (PDMS) was prepared using supercritical carbon dioxide despite the two polymers usually being immiscible and possessing a phase‐separated morphology. This article reports in detail the preparation, microstructure, crystallinity, and mechanical properties of the resulting PE/PDMS composite. The formation mechanism of the PE/PDMS composite consisted of supercritical impregnation of an octamethylcyclotetrasiloxane (D4) monomer and an initiator into a PE substrate followed by in situ polymerization within the substrate. Differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering measurements showed that PE and PDMS were blended at the nanometer level. The PDMS generated in the amorphous region of PE did not affect its crystallinity. Dynamic viscoelastic analyses and tensile tests were used to measure the mechanical properties of the composites including storage and Young's modulus, fracture stress, and strain. These properties were found to depend on the composition of the composite. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of EVA/clay Nanocomposites with improved barrier performance

Poly (ethylene‐co‐vinyl acetate) (EVA)/clay nanocomposites containing two different organoclays with different clay loadings were prepared. The transport of gases (oxygen and nitrogen) through the composite membranes was investigated and the results were compared. These studies revealed that the incorporation of nanoclays in the polymer increased the efficiency of the membranes toward barrier properties. It was also found that the barrier properties of the membranes decreased with clay loadings. This is mainly due to the aggregation of clay at higher loadings. The morphology of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy and X‐ray scattering. Small angle X‐ray scattering results showed significant intercalation of the polymer chains between the organo‐modified silicate layers in all cases. Better dispersed silicate layer stacking and more homogeneous membranes were obtained for Cloisite® 25A based nanocomposites compared with Cloisite® 20A samples. Microscopic observations (SEM and TEM) were coherent with those results. The dispersion of clay platelets seemed to be maximized for 3 wt % of clay and agglomeration increased with higher clay loading. Wide angle X‐ray scattering results showed no significant modifications in the crystalline structure of the EVA matrix because of the presence of the clays. The effect of free volume on the transport behavior was studied using positron annihilation spectroscopy. The permeability results have been correlated with various permeation models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhancement in the thermal and dynamic mechanical properties of high performance liquid crystalline epoxy composites through uniaxial orientation of mesogenic on carbon fiber

In this work, a high performance liquid crystalline epoxy composite was prepared and the effect of the alignment of LCE with long lateral substituent on the carbon fiber surface curing at low temperature on fracture toughness, dynamic mechanical, and thermal properties of liquid crystalline epoxy with lateral substituent (LCE6) was investigated by polarized optical microscopy (POM), wide angle X‐ray diffraction measurements (WAXS), dynamic mechanical analysis (DMA), thermogravimetric (TGA), and scanning electron microscopy (SEM). Curing degree of the composite was observed by FTIR. The experimental results indicate that the fracture toughness, glass transition temperature (T_g), thermal stability, degradation kinetics are associated with the alignment of LCE6 along long axis of carbon fiber. The alignment of LCE6 on carbon fiber surface can increase mesogen network density, which leads to higher fracture toughness, higher thermal stability, increase of the activation energies and higher T_g of the composite. The dynamic mechanical analysis shows that the compoaite possesses extremely higher dynamic storage moduli, which indicates that this LCE6/DDM/CF composite can be a high performance composite. Thus, the compoaite can be a potential candidate for advanced composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40363.     

Thermal and electrical properties of nitrile‐containing polyimide/BaTiO3 composite films

Polyimide composite films were prepared by mixing the BaTiO₃ particles into poly(amic acid) solution followed by film casting and thermal imidization under controlled temperature conditions. The poly(amic acid) was synthesized by solution polycondensation reaction of 4,4′‐oxydiphthalic anhydride with 2,6‐bis(4‐aminophenoxy)benzonitrile, using N‐methyl‐2‐pyrrolidone as solvent. The surface of BaTiO₃ particles was modified by treating with an aminosilane coupling agent, 3‐aminopropyltriethoxysilane. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to characterize the structure and properties of the composites. The influence of BaTiO₃ content on the composite film properties was evidenced. The films exhibited good thermal stability having the initial decomposition temperature above 520°C. They had stable dielectric properties over large intervals of temperature and frequency. The dielectric constant and the dielectric loss increased with the increase of BaTiO₃ content. The dynamic mechanical analysis and dielectric spectroscopy revealed subglass transitions γ and β. At higher temperature an α‐relaxation that corresponds to the glass transition and a conductivity process were evidenced. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

X‐ray diffraction study of iPP/cand iPP/TiO2 composites relating to micromechanical properties

Composites of isotactic polypropylene with various contents of white clay or titanium dioxide TiO₂ were prepared by extrusion molding. The extruded composites were melt‐pressed at two different temperatures, and, thereafter, either slowly cooled, or quenched to room temperatures. It is shown that the structure of all the samples, as revealed by wide‐angle X‐ray scattering and small‐angle X‐ray scattering (SAXS), depends on the processing conditions. The lack of SAXS maxima in the composites suggests that the presence of the microadditives hinders the stacking of iPP lamellae. Furthermore, the microindentation hardness H in the slowly cooled composites is influenced by the type and amount of the filler used. However, in the quenched samples H depends only on the amount of the filler used, and not on its type. In case of the quenched iPP/clay composites, the relationship between H and the Young's modulus E is found to be H/E ≈ 0.12, in good agreement with Struik's theoretical predictions of σ_e ≈ E/30, in consonance with results previously obtained for a series of polyethylene samples with different morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization and thermal properties of polylactide/palygorskite composites

Polylactide palygorskite (fibrous clay) composites were prepared by solvent casting method. Both pristine and organically modified palygorskite were used for composite preparation. The detailed crystallization behavior, morphology, and thermal properties of neat polylactide and the corresponding composites were investigated by using differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy and wide angle X‐ray diffraction techniques. The results showed that the crystallization and thermal characteristics of neat PLA were influenced significantly by the presence of palygorskite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40414.     

Improving the thermal and mechanical properties of poly(propylene carbonate) by incorporating functionalized graphite oxide

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability, low glass transition temperatures (T_g), and relatively low mechanical property have limited its applications. To improve the thermal and mechanical properties of PPC, functionalized graphite oxide (MGO) was synthesized and mixed with PPC by a solution intercalation method to produce MGO/PPC composites. A uniform structure of MGO/PPC composites was confirmed by X‐ray diffraction and scanning electron microscope. The thermal and mechanical properties of MGO/PPC composites were investigated by thermal gravimetric analysis, differential scanning calorimetric, dynamic mechanical analysis, and electronic tensile tester. Due to the nanometer‐sized dispersion of layered graphite in polymer matrix, MGO/PPC composites exhibit improved thermal and mechanical properties than pure PPC. When the MGO content is 3.0 wt %, the MGO/PPC composites shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Relationship between structure and rheological,mechanical and thermal properties of polylactide/Cloisite 30B nanocomposites

Melt‐state and solid state mechanical properties and thermal stability of polylactide layered silicate nanocomposites elaborated by melt intercalation were studied as a function of clay content. Wide angle X‐ray scattering results, transmission electron microscopy observations, and rheological measurements indicated that the clay was finely distributed in the polylactide matrix. Contrary to nonlinear mechanical properties, thermal and linear mechanical properties were shown to increase with increasing clay fraction. The nanoindentation measurements confirm the significant increase of linear mechanical properties previously observed by tensile tests. The good correlation of linear mechanical properties at the macrometric and nanometric scales is explained by the high dispersion degree of the nanofiller in the biodegradable polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Effect of BaTiO3 on the microwave absorbing properties of Co‐doped Ni‐Zn ferrite nanocomposites

Coprecipitation and hydrothermal method were utilized for the synthesis of Co‐doped Ni‐Zn ferrite and barium titanate nanoparticles. The microwave absorption properties of Co‐doped Ni‐Zn ferrite/barium titanate nanocomposites with single layer structure were studied in the frequency range of 8.2–12.4 GHz.The spectroscopic characterizations of the nanocomposites were examined using X‐ ray diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering measurement. Thermogravimetric analysis indicated the high thermal stabilities of the composites. The composite materials showed brilliant microwave absorbing properties in a wide range of frequency in the X‐band region with the minimum return loss of ?42.53 dB at 11.81 GHz when sample thickness was 2 mm and the mechanisms of microwave absorption are happening mainly due to the dielectric loss. Compared with pure Co‐doped Ni‐Zn ferrite, Co‐doped Ni‐Zn ferrite/BaTiO₃ composites exhibited enhanced absorbing properties. The microwave absorbing properties can be modulated by controlling the BaTiO₃ content of the absorbers and also by changing the sample thicknesses. Therefore, these composites can be used as lightweight and highly effective microwave absorbers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39926.     

Nanostructure and micromechanical properties of reversibly crosslinked isotactic polypropylene/clay composites

Recent developments concerning the methodology used to prepare composites of iPP and nanoclays are reported. Conventional (reactive melt mixing) and in situ preparations were performed, and the structural properties exhibited by the composites are discussed. Results suggest that the nanoclay could exhibit partial and, maybe, total exfoliation within the composites. Adhesion between the polymeric matrix and the nanoclay layers is similar to that obtained after grafting. The experimental procedure used and the analysis performed by means of the wide‐angle X‐ray scattering and differential scanning calorimetry techniques permit to describe, at nanoscale level, the contribution of the nanoclay to the polymer composite system. The microhardness values of the iPP–clay composites depend on the clay content and on the preparation method, and linearly correlate, according to the additivity law, with the degree of crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of clay content on the melting behavior and crystal structure of nonisothermal crystallized poly(L‐lactic acid)/nanocomposites

To study the effect of organophilic clay concentration on nonisothermal crystallization, poly(L ‐lactic acid) (PLLA)/montmorillonite (MMT) nanocomposites were prepared by mixing various amounts of commercial MMT (Cloisite^® 30B) and PLLA. The effect of MMT content on melting behavior and crystal structure of nonisothermal crystallized PLLA/MMT nanocomposites was investigated by differential scanning calorimetry (DSC), small‐angle X‐ray scattering, and wide‐angle X‐ray diffraction (XRD) analyses. The study was focused on the effect of the filler concentration on thermal and structural properties of the nonisothermally crystallized nanocomposite PLLA/MMT. The results obtained have shown that at filler loadings higher than 3 wt %, intercalation of the clay is observed. At lower clay concentrations (1–3 wt %), exfoliation predominates. DSC and XRD analysis data show that the crystallinity of PLLA/MMT composites increases drastically at high clay loadings (5–9 wt %). In these nanocomposites, PLLA crystallizes nonisothermally in an orthorhombic crystal structure, assigned to the α form of PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012