Melt compounded epoxidized natural rubber/layered silicate nanocomposites: structure-properties relationships

Epoxidized natural rubber (ENR)-layered silicate composites were produced by melt compounding and sulfur curing. Pristine (sodium bentonite and sodium fluorohectorite) and organophilic modified silicates (organoclays with primary amine and quaternary ammonium modifications) were introduced in 10 parts per hundred rubber (phr) in the recipes and their effect on the curing and (thermo)mechanical properties determined. The dispersion state of the silicates was studied by X-ray diffraction and transmission electron microscopy. Fastest curing and best mechanical properties were found for the ENR containing the organoclay with primary amine modification. This organoclay was partly exfoliated, partly intercalated and partly confined (reaggregated). Due to the high shearing during compounding the pristine fluorohectorite was also intercalated by ENR. The complex dispersion state of the layered silicates was well reflected in the glass transition relaxation, which showed multiple peaks. Intercalation/exfoliation of the silicates were best displayed in stiffness- and strength-related mechanical parameters.     

Morphology, thermal relaxations and mechanical properties of layered silicate nanocomposites based upon high-functionality epoxy resins

This paper investigates the possibility of improving the mechanical properties of high-functionality epoxy resins through dispersion of octadecyl ammonium ion-modified layered silicates within the polymer matrix. The different resins used are bifunctional diglycidyl ether of bisphenol-A (DGEBA), trifunctional triglycidyl p-amino phenol (TGAP) and tetrafunctional tetraglycidyldiamino diphenylmethane (TGDDM). All resins are cured with diethyltoluene diamine (DETDA). The morphology of the final, cured material was probed by wide-angle X-ray scattering, as well as optical and atomic force microscopy. The α- and β-relaxation temperatures of the cured systems were determined using dynamic mechanical thermal analysis. It was found that the presence of organoclay steadily decreased both transition temperatures with increasing filler concentration. Further, the effect of different concentrations of the alkyl ammonium-modified layered silicate on the toughness and stiffness of the different epoxy resins was analyzed. All resin systems have shown improvement in both toughness and stiffness of the materials through the incorporation of layered silicates, despite the fact that it is often found that these two properties cannot be simultaneously achieved.     

A solution blending route to ethylene propylene diene terpolymer/layered double hydroxide nanocomposites

Ethylene propylene diene terpolymer (EPDM)/MgAl layered double hydroxide (LDH) nanocomposites have been synthesized by solution intercalation using organically modified LDH (DS-LDH). The molecular level dispersion of LDH nanolayers has been verified by the disappearance of basal XRD peak of DS-LDH in the composites. The internal structures, of the nanocomposite with the dispersion nature of LDH particles in EPDM matrix have been studied by TEM and AFM. Thermogravimetric analysis (TGA) shows thermal stability of nanocomposites improved by ≈40 °C when 10% weight loss was selected as point of comparison. The degradation for pure EPDM is faster above 380 °C while in case of its nanocomposites, it is much slower.     

Natural rubber-based nanocomposites by latex compounding with layered silicates

Natural rubber (NR) based nanocomposites with 10 wt% natural and synthetic layered silicates were produced via the latex compounding method. As layered silicates, sodium bentonite (natural) and sodium fluorohectorite (synthetic) were selected in addition to a non-layered inert filler (English India clay or commercial clay) as reference material. The nanocomposites were prepared by compounding the dispersions of clays and other latex chemicals necessary for vulcanization. The vulcanized nanocomposites were subjected to mechanical, thermal and swelling tests. The silicate dispersion was studied by transmission electron microscopy. Layered silicates outperformed the reference material (commercial clay) in all aspects. This was attributed to the intercalation/exfoliation of the silicates and to the formation of a skeleton ‘(house of cards)’ silicate network in the NR matrix.     

Dynamic and viscoelastic behavior of natural rubber/layered silicate nanocomposites obtained by melt blending

Vulcanized natural rubber/layered silicate (montmorillonite) nanocomposites prepared by melt blending with different contents of organoclay (0, 5, 10, 20 wt%) were investigated. The morphological characteristics of the materials were studied by transmission electron microscopy (TEM), wide angle X-ray diffraction, and dynamic mechanical thermal analysis (DMTA). X-ray spectra evidence some intercalation of the clay, while TEM results show a good dispersion of the clay and the occurrence of partial delamination. DMTA analysis with varying temperature shows that the peak of the loss modulus broadens by increasing the clay content within the material, though the peak temperature is scarcely affected. Mechanical reinforcement induced by the presence of the clay is evidenced by static tensile tests. At every clay content explored, dynamic experiments show a nonlinear behavior (Payne effect), which strongly increases with the amount of clay incorporated and is considerably more pronounced than in natural rubber filled with comparable amounts of conventional fillers. The viscoelastic behavior of the materials is investigated by recovery tests of low amplitude storage modulus, carried out after the application of a large strain perturbation, and by stress relaxation experiments. POLYM. ENG. SCI., 47:1650–1657, 2007. © 2007 Society of Plastics Engineers     

Quantitative estimation of the reinforcing effect of layered silicates in PP nanocomposites

Various polypropylene/layered silicate composites were prepared with different silicate contents. Montmorillonites with and without organophilization as well as three maleinated polypropylenes were used to change the extent of exfoliation and hence the properties of the composites. Structure was characterized by X-ray diffraction (XRD), scanning (SEM) as well as transmission electron microscopy (TEM) and tensile properties were also measured. The analysis of the tensile yield stress values of a large number of composites showed a broad range of variation in mechanical properties. XRD and TEM results do not reflect the differences in properties and they usually do not give quantitative information about the extent of exfoliation either. PP/clay composites containing maleinated PP, which do not exhibit a silicate reflection in XRD, may have very poor mechanical properties indicating small extent of exfoliation. The composition dependence of tensile yield stress of these composites may be described and evaluated quantitatively by a simple model developed earlier for particulate filled polymers. The use of a few simple assumptions most of which are supported by previous results allows us to estimate the extent of exfoliation quantitatively. The tensile yield stress of about 40 composites was analyzed with the model. Some of the composites were prepared by us, while results on others were taken from papers published in the literature. The analysis indicated that the extent of exfoliation is very low in most composites; it reaches maximum 8% of the theoretically possible value in the best case. This result is in agreement with our observation that complete exfoliation can be seldom reached in thermoplastic/clay composites; the structure is complex and hierarchical including large particles and individual silicate layers. The results prove that further efforts must be done to increase the extent of exfoliation in order to achieve reinforcement levels forecasted earlier.     

Preparation and mechanical properties of nitrile butadiene rubber/silicate nanocomposites

Elastomer nanocomposites consisting of nitrile butadiene rubber (NBR) latex and layered silicates are prepared by a modified latex shear blending process aided with ball milling. The mode of dispersion of layered silicates in NBR is partially exfoliated and intercalated when the concentration of layered silicates is below 7.5 wt%, as evidenced by transmission electron microscopy and X-ray diffraction results. The tensile and tear mechanical properties are much higher than that of neat NBR. Specifically, the tensile and tear mechanical properties of the NBR/layered silicates increase by 200 and 60%, respectively. The decomposition temperature of the nanocomposites increases slightly.     

Effect of matrix features on polypropylene layered silicate nanocomposites

The aim of this study was to examine the effect of the polypropylene based resin on the properties of organoclay-PP nanocomposites prepared by melt compounding using a twin screw extruder.The characterization of the obtained materials was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), melt flow rate (MFR) and mechanical tests.The study has shown the effect of the polymer matrix molecular weight on the possibility of producing by melt compounding nanocomposites based on PP homopolymers or heterophasic PP-PE copolymers and an organically modified montmorillonite, in presence of maleic anhydride-modified polypropylene (PP-g-MAH).An increase of mechanical properties was achieved both for homopolymers and heterophasic copolymers. However the reinforcing effect of clay dispersed in heterophasic copolymers was not as high as found for the homopolymers.     

New bifunctional catalyst based on Pt containing layered silicate Na-ilerite

Silica-supported Pt nanoparticles were prepared by intercalation of [Pt(NH₃)₄]²⁺ ions into layered silicate Na-ilerite. This material, with a high amount of Pt (20 wt.%), was used as a metal support in mechanical mixtures with the acidic zeolite, H-erionite, and tested for the conversion of n-hexane. The activity of these mechanical mixtures is comparable to those of the classical bifunctional systems consisting of Pt/H-erionite. The synergistic effect is explained in terms of the spillover of activated hydrogen.     

Styrene-acrylonitrile (SAN) layered silicate nanocomposites prepared by melt compounding

Poly(styrene-co-acrylonitrile) (SAN) nanocomposites were successfully made by melt compounding and exhibited improved thermal stability and reduced flammability. The organoclays used in these nanocomposites were based upon fluorinated synthetic mica (FSM) or montmorillonite (MMT). Four different organic treatments were used on the clay surface to study the effect of organic treatment on clay dispersion: dimethyl, bis(hydrogenated tallow) ammonium (DMHTA), methyl tallow bis-2-hydroxyethyl ammonium (MTBHA), triphenyl, n-hexadecyl phosphonium (TPHDP), and 1,2-dimethyl-3-n-hexadecyl imidazolium (DMHDI). Along with studying the effect of clay organic treatment on the nanocomposite formation and flammability, the effect of acrylonitrile content in the SAN on nanocomposite formation and flammability was also studied. The overall findings suggest that dispersion of clay into SAN is rather facile, but certain combinations of organic treatment and clay type resulted in microcomposites rather than nanocomposites. Flammability of these materials was measured by pulse-combustion flow calorimetry (PCFC), also known as micro-cone calorimetry.     

Polyamide-6,6/in situ silica hybrid nanocomposites by sol-gel technique: synthesis, characterization and properties

The organic-inorganic hybrid nanocomposites comprising of poly(iminohexamethyleneiminoadipoyl), better known as Polyamide-6,6 (abbreviated henceforth as PA66), and silica (SiO₂) were synthesized through sol-gel technique at ambient temperature. The inorganic phase was generated in situ by hydrolysis-condensation of tetraethoxysilane (TEOS) in different concentrations, under acid catalysis, in presence of the organic phase, PA66, dissolved in formic acid. Infrared (IR) spectroscopy was used to monitor the microstructural evolution of the silica phase in the PA66 matrix. Wide angle X-ray scattering (WAXS) studies showed that the crystallinity in PA66 phase decreased with increasing silica content. Atomic force microscopy (AFM) of the nanocomposite films revealed the dispersion of SiO₂ particle with dimensions of <100 nm in the form of network as well as linear structure. X-ray silicon mapping further confirmed the homogeneous dispersion of the silica phase in the bulk of the organic phase. The melting peak temperatures slightly decreased compared to neat PA66, while an improvement in thermal stability by about 20 °C was achieved with hybrid nanocomposite films, as indicated by thermogravimetric analysis (TGA). Dynamic mechanical analysis (DMA) exhibited significant improvement in storage modulus (E′) for the hybrid nanocomposites over the control specimen. An increase in Young's modulus and tensile strength of the hybrid films was also observed with an increase in silica content, indicating significant reinforcement of the matrix in the presence of nanoparticles. Some properties of the in situ prepared PA66-silica nanocomposites were compared with those of conventional composites prepared using precipitated silica as the filler by solution casting from formic acid.     

熔体法制备有机黏土/橡胶纳米复合材料的结构及性能

将有机黏土(OC)分别加入到天然橡胶(NR)、丁苯橡胶(SBR)、丁基橡胶(IIR)和三元乙丙橡胶(EPDM)中,通过熔体法制备了纳米复合材料。探讨了橡胶黏度及其分子结构对OC在复合材料中分散状况的影响,研究了复合材料的力学性能。结果表明,在以NR为基体的复合材料中。OC片层分散均匀,且剥离程度较高;在SBR,IIR,EPDM中,OC以插层结构为主,且插层效果从大到小的顺序依次为SBR,IIR,EPDM。与相应的纯胶相比,OC／NR纳米复合材料的定伸应力提高,拉伸强度和扯断伸长率有所下降;OC／SBR,OC／IIR,OC／EPDM纳米复合材料的定伸应力变化不大,拉伸强度和扯断伸长率明显提高,且OC／SBR和OC／EPDM复合材料的撕裂强度提高。     

Preparation and characterization of polypropylene/layered silicate nanocomposites using an antioxidant

Polypropylene (PP)/layered silicate nanocomposites were prepared via simple melt mixing of three components, PP, layered silicates modified with octadecylamine (C18-MMT) and antioxidant, to investigate the role of antioxidant. TEM and X-ray scattering results confirmed the intercalated state of silicates in PP/layered silicate nanocomposites with antioxidant. In rheological and mechanical study, the nanocomposites with antioxidant showed higher properties than those of the unfilled PP. The nanocomposite with 5 wt% C18-MMT and 0.5 phr antioxidant exhibited about 1.4 times higher tensile modulus and 1.3 times higher storage modulus than the unfilled PP. However, PP/C18-MMT without antioxidant showed lower rheological values owing to the thermal decomposition of PP and the poor compatibility between PP and C18-MMT. It could be concluded that antioxidants played an important role in enhancing the compatibility between PP and C18-MMT. According to the real time X-ray diffraction, the nanocomposite showed the weak ordering of PP crystals than the unfilled PP in the load-extension plateau region of elongation.     

Preparation and characterization of polymer/layered silicate pharmaceutical nanobiomaterials using high clay load exfoliation processes

The purpose of this study was to prepare and characterize lamellar silicate nanocomposites using exfoliation processes, high clay load and polyvinylpyrrolidone (PVP), ethylcellulose (EC) and polyquaternium-H (PQH). The clays (sodium montmorillonite, Viscogel S4™, S7™ and B8™) were pre-treated with ultrasonic energy in order to increase clay exfoliation yields. Polymeric nanocomposites were characterized by XRPD, DSC, TGA, DLS and NMR. The results revealed a new exfoliation method and new intercalated nanocomposites. High clay load was used to obtain the nanocomposites, which enables its application at an industrial scale. These nanocomposites could be broadly applied across the pharmaceutical, medical and food industries.     

层状硅酸盐／橡胶纳米复合材料（一）：用熔融插层法提高层状硅酸盐／天然橡胶纳米复合材料的工艺和加工性能

天然橡胶纳米复合材料是通过天然橡胶与有机改性的硅酸盐熔融复合制备的。该研究亦对比使用了未有机化的原始层状硅酸盐和非层状硅酸盐（EIC）。所用的层状硅酸盐是钠皂土（BNT）；而所用的有机粘土则是以十八烷基铵类改性的蒙脱土（MMT-ODA）和以甲基牛脂基双（2-羟乙基）季铵类改性的蒙脱土（MMT-TMDA）。采用加有促进剂的硫黄硫化体系进行硫化。借助X-射线衍射和透射电子显微镜研究这些硅酸盐的分散。加入有机粘土的纳米复合材料显示出较快的硫化速度和提高了的物理机械性能。复合材料的物理机械性能提高度按如下顺序排列：MMT-ODA〉MMT-TMDA〉EIC〉BNT。这种性能的提高归因于有机硅酸盐的插层／剥离，而硅酸盐的插层／剥离行为又是因其层内间距较大所致。     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Synthesis, structure, thermal and mechanical properties of nanocomposites based on linear polymers and layered silicates modified by polymeric quaternary ammonium salts (ionenes)

Polymer–clay composites has been prepared by melt blending an organo-bentonite with linear polymers (polyamide, polysterene and polypropylene) in a disk-screw extruder. In first time organo-clay was prepared by surface treatment of Na-forms bentonite with polymeric quaternary ammonium salts (PQAS). XRD indicated that organo-bentonite layers were exfoliated and dispersed into polyamide and polystyrene. Addition of 2 wt% organo-bentonites (optimal concentration) to polyamide increased tensile strength by 53% and Sharpy impact by 140%. With the incorporation of 2 wt% organo-bentonites (optimal concentration) into polystyrene the tensile strength increased to 28% and the Sharpy impact increased to 25%. For polypropylyne–organo-bentonites composites we did not observe delamination of layered structure, and as result absence of reinforcements. TGA showed that the polyamide and polystyrene nanocomposites have higher decomposition temperature in comparison with the original polymers.     

Possible mechanism of interaction among the components in MAPP modified layered silicate PP nanocomposites

Model reactions were carried out with components frequently used for the preparation of intercalated or exfoliated polypropylene (PP) nanocomposites. The results prove that maleinated polypropylene (MAPP) can react chemically with the surfactant applied for the organophilization of the filler, if this latter contains active hydrogen groups. The reaction of hexadecylamine (HDA) and MAPP was detected by MALDI-TOF spectroscopy, DSC measurements and FTIR spectroscopy. Anhydride groups are consumed and mainly amide groups form in the reaction. The formation of cyclic imides could not be proved by the techniques used. MAPP reacts also with the surfactant adsorbed on the surface of the silicate in ionic form. On the other hand, N-cetylpyridinium chloride (CPCl) not containing active hydrogen atoms does not react with maleinated PP. Intercalated or exfoliated composites could be prepared from the silicate organophilized with HDA, while microcomposites formed from the filler treated with CPCl. Chemical reactions remove the surfactant from the surface of MMT and hydrogenated silicate sites are left behind. The high energy surface interacts either with the anhydride or the amide groups by dipole-dipole interactions. Even the unmodified polypropylene chains may be attached much stronger to the surface by London dispersion forces than to the silicate covered with aliphatic chains. Although the effect of competitive adsorption (MAPP, HDA) and mutual solubility of the components (PP, MAPP, surfactant, reaction products) cannot be neglected, chemical reactions play a crucial role in structure formation in PP nanocomposites containing a functionalized polymer. Direct interaction of the silicate surface and the functionalized polymer as well as the formation of hydrogen bridges seem to play a lesser role, but the relative influence of processes may change with the type of surfactant, functionalized polymer, surface coverage and processing conditions.     

Mechanical and gas permeation properties of compatibilized polypropylene–layered silicate nanocomposites

Nanocomposites of polypropylene with montmorillonite modified with dimethyldioctadecylammonium ions were prepared and the effect of compatibilizers on the mechanical and permeation properties was investigated. Compatibilizers were selected on the basis of their chemical nature, molecular weight, amount of grafting and location of the polar groups. Addition of small amount of compatibilizers led to improvements in the basal spacings of clay platelets indicating enhanced exfoliation. The modulus of the composites increased as compared with the values without compatibilizer. The oxygen permeation through the composite films either increased or remained unaffected due to possible interfacial free volume enhancement owing to the incompatibility of the surface modification and the compatibilizer. Increasing the amount of compatibilizer also increased correspondingly the extent of exfoliation. The modulus reached a plateau value after which the increasing compatibilizer led to its decrease. The gas permeation through the composite films remained unchanged with increase in the amount of compatibilizer owing to a possible balance between the decrease in permeation due to path tortuity and exfoliation and increase in permeation due to interfacial incompatibility. The improving exfoliation improved the yield and break stress indicating that the absence of tactoids can hinder the premature failure owing to better stress transfer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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