Dynamic viscoelastic properties of fluoroelastomer/clay nanocomposites

Nanocomposites based on fluoroelastomer and modified and unmodified sodium montmorillonite clays were prepared. Dynamic mechanical thermal analysis was performed on these nanocomposites over a range of temperatures (?60 to +60°C), frequencies (0.032–32 Hz), and strains (0.002%–2%). The results showed that there were significant changes in the glass transition temperature and storage modulus with the addition of small amount (4 phr) of the modified and the unmodified nanofillers. The tan δ peak heights decreased and the storage modulus increased in general, but it was more prominent in the case of the unmodified clay. With the addition of the nanoclays, the cross‐over point in the double logarithmic plot of storage modulus (E′) and complex viscosity (η*) with frequency, shifted toward higher frequency. Interestingly, with increasing strain, the nanocomposites demonstrated a sudden upturn in the storage modulus after ～0.2% strain amplitude, because of the formation of α‐crystallization in the elastomer structure. The uniaxial strain before strain sweep experiment increased the storage modulus remarkably. The results were explained with the help of X‐ray diffraction and transmission electron microscopy. POLYM. ENG. SCI., 47:1777–1787, 2007. © 2007 Society of Plastics Engineers     

Reaction kinetics and characteristics of polyurethane/clay nanocomposites

The reaction behavior and physical properties of polyurethane (PU)/clay nanocomposite systems were investigated. Organically modified clay was used as nanofillers to formulate the nanocomposites. Differential scanning calorimetry was used to study the reaction behavior of the PU/clay nanocomposite systems. The reaction rate of the nanocomposite systems increased with increasing clay content. The reaction kinetic parameters of proposed kinetic equations were determined by numerical methods. The glass transition temperatures of the PU/clay nanocomposite systems increased with increasing clay content. The thermal decomposition behavior of the PU/clay nanocomposites was measured by using thermogravimetric analysis. X‐ray diffractometer and transmission electronic microscope data showed the intercalation of PU resin between the silicate layers of the clay in the PU/clay nanocomposites. A universal testing machine was used to investigate the tensile properties of the PU/clay nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1641–1647, 2005     

Novel nanostructured polyamide 6/fluoroelastomer thermoplastic elastomeric blends: Influence of interaction and morphology on physical properties

Novel polyamide 6 (PA6)/fluoroelastomer nanostructured thermoplastic elastomeric blends were developed in the present work. The influence of interaction between the components and morphology on physical properties of the blends was analyzed. Scanning electron microscopy and atomic force microscopy studies, solubility and theoretical analysis of complex modulus clearly indicated that PA6 was the continuous matrix in which fluorocarbon elastomer was present in nanoscale. Low torque ratio (0.34) of rubber/plastic, high mixing speed and long mixing time had an important role in developing the nanostructured morphology of the blend. Tensile strength of the thermoplastic elastomer was about 39.0 MPa which was much higher than that reported earlier and showed significant improvement with increasing PA6 content. Large shifting of the glass transition temperature of the rubber and the plastic phases towards the lower temperature compared to those pristine polymers was also observed. The above properties were explained with the help of interaction between the components and morphology.     

Allyl-Functionalization enhanced thermally stable graphene/fluoroelastomer nanocomposites

Development of new elastomers with novel functionality has continued since their discovery in order to meet industrial and defense needs in harsh environments. The recent advance of carbon nanomaterials inspired innovative material design strategies and enable more effective production of high-performance elastomers. In this paper, the free radical initiated crosslinking reaction in graphene/fluoroelastomer nanocomposites was studied and the effects of chemical functionalization of graphene nanosheets were analyzed. It indicated that graphene oxide (GO) enhanced fluoroelastomer nanocomposites demonstrated poor high-temperature stability due to the pyrolysis at around 200 °C. In contrast, reduced graphene oxide (RGO) enhanced fluoroelastomer exhibited good thermal stability, but RGO didn't participate in the crosslinking, resulting in very limited improvement in mechanical properties. In this paper, reduced allyl functionalized graphene was studied for the first time to enhance free radical initiated elastomers. The reduced allyl functionalization of graphene was demonstrated to impart superior thermal stability and enhanced mechanical properties to the elastomer matrices. The study of vulcanization kinetics provided insights that the allyl functional groups participated in and accelerated the crosslinking. These results indicated a scalable method to incorporate the advantages of graphene into polymer matrices through free radical reaction. The discovery is very promising to be used in the industry to fabricate gaskets, o-rings, and membranes for high temperature applications.     

Influence of thermal processing on the perfection of crystals in polyamide 66 and polyamide 66/clay nanocomposites

A study of the changes in crystal perfection of polyamide 66 (PA66) and polyamide 66/clay nanocomposites (PA66CN) due to different thermal processing was carried out. We designed three series of thermal processing including melt-quench (MQ), post-annealing MQ sample (MQA), and melt–slow cooling–annealing (MSA). The annealing temperature was set as 180 or 210 °C, which is within Brill temperature range of PA66. Fourier transform infrared (FT-IR) spectroscopy and wide angle X-ray diffraction (WAXD) were employed to characterize the perfection in short-range order and long-range order structures, respectively. The results showed that the crystal perfection of PA66 and PA66CN with different thermal processing is quite different, and the changing fashions with thermal processing for different ordered structures are not similar. In this work, MSA is optimal thermal processing for high crystallinity and crystal perfection. Exfoliated nanoclay layers exert considerable impact on the perfection of long-range ordered structures, but little on that of short-range ordered ones.     

Polymerization kinetics and thermal properties of dicyanate/clay nanocomposites

The polymerization kinetics and thermal properties of dicyanate/clay nanocomposites were investigated. A type of organically modified clay was used as nanometer‐size fillers for the thermosetting dicyanate resin. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/clay nanocomposite systems. The polymerization rate of the nanocomposite systems increased with increasing clay content. An autocatalytic reaction mechanism could adequately describe the polymerization kinetics of the dicyanate/clay nanocomposite systems. The polymerization kinetic parameters were determined by fitting the DSC conversion data to the proposed kinetic equation. The glass‐transition temperature of the dicyanate/clay nanocomposites increased with increasing clay content. The thermal decomposition behavior of the dicyanate/clay nanocomposites was investigated by thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1955–1960, 2004     

Nonisothermal cure kinetics in the synthesis of polybenzoxazine–clay nanocomposites

The ability to understand and model the mechanism of cure kinetics accurately is crucial for the production of thermosetting resin‐based nanocomposites. This article reports on work performed to elucidate an accurate model of cure kinetics for the formation of polybenzoxazine–montorillonite nanocomposites through the use of differential scanning calorimetry with nonisothermal methods, including single‐heating and multiple‐heating methods. The results indicated that both the Kissinger and Ozawa methods for calculating the activation energy gave fairly close results of 115 and 120 kJ/mol, respectively. The reaction order was about 1.31, calculated from the single‐heating method based on the autocatalytic method, and a comparison was made of the dynamic curing behaviors in the syntheses of polybenzoxazine and polybenzoxazine–montorillonite nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 194–200, 2003     

The effect of clay on the thermal degradation of polyamide 6 in polyamide 6/clay nanocomposites

The degradation pathway of polyamide 6/clay nanocomposites was studied as a function of clay content. Well-dispersed polymer-clay nanocomposites can be easily obtained by simple melt blending between organically-modified clays and polyamide 6. Polyamide 6-clay nanocomposites exhibit a large reduction in the peak heat release rate, 60%, measured by cone calorimetry. There are no significant differences in the evolved products during thermal degradation of polyamide 6 and polyamide 6/clay nanocomposites in terms of composition and functionality. The main degradation pathway of polyamide 6 is aminolysis and/or acidolysis, primarily through an intra-chain reaction, producing ε-carprolactam, which is the monomer of polyamide 6. As the clay loading is increased, the relative quantity of ε-carprolactam in the evolved products decreases and the viscosity of the soluble solid residues increases. It is thought that inter-chain reactions become significant in the presence of clay because the degrading polymer chains are trapped in the gallery space of the clay during thermal degradation.     

Characterization of latex-based isotactic polypropylene/clay nanocomposites

Polypropylene/clay nanocomposite (PCN) containing 1 wt% organo-modified clay was prepared by latex technology, previously successfully applied for preparation of carbon nanotubes (CNTs)/polymer composites. The level of dispersion of organoclay and the microstructure of the resulting PCNs were characterized by means of X-ray diffraction analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The obtained results have demonstrated that the latex technique represents a promising method for preparation of PP/clay nanocomposites with good dispersion of exfoliated nanoclay particles. The influence of clay nanoparticles on nonisothermal crystallization of PCN was investigated by DSC. The crystallization onset temperature of the matrix rises for about 5 °C when crystallizing from the quiescent melt. Improved thermal stability of PP/nanoclay was observed as evaluated by TGA. The dynamic mechanical analysis reveals an increase in storage modulus of PP matrix in the nanocomposites for 30% over a temperature range, indicating an increase in the stiffness of the material with the addition of organically modified clay.     

Flame retardant mechanism of polymer/clay nanocomposites based on polypropylene

The combustion behavior and thermal-oxidative degradation of polypropylene/clay nanocomposite has been studied in this paper. The influence of compatibilizer, alkylammonium, organoclay, protonic clay and pristine clay is considered, respectively. The decrease of heat release rate (HRR) is mainly due to the delay of thermal-oxidative decomposition of the composites. The active sites on clay layers can catalyze the initial decomposition and the ignition of the composites. On the other hand, the active sites can catalyze the formation of a protective coating char on the samples. Moreover, the active sites can catalyze the dehydrogenation and crosslinking of polymer chains. Accordingly, the thermal-oxidative stability is increased and HRR is decreased.     

The effect of organic modifier of the clay on morphology and crystallization properties of PET nanocomposites

PET nanocomposites were prepared using montmorillonite with different organic modifiers (Cloisite^® 15A, 30B and 10A). TEM, WAXD and DSC were used for the characterization. Nanocomposites of intercalated and exfoliated morphologies were obtained, and an average maximum distance between the platelets was observed in the intercalated morphology. The clay nucleated the PET crystallization process, and the nucleating effect was higher when Cloisite 10A was used. This study allowed the evaluation of the characteristics of the organic modifiers' influence on the intercalation and exfoliation processes in PET. Tactoids were obtained when only apolar modifiers were present. It was observed that PET nanocomposites were intercalated and exfoliated when polar modifiers were present.     

Crystal morphology and crystallization kinetics of polyamide‐11/clay nanocomposites

Polyamide‐11 (PA11)/clay nanocomposites were prepared by in situ intercalative polymerization. The crystal morphology and crystallization kinetics of these nanocomposites were investigated via polarized light microscopy (PLM), small‐angle laser scattering (SALS) and differential scanning calorimetry (DSC). PA‐11 can crystallize into well‐formed spherulites, while only very tiny crystallites were observed by PLM and SALS for the nanocomposites. Both isothermal and non‐isothermal crystallization methods were employed to investigate the crystallization kinetics by DSC. Both techniques showed an increased crystallization rate with the addition of clay. However, the Avrami exponent decreased with the addition of clay in isothermal crystallization but showed a wide range of values depending on the cooling rate in the non‐isothermal crystallization. The changes in crystal morphology and crystallization kinetics can be understood as being due to the ‘supernucleating’ effect of the nanodispersed clay layers. Copyright © 2004 Society of Chemical Industry     

Effect of clay on the morphology and properties of PMMA/poly(styrene-co-acrylonitrile)/clay nanocomposites prepared by melt mixing

Nanocomposites of blends of polymethylmethacrylate (PMMA) and poly(styrene-co-acrylonitrile) (SAN) with natural and organically modified montmorillonite clays (Cloisite^®25A and Cloisite^®15A) were prepared by melt mixing in a twin-screw extruder and the effect of clay on the phase separation morphology and physical properties of nanocomposites was investigated. Multi-pass samples were; those extruded once (one-pass), twice (two-pass) and three times (three-pass). Dispersion of clays in the matrix polymers was investigated using XRD and TEM. Interestingly enough, the clays were observed to be mainly located at the boundaries of PMMA and SAN for most of the nanocomposites. As the number of pass increased, the phase-separated domain size became larger for nanocomposites of PMMA/SAN containing PM, while nanocomposites with clay 25A or 15A showed less degree of growth in domain size in the TEM pictures. Viscosities of the continuous phase and separated domains, and the compatibilizing effect of clays were discussed as the probable explanations for these observations. These were supported by the rheological properties measurements, where the nanocomposites with clay 25A or 15A showed the higher complex viscosities than those of PM and also showed some shear thinning behavior. DSC and TGA analyses were also conducted.     

天然橡胶硫化动力学研究

采用硫化仪测定了2种不同凝固工艺的天然橡胶（NR）的硫化过程,探讨了制胶工艺、配方和温度对硫化动力学参数的影响。研究结果发现,随着温度的上升,硫化速率常数迅速上升。在纯胶体系中,微生物凝固胶的活化能高于酸凝固胶。当加入炭黑后,酸凝固胶的活化能升高,而微生物凝固胶的活化能下降。     

The influence of clay and elastomer concentration on the morphology and fracture energy of preformed acrylic rubber dispersed clay filled epoxy nanocomposites

The influence of toughener and clay concentration on the morphology and mechanical properties of three-phase, rubber-modified epoxy nanocomposites was studied. Nanocomposite samples were prepared by adding octadecyl ammonium ion exchanged clay to a dispersion of pre-formed acrylic rubber particles in liquid epoxy, so as to minimize alteration to the rubber morphology in the final cured specimen. The state of clay platelet exfoliation and rubber dispersion in the cured nanocomposites was studied using transmission electron microscopy. The amounts of clay platelet separation and dispersion of clay aggregates in the epoxy matrix were found to be sensitive to clay and toughener concentration, and clay platelets preferentially adsorb to the rubber particles. Tensile modulus and strength increase and ductility decreases with increasing organoclay content, while rubber has the opposite effects on the properties of epoxy resin. When both additives are present in epoxy resin, a favorable combination is produced: ductility is enhanced without compromising modulus and strength. Modulus and strength are improved by nano and micro dispersion of nanoclay in the epoxy matrix, whereas elongation and toughness are improved by clay adsorption to the rubber particle surface, which promotes cavitation. The glass transition temperature of epoxy resin remains relatively unchanged with clay addition.     

Preparation of clay/epoxy nanocomposites by layered-double-hydroxide initiated self-polymerization

An anionic clay, magnesium-aluminum layered double hydroxide (Mg₂Al-NO₃-LDH), was prepared by a co-precipitation method and intercalated with poly(oxypropylene)-amindocarboxylic acid (POP-amido acid). Depending on the POP-intercalating agents with molecular weight at 2000 or 400 g/mol, the intercalated LDHs were analyzed to have d spacing of 6.8 or 2.7 nm and organic incorporation of 80 and 55 wt%, respectively. Two comparative POP/LDH hybrids were allowed to initiate the self-polymerization of the epoxy resin, diglycidyl ether of bisphenol-A (DGEBA). The curing rate was significantly increased by using the hybrids as initiators for epoxy curing, demonstrated by DSC thermal analysis that the exothermic peak shifted from 182 to 152 °C by increasing organoclay addition. The resultant nanocomposites prepared from the anionic LDH initiated epoxy self-polymerization have the improved thermal and physical properties, evidenced by TGA, XRD, TEM, and SEM analyses.     

Tuning the curing behavior of fluoroelastomer (FKM) by incorporation of nitrogen doped graphene nanoribbons (CNx-GNRs)

Graphene nanoribbons (GNRs), obtained by different methods from carbon nanotubes (CNTs) or graphene, are attractive materials for polymer nanocomposites due to their considerably high interfacial area, as compared to CNTs. Consequently, a better adhesion with a polymer matrix is anticipated for GNRs. Also, surface modification of these nanofillers, such as nitrogen doping, is known to be an efficient method to improve their properties. In this work, fluoroelastomers (FKM) were used as the polymer matrix to host GNRs. Undoped and nitrogen doped GNRs were synthesized from the parent multiwall carbon nanotubes (MWCNTs). MWCNT/FKM and GNR/FKM nanocomposites were prepared via a solution mixing/melt mixing protocol.     

High improvement in the properties of exfoliated PU/clay nanocomposites by the alternative swelling process

In this work, a stable de-aggregated solvent-swollen organic modified clay, ALA-MMT, suspension is prepared by an efficient solvent swelling process using a home-made shaking mixer. It is found that the estimated average size of the as-prepared organoclay particles in the suspension is reduced to about 155 nm, which has not been reported before. The X-ray diffraction (XRD) patterns confirm that the d-spacing of the silicate layers of the solvent-swollen ALA-MMT expands from 1.4 nm to about 2.1 nm. The de-aggregated solvent-swollen ALA-MMT suspension is then used with polyurethane (PU) to prepare a series of highly exfoliated and high-organoclay-loading nanocomposites, PU/ALA-MMT. Both the XRD patterns and the TEM photographs of the as-prepared PU/ALA-MMT nanocomposites indicate that the organoclay is uniformly dispersed in the PU matrix with a highly exfoliated morphology structure of up to 7 wt% loading. Meanwhile, the TEM photographs give the first report for PU/clay nanocomposites which are almost completely exfoliated, and ∼1-nm thin silicate nanolayers are homogeneously dispersed in the polymer matrix with a high aspect ratio of 30-100. The thermal, mechanical, and anti-corrosion properties are all tremendously enhanced for the as-prepared nanocomposites. The results obtained for the PU nanocomposite with 7 wt% ALA-MMT loading (PUC7) reveal a 19 °C increment in T_g, a 48 °C increment in T_5%, a 248% increase in the tensile strength, and a 123% increase in the elongation. The stainless steel disk (SSD) coated with PUC7 shows the lowest corrosion rate of 2.01 × 10⁻⁶ mm/year, which is 469% lower than that of the SSD coated with pure PU. The reinforcements are much greater than the previously reported PU/clay nanocomposites with comparable clay loadings ascribed to the exceptional homogeneity of as-prepared nanocomposites, which are accredited largely to the stable de-aggregated solvent-swollen organoclay suspension generated by the efficient solvent swelling process.     

Properties of novel epoxy/clay nanocomposites prepared with a reactive phosphorus-containing organoclay

In this study, a reactive phosphorus-containing organoclay (RPC) was successfully prepared through the cationic exchange reaction of sodium montomorillonite clay with hexyltriphenylphosphonium bromide and surface modification by grafting it with glycidyloxypropyltrimethoxy silane. It is characterized using X-ray diffraction (XRD) and Fourier transform IR (FTIR) measurements. A series of novel epoxy/clay nanocomposites (ERPC) was then prepared with a selected epoxy resin and varying amounts of RPC. The results of XRD and TEM of the nanocomposites showed that the RPC particles were well dispersed in the epoxy matrix with a highly exfoliated structure due to the presence of the reactive epoxide group of RPC. The as-prepared epoxy/RPC nanocomposites (ERPC) were thermally stable up to 388 °C. Thermal stability was increased by increasing the RPC content as indicated by the corresponding activation energies (E_a) and the integral procedural decomposition temperatures (IPDT). Furthermore, the storage modulus in the glass state of the nanocomposites was dramatically increased with the increase in RPC content. In addition, the large increment of limiting oxygen index (LOI) which was 11 units higher than that of the neat epoxy indicates that an extraordinary enhancement of flame retardancy was obtained from the nanocomposite containing 5 wt% of RPC.