Structure Characterization and Thermal Properties of PMMA/Montmorillonite Nanocomposites via Emulsion Polymerization

Montmorillonite(MMT) modified with sodium silicate can change the arrangement of its layers from edge-face and edge-edge to face-face. With the fine dispersion of the modified MMT in water,the cation-exchange reaction was carried out with cetyltrimethyl ammonium bromide(CTAB) to obtain organo-montmorillonite(OMMT). As OMMT was uniformly dispersed in methyl methacrylate(MMA) monomer,PMMA/OMMT nanocomposites were formed via a common emulsion polymerization. The products were extracted with hot acetone and characterized by FTIR,molecular weight,X-ray diffraction(XRD),transmission electron microscopy(TEM),DSC and TGA. These results show that most of the OMMT layers have been exfoliated,while the thermal stability is increased obviously. By means of FTIR spectral analysis,the ratios of the macromolecular radicals′ termination of disproportionation patterns to combination are increased with the addition of OMMT. This result further confirms the increase of the thermal degradation temperatures and glass transition temperatures of the PMMA/OMMT nanocomposites.

Some basic aspects of polymer nanocomposites: A critical review

Polymer nanocomposites have been investigated for about three decades. To get deep insights into the modifying effects of various nanofillers on mechanical and physical properties of polymer nanocomposites, the three basic aspects of processing, characterization and properties are critically reviewed in this paper. Nanofillers can be classified into three major types of two-dimensional (2D) layered, one-dimensional (1D) fibrous and zerodimensional (0D) spherical ones and this review thus discusses in detail the processing, characterization and properties of the three types of polymer nanocomposites. It starts with an introduction of various nanoscale fillers such as two-dimensional (2D) nano-clay, graphene and MXene, one dimensional (1D) carbon nanofibers and nanotubes, zero dimensional (0D) silica nanoparticles and ZnO quantum dots as well as nanofiller-polymer interfaces. The processing of these polymer nanocomposites using different methods and the characterization of nanofillers and polymer nanocomposites using various techniques are described. Finally, the mechanical and physical properties of these polymer nanocomposites are discussed by considering the effects of nanofiller type, dispersion and contents;also, interface properties show significant effects on the mechanical properties of polymer nanocomposites and are discussed in some details.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.

DISPERSION AND TENSILE BEHAVIOR OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES PRODUCED VIA MELT INTERCALATION

Most of the articles on polymer nanocomposites focus on the importance of chemistry used to modify the surface of the clay, usually montmorillonite (MMT), and characterization of the nano-scale structure obtained. The role and importance of processing were also discussed recently. However, few papers concerning the correlation between morphology of MMT and mechanical properties were published. In order to understand. the tensile behavior of PP/Montmorillonite (MMT) nanocomposites better, and to further improve the reinforcement efficiency, we first prepared the PP nanocomposites via direct melt intercalation using conventional twin-screw extrusion. The dispersion and tensile property of the composites were then investigated by SEM, XRD, TEM and a video-controlled tensile set-up. The macroscopic and microscopic dispersion of MMT in PP matrix was verified by XRD and TEM, combined with SEM. The tensile properties were obtained by video-controlled tensile set-up, which gives true stress-strain curve. It was found that a partly intercalated and partly exfoliated structure (also called incomplete exfoliation) existed in the system. Though the tensile strength of PP nanocomposites is not much improved in engineering stress-strain curves, more than 20% increase of true stress was found in a true stress-strain experiment at high true strain, which indicates that only oriented silicate layers can have a big effect on tensile properties: Not only orientation of silicate platelets but also the degree of exfoliation is a key factor to determine the reinforcement efficiency. The reinforcement efficiency of MMT has been discussed based on the 'continuum' Halpin-Tsai equations. A good agreement was found between experimental data and theoretical prediction by changing N value (number of platelets per stack) which corresponding to different state of the dispersion of MMT in PP matrix.

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

Preparation and Characterization of Polylactide/Montmorillonite Nanocomposites

The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.

Design of Wood/Montmorillonite (MMT) Intercalation Nanocomposite

Studying new wood composites through nano science and technology (NSC) will develop new compounding theory of wood, and accelerate the combination of new technology, wood science, material science and other disciplines. The compounding of wood and inorganic MMT on nanoscale molecular level has high potential to greatly improve the mechanical properties, fire retardance, abrasion resistance, decay resistance, dimensional stability and other properties of wood. Based on the great achievements of polymer/montmorillonite (MMT) nanocomposites, this paper reviewed nano intercalation compounding methods (i.e. in-situ intercalative polymerization and direct polymer intercalation), and discussed the structure, properties and modification of montmorillonite (MMT). According to the main chemical components and particular structure of wood, the authors discussed the liquefaction and plasticization of wood, compared the dissolvability and meltability between wood and polymer, and then systematically put forward the basic idea, technological processes and schematic diagram to prepare wood/MMT nanocomposites (WMNC). The key technology to prepare WMNC is either to introduce delaminated MMT nanolayers into wood with the help of some intermediate polymers, or to obtain liquefied wood or plasticized wood from the complicated natural composite. It is applicable and effective to realize wood/MMT nanoscale compounding with the help of proper intercalation agent and medium polymer through the proposed 搊ne-step?or 搕wo-step?impregnating processes.

STRESS-INDUCED CRYSTALLIZATION OF POLYURETHANE/MONTMORILLONITE NANOCOMPOSITE

Exfoliated polyurethane/montmorillonite nanocomposites with both high elongation at break and high tensilestrength were studied by dynamic-infrared spectroscopy (dynamic-IR). The results show that crystallization induced byadditional stress is impeded by the nano-layered organo montmorillonite.

Modification of Montmorillonite through Intercalative Polymerization

Montmorillonite (MMT) was modified through intercalative polymerization of phenol and formaldehyde catalyzed by oxalic acid. The modified montmorillonite was delaminated at large, as demonstrated by XRD and TEM studies. It can disperse easily in epoxy resin to form exfoliated nanocomposites. The nanoscale silicate platelets dispersed in water can be metallized by silver deposition.

The Dynamic Viscoelasticity of Polyethylene Based Montmorillonite Intercalated Nanocomposites

The viscoelastic behavior of melts for two systems composed of intercalated nanocomposites based on low density polyethylene and 3 wt% loading of cetyltrimethyl- ammonium bromide modified montmorillonite was studied. The results obtained through examining the dynamic storage module G' and dynamic loss module G' values of the composite revealed that the dynamic viscoelastic properties of composite strongly depended on intercalation of polymer, and exhibited dramatically change with altering intercalation conditions. Only when modified montmorillonite content was about 3 wt%, the composite showed a trend of pseudo-solidlike at lower frequencies.

Chlorinated butyl rubber/two-step modified montmorillonite nanocomposites:Mechanical and damping properties

Montmorillonite(MMT) was modified by ultrasound and castor oil quaternary ammonium salt intercalation method to prepare a new type of organic montmorillonite(OMMT). The surface structure, particle morphology, interlayer distance, and thermal behavior of the samples obtained were characterized. The modified OMMT was then added to chlorinated butyl rubber(CIIR) by mechanical blending, and a composite material with excellent damping properties was obtained. The mechanical experiment results of CIIR nanocomposites showed that the addition of OMMT improved their tensile strength, hardness,and stress relaxation rate. Compared with pure CIIR, when the content of OMMT was 5 phr(part per hundred of rubber), the tensile strength of the nanocomposite was increased by 677% and the elongation at break was also increased by 105.4%. The enhancement of this performance was mainly due to the dispersion of the nanosheets in CIIR rubber and the chemical interaction between the organoclay and the polymer matrix, which was confirmed by morphology and spectral analysis. OMMT also endowed a positive effect on the damping properties of CIIR nanocomposites. After adding 5 phr of OMMT, the nanocomposite owned the best damping performance, and the damping factor, tanδmax, was 37.9% higher than that of pure CIIR. Therefore, the good damping and mechanical properties of these CIIR nanocomposites provided some novel and promising methods for preparing high-damping rubber in a wide temperature range.

Recent Advances in Fabrication and Characterization of Graphene-Polymer Nanocomposites

Graphene has attracted considerable interest over recent years due to its intrinsic mechanical, thermal and electrical properties. Incorporation of small quantity of graphene fillers into polymer can create novel nanocomposites with im- proved structural and functional properties. This review introduced the recent progress in fabrication, properties and potential applications of graphene-polymer composites. Recent research clearly confirmed that graphene-polymer na-nocomposites are promising materials with applications ranging from transportation, biomedical systems, sensors, elec-trodes for solar cells and electromagnetic interference. In addition to graphene-polymer nanocomposites, this article also introduced the synergistic effects of hybrid graphene-carbon nanotubes (CNTs) on the properties of composites. Finally, some technical problems associated with the development of these nanocomposites are discussed.

Flame Retardant and Pyrolytic Behaviors of Polyamide 6/Montmorillonite Nanocomposite

Na +-montmorillonite(Na +-MMT) was converted to organic montmorillonite(OMMT) using modifier which was synthesized at authors’ laboratory. PA6/OMMT nanocomposite was prepared via in situ intercalative polymerization. The limiting oxygen index (LOI), UL 94V flame retardancy and thermal stability of PA6/OMMT using thermal gravity analysis (TGA) were measured. The Fourier transform infrared (FTIR) technique was used to analyze the pyrolytic residuum and the cone calorimeter (CONE) was applied to determine a number of combustion parameters which were closely related to fire safety, including heat release rate, mass loss rate, effective combustion heat, total heat release, specific extinction area and the time of ignition. In addition, the elemental composition of the surface pyrolytic residuum and the corresponding X-ray photoelectron spectroscopy (XPS) data were obtained, and the morphology of the residuum from CONE measurement was examined by scanning electron microscope (SEM).

Rheological Behavior of the Melts for Polyethylene-based Montmorillonite Nanocomposites

The viscoelastic properties of melts of nanocomposites with partially exfoliated structures, which were composed of low-density polyethylene （LDPE）, ethylene vinyl acetate copolymer （EVA）, and montmofillonite and modified by cetyltrimethyl ammonium bromide and octadecyltrimethyl ammonium bromide, were studied. The results obtained through measurements of the dynamic storage modulus G′, the dynamic loss modulus G″, and the transiem stress relaxation modulus G（t） of the composites, reveal that the viscoelastic properties of the composites strongly depend on the amount of montmorillonite that is exfoliated into the composites. With the increase in montmoriUonite content, the composites show an obvious property of pseudo solid-like materials within the region of lower frequencies （ω）. The montmorillonite layers are aligned along the stress direction, and the dependence of dynamic modulus on ω, appears quite different for the composites before and after being exposed to a large amplitude oscillatory shears.

Layered Foam/Film Polymer Nanocomposites with Highly Efficient EMI Shielding Properties and Ultralow Reflection

Lightweight,high-efficiency and low reflection electromagnetic interference(EMI)shielding polymer composites are greatly desired for addressing the challenge of ever-increasing electromagnetic pollution.Lightweight layered foam/film PVDF nanocomposites with efficient EMI shielding effectiveness and ultralow reflection power were fabricated by physical foaming.The unique layered foam/film structure was composed of PVDF/SiCnw/MXene(Ti_(3)C_(2)Tx)composite foam as absorption layer and highly conductive PVDF/MWCNT/GnPs composite film as a reflection layer.The foam layer with numerous heterogeneous interfaces developed between the SiC nanowires(SiCnw)and 2D MXene nanosheets imparted superior EM wave attenuation capability.Furthermore,the microcellular structure effectively tuned the impedance matching and prolonged the wave propagating path by internal scattering and multiple reflections.Meanwhile,the highly conductive PVDF/MWCNT/GnPs composite(~220 S m^(−1))exhibited superior reflectivity(R)of 0.95.The tailored structure in the layered foam/film PVDF nanocomposite exhibited an EMI SE of 32.6 dB and a low reflection bandwidth of 4 GHz(R<0.1)over the Kuband(12.4-18.0 GHz)at a thickness of 1.95 mm.A peak SER of 3.1×10^(-4) dB was obtained which corresponds to only 0.0022% reflection efficiency.In consequence,this study introduces a feasible approach to develop lightweight,high-efficiency EMI shielding materials with ultralow reflection for emerging applications.

Polynaphthoxazines-Montmorillonite Nanocomposites: Synthesis and Characterization

Polynaphthoxazines-clay nanocomposites were prepared from 1, 5-dihydroxynaphthalene, aniline, formaldehyde and different proportion montmorillonite(MMT) by in-situ reaction in ethanol. Dynamic TGA showed that nanocomposites have delayed decomposition temperatures when compared with pristine polynaphthoxazine indicating the enhancement in the thermal stability.

Organic/inorganic nanocomposite polymer electrolyte

The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocomposites membrane materials and their lithium salt complexes have been found thermally stable below 200 °C. The conductivity of the organic/inorganic nanocomposites polymer electrolytes prepared at room temperature was at magnitude range of 10(?6) S/cm.

Synthesis and characterization of carboxymethyl cellulose/organic montmorillonite nanocomposites and its adsorption behavior for Congo Red dye

A series of carboxymethyl cellulose/organic montmorillonite （CMC/OMMT） nanocomposites with different weight ratios of carboxymethyl cellulose （CMC） to organic montmorillonite （OMMT） were synthesized under different conditions. The nanocomposites were characterized by the Fourier transform infrared （FT-IR） spectrophotometer, X-ray diffraction （XRD） method, transmission electron microscope （TEM）, scanning electron microscope （SEM）, and thermal gravimetric （TG） analysis. The results showed that the introduction of CMC may have different influences on the physico-chemical properties of OMMT and intercalated-exfoliated nanostructures were formed in the nanocomposites. The effects of different reaction conditions on the adsorption capacity of samples for Congo Red （CR） dye were investigated by controlling the amount ofhexadecyl trimethyl ammonium bromide （CTAB）, the weight ratio of CMC to OMMT, the reaction time, and the reaction temperature. Results from the adsorption experiment showed that the adsorption capacity of the nanocomposites can reach 171.37 rag/g, with the amount of CTAB being 1.0 cation exchange capacity （CEC） of MMT, the weight ratio of CMC to OMMT being l：l, the reaction time being 6 h, and the reaction temperature being 60~C. The CMC/OMMT nanocomposite can be used as a potential adsorbent to remove CR dye from an aqueous solution.

Vapor Phase Polymerization Deposition Conducting Polymer Nanocomposites on Porous Dielectric Surface as High Performance Electrode Materials

We report chemical vapor phase polymerization(VPP) deposition of poly(3,4-ethylenedioxythiophene)(PEDOT) and PEDOT/graphene on porous dielectric tantalum pentoxide(Ta_2O_5) surface as cathode films for solid tantalum electrolyte capacitors. The modified oxidant/oxidant-graphene films were first deposited on Ta_2O_5 by dip-coating, and VPP process was subsequently utilized to transfer oxidant/oxidant-graphene into PEDOT/PEDOT-graphene films. The SEM images showed PEDOT/PEDOT-graphene films was successfully constructed on porous Ta_2O_5 surface through VPP deposition, and a solid tantalum electrolyte capacitor with conducting polymer-graphene nano-composites as cathode films was constructed. The high conductivity nature of PEDOT-graphene leads to resistance decrease of cathode films and lower contact resistance between PEDOT/graphene and carbon paste. This nano-composite cathode films based capacitor showed ultralow equivalent series resistance(ESR) ca. 12 m? and exhibited excellent capacitance-frequency performance, which can keep 82% of initial capacitance at 500 KHz. The investigation on leakage current revealed that the device encapsulation process has no influence on capacitor leakage current, indicating the excellent mechanical strength of PEDOT/PEDOT-gaphene films. This high conductivity and mechanical strength of graphene-based polymer films shows promising future for electrode materials such as capacitors, organic solar cells and electrochemical energy storage devices.

Atomic insights into synergistic effect of pillared graphene by carbon nanotube on the mechanical properties of polymer nanocomposites

Molecular dynamics simulations have been performed to explore the underlying synergistic mechanism of pillared graphene or non-covalent connected graphene and carbon nanotubes(CNTs) on the mechanical properties of polyethylene(PE) nanocomposites. By constructing the pillared graphene model and CNTs/graphene model, the effect of the structure, arrangement and dispersion of hybrid fillers on the tensile mechanical properties of PE nanocomposites was studied. The results show that the pillared graphene/PE nanocomposites exhibit higher Young’s modulus, tensile strength and elongation at break than non-covalent connected CNTs/graphene/PE nanocomposites. The pull-out simulations show that pillared graphene by CNTs has both large interfacial load and long displacement due to the mixed modes of shear separation and normal separation. Additionally, pillared graphene can not only inhibit agglomeration but also form a compact effective thickness(stiff layer), consistent with the adsorption behavior and improved interfacial energy between pillared graphene and PE matrix.