Properties of Poly(Lactic Acid)/ Organo-Montmorillonite Nanocomposites Prepared by Solution Intercalation

Poly(lactic acid)/organo-montmorillonite (PLA/OMMT) nanocomposite films were prepared through solution intercalation using dichloromethane as solvent. X-ray diffraction indicated that organo-montmorillonite (OMMT) was well intercalated and the interlayer spacing d increased by 0.94–1.47 nm. Transmission Electron Microscopy showed that a majority of OMMT was fully exfoliated and uniformly dispersed in the PLA matrix at low filler loading, whereas more intercalated tactoids and aggregates of OMMT existed at high loading. The crystallinity of PLA was hardly changed with the addition of OMMT. Additionally, CO₂ permeability and water vapor transmission rate of the composite films were reduced with increasing content of OMMT. At 5 wt% OMMT loading, CO₂ permeability and water vapor transmission rate were reduced by 75.8% and 23.9%, respectively. The tensile strength (TS) and Young's modulus of the PLA/OMMT nanocomposites were first enhanced, and then decreased with increasing content of OMMT. Compared with pure PLA, a 83.8% increase in the Young's modulus and a 76.0% improvement in TS were obtained with the addition of 3 wt% OMMT.     

Synthesis and Characterization of Novel Poly(1‐Naphthylamine)‐Montmorillonite Nanocomposites Intercalated by Emulsion Polymerization

Nanocomposites of montmorillonite (MMT) with poly(1‐naphthylamine) (PNA) is investigated for the first time by emulsion polymerization using three different oxidants. Polymerization of PNA was confirmed by Fourier transformation infrared (FT‐IR) as well as UV‐visible spectra. The in situ intercalative polymerization of PNA within MMT layers was confirmed by FT‐IR, X‐ray diffraction, conductivity; scanning electron microscopy (SEM) as well as transmission electron microscopy studies. X‐ray diffraction revealed intercalated as well as exfoliated structures of PNA/MMT nanocomposites, which were compared with the reported polyaniline‐MMT nanocomposites. It was found that the increase in the concentration of PNA in the interlayer galleries of MMT led to destruction of the layered clay structure resulting in exfoliation of the nanocomposite. Conductivity of the nanocomposites was found to be in the range of 10^?3 to 10^?2 S cm^?1 which was found to be higher than the ones reported for polyaniline‐clay nanocomposites as well as PEOA‐OMMT nanocomposites at similar concentrations of intercalated species. The morphology of PNA/MMT nanocomposites was found to be governed by the nature of the oxidant used.     

Morphology and Properties of Poly(vinyl alcohol)/MMT Nanocomposite Prepared by Solid-state Shear Milling (S3M)

Poly(vinyl alcohol) (PVA)/montmorillonite (MMT) nanocomposites were prepared by combining solid-state shear milling (S³M) technology with melt intercalation. Compared with the composite obtained by simple melt intercalation, more MMT layers were exfoliated and apparently oriented along the injection molding direction in the nanocomposite prepared by combining S³M technology and melt intercalation, which greatly increased the orientation degree of MMT, resulting in the greater interactions between PVA and MMT layers. Simultaneously, this also promoted the orientation of PVA molecules and produced effective nucleation of the crystallization of PVA. Consequently, the thermal stability and mechanical properties of PVA were obviously improved. For instance, when the MMT content was 3 wt%, the tensile strength and modulus of the nanocomposite with MMT prepared by S³M were 98.9 MPa and 3.1 GPa, respectively, increasing by 52% and 63.2% compared with PVA.     

Dielectric Relaxations and Structures of Nanoclay in Solution Cast Poly(Ethylene Oxide)– Montmorillonite Clay Nanocomposites

The relative complex dielectric function, electric modulus and alternating current electrical conductivity spectra and complex impedance plane plots of aqueous solution cast poly(ethylene oxide)–montmorillonite clay (PEO–MMT) nanocomposite films were investigated over the frequency range 20 Hz to 1 MHz at ambient temperature. The intercalated and exfoliated structures of nanoclay dispersed in PEO matrix were recognized by the significant change in real part of dielectric function with clay concentration in the range 0%–20 wt%. The relaxation times corresponding to PEO chain segmental motion and ionic conduction relaxation processes were used to explore the interactions compatibility between PEO molecules and the dispersed MMT clay nanoplatelets and their effect on PEO chain dynamics. Real part of conductivity spectra of these nanocomposites over five decades of frequency has nonlinear behavior, which is influenced by the MMT clay concentration. The complex impedance plane plots confirm the bulk properties of these nanocomposites over the experimental frequency range.     

Three-dimensional structure of a polymer/clay nanocomposite characterized by transmission electron microtomography

Three-dimensional (3D) morphology of a polymer/clay nanocomposite, an organophilic montmorillonite (MMT) dispersed in poly(ethylene-co-vinylacetate) (EVA), was examined by transmission electron microtomography (TEMT). Using this technique, individual clay layers dispersed in the EVA matrix were clearly visualized. A volume fraction of the clay layers evaluated from the 3D reconstructed image agreed well with that calculated from the weight of the MMT component in the MMT/EVA system. The individual clay layers were digitally extracted by a newly developed 3D particle algorithm. A size distribution of the clay layers was directly obtained from the 3D reconstruction. Anisotropy of each clay layer was characterized by the determination of three semi-axes of an approximating ellipsoid with the same volume. One of the representative semi-axis of the ellipsoid was used to estimate average orientation of the MMT layers in the ultra-thin section used in the TEMT experiment. Thus, the combination of quantitative TEMT and 3D structural analysis is shown to be a powerful tool to investigate a relationship between the MMT distribution and a variety of physical properties of the nanocomposites.     

Preparation and Characterization of Silicon-containing Polyarylacetylene/montmorilloite Nanocomposites

Dimethylphenylpropargyl ammonium bromide (DMPPAB) was synthesized and used to modify pristine montmorillonite (MMT) by a cation exchange process. The organically modified montmorillonite (OMMT) was verified and used to mix with a silicon-containing polyarylacetylene (PSA) as well as MMT. The PSA/MMT and PSA/OMMT nanocomposites were prepared by solution under sonication and melting intercalation processes, respectively, and then cured by a step heating process. The thermal and flexural properties of the cured PSA and nanocomposites were studied by thermogravimetric and dynamic mechanical analysis. The results showed that the intercalation of DMPPAB into the MMT galleries made the d-spacing enlarge. During PSA curing, the cure heat of PSA caused the MMT and OMMT to delaminate and exfoliate in the PSA matrix. The glass transition temperature of the cured PSA and nanocomposites were higher than 500?°C. The inner acetylenic groups in the PSA resin could further crosslink above 300?°C. The temperature at 5% mass loss of the cured PSA decreased by 4.6% with 3% mass fraction of OMMT loading, and the char yield of the cured PSA changed only slightly. The flexural strength of the cured PSA was augmented with addition of MMT or OMMT, but the flexural modulus of the cured PSA decreased slightly. The flexural strength of the cured nanocomposite increased from 20.1?MPa to 30.1?MPa when 3% mass fraction of OMMT was added into the PSA matrix.     

Effect of surface treatment of nanoclay on the mechanical properties of epoxy/glass fiber/clay nanocomposites

A new method of silane treatment of nanoclays is reported where in the clay is nanodispersed in hydrolyzed silanes. The surface functionalization of Cloisite^® 15A nanoclay has been carried out using two different silane coupling agents: 3-aminopropyltriethoxy silane and 3-glycidyloxypropyltrimethoxy silane using varied amounts of silane coupling agents, e.g. 10, 50, 200, and 400 wt% of clay. The surface modification of Cloisite^® 15A has been confirmed by Fourier transform infrared spectroscopy. The modified clays were then dispersed in epoxy resin, and glass fiber-reinforced epoxy clay laminates were manufactured using vacuum bagging technique. The fiber-reinforced epoxy clay nanocomposites containing silane modified clays have been characterized using small angle X-ray scattering, transmission electron spectroscopy and differential scanning calorimetry. The results indicate that the silane treatment of nanoclay aided the exfoliation of nanoclay and also led to an increase in mechanical properties. The optimized amount of silane coupling agents was 200 wt%. The nanocomposites containing clay modified in 200 wt% of silanes exhibited an exfoliated morphology, improved tensile strength, flexural modulus, and flexural strength. The improved interfacial bonding between silane modified nanoclays and epoxy matrix was also evident from significant increase in elongation at break.     

Preparation and properties of polyurethane/MMT nanocomposite actuators

This study dealt with the electrostrictive response of a polyurethane (PU)/clay nanocomposite film, which was a promising candidate for a material to be used in polymer actuators. The nanocomposites were produced by using three types of montmorillonites (MMTs) such as natural MMT (Cloisite^®Na⁺), hydrophobic MMT (Cloisite^® 20A), and hydrophilic MMT (Cloisite^® 30B). The nanometer-scale silicate layers of organo-clay were completely exfoliated in PU for the cases of 1, 3 and 5 wt% PU/MMT nanocomposites as confirmed by wide X-ray diffraction (WAXD) profiles. Actuation tests indicated that the displacement of PU/MMT nanocomposite actuator was larger than pure PU actuator, caused by an increase in dielectric constant. Especially, PU/MMT nanocomposite actuator with Cloisite^® 30B had the largest displacement and it became possible to operate at low voltage.     

Structure and Mechanical Properties of 50/50 NR/SBR Blend/Pristine Clay Nanocomposites

A blend/clay nanocomposites of 50/50 (wt%) NR/SBR was prepared via mixing the latex of a 50/50 NR/SBR blend with an aqueous clay dispersion and co‐coagulating the mixture. The structure of the nanocomposite was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Nanocomposites containing less than 10 phr clay showed a fully exfoliated structure. After increasing the clay content to 10 phr, both nonexfoliated (stacked layers) and exfoliated structures were observed in the nanocomposites. The results of mechanical tests showed that the nanocomposites presented better mechanical properties than clay‐free NR/SBR blend vulcanizate. Furthermore, tensile strength, tensile strain at break, and hardness (shore A) increased with increasing clay content, up to 6 phr, and then remained almost constant.     

Evaluation of thermal and flame properties of HDPE-MWCNT-SiO2 nanocomposites

High-density polyethylene (HDPE) composites reinforced with multiwalled carbon nanotubes (MWCNTs) and nano-silicon dioxide (SiO₂) fillers were evaluated for flame retardancy and thermal properties for cable and wire applications. In this study, the filler percentages of MWCNT and nano-SiO₂ have varied from 0 to 5 wt% in HDPE composite with polyethylene-grafted glycidyl methacrylate compatibilizer and 3-aminopropyl triethoxy silane coupling agent. Addition of MWCNT’s and nano-SiO₂ to the HDPE composite is observed to enhance the limiting oxygen index and char formation. Cone calorimeter results also show a 53% reduction in the peak heat release rate of the HDPE composite with 5 wt% of MWCNT. The existence of synergism between the uniformly dispersed MWCNT and nano-SiO₂ has been verified using Finite Element Method (FEM)-based thermal simulations.     

Preparation and Properties of Organically Modified Montmorillonite/Nitrile Rubber Nanocomposites

A series of organically modified montmorillonite (OMMT)/nitrile rubber (NBR) nanocomposites were prepared by a simple mechanical-mixing method. The structures of OMMT and the dispersion of OMMT in the rubber matrix were detected by X-ray diffraction (XRD). The mechanical properties of the NBR/OMMT nanocomposites were characterized, and the tribological behaviors of the nanocomposites were evaluated on a ring-block (MRH-3) wear tester. The results showed that the OMMT was homogeneously dispersed in the NBR matrix. The tensile strength of the OMMT/NBR nanocomposites increased with increasing OMMT contents. Both the coefficient of friction (COF) and wear of the nanocomposites decreased remarkably with increasing OMMT content. In addition, the influence of the applied load on the tribological properties of the nanocomposites is discussed. It is expected that the research may be of aid in the rational design and use of solid, self-lubricating nanocomposites under different loading states.     

Morphology and Mechanical Properties of Acrylonitrile-Butadiene-Styrene (ABS)/Polyamide 6 (PA6) Nanocomposites Prepared via Melt Mixing

Acrylonitrile-butadiene-styrene (ABS)/polyamide 6 (PA6) blends containing various amounts of organomontmorillonite (OMMT) were prepared using a twin-screw extruder followed by injection molding. The effect of OMMT on the microstructure and properties of the ternary nanocomposites is investigated by wide-angle X-ray diffraction (WAXD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and mechanical properties testing. The results showed the OMMT platelets were preferentially located and exfoliated in the PA6 phase, but some were located at the interface of the ABS and PA6 phase. The effect of the addition of the OMMT on the morphology and mechanical properties was also evaluated. SEM revealed that the dimensions of the dispersed PA6 droplets were greatly reduced when the concentration of the OMMT was less than 4 phr. The domain size was less than the neat ABS/PA6 blends with the increasing of the OMMT content. It was suggested that the OMMT can compatibilize the ABS/PA6 blend. In addition, the flexural strength and modulus increased with increasing OMMT content, but the tensile strength became maximal at 3 phr OMMT. The OMMT had a negligible effect on the impact strength of the ABS/PA6 blend nanocomposite.     

Dielectric Probing of Relaxation Behaviors in PMMA/Organoclay Nanocomposites: Effect of Organic Modification

Poly(methyl methacrylate) (PMMA)–clay nanocomposites (PCN) were prepared with PMMA/clay concentrates and POP-diamines modified clay via melt blending. Partially exfoliated clay layers were uniformly dispersed in the nanocomposites as evidenced from XRD study. The subglassβ relaxation and the segmental α relaxation were observed from the dynamic mechanical thermal analysis (DMTA). The PCNs at 5 wt% clay level from clay concentrate exhibited significantly higher glass-transition temperatures and dynamic storage moduli relative to the neat PMMA. The confinement effect from the tethering of polymer chain to the clay surface would contribute to such a dramatic difference. In addition to the normal-mode relaxations, the αβ-merging process above T _g and the subglass interfacial polarization were detected from the dielectric analysis. Significant increase in dielectric permittivities and dielectric losses due to interfacial polarization and ionic conduction at low frequency were observed for the PCNs. The intensity of the interfacial polarization process increases with the dispersion degree of clay layers and hence the process can be assigned to the space charge polarization of the ionic species in the clay intergalleries.     

Morphology and properties of poly(methyl methacrylate)/clay nanocomposites by in-situ solution polymerization

Poly(methyl metacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by in-situ solution polymerization of methyl methacrylate monomer in the presence of the organic modified MMT-clay. After the organic modification by ionic exchanging with amine salts, the organoclay becomes more hydrophobic and compatible then pristine clay with methyl methacrylate monomer. The modified clays are characterized by wide angle X-ray diffraction (WAXRD). The powdered X-ray diffraction and transmission electron microscopy (TEM) techniques were employed to study the morphology of the PMMA/clay nanocomposites which indicate that the modified clays are dispersed in PMMA matrix to form both exfoliated and intercalated PMMA/modified clay nanocomposites. The thermo-mechanical properties were measured by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC). Gas permeability analyzer (GPA) shows the excellent gas barrier property of the PMMA nanocomposites which is in good agreement with the morphology. The optical property was measured by UV-vis spectroscopy which shows that these materials have good optical clarity, and UV resistance.     

Preparation, characterization and properties of amino-functionalized montmorillonite and composite layer-by-layer assembly with inorganic nanosheets

An amino-functionalized montmorillonite (APTMS-MMT) was prepared by the grafting of 3-aminopropyltrimethoxysilane (APTMS) on the surface of MMT via the ultrasonic synthesis process and characterized by a variety of techniques: FT-IR, thermogravimetic analysis (TGA), particles size analysis and ζ-potential measurement. The results showed the size and size distribution of APTMS-MMT particles were decreased, and the ζ-potential of particles was increased obviously via the ultrasonic synthesis process. The particles of 30% APTMS-MMT_US (MMT modified with 30 wt% APTMS with ultrasonic synthesis process) had a z-average diameter of about 500 nm and a polydispersity index of 0.2. The resultant 30% APTMS-MMT_US was dispersed uniformly and stably in water. The poly(acrylic acid) (PAA)/APTMS-MMT multilayer films were grown through layer-by-layer (LBL) deposition of PAA and APTMS-MMT. SEM results indicated that the ultrasonic synthesis of APTMS-MMT increased dispersability of clay sheets at high loadings. The thermal stability and mechanical properties of PAA/APTMS-MMT composites were investigated by TGA and tensile test respectively. The results showed the ultrasonic synthesis of APTMS-MMT enhanced the thermal stability and mechanical properties of PAA/APTMS-MMT composites significantly. PAA/30% APTMS-MMT_US composite displayed 3 times higher strength and 6 times higher Young's modulus when compared with pure PAA polymer.     

聚丙烯/有机改性蒙脱土纳米复合材料的光氧化降解研究

研究了聚丙烯/有机改性蒙脱土(OMMT)纳米复合材料在365 nm紫外光辐照下的光氧化降解过程中的结构变化。主要利用红外光谱方法进行表征。在辐照初期(紫外光辐照时间小于11 h),复合体系的光氧化降解速率大于纯聚丙烯体系;随着辐照时间的延长(大于11 h),复合体系的光氧化降解速率小于纯聚丙烯体系。主要原因是蒙脱土既有光屏蔽作用,又有加速光氧化降解的作用,这两种作用共存,但在辐照初期,催化光降解作用占主导地位,随着辐照时间延长,光屏蔽作用占主导。蒙脱土的含量对聚丙烯的光氧化降解速率也存在影响。另外,蒙脱土的加入对聚丙烯光氧化降解产物也产生影响,羧酸类及酸酐类产物增多,酯类产物减少。     

Preparation and Rheological Characteristics of Ethylene‐Vinyl Acetate Copolymer/Organoclay Nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) with 40 wt.% vinyl acetate content (EVA40)/organoclay nanocomposites were prepared using a melt intercalation method with several different clay concentrations (2.5, 5.0, 7.5, and 10.0 wt.%). X‐ray diffraction confirmed the formation of exfoliated nanocomposite in all cases with disappearance of the characteristic peak corresponding to the d‐spacing of the pristine organoclay. Transmission electron microscopy studies also showed an exfoliated morphology of the nanocomposites. Morphology and thermal properties of the nanocomposites were further examined by means of scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA), respectively. Rheological properties of the EVA40/organoclay nanocomposites were investigated using a rotational rheometer with parallel‐plate geometry in both steady shear and dynamic modes, demonstrating remarkable differences with the clay contents in comparison to that of pure EVA40 copolymer.     

Polyelectrolyte Nanocomposite Membranes,Based on Chitosan-phosphotungstic Acid Complex and Montmorillonite for Fuel Cells Applications

A polyelectrolyte complex (PEC) of chitosan and phosphotungstic acid (PWA) was prepared and characterized as a proton-conducting membrane for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy showed the presence of stable PWA in PEC. To reduce the methanol permeability, several amounts of montmorilonite (MMT) nanoclays (trade name: Cloisite Na) were introduced to the system. The X-ray diffraction patterns of nanocomposite membranes proved the nanoclay layers were exfoliated in the membranes at loading weights of MMT lower than 3 wt%. Proton conductivity and methanol permeability were measured. According to the selectivity parameter—ratio of proton conductivity to methanol permeability—PEC containing 2 wt% MMT (PEC/2 wt% MMT) was identified as the optimum composition. Finally, DMFC performance tests were investigated at 70°C and 5 M methanol feed and the optimum membrane showed higher maximum power density in comparison with Nafion 117. The results indicated the optimum nanocomposite membrane is a promising polyelectrolyte membrane (PEM) for DMFC applications.     

Nanomechanical modeling of interfaces of polyvinyl alcohol (PVA)/clay nanocomposite

Abstract

We study interfacial debonding of several representative structures of polyvinyl alcohol (PVA)/pyrophillite-clay systems – both gallery-interface (polymer/clay interface in the interlayer region containing polymer between clay layers stacked parallel to each other) and matrix-interphase (polymer/clay interphase-region when individual clay layers are well separated and dispersed in the polymer matrix) – using molecular dynamics simulations, while explicitly accounting for shearing/sliding (i.e. Mode-II) deformation mode. Ten nanocomposite geometries (five 2-D periodic structures for tension and five 1-D periodic structures for shearing) were constructed to quantify the structure-property relations by varying the number density of polymer chains, length of polymer chains and model dimensions related to the interface deformation. The results were subsequently mapped into a cohesive traction–separation law, including evaluation of peak traction and work of separation that are used to characterise the interface load transfer for larger length scale micromechanical models. Results suggest that under a crack nucleation opening mode (i.e. Mode-I), the matrix-interphase exhibits noticeably greater strength and a greater work of separation compared to the gallery-interface; however, they were similar under the shearing/sliding mode of deformation. When compared to shearing/sliding, the tensile peak opening mode stresses were considerably greater but the displacement at the peak stress, the displacement at the final failure and the work of separation were considerably lower. Results also suggest that PVA/clay nanocomposites with higher degree of exfoliation compared with nanocomposites with higher clay-intercalation can potentially display higher strength under tension-dominated loading for a given clay volume fraction.     

Clay‐induced Preferred Orientation in Polyethylene/Compatibilized Clay Nanocomposites

Nanocomposites of the organically modified clay Cloisite^® 15A (CL15A) dispersed in HDPE‐g‐MA were prepared by melt‐compounding. Microcomposites of the same clay with HDPE were also obtained with similar procedures. The spherulitic morphology of the polymer matrix was evidenced by optical microscopy in thin films, whereas the structure of the up to 2‐mm–thick, compression‐molded samples was investigated by WAXD and SAXS. Preferred orientation of both the clay and the HDPE crystallites were evidenced in the microcomposites and, to a greater extent, in nanocomposites, whereas in HDPE and HDPE‐g‐MA control specimens hardly any anisotropy was detected. The degree of orientation of PE crystals increases with CL15A concentration, but also with clay exfoliation, with lower cooling rates and decreasing sample thickness. The orientation of the clay platelets parallel to the compression‐molded surface appears to be determined by the platelets anisotropy and by shear in the mixing and the compression‐molding procedures. In turn, it determines the preferred uniaxial orientation of HDPE crystals, which have their crystallographic a axis orthogonal, while b and c are coplanar, to the sample surface, as already reported in the literature for melt‐crystallized HDPE films with thickness below 0.3 μm. It is proposed that the HDPE orientation results from confined crystallization between parallel clay platelets which are on average less than 0.1 μm apart. Simple models, qualitatively accounting for the observed orientation of HDPE, are discussed. Organized architectures resulting from confined crystallization of the polymer matrix in nanocomposites with appropriate anisotropic fillers may be a general feature, important in determining key properties of these systems.