Morphologies and properties of nanocomposite films based on a biodegradable poly(ester)urethane elastomer

Biodegradable poly(ester)urethane (PU) elastomer‐based nanocomposite films incorporated with organically modified nanoclay were prepared with melt‐extrusion compounding followed by a casting film process. These films were intended for application as biodegradable food packaging films, with their enhanced gas barrier, mechanical, and thermal properties and good flexibility. From both X‐ray diffraction measurements and transmission electron microscopy observations, the coexistence of intercalated tactoids and exfoliated silicate layers in the compounded PU/clay nanocomposite films was confirmed. In addition, the morphology exhibited a clay dispersion state in the matrix and was influenced by the incorporated nanoclay content. The effects of the nanoclay loading level on the thermal, mechanical, and barrier properties of the compounded nanocomposites were also investigated. As a result, it was revealed that the addition of nanoclay up to a certain level resulted in a remarkable improvement in the thermal properties in terms of thermal stability and the degree of thermal shrinkage; mechanical properties, including dynamic storage modulus and tensile modulus; and oxygen/water‐vapor barrier properties of the nanocomposite films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of polynorbornene/sepiolite hybrid nanocomposite films

Polynorbornene/sepiolite hybrid nanocomposite films were prepared using polynorbornene dicarboximide and modified sepiolite with 3‐ aminopropyltriethoxysilane (3‐APTES). Exo‐N‐(3,5‐dichlorophenylnorbornene)‐5,6‐dicarboxyimide (monomer) and their copolymers were synthesized via ring‐opening polymerization using ruthenium catalysts. Subsequently, the surface‐modified sepiolite by 3‐APTES was mixed with the polynorbornene copolymers to prepare hybrid nanocomposite films. The modified sepiolite particles were well dispersed in N,N‐dimethylacetamide and distributed randomly throughout the polynorbornene matrix in the hybrid films, which enhanced the dimensional stability and mechanical and oxygen barrier properties of the polynorbornene/sepiolite hybrid nanocomposite films. © 2014 Society of Chemical Industry     

Advance polymeric carbon nanocomposite films with enhanced thermo‐mechanical properties

The homogenous nanocomposite films of UV/O₃ oxidized multiwall carbon nanotubes (MWCNTs) subsequently modified with aniline moiety were synthesized with polymethylmethacrylate (PMMA) through free radical polymerization. The phenylamine functional groups present on the surface of MWCNTs providing an anchoring sites for deposition of Ag metal nanoparticles (NP).The in situ free radical polymerization of MMA in the presence of these well dispersed nanotubes gave a new class of radiation resistant nanocomposite films. The synthesized materials were characterized by FT‐IR, TGA, TEM, EDX, TC, DMA, universal testing machine, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. The microscopic and structural properties reflect the homogenous mixing of modified MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% addition of modified nanofiller. Thermal and thermo‐mechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films have been compared with neat polymer. The results revealed that modified nanofiller network can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thermal stability of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/modified montmorillonite bio‐nanocomposites

Poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P34HB)/modified montmorillonite (EMMT) bio‐nanocomposites were prepared via melt intercalation method. The thermal stability of the bio‐nanocomposites was investigated. The results showed that the decomposition temperature (T _5%) of P34HB/EMMT bio‐nanocomposite reached 271.4°C, 39.9°C higher than that of pure P34HB. The remarkable thermal stability enhancement was presumably originated from the uniform dispersion of EMMT in the matrix and intercalated structures of P34HB/EMMT bio‐nanocomposites, which was related to the increased compatibility of EMMT and P34HB caused by the ester group in EMMT. TGA‐FTIR analysis on the thermal degradation procedures of the bio‐nanocomposites manifested that the introduction of EMMT did not alter the degradation mechanism of P34HB. However, the intercalated structures hindered the mobility of P34HB macromolecular and slowed down the decomposing process of P34HB. POLYM. COMPOS., 38:673–681, 2017. © 2015 Society of Plastics Engineers     

Preparation and characterization of wood/styrene‐acrylonitrile copolymer/MMT nanocomposite

Wood polymer nanocomposite (WPNC) was prepared by impregnating Simul (Salmalia malabarica) wood with styrene‐acrylonitrile copolymer (SAN), glycidyl methacrylate(GMA), and a reactive polymerizable surfactant modified montmorillonite (MMT). The physical and mechanical properties of WPNC were investigated by using XRD, tensile tester, SEM, and FTIR. The polymer loading, dimensional stability, water uptake, mechanical property, and thermal stability were found to improve due to inclusion of MMT. SEM micrographs showed the presence of polymer and MMT into cell wall and cell lumen. FTIR analysis confirmed the presence of MMT and SAN in WPNC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of biodegradable poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/silica nanocomposites

Biodegradable poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐co‐4HB)]/silica nanocomposites were prepared by melt compounding. The effects of silica on the morphology, crystallization, thermal stability, mechanical properties, and biodegradability of P(3HB‐co‐4HB) were investigated. The nanoparticles showed a fine and homogeneous dispersion in the P(3HB‐co‐4HB) matrix for silica contents below 5 wt%, whereas some aggregates were detected with further increasing silica content. The addition of silica enhanced the crystallization of P(3HB‐co‐4HB) in the nanocomposites due to the heterogeneous nucleation effect of silica. However, the crystal structure of P(3HB‐co‐4HB) was not modified in the presence of silica. The thermal stability of P(3HB‐co‐4HB) was enhanced by the incorporation of silica. Silica was an effective reinforcing agent for P(3HB‐co‐4HB), and the modulus and tensile strength of the nanocomposites increased, whereas the elongation at break decreased with increasing silica loading. The exciting aspect of this work was that the rate of enzymatic degradation of P(3HB‐co‐4HB) was enhanced significantly after nanocomposites preparation. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Preparation of highly emissive,thermally stable,UV‐cured polysilsesquioxane/ZnO nanoparticle composites

A high molecular weight polysilsesquioxane (LPMSQ)/ZnO nanocomposite was prepared by blending a methacryl‐substituted polysilsesquioxane and PMMA‐coated ZnO nanoparticle (NP) followed by UV‐curing process. These LPMSQ/ZnO nanocomposites gave high thermal and mechanical stabilities originated from the rigid ladder structured siloxane backbone of LPMSQ. The polysilsesquioxane and surface‐modified ZnO nanoparticles showed excellent compatibility between MMA groups in LPMSQ‐ and PMMA‐capped ZnO nanoparticles to give well‐dispersed LPMSQ/ZnO nanocomposites. Mechanically pliant and flexible free standing films were obtained, and the photo and optical properties of these hybrid nanocomposites were examined. The high photoluminescent properties were maintained even after severe thermal treatments exceeding 400°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42333.     

Fabrication and properties of clay-supported carbon nanotube/poly (vinyl alcohol) nanocomposites

Clay-supported carbon nanotubes (Cs-CNTs) were used as novel nanofillers to improve the thermal and mechanical properties of a polymer. Cs-CNT/poly (vinyl alcohol) (PVA) nanocomposite films were successfully fabricated, and their relative properties were investigated by using differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. Experimental results showed that the thermal stability and dynamic mechanical properties of PVA were remarkably enhanced by incorporating the Cs-CNTs into PVA matrix. The largest T_g difference of 14°C was obtained between pure PVA and PVA nanocomposite with 7 wt% Cs-CNTs. Moreover, the storage modulus of PVA was significantly improved by 133% at 50°C, when 7 wt% Cs-CNTs was added to PVA matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Starch nanocomposite films incorporating grape pomace extract and cellulose nanocrystal

The objectives of this study were to prepare starch nanocomposite films incorporating grape pomace extract (GPE) and cellulose nanocrystal (CNC) using a solvent‐casting method, and to characterize the mechanical properties, color, water vapor transmission rate (WVTR), crystalline structure, morphology, thermal stability, phenolic compound release profile and antibacterial activity of the films. Incorporating CNC and GPE significantly (P < 0.05) increased the films’ thickness, mechanical properties, and opacity. Brightness and color were mainly influenced by GPE level, while CNC had a great impact on the reduction of WVTR values of the film. Three characteristic cellulose I crystalline peaks were observed using X‐ray diffraction in CNC‐containing nanocomposite films. However, the effect of CNC levels on thermal stability was not significant. Phenolic compound releases were time and film dependent, and the nanocomposite films incorporating with GPE and CNC exhibited stronger inhibitory effect against Staphylococcus aureus ATCC 29213 compared to Listeria monocytogenes ATCC 7644. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44438.     

The effect of clay type and of clay–masterbatch product in the preparation of polypropylene/clay nanocomposites

Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ～ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of 4HB content on the properties of poly(3‐hydroxylbutyrate‐co‐4‐hydroxylbutyrate) based on melt molded sheets

A series of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)s[P(3HB‐co‐4HB)s] sheets with the 4HB contents from about 9 to 34 mol % were prepared via melt molding. Their crystallinity, crystalline structures, thermal and mechanical properties were characterized by differential scanning calorimetry, X‐ray diffraction, thermogravimetric analysis, dynamic mechanical analysis, and tensile test. It was found that the melt temperatures (T_m), glass transition temperatures (T_g), and storage modulus (E′) of all the [P(3HB‐co‐4HB)s] copolymers investigated decreased continuously with increasing the amount of the 4HB; the yield stress and breaking stress nearly decreased with the increase of the 4HB contents while the elongation at the yield and break points increased; and the thermal stability of the P(3HB‐co‐4HB)s improved with increasing 4HB contents. The results suggest that the mechanical properties and crystal lattice parameters of the melt molded sheets are somewhat different from those of the solution cast films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyimide‐silica nanocomposites exhibiting low thermal expansion coefficient and water absorption from surface‐modified silica

In this study, a commercially available nano‐sized silica (SiO₂) was surface‐modified via esterification with oleic acid (OA), a relatively inexpensive and hydrophobic modifier, and characterized by FTIR, NMR, SEM, EDS, and TGA measurements. Various amounts of the surface‐modified silica nanoparticles (SiO₂‐OA) were dispersed in a poly(amic acid), which were then cyclized at high temperatures to form a series of PI/SiO₂‐OA nanocomposite films (PISA). The effect of the addition of the SiO₂‐OA nanoparticles on the properties of the as‐prepared polyimide nanocomposite was studied. The results indicated that, comparing with pure PI and PI/pristine‐SiO₂ composite film (PISI), the as‐prepared PISA films had enhanced dynamic mechanical properties and thermal stability, as well as reduced water absorption and thermal expansion. The as‐prepared PI/SiO₂‐OA nanocomposites have potential for applications in high performance microelectronic devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4096–4105, 2007     

Reinforcement of polybenzoxazine matrix with organically modified mica

Novel polybenzoxazine–clay hybrids were prepared by the in situ polymerization of the typical benzoxazine monomer, bis(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazinyl)isopropane (B‐a) in the presence of aminolauric acid‐modified mica (ALA‐mica). Various ratios of ALA‐mica were dispersed into solutions of B‐a in N,N‐dimethylacetamide, followed by casting into film form. The hybrids were thermally cured up to 230°C, affording transparent nanocomposite films up to 10 wt% of mica loadings. The cure behavior was monitored by both IR and differential scanning calorimetry, indicating the catalytic effect of the modified mica. The morphology of the nanocomposites was studied by XRD, showing a featureless pattern, which suggests the disordered dispersion of mica into polybenzoxazine matrix. The dynamic mechanical properties of some hybrids show that the nanocomposites have higher storage modulus over the whole temperature range than the neat polybenzoxazine. Thermogravimetric analysis results confirmed that the thermal stability and char yield of polybenzoxazine resin increased apparently by hybridization with mica corresponding to the mica content. POLYM. COMPOS., 28:680–687, 2007. © 2007 Society of Plastics Engineers     

Preparation of polybenzimidazole/functionalized carbon nanotube nanocomposite films for use as protective coatings

Functionalized multi‐walled carbon nanotubes (MWCNTs) via microwave‐induced polymerization modification route, and polybenzimidazole (PBI) nanocomposite films containing 0.1‐5 wt% functionalized MWCNTs were successfully synthesized. The functionalized MWCNTs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). The results verify that the polymer was successfully grafted to the MWCNTs with a polymer layer that was several nanometers thick. The TGA results showed that the quantity of the attached polymer reached approximately 9.4 wt%. The mechanical properties of the nanocomposite films were measured by tensile test and dynamic mechanical analysis (DMA). The tensile test results indicated that the Young's modulus increased by about 43.9% at 2 wt% CNT loading, and further modulus growth was observed at higher filler loading. The DMA studies indicated that the nanocomposite films had a higher storage modulus than pure PBI film in the temperature range of 30‐300°C, and the storage modulus was maintained above 0.82 GPa. Simulation results confirmed that the PBI nanocomposite films had desirable mechanical properties for use as a protective coating. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Harmless hydrogels based on PVA/Na+‐MMT nanocomposites for biomedical applications: Fabrication and characterization

A series of nanocomposite hydrogels were prepared by a freeze‐thaw process, using polyvinyl alcohol (PVA) as polymer matrix and 0–10 wt% of hydrophilic natural Na‐montmorillonite (Na⁺‐MMT), free from any modification, as composite aggregates. The effect of nanoclay content and the sonication process on the nanocomposite microstructure and morphology as well as its properties (physical, mechanical, and thermal) were investigated. The microstructure and morphology were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X‐ray diffraction technique. The thermal stability and mechanical properties of nanocomposite hydrogels were examined using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis; moreover hardness and water vapor transmission rate measurements. It was concluded that the microstructure, morphology, physical (thermal) and mechanical properties of nanocomposite hydrogels have been modified followed by addition of nanoclay aggregates. The results showed that Na⁺‐MMT may act as a co‐crosslinker. Based on the results obtained, the nanocomposite hydrogel PVA/Na⁺‐MMT synthesized by a freeze‐thaw process, appeared to be a good candidate for biomedical applications. POLYM. COMPOS., 38:1135–1143, 2017. © 2015 Society of Plastics Engineers     

Cellulose acetate/polysilsesquioxane composites: Thermal properties and morphological characterization by electron spectroscopy imaging

Cellulose acetate (CA) composites using two types of silane coupling agents (methyltrimethoxysilane and phenyltriethoxysilane) were prepared through two methodologies: direct reaction between CA and the specific monomer and reaction of CA with oligomers, which were produced by prehydrolysis of the same monomers. The thermal behavior and morphology of the materials were studied. The composites showed thermal stability similar to pure CA, increase of residue content at 790°C and reduction in the glass transition temperature. Complementary microscopy techniques were applied to investigate the distribution of polysilsesquioxane in the CA matrix. Silicon mapping images showed the presence of domains with higher polysilsesquioxane concentration than the matrix and also the presence of silicon‐rich nanodomains dispersed throughout the matrix. Based on mapping characterization, a schematic representation of the CA/polysilsesquioxane composite morphology was proposed. The organosilane type and architecture influenced the thermal behavior and the morphology of these materials. The results suggest that the silane coupling agents could be used to produce CA films with a range of properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PMMA/o‐MMT nanocomposites obtained using thermally stable surfactants

In the preparation of polymer/montmorillonite (MMT) nanocomposites, the commonly used compatibilizers (cations of long carbon‐chain alkyl ammonium salts) present the drawback of a poor thermal stability. During bulk processing of nanocomposites elevated temperatures are usually required and, if processing temperature is close to decomposition temperature of the surfactant, decomposition will occur altering the interface between filler and polymer. To solve this problem, organically modified MMTs with thermally stable imidazolium surfactants have been prepared. A series of nanocomposites were obtained by dispersing o‐MMT in poly(methyl methacryate) (PMMA) matrix via an in situ free radical polymerization. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, gel permeation chromatography, thermogravimetric analysis, dynamic mechanical analysis, and nanoindentation measurements. The results showed that nanocomposite thermal stability depended on both the kind of used surfactant and degree of exfoliation. Under the same values of molecular weight, the nanocomposites containing imidazolium cations showed a better thermal stability with respect to the nanocomposite obtained using a standard alkylammonium surfactant. Dynamic mechanical and Nanoindentation measurements showed an improvement of mechanical properties, such as modulus and hardness, with respect to pure PMMA. Solution blending treatments on these nanocomposites led to obtaining of further improvement of the thermal performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41393.     

Synergistic enhancement of mechanical,crystalline and dielectric properties of polyarylene ether nitrile‐based nanocomposites by unidirectional hot stretching–quenching

Copper tetra‐amine phthalocyanine (NH₂‐CuPc) was grafted onto barium titanate (BaTiO₃) whose surface was modified by carboxylic polyarylene ether nitrile (CPEN) to afford a nano‐filler (CPEN‐f‐BaTiO₃@NH₂‐CuPc). Through a solution‐casting method combined with ultrasonic dispersion technology, the obtained CPEN‐f‐BaTiO₃@NH₂‐CuPc was successfully incorporated into biphenyl polyarylene ether nitrile (BP‐PEN) matrix to prepare nanocomposite films with various mass fractions of CPEN‐f‐BaTiO₃@NH₂‐CuPc (0, 2.0, 5.0, 10.0 and 20.0 wt%). After that, the nanocomposite films were unidirectionally stretched with various stretching ratios at 280 °C. All the nanocomposite films show excellent mechanical and thermal stability, which is provided by the BP‐PEN matrix. The crystallinity and mechanical, thermal and dielectric properties of the nanocomposite films are efficiently enhanced after the unidirectional hot‐stretching process. The results show that hot‐stretching is a useful method for improving the mechanical and crystallization behaviors as well as the thermal and dielectric properties of the nanocomposite films. © 2017 Society of Chemical Industry     

Siloxane surfactant‐modified clay and its effect in reinforcing the laminate of polymethylsilsesquioxane

To achieve good compatibility between clay layers and siloxane polymer, polymethylsilsesquioxane (PMSQ), montmorillonite was modified by a novel siloxane surfactant with M?_w = 1900 and then environmentally friendly solution‐compounded with PMSQ to prepare glass fiber laminates. Transmission electronic microscope shows the orderly, exfoliated structure of the modified clay in PMSQ matrix; scanning electronic microscope demonstrates the fine dispersion of the clay layers in the matrix because of the good compatibility between the grafted surfactant and the matrix. Both the modified clay and its nanocomposite indicate much improved thermal stability. By incorporation of merely 0.3 wt % of the clay, the flexural modulus and strengths of fiber/PMSQ laminate are increased by 21 and 62%, respectively. This study illuminates the importance of the compatibility of the grafted siloxane surfactant with the matrix polymer in achieving both exfoliation and dispersion of clay as well as ideal mechanical properties for silicone‐based polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3974–3980, 2006     

Dispersion of multiwalled carbon nanotubes in thermoplastic elastomer gels: Morphological,rheological, and electrical properties

An investigation was reported here with an aim to prepare nanocomposite thermoplastic elastomer gels by dissolving polystyrene‐b‐poly(ethylene/butylene)‐b‐polystyrene (SEBS) triblock copolymer in selective hydrocarbon oils with the presence of multiwalled carbon nanotubes (MWCNTs). The properties related to morphology, viscoelasticity, electrical and mechanical properties, and thermal stability were explored and discussed. Dynamic rheological measurements of the resultant nanocomposite thermoplastic elastomer gels (NCTPEGs) confirmed that addition of MWCNTs affects the linear viscoelastic properties in which dynamic storage and loss moduli increase to some extent. At a temperature between 30°C and 40°C below the gel point the NCTPEGs have dynamic storage modulus greater than loss modulus (G′ and G″), thereby indicating that at room temperature a physical network is still present despite the addition of MWCNTs. The morphological properties revealed that MWCNTs were dispersed and exfoliated within the swollen TPE. The incorporation of small quantity of MWCNTs improved the thermal stability and mechanical properties of NCTPEGs. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers