Morphological characteristics and thermal,rheological, and mechanical properties of cellulose nanocrystals-containing biodegradable poly(lactic acid)/poly(ε-caprolactone) blend composites

This work investigates the effect of cellulose nanocrystal (CN) loading on the properties of polylactide / poly(ε-caprolactone) (PLA/PCL) (70/30) blend processed in a twin-screw extruder as a potential material that can be utilized in various applications where biodegradation is highly desired. The morphological analysis revealed a reduction in droplet size of dispersed PCL phase upon addition of CN at low concentrations (1 and 2 wt %) with maximum reduction at 2 wt % which led to maximum improvement in mechanical properties. The reinforcing effect of CN in increasing the DMA storage modulus of the prepared systems was noticed when CN concentration was increased. Further, CN enhanced the crystallization of PCL, whereas the cold crystallization of PLA remained the same with CN addition. Both melt strength and viscosity of PLA improved with the incorporation of PCL and CN. In general, a green composite material with improved properties was successfully prepared using an environmentally friendly filler material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48665.     

Effect of a chain extender on the properties of poly(lactic acid)/zinc oxide/copper chlorophyll acid antibacterial nanocomposites

Poly(lactic acid) (PLA)/nano zinc oxide/copper chlorophyll acid (CCA) antibacterial nanocomposites with excellent mechanical properties were prepared in the presence of a chain extender named tolylene diisocyanate (TDI). The effect of the chain extender on the PLA long chain was confirmed by the increased molecular weight shown in the mass flow rate and gel permeation chromatography. Escherichia coli were adopted to examine the antibacterial ability of the blends. The effect of CCA is also discussed with regard to the enhancement of the antibacterial effect of zinc oxide (ZnO) over E. coli. Scanning electron microscopy and transmission electron microscopy were used to view the agglomeration and dispersion of ZnO in the PLA matrix. Differential scanning calorimetry and thermogravimetric analysis revealed a relatively stable thermal performance of the nanocomposites with and without TDI. A sharp increase in the mechanical properties was also observed after the addition of the chain extender under different processing conditions. Additionally, we found that the nanocomposites with the incorporation of TDI and the masterbatches in batches effectively improved the mechanical properties of PLA/ZnO/CCA without a sacrifice of the antibacterial effect. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41561.     

Synthesis and characterization of poly(methyl methacrylate)/polysiloxane composites and their coating properties

A series of poly(methyl methacrylate) (PMMA)/polysiloxane composites and their coatings were prepared as designed. A copolymer (PMMAVTEOS) containing methyl methacrylate (MMA) and vinyltriethoxysilane (VTEOS) was prepared by free radical polymerization and then condensed with methyl triethoxysilane (MTES) to fabricate PMMA/polysiloxane composites; their corresponding coatings were obtained via a curing process in an oven (at 75 °C). The polymers were characterized by gel permeation chromatography and Fourier transform infrared spectroscopy. The surface property, hardness, water contact angle, thermal stability, and optical property of the coatings were investigated by scanning electron microscopy, pencil hardness testing, water contact angle testing, thermogravimetric analysis, and ultraviolet–visible spectroscopy, respectively. The results showed that, after addition of MMA, the pencil hardness of the coatings was reduced from 6H to 2H and the thermal stability decreased from 365 to 314 °C. However, it increased the flexibility and adhesion properties (the water contact angle increased from 94.7° to 102.1°). The transparent PMMA/polysiloxane coatings showed excellent scratch resistance, a smooth surface, high thermal stability, and a strong adhesion property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46358.     

Effect of silk nano‐disc dispersion on mechanical,thermal, and barrier properties of poly(lactic acid) based bionanocomposites

Exacerbated environmental concerns about petroleum‐based plastics provide the impetus to foster sustainable poly(lactic acid) (PLA) based food packaging. Nonetheless, PLA has its foibilities such as its brittleness, higher gas permeability, and slow crystallization. With the intent to mitigate the above shortcomings, we report a maiden effort for the fabrication of PLA/crystalline silk nano‐discs (CSNs) based bionanocomposites by melt‐extrusion for high temperature engineering and food packaging applications. Acid hydrolyzed silk fibroin from muga silk (Antheraea assama) yields CSNs, a crystalline hydrophobic discotic nanofiller with diameter of ～50 nm and thickness ～3 nm. At optimum loadings of 1 wt % uniform dispersed CSNs with percolated network structures covering the entire matrix can be seen. Due to enhanced crystal nucleation density, water vapor, and oxygen permeability reduced by ～30% and ～70%, respectively. Enhancement in toughness, percentage elongation, and tensile strength up to ～65%, ～40%, and ～10%, respectively, is obtained. Onset of thermal decomposition for the PLA/CSN improved ～10 °C, confirming the role of CSN in enhancing melt stability. Accordingly, this investigation renders a novel non‐invasive approach for increasing the crystallinity with improvement in thermomechanical and barrier properties which make this bionanocomposite, a promising candidate for food packaging applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46671.     

The impact of intense types of effects on poly(N-vinyl caprolactam) and composites in the system nanoscale anatase – poly(N-vinyl caprolactam)

For the first time, the effects of microwave and ultrasonic treatments and an alternating electric field on poly(N-vinyl caprolactam) (PVCL40) both in the original and in the composite with nanoscale anatase have been studied. Comparison of the results of studying the samples by X-ray diffraction, IR spectroscopy, differential scanning calorimetry (DSC) before and after treatments allowed us to identify, and explain the response of objects to different types of effects with a change in their characteristics. Analysis and comparison of the results do not exclude the misorientation of the PVCL40 domains in thin films (microwave processing), which becomes flat-ordered after their rubbing, the destruction of the PVCL40 and the disorder of the side substituent are found, accompanied by a change in the periodicity chains (microwave processing, electric field), a decrease in the water content in the system (microwave processing) and amorphization of nanoscale anatase (microwave processing, electric field) were revealed. The implementation of the revealed effects as response to microwave, ultrasonic, and electric field treatments on a similar type of polymers with a different composition and structure is not ruled out.     

Microwave processing of SiC nanoparticles infused polymer composites: Comparison of thermal and mechanical properties

The goal of this study is to compare thermal and mechanical properties of an epoxy resin system reinforced with SiC nanoparticles using both conventional thermal curing and microwave irradiation techniques. The microwave curing technique has shown potential benefits in processing polymeric nanocomposites by reducing the curing time without compromising the thermo‐mechanical performances of the materials. It was observed from this investigation that, the curing time was drastically reduced to ～30 min for microwave curing instead of 12 h room temperature curing with additional 6 h post curing at 75°C. Ductile behavior was more pronounced for microwave curing technique while thermal curing showed brittle like behavior as revealed from flexural test. The maximum strain to failure was increased by 25–40% for microwave‐cured nanocomposites over the room temperature cured nanocomposites for the same loading of nanofillers. The glass transition temperature (T_g) also increased by ～14°C while curing under microwave irradiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41708.     

Novel approach to recover copper ions using poly(ethylene imine) based layer-by-layer coatings on icosane particles

The low-density materials are developed for the wastewater treatment, the particles could be easily recovered when floating upon water surface and be recycling of a large fraction. Simultaneously, we selected the low melting point of material, which is possible to separate easily the compounds after usage. We chose icosane as a core material with layer-by-layer (LbL) films as an adsorbent for wastewater containing copper ions. The icosane particles were coated by poly(ethylene imine) (PEI) as positively charged layer and either poly(acrylic acid) (PAA) or poly(styrene sulfonate) as counterpart. Glutaraldehyde was introduced as a crosslinking agent to create multilayered shells with various active sites as scavenger. The copper adsorption abilities of PEI-PAA-coated particles were examined by inductively coupled plasma mass spectrometry. Interestingly, the adsorption amount of copper ions on PEI/PAA coated particles (16.5 mg) was optimized at 82 μg/L after 5 min of elution time, which shows a good potential of our material in the field of application. With the facile and consistent separation of the core and LbL coating, the thermal properties were revealed a stable melting temperature at around 38°C.     

Synthesis of poly(butyl acrylate)—laponite nanocomposite nanoparticles for improving the impact strength of poly(lactic acid)

This work aims at preparing and characterizing poly(butyl acrylate) (PBA)—laponite (LRD) nanocomposite nanoparticles and nanocomposite core (PBA‐LRD)‐shell poly(methyl methacrylate) (PMMA) nanoparticles, on the one hand, and the morphology and properties of poly(lactic acid) (PLA)‐based blends containing PBA‐LRD nanocomposite nanoparticles or (PBA‐LRD)/PMMA core–shell nanoparticles as the dispersed phase, on the other hand. The PBA and (PBA‐LRD)/PMMA nanoparticles were synthesized by miniemulsion or emulsion polymerization using LRD platelets modified by 3‐methacryloxypropyltrimethoxysilane (MPTMS). The grafting of MPTMS onto the LRD surfaces was characterized qualitatively using FTIR and quantitatively using thermogravimetric analysis (TGA). The amounts of LRD in the PBA‐LRD nanocomposites were characterized by TGA. The PBA/PMMA core–shell particles were analyzed by ¹H‐NMR. Their morphology was confirmed by SEM and TEM. Mechanical properties of (PBA‐LRD)/PLA blends and (PBA‐LRD)/PMMA/PLA ones were tested and compared with those of the pure PLA, showing that core–shell particles allowed increasing impact strength of the PLA while minimizing loss in Young modulus and tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of biodegradable composites from poly lactic acid (PLA) and microcrystalline cellulose (MCC)

Biodegradable composites were prepared using microcrystalline cellulose (MCC) as the reinforcement and polylactic acid (PLA) as a matrix. PLA is polyester of lactic acid and MCC is cellulose derived from high quality wood pulp by acid hydrolysis to remove the amorphous regions. The composites were prepared with different MCC contents, up to 25 wt %, and wood flour (WF) and wood pulp (WP) were used as reference materials. Generally, the MCC/PLA composites showed lower mechanical properties compared to the reference materials. The dynamic mechanical thermal analysis (DMTA) showed that the storage modulus was increased with the addition of MCC. The X‐ray diffraction (XRD) studies on the materials showed that the composites were less crystalline than the pure components. However, the scanning electron microscopy (SEM) study of materials showed that the MCC was remaining as aggregates of crystalline cellulose fibrils, which explains the poor mechanical properties. Furthermore, the fracture surfaces of MCC composites were indicative of poor adhesion between MCC and the PLA matrix. Biodegradation studies in compost soil at 58°C showed that WF composites have better biodegradability compared to WP and MCC composites. The composite performances are expected to improve by separation of the cellulose aggregates to microfibrils and with improved adhesion. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2014–2025, 2005     

Preparation and thermomechanical properties of nanocrystalline cellulose reinforced poly(lactic acid) nanocomposites

A two‐step process was developed to prepare nanocrystalline cellulose (NCC) reinforced poly(lactic acid) (PLA) nanocomposites using polyethylene glycol (PEG) as a compatibilizer. It was composed of solvent mixing and melt blending. The NCC was well dispersed in the PLA matrix. A network was formed at high NCC‐to‐PEG ratio at which the amount of the PEG was not enough to cover all the surfaces of the NCC. The formation of the network was confirmed by the occurrence of a plateau for the storage modulus at low frequency. The incorporation of the PEG and NCC could improve the crystallinity of the PLA. The elongation at break increased from 11.0% for the neat PLA to 106.0% for the composites including 6 wt % NCC, impact strength was improved from 0.864 to 2.64 kJ m^?2 and tensile strength did not change significantly for the same 6 wt % NCC composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44683.     

A model for water vapor permeability reduction in poly(lactic acid) and nanoclay nanocomposites

Poly(lactic acid) (PLA) is used in packaging applications, but its moisture barrier properties are inferior to poly(ethylene terephthalate) and polystyrene. One objective of the study was to improve these by dispersing nanoclay in PLA. It was found that Cloisite 30B nanoclay showed the best dispersion based on both permeability and transmission electron microscopy results. Compression molded nanocomposite films were amorphous, and moisture permeability measurements revealed that, at the highest loading level of 5.3 vol % organoclay, permeability was reduced by 69% compared to neat PLA. Additionally, independent experiments demonstrated that moisture solubility in the polymer remains unchanged even as solubility in the nanocomposite increases with increasing clay content. A second objective was to explain the measured permeability reduction. A new model is proposed where both the mass flux and area for mass transfer are reduced due to a tortuous path around the impermeable barriers. It is shown that the permeability decreases by a factor of where h/t is the aspect ratio of the nanoplatelets, and ? is their volume fraction. Model predictions agree quantitatively with the measured permeability values when data are obtained as a function of filler volume fraction, temperature of measurement, and the concentration driving force. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46506.     

Cellulose nanocrystal driven crystallization of poly(d,l‐lactide) and improvement of the thermomechanical properties

The technological exploitation of polylactide in fields requiring wide range of operating conditions is limited by the low crystallization rate of the polymer and therewith the low thermomechanical stability. Here we report the crystallization and consequent improvement of the thermomechanical properties of originally amorphous poly(d,l ‐lactide) (d : l ratio 11 : 89) loaded with cellulose nanocrystals (CNCs). Isothermal treatment of samples with different CNC contents and at various temperatures, showed up to 6 wt % crystalline phase formation, as confirmed by differential scanning calorimetry and X‐ray diffraction measurements. Under a particular set of annealing conditions, CNCs promote the formation of a lamellar structure. This provides the system with higher order and cohesion which in combination with stress‐transfer between CNCs, led to an increase of the storage modulus in the rubbery plateau up to 30 times (from 2.7 MPa up to 79 MPa), a rise of the melting temperature up to 50°C, and an improvement of the Young's modulus up to 40%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41607.     

The morphology and properties of poly(methyl methacrylate)‐cellulose nanocomposites prepared by immersion precipitation method

Poly(methyl methacrylate) (PMMA)‐cellulose nanofibers nanocomposite were prepared by an immersion precipitation method using various nanofiber contents. Solvent exchange was used to disperse the cellulose nanofibers in dimethylacetamide (DMAc) so that they could be easily mixed with PMMA solution. Atomic force microscopy images show that the thickness of the nanofibers dispersed in DMAc is around 2–3 nm. The nanocomposites obtained were translucent. The thermogravimetric and differential scanning calorimetry analyses show that with increasing cellulose nanofiber content the thermal stability and the glass transition temperature (T_g) of polymer matrix shift to higher temperature. The tensile modulus and strength increased with increasing nanofiber content. Dynamic mechanical analysis profiles show that the presence of cellulose nanofibers affects the storage modulus of PMMA nanocomposites over the whole range of temperatures studied. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improved thermomechanical properties of carbon fiber reinforced epoxy composite using amino functionalized XDCNT

Carbon fiber‐reinforced epoxy composites (CFEC) are fabricated infusing up to 0.40 wt % amino‐functionalized XD‐grade carbon nanotubes (XDCNT) using the compression molding process. Interlaminar shear strength (ILSS) and thermomechanical properties of these composites are evaluated through short beam shear and dynamic–mechanical thermal analysis tests. XDCNTs are infused into Epon 862 resin using a mechanical stirrer followed by sonication. After the sonication, the mixture was placed in a three roll milling processor for three successive cycles at 140 rpm for uniform dispersion of CNTs. Epikure W curing agent was then added to the resin using a high‐speed mechanical stirrer. Finally, the fiber was reinforced with the modified resin using the compressive mold. ILSS was observed to increase by 22% at 0.3 wt % XDCNT loading. Thermal properties, including storage modulus, glass transition temperature, and crosslink density demonstrated linear enhancement up to the 0.3 wt % XDCNT loading. Scanning electron microscopy revealed better interfacial bonding in the CNT‐loaded CFEC. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40709.     

Effects of thermoplastic poly(ether-ester) elastomer and bentonite nanoclay on properties of poly(lactic acid)

This work presented the influence of thermoplastic poly(ether-ester) elastomer (TPEE) and bentonite (BTN) on improving the mechanical and thermal properties of poly(lactic acid) (PLA). PLA was initially melt mixed with TPEE at six different loadings (5–30 wt%) on a twin screw extruder and then injection molded. The mechanical tests revealed an increasing impact strength and elongation at break with increasing TPEE loading, but a diminishing Young's modulus and tensile strength with respect to pure PLA. The blend at 30 wt% TPEE provided the optimum improvement in toughness, exhibiting an increase in the impact strength and elongation at break by 3.21- and 10.62-fold over those of the pure PLA, respectively. Scanning electron microscopy analysis illustrated a ductile fractured surface of the blends with the small dispersed TPEE domains in PLA matrix, indicating their immiscibility. The 70/30 (wt/wt) PLA/TPEE blend was subsequently filled with three loadings of BTN (1, 3, and 5 parts by weight per hundred of blend resin [phr]), where the impact strength, Young's modulus, tensile strength and thermal stability of all the blends were improved, while the elongation at break was deteriorated. Among the three nanocomposites, that with 1 phr BTN formed exfoliated structure and so exhibited the highest impact strength, elongation at break, and tensile strength compared to the other intercalated nanocomposites. Moreover, the addition of BTN was found to increase the thermal stability of the neat PLA/TPEE blend due to the barrier properties and high thermal stability of BTN.     

Improvement of the thermal transport performance of a poly(vinylidene fluoride) composite film including silver nanowire

The miniaturization trend of electronic devices requires that components have a high heat dissipation in industrial applications and in daily life. In this context, a highly thermally conductive film was fabricated with silver nanowire (AgNW) and poly(vinylidene fluoride) (PVDF) with a bar‐coating method. The thermal transport performance and mechanism of the AgNW/PVDF composite film were investigated. The through‐plane and in‐plane thermal conductivity of the AgNW/PVDF composite film reached 0.31 and 1.61 W m^?1 K^?1, respectively; these values far exceeded those of the pristine PVDF film. The experiment illustrated that the thermally conductive pathways formed successfully in the PVDF substrate with the addition of AgNW, and the heat tended to transfer along the thermally conductive pathway rather than along the PVDF substrate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43554.     

Improving mechanical properties of poly(vinyl chloride) by doping with organically functionalized reactive nanosilica

Nanosilica particles are functionalized by in situ surface‐modification with trimethyl silane and vinyl silane. Resultant reactive nanosilica (coded as RNS) contains double bonds and possesses good compatibility with vinyl chloride (VC) and polyvinyl chloride (PVC). This makes it feasible for RNS to copolymerize with VC generating RNS/PVC composites via in situ suspension polymerization. As‐prepared RNS/PVC composite resins are analyzed by means of FTIR. The tensile strength and impact strength of compression‐molded RNS/PVC composites are measured and compared with that of compression‐molded PVC composites doped with dispersible nano‐SiO₂ particles (abridged as DNS) surface‐modified with trimethyl silane alone. Moreover, the thermal stability of compression‐molded RNS/PVC and DNS/PVC composites is evaluated by thermogravimetric analysis. It has been found that RNS/PVC composites possess greatly increased impact strength and tensile strength than PVC matrix, while DNS/PVC composites possess higher impact strength than PVC matrix but almost the same tensile strength as the PVC matrix. This implies that DNS is less effective than RNS in improving the mechanical strength of PVC matrix. Particularly, RNS/PVC composites prepared by in situ suspension polymerization have much higher mechanical strength than RNS/PVC composites prepared by melt‐blending, even when their nanosilica content is only 1/10 of that of the melt‐blended ones. Besides, in situ polymerized RNS/PVC and DNS/PVC composites have better thermal stability than melt‐blended nanosilica/PVC composites. Hopefully, this strategy, may be extended to fabricating various novel high‐performance polymer‐matrix composites doped with organically functionalized nanoparticles like RNS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High‐k dielectric composites of poly(2‐cyanoethyl vinyl ether) and barium titanate for flexible electronics

High‐k dielectric composite material for electronic applications was obtained by mixing a polymer with high dielectric constant, poly(2‐cyanoethyl vinyl ether) (CEPVA), and highly crystalline barium titanate (BT). Barium titanate nanoparticles of a size in the range 40–90 nm were prepared by the solvothermal method. By optimizing the reaction conditions, the formation of carbonate impurities and the agglomeration of formed nanoparticles were significantly reduced compared to state‐of‐the‐art procedures. Dielectric spectroscopy was measured in the range of 0.01 Hz to 10 MHz and showed the dielectric constant to be ?′ ～ 35–40 with only 30 vol % content of BT in the composite. Extrapolating to 100% BT nanoparticle concentration and using the Lichtenecker model, the dielectric constant ?′ = 365 ± 27 at 10 kHz was obtained. The relaxation and electrical properties were investigated in depth, and a new relaxation phenomenon was revealed. CEPVA/BT composite is considered suitable for electronic applications, in which high ?′ together with a good mechanical flexibility are required, such as organic field effect transistors. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45236.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Physicomechanical properties of wollastonite (CaSiO3)/styrene butadiene rubber (SBR) nanocomposites

The purpose of this study was to investigate the effect of bare wollastonite (BW) and modified wollastonite (MW) nano‐rods into the styrene butadiene rubber (SBR). SBR nanocomposites were prepared by the incorporation of different wt % (0.3–4.5) of BW and MW nanorods. All nanocomposites were characterized by thermal gravimetric analyzer (TGA) and differential scanning calorimeter (DSC). The particle size and morphology of BW and MW nanorods were characterized by field‐emission scanning electron microscope (FE‐SEM), transmission electron microscope (TEM), and Fourier transform infrared (FTIR) spectrophotometer, while FE‐SEM and AFM analyses were performed for BW/SBR and MW/SBR nanocomposites. The obtained results revealed the existence of stronger interaction between the SBR and MW nanorods into MW/SBR as compared to BW/SBR nanocomposites. FE‐SEM and AFM images showed a perfect dispersion of the MW nanorods in SBR matrix at 3 wt % loading. Thermal stability of MW/SBR nanocomposites was also increased significantly by the addition of MW nanorods. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42811.