Effects of multi‐walled carbon nanotube functionalization on the morphological and mechanical properties of nanocomposite foams based on poly(vinyl chloride)/(wood flour)/ (multi‐walled carbon nanotubes)

Experimental results are presented for nanocomposite foams based on unplasticized poly(vinyl chloride)/(wood flour)/(multi‐wall carbon nanotubes) (PVC/WF/MWCNTs). The nanocomposite samples were prepared in an internal mixer and foamed via a batch processing method using compression molding. Nanoparticles were functionalized by sodium hypochlorite solution, and the functionalization process was monitored by Fourier‐transform infrared spectroscopy. The effects of MWCNTs (both neat and functionalized) and blowing agent concentration on the morphological properties (cell size and cell density) and mechanical properties (tensile and flexural strength) of the foam samples were studied. The results revealed that foam cell sizes decreased and cell densities increased with addition of MWCNTs. The dispersion of nanoparticles in the PVC medium was increased by functionalization, and the morphological properties of the foams containing functionalized nanoparticles were improved. Density of nanocomposite foams decreased more with functionalized MWCNTs as compared to other samples. Chemical blowing agent concentration had no significant effect on sample density. Mechanical properties of the samples were improved by using functionalized MWCNTs in comparison with those of foams without this component. J. VINYL ADDIT. TECHNOL., 18:161–167, 2012. © 2012 Society of Plastics Engineers     

Interlaminar fracture toughness of woven fabric composite laminates with carbon nanotube/epoxy interleaf films

The Mode I interlaminar fracture behavior of woven carbon fiber/epoxy composite laminates incorporating partially cured carbon nanotube/epoxy composite films has been investigated. Laminates with films containing carbon nanotubes (CNTs) in the as‐received state and functionalized with polyamidoamine were evaluated, as well as laminates with neat epoxy films. Double‐cantilever beam (DCB) specimens were used to measure G_Ic, the critical strain energy release rate (fracture toughness) versus crack length. Post‐fracture microscopic inspection of the fracture surfaces was performed. Results show that initial fracture toughness was improved with the amino‐functionalized CNT/epoxy interleaf films, but the important factor appears to be the polyamidoamine functionalization, not the CNTs. The initial fracture toughness remained relatively unaffected with the incorporation of neat epoxy and as‐received CNT/epoxy interleaf films. Plateau fracture toughness was unchanged with the use of functionalized CNT/epoxy interleaf films, and was reduced with the use of neat epoxy and as‐received CNT/epoxy interleaf films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical and morphological characterization of polymer-carbon nanocomposites from functionalized carbon nanotubes

Carbon nanotubes were functionalized with poly(vinyl alcohol) (PVA). The water-soluble PVA-functionalized carbon nanotubes were then embedded into PVA matrix via a wet-casting method, resulting in polymer-carbon nanocomposite films with homogeneous nanotube dispersion. Composites with pristine and functionalized nanotubes were tested in tension. It was found that the mechanical properties of these nanocomposite films were significantly improved compared to the neat polymer film. Functionalization allowed good distribution of the nanotubes in the matrix, leading to higher film strength. Scanning electron microscopy shows an apparent good wetting of the nanotubes by the PVA matrix. These results are supportive of good interfacial bonding between the functionalized carbon nanotubes and the hosting polymer matrix.     

Radiation resistant metal decorated MWCNTs/PMMA nanocomposite films with enhanced thermomechanical properties

UV/O₃ radiation and chemical resistant nanocomposite films of functionalized/metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) are synthesized. Silver nanoparticles are decorated on the surface of UV/O₃ functionalized MWCNTs by both reduction and in situ growth from AgNO₃ aqueous solution. Microscopic studies reflect the better dispersion of UV/O₃ functionalized/silver decorated MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermomechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% MWCNTs additions. The thermal stability of nanocomposite film (0.25 wt% loading), prepared by using a surfactant (Sodium dodecyl sulfate) is increased to about 27°C while the thermomechanical properties are raised up to 76% at 100°C. Thermal and thermomechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films are compared with neat polymer. The results reveal that UV/O₃ functionalized MWCNTs can effectively disperse the radiation and have a dramatic reinforcement effect on the nature of the degradation of PMMA matrix. POLYM. COMPOS., 36:969–978, 2014. © 2014 Society of Plastics Engineers     

Amino‐functionalized multiple‐walled carbon nanotubes‐polyimide nanocomposite films fabricated by in situ polymerization

For the preparation of high‐quality polymeric carbon nanocomposites, it is required that carbon nanotubes are fully compatible with matrix polymers. For this purpose, amino‐functionalized multiple‐walled carbon nanotubes (a‐MWNTs) were synthesized. The a‐MWNTs/polyimide nanocomposite films were prepared through in situ polymerization. According to the spectroscopic characterizations, the a‐MWNTs were homogeneously dispersed in the nanocomposite films as the acid‐functionalized MWNTs. The mechanical properties of the polyimide composite were also studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and mechanical behavior of poly(vinyl butyral)‐modified novolac epoxy/multiwalled carbon nanotube nanocomposites

The effects of poly(vinyl butyral) (PVB) and acid‐functionalized multiwalled carbon nanotube modification on the thermal and mechanical properties of novolac epoxy nanocomposites were investigated. The nanocomposite containing 1.5 wt % PVB and 0.1 wt % functionalized carbon nanotubes showed an increment of about 15°C in the peak degradation temperature compared to the neat novolac epoxy. The glass‐transition temperature of the novolac epoxy decreased with increasing PVB content but increased with an increase in the functionalized carbon nanotube concentration. The nanocomposites showed a lower tensile strength compared to the neat novolac epoxy; however, the elongation at break improved gradually with increasing PVB content. Maximum elongation and impact strength values of 7.4% and 17.0 kJ/m² were achieved in the nanocomposite containing 1.5 wt % PVB and 0.25 wt % functionalized carbon nanotubes. The fractured surface morphology was examined with field emission scanning electron microscopy, and correlated with the mechanical properties. The functionalized carbon nanotubes showed preferential accumulation in the PVB phase beyond 0.25 wt % loading. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43333.     

Synthesis and characterization of transparent alumina reinforced polycarbonate nanocomposite

Transparent nanocomposite films were fabricated by blending a concentrated nanocomposite formed by in-situ polymerization of polycarbonate in the presence of alumina nanowhisker with a high molecular weight polycarbonate. Polycarbonate was grafted to the alumina nanowhisker surface to improve nanofiller dispersion and load transfer to polymer matrix. Fourier transform infrared spectroscopy confirmed the functionalization of the nanowhisker with polycarbonate. Samples produced using functionalized alumina exhibited improved dispersion compared to the raw alumina nanowhiskers in the PC. Functionalization of alumina nanowhisker enhanced tensile properties (Young’s modulus and tensile strength) relative to the pure polycarbonate and blends produced with raw alumina nanowhisker. Additionally, the nanocomposite formed using in-situ polymerization showed small decreases in transparency in the visual range compared to the base polymer with increased absorption in the UV range. The effect of reaction temperature during in-situ polymerization on the properties of the nanocomposite was investigated. Higher reaction temperature resulted in improved dispersion and sharp increases in tensile modulus and shear strength.     

Enhanced mechanical and anisotropic thermal conductive properties of polyimide nanocomposite films reinforced with hexagonal boron nitride nanosheets

To attain thermally conductive but electrically insulating polymer films, in this study, polyimide (PI) nanocomposite films with 1–30 wt% functionalized hexagonal boron nitride nanosheets (BNNSs) were fabricated via solution casting and following imidization. The microstructures, mechanical and thermal conductive properties of PI/BNNS nanocomposite films were examined by taking account of the relative content, anisotropic orientation, and interfacial interaction of BNNS and PI matrix. The scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffractometry data revealed that BNNSs with hydroxy and amino functional groups have specific molecular interactions with PI matrix and they form stacked aggregates in the nanocomposite films with high BNNS loadings of 10–30 wt%. The tensile mechanical strength/modulus, thermal degradation temperatures, and thermal conductivity of the nanocomposite films were found to be significantly enhanced with increasing the BNNS loadings. For the nanocomposite films with 1–30 wt% BNNS loadings, the in-plane thermal conductivity was measured to be 1.82–2.38 W/mK, which were much higher than the out-of-plane values of 0.35–1.14 W/mK. The significant anisotropic thermal conductivity of the nanocomposite films was found to be owing to the synergistic anisotropic orientation effects of both BNNS and PI matrix. It is noticeable that the in-plane and out-of-plane thermal conductivity values of the nanocomposite film with 30 wt% BNNS were ~1.31 and ~3.35 times higher than those of neat PI film, respectively.     

Thermal,mechanical, and gas barrier properties of ethylene–vinyl alcohol copolymer‐based nanocomposites for food packaging films: Effects of nanoclay loading

For the application of single‐layer food packaging films with improved barrier properties, an attempt was made to prepare ethylene‐vinyl alcohol (EVOH) copolymer‐based nanocomposite films by incorporation of organically modified montmorillonite nanoclays via a two‐step mixing process and solvent cast method. The highly intercalated tactoids coexisted with exfoliated clay nanosheets, and the extent of intercalation and exfoliation depended significantly on the level of clay loadings, which were confirmed from both XRD measurements and TEM observations. It was revealed that the inclusion of nanoclay up to an appropriate level of content resulted in a remarkable enhancement in the thermal, mechanical (tensile strength/modulus), optical, and barrier properties of the prepared EVOH/clay nanocomposite films. However, excess clay loadings gave rise to a reduction in the tensile properties (strength/modulus/elongation) and optical transparency due to the formation of clay tactoids with a larger domain size. With the addition of only 3 wt % clay, the oxygen and water vapor barrier performances of the nanocomposite films were substantially improved by 59 and 90%, respectively, compared to the performances of the neat EVOH film. In addition, the presence of clay nanosheets in the EVOH matrix was found to significantly suppress the moisture‐derived deterioration in the oxygen barrier performance, implying the feasibility of applying the nanocomposite films to single‐layer food packaging films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40289.     

ABS nanocomposite films based on functionalized‐graphene sheets

Acrylonitrile‐butadiene‐styrene (ABS)/functionalized‐graphene nanocomposites were synthesized using the solution‐blending method in chloroform. A dispersion of graphite oxide was added to a solution of the ammonium salt of octadecylamine (C18) to form octadecylamine‐graphene (C18‐graphene), which was then used as a functionalized graphene in the preparation of ABS nanocomposite films. ABS nanocomposite films with different C18‐graphene contents (0–3 wt %) were compared in terms of their thermomechanical properties and morphology. Despite the relatively low C18‐graphene loadings studied, the nanocomposite films exhibited greatly improved thermomechanical properties compared with pure ABS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

Preparation and properties of single-walled carbon nanotubes/poly(butylene terephthalate) nanocomposites

A neat poly(butylene terephthalate) (PBT) polymer and functionalized single-walled carbon nanotubes (F-SWNTs)/PBT nanocomposite films were prepared by solution casting technique. The SWNTs were functionalized by acid treatment, which introduced carboxylic groups onto the SWNTs. The morphological studies showed that the F-SWNTs were embedded and dispersed well within the PBT polymer matrix. The POM study illustrated that a neat PBT showed Maltese-type spherulites. It was also observed that the size of neat PBT spherulites was larger than F-SWNTs/PBT nanocomposite spherulites, which might be due to the nucleation effect of F-SWNTs in the case of nanocomposites. The thermal stabilities and mechanical properties such as stress yield and moduli of F-SWNTs/PBT nanocomposites were enhanced as compared to neat PBT. The DSC study showed that the melting temperature (T _m) of PBT was slightly increased by addition of F-SWNTs. This increase in T _m might be due to the formation of compact structure, which was formed through different types of molecular interactions with addition of F-SWNTs. It was also found that initially the solvent (distilled water, kerosene, 2 M HNO₃ solution) uptake by neat PBT polymer and its nanocomposites increased gradually, which became steady after specific intervals for each sample. The results also exhibited that the solvent uptake of F-SWNTs/PBT nanocomposites was less than neat PBT.     

Application of paraffin and silver coated titania nanoparticles in polyethylene nanocomposite food packaging films

In this work, 3% and 5% TiO₂/Ag nanoparticles were dispersed in low‐density polyethylene through melt blending process, and subsequently nanocomposite films were prepared by hot pressing. Paraffin was used for the first time in this work as compatibilizer agent. The effect of TiO₂/Ag nanoparticle content, as well as compatibilizer dosage on the antimicrobial, morphological, mechanical, and optical performance of the nanocomposite films was investigated. Improved mechanical properties of the nanocomposite films were found on using paraffin as compatibilizer in comparison with the neat low‐density polyethylene (LDPE) films. The optical study results also showed that the addition of TiO₂/Ag to the LDPE films does not drastically change the film appearance other than making them more reddish. The fabricated nanocomposites presented in this study could be a suitable choice for food packaging (subject to further investigation of the food packaging behavior). The results showed that both TiO₂/Ag nanoparticle and compatibilizer are needed to prevent the bacteria growth in the film. The best result was obtained by using 5% nanoparticle and 4% paraffin compatibilizer where the bacteria growth rate was significantly reduced by 95%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45913.     

Drug release behavior of polyurethane/clay nanocomposite: Film vs. nanofibrous web

In the present study, polyurethane/clay nanocomposite films have been prepared by solvent casting method. Antiseptic drug chlorhexidine acetate was intercalated into montmorillonite clay and then incorporated into the polyurethane film. For comparison, the drug was also added directly into the polymeric dope used for film casting. In addition to that, nanofibrous web containing neat drug and drug loaded clay were fabricated using electrospinning technique. The emphasis of the study was on investigating the effect of drug intercalated into nanoclay vis‐à‐vis direct drug loading in the polymer on the drug release behaviour of polyurethane nanocomposite films as well as nanofibrous webs. The effect of morphology (film vs. nanofibrous web) on the drug release kinetics has also been discussed. It is observed that the nanoclay is acting as a sustained release carrier of drug, and nanofibrous web exhibits higher drug release rate as compared to the film. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40824.     

Synthesis and properties of the amino‐functionalized multiple‐walled carbon nanotubes/polyimide nanocomposites

The 1,6‐hexanediamine‐functionalized multi‐walled carbon nanotubes(a‐MWNTs)/polyimide(PI) nanocomposite films were prepared through in‐situ polymerization followed by mixture casting, evaporation, and thermal imidization. To increase the compatibility of carbon nanotubes with the matrix polyimide, a‐MWNTs was used as the filler. According to the results, a‐MWNTs were homogeneously dispersed in the nanocomposite films. With the incorporation of a‐MWNTs, the mechanical properties of the resultant films were improved due to the strong chemical bonding and interfacial interaction between a‐MWNTs and 4,4′‐oxydiphthalic anhydride(ODPA)/4,4′‐Oxydianiline(ODA) polyimide matrix. The thermal stability of the a‐MWNTs/polyimide nanocomposite was also improved by the addition of a‐MWNTs. The electrical tests showed a percolation threshold at about 0.85 vol% and the electrical properties were increased sharply. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of graphene nanoplatelets presence on the morphology,structure, and thermal properties of polypropylene in fiber melt‐spinning process

Melt spinning of graphene nanoplatelets (GnPs)‐polypropylene (PP) nanocomposite fibers are reported for the first time. PP/GnPs fibers were spun with a pilot‐plant spinning machine with varying concentration of GnPs by mixing PP/GnPs masterbatch with PP. The effect of inclusion of GnPs on the morphology and crystalline structure of PP fibers was investigated. The thermal stability of the fibers was also evaluated by thermogravimetric analysis. The light microscopy images showed that the GnPs are uniformly distributed over the PP matrix. The differential scanning calorimetry (DSC) results revealed that presence of GnPs affects both the melting and crystallization behaviors. The melting peaks of PP/GnPs nanocomposite fibers were broader than that of neat PP fibers, indicating a broader crystal size distribution in PP/GnPs nanocomposite fibers as compared to the neat PP fibers. Besides, an obvious increment in the crystallization peak temperature was observed in GnPs‐PP nanocomposite fibers. The wide‐angle X‐ray diffraction spectra (WAXD) results showed that the crystal type of nanocomposite fibers did not change and was still the α‐monoclinic crystal form. Moreover, the morphology of spherulites demonstrated that GnPs increased the nucleation sites in the nanocomposite fibers which in turn restricted the crystal growth of PP chains. This finding supported the DSC and WAXD results. Activation energies were calculated by Horowitz and Metzger's method as 77.87 and 105.41 kJ/mol for neat PP and PP/0.2 wt% GnPs fibers, respectively, suggesting an increase in the thermal stability of GnPs‐PP nanocomposite fibers. POLYM. COMPOS., 36:367–375, 2015. © 2014 Society of Plastics Engineers     

PE-LD/硅烷偶联剂改性石墨烯复合薄膜的制备及性能表征

将硅烷偶联剂KH-560接枝到氧化石墨烯上制得KH-560改性氧化石墨烯（KGO）,通过水合肼还原得到KH 560改性石墨烯（KG）,最后将KG和石墨烯（G）分别与低密度聚乙烯（PE-LD）熔融共混、中空吹塑成PE LD/KG复合薄膜和PE-LD/G复合薄膜。对样品的结构、形貌、光学性能、阻透性能、热性能和力学性能等进行表征。结果表明,KH-560成功接枝到KG上;KG无序度增加,KG的层间距比G增加约80 %;KG在PE-LD中分散均匀,团聚较少;G对复合薄膜的光学性能和阻透性能的增强效果优于KG;而KG对复合薄膜的热性能和力学性能的改善明显优于G;当KG的含量为0.5 %（质量分数,下同）时,PE-LD/KG复合薄膜的结晶度和弹性模量分别比纯PE-LD薄膜提高了8.4 %和63.9 %。     

Microstructure and crystallography in microcellular injection‐molded polyamide‐6 nanocomposite and neat resin

The effects of adding nanoclay to polyamide‐6 (PA‐6) neat resin, and the effects of processing parameters on cell density and size in microcellular injection‐molded components were investigated. In addition, the crystal sizes, structures, and orientation were analyzed with the use of x‐ray diffraction (XRD) and a polarized optical microscope. The standard ASTM D 638‐02 tensile bars for the analyses were molded according to a fractional four‐factor, three‐level, L9 Taguchi design of experiment (DOE) with varying melt temperature, injection speed, supercritical fluid (SCF) concentration, and shot size. It was found that the presence of montmorillonite (MMT) nanoclay greatly reduced the size of the cells and crystals, but increased their density in comparison with neat resin processed under identical molding conditions. In addition, at the sprue section downstream of the machine nozzle, cell size gradually decreased from the part center toward the skin for both the neat resin and the nanocomposite. It was also found that shot size was the most important processing parameter for both the neat resin and nanocomposite in affecting cell density and size in microcellular injection molding components. Weakly preferred crystal orientations were observed on the surface of microcellular injection‐molded PA‐6/MMT tensile bars. Finally, the addition of nanoclay in PA‐6 neat resin facilitated the formation of γ‐phase crystals in the molded components. Polym. Eng. Sci. 45:52–61, 2005. © 2004 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.     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry