Experimental Investigation of Cellulose/Silver Nanocomposites Using In Situ Generation Method

Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO₃ solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO₃. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.     

Effect of Sequential Mixing and Compounding Conditions on Cellulose Acetate/Layered Silicate Nanocomposites

Injection molded nanocomposites have been successfully fabricated from cellulose acetate (CA), eco-friendly triethyl citrate (TEC) plasticizer, and organically modified clay with and without maleic anhydride grafted cellulose acetate butyrate (CAB-g-MA) as a compatibilizer. The effects of processing conditions such as mixing methods, pre-plasticizing times, extruder retention times (RT) and addition of compatibilizer on the performance of these nanocomposites have been evaluated. The cellulosic plastic with CA/TEC (80/20 wt%) was used as the polymer matrix for nanocomposite fabrication. The morphologies of these nanocomposites were evaluated through X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies. The mechanical properties of the nanocomposites were measured and have been correlated with the XRD and TEM observations. From all of the sequential mixing methods used, powder–powder mixing leads to the most transparent nanocomposites. Cellulosic plastic-based nanocomposites obtained using increased pre-plasticizing times and RT showed better exfoliated structures. In the system containing compatibilizer, the minimum retention time required for obtaining almost completely exfoliated hybrid nanocomposites was shorter than in the system without compatibilizer.     

Effect of Varying Filler Concentration on Zinc Oxide Nanoparticle Embedded Chitosan Films as Potential Food Packaging Material

Prevailing scenario of non-biodegradable food packaging materials worldwide was the motivation for this research. More than half of the packaging materials used today are non-biodegradable and lack one or the other feature that keeps it from being an ideal food packaging material. Based on the current need of food grade packaging materials, the present study illustrates the amelioration of the properties of biodegradable chitosan films with the incorporation of zinc oxide (ZnO) nanoparticles in varying concentration. The ZnO nanoparticles (ZnONPs) used as fillers in the chitosan films were synthesized by supersaturation method. They were characterized using UV–visible spectrophotometry, X-ray diffraction and field emission scanning electron microscopy (FE-SEM). The particles were observed to be around 100–200 nm in size. The chitosan films with varying concentration of ZnONPs were synthesized and characterized using Fourier transform infrared spectroscopy and FE-SEM. The films were studied for their thermal stability, water vapor transmission rate (WVTR) and mechanical properties. The thermal stability, as determined by Thermo Gravimetric Analysis and Differential Scanning Calorimetry increased slightly with increasing percentage of embedded ZnONPs while a substantial decrease in WVTR was observed. Mechanical properties also showed improvements with 77% increment in tensile modulus and 67% increment in tensile strength. The antimicrobial activity of the films was also studied on gram positive bacterium Bacillus subtilis (B. subtilis) and gram negative bacterium Escherichia coli (E. coli) by serial dilution method. A twofold and 1.5-fold increment in the antimicrobial activity was observed for B. subtilis and E. coli, respectively, with increased ZnONPs concentration in the films from 0(w/w) to 2%(w/w). Films thus prepared can prove to be of immense potential in the near future for antimicrobial food packaging applications.     

Preparation and Properties of Thermoplastic Starch/Montmorillonite Nanocomposite Using N-(2-Hydroxyethyl)formamide as a New Additive

N-(2-Hydroxyethyl)formamide (HF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite nanocomposite (TPS/MMT). Here, HF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among HF, starch and MMT was proven by Fourier-transform infrared (FT-IR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposite was formed. The crystallinity of corn starch, MMT, HF-plasticized TPS (HTPS) and TPS/MMT nanocomposite was characterized by X-ray diffraction (XRD). Thermal stability of HTPS and TPS/MMT was determined by thermogravimetric analysis (TGA). The water resistance of TPS/MMT nanocomposite increased compared with that of pure HTPS. Tensile strengths of TPS/MMT nanocomposites were higher than those of HTPS, but just the reverse for elongations at break.     

The Effect of Acetylation on the Hydrolytic Degradation of PLA/Clay Nanocomposites

In this study, the hydrolytic degradation of Poly(lactic acid) (PLA) and acetylated PLA (PLA-Ac)–clay nanocomposites were investigated. The organo clay was obtained by ion exchange reaction using cetyl tri methyl ammonium bromide (CTAB). Nanocomposites containing 2, 5 and 8% mass ratio of organo clay (CTAB-O) were prepared. PLA and its organo clay nanocomposites were characterized by scanning electron microscope (SEM), thermo gravimetric analysis (TGA) and X-ray diffraction (XRD) to determine the morphology before and after hydrolytic degradation. Fourier transform infrared (FTIR) analyses of PLA and PLA-Ac were also obtained. The hydrolytic degradation of polymers and their composites were investigated in the phosphate buffered saline solution (PBS). The results showed that controlled hydrolytic degradation was observed in the samples with end group modification of PLA. While weight loss of PLA films was 28%, that of PLA-Ac films was 18% after 60 days degradation time. The weight loss was obtained as 29.5 and 25.5% for PLA-5 wt% organo clay (PLA/5CTAB-O) and PLA-Ac-5 wt% organo clay (PLA-Ac/5CTAB-O) nanocomposites films, respectively. It was also observed that thermal degradation of PLA-Ac was much more than that of PLA. Hydrolytic degradation increased depending on organo clay content. The end group modificated PLA results in controlled hydrolytic degradation. While hydrolytic degradation in polymer films occurred as surface erosion, bulk erosion was observed in composite films.     

Synthesis and Properties of Biodegradable Poly(vinyl alcohol)/Organo-nanoclay Bionanocomposites

Biodegradable nanocomposites comprising of biodegradable polymers and bioactive organically modified layered silicates commonly reveal extremely enhanced mechanical and various other properties when compared to those of virgin polymers. This work was undertaken with a view to preparation of polymer bionanocomposites consisting of biodegradable poly(vinyl alcohol) (PVA) and organo-nanoclay. Cloisite Na⁺ and ammonium salt of l-isoleucine amino acid was used for the preparation of the novel chiral organo-nanoclay via an intercalation reaction in an aqueous solution. PVA/organo-nanoclay bionanocomposites of various compositions were created through the solution intercalation method by ultrasound-assisted technique. The resulting novel materials were characterized by X-ray diffraction and Fourier transform infrared spectroscopy techniques. Thermogravimetric analysis (TGA) and UV/vis spectroscopy were applied to test the properties of PVA bionanocomposites. TGA indicate that the thermal stability is enhanced distinctly, without a sacrifice in optical clarity. The improvement of thermal properties was attributed to the homogeneous and good dispersion of organo-nanoclay in polymeric matrix and the strong hydrogen bonding between O?CH groups of PVA and the oxygen atoms of silicate layers or carbonyl group as well as OH group of intercalated amino acid. The morphology of the organo-nanoclay and PVA bionanocomposites was examined by scanning electron microscopy and transmission electron microscopy techniques. Uniform distribution of clay due to intimate interaction between clay and polymer appears to be the cause for improved properties.     

Enhancement of Tensile Strength and Flexibility of Polycaprolactone/Tapioca Starch Blends by Octadecylamine Modified Clay

Polycaprolactone/tapioca starch/octadecylamine modified clay (OMMT) nanocomposites were successfully prepared by melt blending. X-ray diffraction and transmission electron microscopy (TEM) of the products showed that they are nanocomposites of a mixture intercalated and exfoliated types. In addition, the TEM also revealed that the OMMT layers are homogeneously distributed in the polymer matrix. The presence of 1 php of OMMT improved the compatibility of the polymers in the blends which consequently increased the tensile strength of the blend of more than 60% and elongation at break of more than 1,000%.     

A Study of Physicomechanical and Morphological Properties of Starch/Poly(vinylalcohol) Based Films

Starch/Poly(vinylalcohol) blends in two different ratios (60:40 and 50:50) were prepared with glycerol as a plasticizer. Films were cast by a solution casting method. One set of films were filled with 10 wt% of unmodified bentonite clay and another set of films were crosslinked with epichlorohydrin in an alkaline medium. The prepared film samples were subjected to X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), mechanical characterization and scanning electron microscope (SEM). Significant changes in the tensile properties were observed depending on the different chemical constituents of the films. The presence of clay and crosslinking with epichlorohydrin were both found to have considerable effect on the morphology and mechanical property of the films. The SEM investigations, XRD analysis and FTIR studies revealed the interaction between the various chemical components of the films.     

Mechanical and Thermal Properties of PLLA/PCL Modified Clay Nanocomposites

Poly(l-lactic acid) (PLLA)/poly(caprolactone) (PCL) and two types of organoclay (OMMT) including a fatty amide and ocatdecylamine montmorillonite (FA-MMT and ODA-MMT) were employed to produce polymer nanocomposites by melt blending. Materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties were also investigated for these nanocomposites. The nanocomposites showed increasing mechanical properties and thermal stability. XRD results indicated that the materials formed nanocomposites. SEM morphology showed that increasing content of OMMT reduced the domain size of phase separated particles. TEM outcomes have confirmed the intercalated type of nanocomposite. Additionally, a solution casting process has been used to prepare these nanocomposites and characterized to compare these results with the above process.     

The Influence of Artificial Photodegradation on Properties of Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate)(PHBV)/Graphite Nanosheets (GNS) Nanocomposites

The potential use of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/graphite nanosheets (GNS) as a biodegradable nanocomposite has been explored. PHBV/GNS nanocomposites films were prepared by solution casting at various concentrations of GNS—0.25, 0.50 and 1.00 wt% GNS. The films were exposed to artificial ultraviolet radiation (UV) during 52 h. The effect of GNS on PHBV photodegradation was investigated and compared to neat PHBV film. The artificial photodegradation induced changes in physical (weight loss), chemical carbonyl index by Fourier transform infrared spectroscopy, thermal degree of crystallinity and melting temperature by differential scanning calorimetry and morphological scanning electron microscopy characteristics. Based on the results obtained from aforementioned analyzes it was verified that GNS inhibits the oxidative degradation of PHBV matrix.     

New Biopolymer Nanocomposite of Starch-Graft Polystyrene/Montmorillonite Clay Prepared Through Emulsion Polymerization Method

Starch-g-polystyrene (Starch-g-PS)/Montmorillonite nanocomposites were prepared via free-radical graft copolymerization of styrene and starch in the presence of montmorillonite clay, by emulsion polymerization method using potassium persulfate (KPS) as an initiator/catalyst and sodium dodecylbenzensulfonate (SDBS) as an emulsifier. The nanocomposites with different clay content 0, 2.5, 5.0, 7.5 and 10 weight percent of starch were prepared and the changes in layer-stacked structures of the clay particles in the resulted nanocomposite compounds were examined by using of X-ray diffraction and FT-IR spectroscopy. Finally the thermal degradation behavior and morphology of nanocomposites were studied using thermal gravimetric analysis (TGA) and SEM, respectively.     

Preparation and Properties of Starch/Nanosilicate Layer/Polycaprolactone Composites

Starch nanocomposites have been prepared using mineral clay. Montmorillonite, kaolin and a surface-modified montmorillonite by dimethyl (hydrogenated tallow alkyl) ammonium cation were used. Starch-g-PCL nanocomposites have been prepared with graft polymerization through in situ ring-opening polymerization of ε-caprolactone in the presence of starch, Sn(Oct)₂ (Tin(II) 2-ethyl hexanoate) as an initiator/catalyst and silicate layers. In fact, the related composites were prepared in solution method, bulk polymerization and in situ polymerization methods with introducing the mineral clay. The effect of kind of clay on d-spacing of silicate layers was investigated and the obtained nanocomposites were analyzed using X-ray diffraction. The obtained compounds were characterized by Fourier transform infrared (FT-IR). Morphology of the prepared nanocomposites was investigated using scanning electron microscopy and DSC enhanced the study of thermal behaviour of the prepared composite compounds.     

<Emphasis Type="Italic">Mesua ferrea</Emphasis> L. Seed Oil Based Highly Branched Environment Friendly Polyester Resin/Clay Nanocomposites

To develop a high performance environment friendly material, highly branched polyester/clay nanocomposites have been prepared from Mesua ferrea Linn seed oil-based polyester resin and hydrophilic bentonite nanoclay. The prepared nanocomposites were characterized by Fourier transform infra-red spectroscopy, X-ray diffractometer, scanning electron microscope, transmission electron microscope and rheological studies. Partial exfoliation of clay layers by the polymer chains with good interfacial interactions was observed in the nanocomposites. The formation of delaminated nanocomposites was manifested through the enhancement of tensile strength, scratch hardness, chemical resistance, impact resistance, thermostability, etc. The results show enhancement of three times in tensile strength and 18 °C in thermostability by inclusion of 5 wt% nanoclay as compared to the pristine polymer. By the influence of 5 wt% nanoclay four times enhancement in elongation at break as compared to the pristine polymer was noticed. Thus these nanocomposites have the potential to be used in many advanced applications.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Study of fine sediments for making lightweight aggregate.

The objective of this study was to investigate the recycling of the fine sediments of Shih-Men Reservoir to manufacture lightweight aggregate. By qualitative and quantitative analysis of the fine sediment and sintered aggregate through soil test, X-ray fluorescence, X-ray diffraction and scanning electron microscopy, a strategy of recycling fine sediment as aggregate for other similar material is proposed. The test results indicate that such fine sediment can be classified as low plastic clay, and clay of such chemical composition is located in the Riley's 'area of bloating'. The particle density of sintered lightweight aggregate decreases when the sintering temperature increases especially above 1200 degrees C due to phase transformation and formation of a vitrified layer on the surface through subsequent dehydration, bloating and collapsing stages. Our findings show that the fine sediment of Shin-Men Reservoir could be a suitable raw material for making expanded lightweight aggregate sintered at 1200 to 1300 degrees C for 10 to 12 min by a programmable furnace and a diffusion process.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Water Transport in Polylactide and Polylactide/Montmorillonite Composites

Polylactide–montmorillonite composites were fabricated by melt-blending followed by compression molding, and water permeability of the composites was studied by both experiments and theoretical models. The water permeation in composites decreases with increasing concentration of montmorillonite. Specifically, at a concentration of 10 wt% of montmorillonite, the water permeation is 34 % less than in the neat polymer. Transmission electron microscopy (TEM) and wide-angle X-ray scattering (WAXS) results show that most of the montmorillonite particles are well-dispersed and randomly exfoliated in the polymer matrix. A fit of theoretical models to the permeation data estimates that montmorillonite platelets are mostly exfoliated in the polymer matrix and oriented randomly, which matches with results from WAXS and TEM.     

Non-isothermal Crystallization Behaviors of Polyvinyl alcohol/Hydroxyethyl Cellulose Blend Films

In this work, polyvinyl alcohol/hydroxyethyl cellulose (PVA/HEC) blend films were fabricated by solution casting and the crystalline morphology as well as non-isothermal crystallization kinetics of the blends was investigated detailedly with polarized optical microscopy, X-ray diffraction and differential scanning calorimetry. With fixed cooling rate, the crystallization time for PVA/HEC was less than that for neat PVA. The crystallization peak temperature of PVA/HEC decreased first and then increased with the increase of HEC. With higher cooling rate, the crystallinity and crystallization time decreased. It worth noting that large spherocrystal with a size of 35 μm was observed by polarized optical microscopy for PVA/HEC blends for the first time.     

Synthesis and Characterization of Novel Heat Stable and Processable Optically Active Poly(Amide–Imide) Nanostructures Bearing Hydroxyl Pendant Group in an Ionic Green Medium

Ionic liquids (IL)s have been recognized as ‘green’ alternatives to the organic solvents in a range of synthesis, catalysis and electrochemistry due to their unique chemical and physical properties. In this investigation, a series of organosoluble, thermally stable and optically active hydroxyl-containing poly(amide–imide)s (PAI)s were prepared via polycondensation reaction of an aromatic diamine, 3,5-diamino-N-(4-hydroxyphenyl)benzamide (4), and different chiral amino acid-based diacids (3a–3e) in the presence of molten tetrabutylammonium bromide as a molten IL and triphenyl phosphite under classical heating method. This process is safe and green since toxic and volatile organic solvents such as N-methylpyrrolidone (NMP) and N,N′-dimethylacetamide (DMAc) were eliminated. The resulting new polymers were obtained in good yields with inherent viscosities ranging between 0.23 and 0.54 dL g^?1 and were characterized by Fourier transform infrared spectroscopy, specific rotation, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis, elemental analysis, and in some cases by ¹H-NMR techniques. The FE-SEM micrographs and XRD showed that the synthesized PAIs were nanostructured and amorphous polymers. The effect of ultrasonic irradiation on the size of polymer particles was also investigated and the results showed that the size of polymer nanoparticles after ultrasonication became smaller than the size of them, before ultrasonic radiation. All of the polymers were readily soluble in many organic solvents such as N,N′-dimethyl sulfoxide, DMAc and NMP.     

Cellulose and Nanocellulose from Maize Straw: An Insight on the Crystal Properties

In this work cellulose was extracted from corn/maize straw (Zea mays) by means of an environmental-friendly multistep procedure involving alkaline treatment and a totally chlorine-free bleaching. This multistep procedure efficiently removed lignin and hemicelluloses. The pulp resulting from each step was characterized by attenuated total reflectance fourier transform infrared spectroscopy (ATR-FTIR). The optimum pulping time (time of alkaline treatment) was determined by means of thermogravimetric analysis. The extracted cellulose is highly crystalline as verified by X-ray diffraction. The partial acid hydrolysis with sulfuric acid led to the isolation of cellulose whiskers in aqueous suspension as confirmed by light scattering and transmission electron microscopy. The depolarization ratio value of these nanocrystals is the same as that determined for cotton whiskers, showing that this ratio does not depend on the cellulose source. The maize whiskers are arranged laterally in bundles with average thickness around five times that of the crystallite.