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.     

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.     

<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.     

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%.     

Thermal and Biodegradable Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Poly(ε-Caprolactone) Compounded with Functionalized Organoclay

Poly(l-lactide) (PLLA)/Poly(ε-caprolactone) (PCL) blends were compounded with commercially available organoclay Cloisite 25A (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Functionalized Organoclay (F-C25A). The silicate layers of PLLA/PCL/F-C25A were exfoliated to a larger extent than PLLA/PCL/C25A. Incorporation of the epoxy groups on C25A improved significantly mechanical properties of PLLA/PCL/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PCL/F-C25A as compared with that in PLLA/PCL/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that the nanocomposites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. The biodegradability of the neat PLLA/PCL and corresponding nanocomposite was studied under compost, and the rate of biodegradation of PLLA/PCL increased after nanocomposite preparation.     

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.     

Biodegradable nanocomposites based on poly(butylene succinate)/organoclay

In this work, we try to incorporate the inorganic system into the biodegradable polymers to compose an organic/inorganic polymer hybrid. Various nanocomposites of poly(butylene succinates) (PBS) with different ratios of organically modified layered silicates (OMLS) prepared by solution blending were investigated. The OMLS used for the preparation of nanocomposites were functionalized ammonium salts modified montmorillonite. The effects of OMLS on the nanocomposites were investigated by XRD, TEM, DMA and TGA in the aspect of the d-spacing of clay, mechanical and thermal properties. Interestingly, all these nanocomposites exhibited improved properties when compared with the pristine PBS sample. XRD indicates that the layers of clay were intercalated by the modifiers, and the interlayer distance of organoclay in the nanocomposites could be extended to about 29.4 Å. Moreover, the thermal stability of the nanocomposites was enhanced by the addition of organoclay via TGA study, closely related to the organoclay content in the PBS matrix. DMA data shows that the storage and loss moduli were concurrently enhanced by the addition of organoclay as compared to the pristine PBS sample. Moreover, the glass transition temperatures also increased about 5 to 20 °C (from DMA, peak of tanδ) for the various organoclay-containing samples. The enhanced mechanical and thermal properties can be achieved from these organoclay modified-nanocomposites.     

Improvement of Synthesis and Dielectric Properties of Polyurethane/Mt-QASs<Superscript>+</Superscript> (Novel Synthesis)

Polyurethane-based nanocomposites were prepared and their dielectric properties were characterized. Polyurethane (PU) composites were prepared with different organoclay content (1, 3, 5, and 10 wt% for all cases). The composites included quaternary ammonium salts such as 1-methyl-di-octyl-1 phenyl ammonium iodide (QAS-1), 1-methyl-di-nonyl-1 phenyl ammonium iodide (QAS-2), and 1-methyl-di-dodecyl-1 phenyl ammonium iodide (QAS-3) which were newly synthesized for modification of Na⁺-montmorillonite. Addition of aluminum silicate enhanced the dielectric properties at a constant concentration. Dielectric constants of nanocomposites compounded with 3 %- and 5 %-organoclay were close in value. The characterization of PU/organoclay composites was carried out using Fourier transform infrared and X-ray diffraction.     

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.     

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/Organomodified Montmorillonite Nanocomposites for Potential Food Packaging Applications

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is a versatile, biobased and biodegradable copolymer from the family of polyhydroxyalkanoates. This study aims to further ameliorate its properties in order to enhance its applicability for food packaging purposes through preparation of organomodified montmorillonite clay (OMMT) nanocomposites. Nanocomposites based on pure PHBHHx as well as commercial PHBHHx granulate, after a previous dry-mixing with OMMT in concentrations of 1, 3, 5 and 10 wt%, were prepared using melt blending and compression molding. Investigation of the samples showed well dispersed nanofiller and highly intercalated nanocomposites, resulting in a continuous decrease in gas permeability, lowering O₂, CO₂ and water vapor permeability with about 5–7 % and approximately 40 % at OMMT concentration of 1 and 10 wt%, respectively. Besides gas permeability, other properties were affected as well. Thermal stability of the samples increased gradually up to 5 wt% nanofiller, but was reduced at 10 wt%. In order to investigate the effects of OMMT and molecular weights on PHBHHx crystallization, nanocomposites were also produced by solvent-casting and compared to those obtained by melt-blending. Crystallization was retarded, because of severe lowering of molecular weight due to processing-induced chain scission, catalyzed by OMMT moisture. However, this reduction was counteracted for a large part by using commercial PHBHHx granulate, which has shown better crystallization properties. The samples were rendered increasingly more brittle, displaying higher Young’s modulus and severely reduced elongation at break. From this study it appeared that, upon viewing all affected properties as a whole, the sample based on commercial PHBHHx and containing 3 wt% OMMT shows most promise for possible applications, however further research must be performed in order to exploit their fullest potential.     

Preparation and characterization of sorbents prepared from ash (waste material) for sulfur dioxide (SO2) removal

Sorbents synthesized from various types of ash (coal fly ash, coal bottom ash, oil palm ash, and incinerator ash) for flue gas desulfurization were investigated. The sorbents were prepared by mixing the ashes with calcium oxide and calcium sulfate using the water hydration method. The effects of various sorbent preparation variables, such as the hydration period, the ratio of calcium oxide to ash, and the amount of calcium sulfate, on the Brunauer-Emmett-Teller (BET)-specific surface area of the resulting sorbent were studied using a two-level full factorial design. The surface area of the sorbents obtained range from 15.4 to 122.1m²/g. Regression models were developed to correlate the significant variables to the surface area of the sorbents. An analysis of variance (ANOVA) showed that the model was significant at a confidence level of 95%. It was found that apart from all the individual variables studied, interactions between variables also exerted a significant influence on the surface area of the sorbent. From the activity test results, it was found that sorbents prepared from coal fly ash and oil palm ash have the highest SO₂ absorption capacity. Scanning electron microscope (SEM) analysis showed that the sorbent was composed of a compound with a high structural porosity, while an X-ray diffraction spectrum showed that calcium aluminum silicate hydrate compounds are the main products of the hydration reaction.     

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.     

Study of Thermo-Mechanical and Morphological Behaviour of Biodegradable PLA/PBAT/Layered Silicate Blend Nanocomposites

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) blend nanocomposites were prepared using melt blending technique followed by compression moulding. The blend nanocomposites were prepared with a variation of PBAT loading along with maleic anhydride and benzoyl peroxide ranging from 5 to 20 wt% along with two different commercially available nanoclays cloisite 93A and cloisite 30B (C30B) at 3 wt% loading. The maleic anhydride and benzoyl peroxide were used during the melt blending of the blend nanocomposites as a compatibilizer and as an accelerator respectively. Maleic anhydride used to enhance the compatibility of the PLA/PBAT blend and as well as the uniform adhesion of the nanoclays with them. The properties and characterizations of PLA matrix and the PLA/PBAT blend nanocomposites have been studied. The tensile strength, % elongation and impact strength increased with the preparation of PLA/PBAT blend nanocomposites as compared with PLA matrix. PLA/PBAT/C30B blend nanocomposites exhibited optimum tensile strength at 15 wt% of PBAT loading. Differential scanning calorimetry and thermogravimetric analysis also showed improved thermal properties as compared with virgin PLA. The wide angle X-ray diffraction studies indicated an increase in d-spacing in PLA/PBAT/C30B blend nanocomposite thus revealing intercalated morphology.     

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.     

Some Investigations on the Nylon 6/Zn Composite Material Obtained by Simultaneous Anionic Polymerization-Molding Process

This study is concerned with the behavior of samples based on nylon 6/zinc (Ny6/Zn) composite material in high salinity water that contains NaCl (3.5 wt%) and in aqueous solution of HCl (0.5 N and 1 N). The samples were obtained from parts prepared by in situ anionic ring-opening polymerization of ?-caprolactam (CL) in the presence of zinc (Zn), as filler (15 wt%) using the rotational molding technique. This type of composite was evaluated by the testing of swelling degree, structural modifications, evolution of hydrogen and electrochemical behavior. The properties of Ny6/Zn composite material have ascertained through the combined use of more analysis methods: attenuated total reflectance Fourier transform infrared spectroscopy, wide-angle X-ray diffraction technique, scanning electron microscopy, swelling and electrochemical measurements. It was revealed that regarding swelling behavior the Ny6 matrix has an important role while Zn filler contributes especially to the (electro)chemical corrosion.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

Biobased Epoxy/Layered Silicate Nanocomposites: Thermophysical Properties and Fracture Behavior Evaluation

The biobased epoxy containing epoxidized linseed oil (ELO) and its clay nanocomposites were processed with an anhydride curing agent. The certain amount of diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO. The selection of the DGEBF, ELO, an anhydride curing agent, and organo-montmorillonite clay resulted in an excellent combination, to provide new biobased epoxy/clay nanocomposites showing high elastic modulus, high glass transition temperature, and high fracture toughness with larger amount of ELO. Izod impact strength was almost constant while changing the amount of ELO. This is a promising result for future applications in different engineering industries.     

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial,UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance (¹HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.     

Cardanol Polymerization Under Acid Conditions By Addition And Condensation Reactions

Cashew nut shell liquid (CNSL) is a byproduct of the cashew nut industry and consists predominantly of phenolic compounds that have an side chain with different degrees of unsaturation. Cardanol, one of these components, is biodegradable and widely available. Studies have revealed several polymerization reactions involving cardanol. However, the mechanisms and detailed structures of polymerization reactions have not been explored, although the final product shows different applications. In this work, we evaluated the mechanism and the products structure of the reaction of cardanol with: (i) boron trifluoride diethyl etherate (BF₃O(CH₂CH₃)₂), and (ii) formaldehyde. The characterizations were performed by FTIR, ¹H NMR, SEC and TGA. The results show that the reaction of cardanol with aldehyde produces the expected like-comb structure with a long hydrocarbon pendent chain. Nevertheless, the reaction of cardanol with BF₃O(CH₂CH₃)₂ can exhibits a more complex structure since it was identified aromatic ring linkages, besides the expected polymerization through C=C.     

Predicted performance of clay-barrier landfill covers in arid and semi-arid environments

Conventional landfill cover systems for municipal solid waste include low-permeability compacted clay barriers to minimize infiltration into the landfilled waste. Such layers are vulnerable in climates where arid to semi-arid conditions prevail, whereby the clay cover tends to desiccate and crack, resulting in drastically higher infiltration, i.e., lower cover efficiency. To date, this phenomenon, which has been reported in field observations, has not been adequately assessed. In this paper, the performance of a cover system solely relying on a clay barrier was simulated using a numerical finite element formulation to capture changes in the clay layer and the corresponding modified hydraulic characteristics. The cover system was guided by USEPA Subtitle-D minimum requirements and consisted of a clay layer underlying a protective vegetated soil. The intrinsic characteristics of the clay barrier and vegetative soil cover, including their saturated hydraulic conductivities and their soil-water characteristic curves, were varied as warranted to simulate intact or "cracked" conditions as determined through the numerical analyses within the proposed methodology. The results indicate that the levels of percolation through the compromised or cracked cover were up to two times greater than those obtained for intact covers, starting with an intact clay hydraulic conductivity of 10(-5)cm/s.