Effect of Solvent Composition on Porosity,Surface Morphology and Thermal Behavior of Metal Alginate Prepared from Algae (<Emphasis Type="Italic">Undaria pinnatifida</Emphasis>)

Alginates, extracted from algae are linear unbranched polymers containing β-(1→4)-linked d-mannuronic acid (M) and α-(1→4)-linked l-guluronic acid (G) residues. The conversion of alginic acid into the metal alginate is confirmed using FTIR spectroscopy. Asymmetric and symmetric stretching of free carboxyl group present in metal alginate occurs almost at the same position in various solvent compositions. Total intrusion volume of metal alginate prepared in propanol (0.0742 mL/g) is greater compared to those in ethanol (0.0648 mL/g) and methanol (0.0393 mL/g) as solvent. Surface morphology as well as porosity and pore size distribution of metal alginate are greatly influenced by solvent. It can be seen from thermal analysis results that calcium alginate prepared using different solvent compositions started decomposing at 100 °C, but rapid degradation started around 200 °C. The results showed a stepwise weight loss during thermal sweep, indicating different types of reactions during degradation. First and second step of rapid degradation was situated around 200–300 and 300–550 °C, respectively; whereas the final step is situated around 550–650 °C. The trend of degradation was similar for all the solvents, although the amount of final residue varied from one solvent to another. At the same time, lower thermal stability was also observed with higher heating rates. Additionally, a kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive first order reactions.     

Optimization of two-step catalyzed biodiesel production from soybean waste cooking oil

An acid–base-catalyst-based two-step biodiesel production experiment from soybean waste cooking oil was carried out to identify which parameter is the most influential among the experimental parameters by using the Taguchi method. Heterogeneous catalysts were used to avoid a water-consuming homogeneous catalyst removal process. Ferric sulfate and calcium oxide were used as acid and base catalysts, respectively, for the heterogeneous reaction. Reaction time and methanol-to-triglyceride mole ratio were significant factors. The optimum parameters for step 1 (acid esterification) were 4 h of reaction time, 4 wt. % of ferric sulfate amount, a 16:1 methanol to triglyceride mole ratio, and 400 rpm of mixing speed, respectively. For the transesterification step, the most influential factor was reaction time, and CaO amount was significant as well. On the other hand, the mole ratio of methanol and oil was relatively less significant. Optimum parameters were 3 h of reaction time, 2 wt. % of CaO, and a 12:1 methanol to triglyceride mole ratio with mixing speed at 400 rpm in this experimental range. Under the optimum conditions, waste cooking oil with 5.27 mg KOH/g of acid value was converted into crude biodiesel by a two-step process with fatty acid methyl ester content reaching 89.8 % without any further post-purification.     

Preparation of Alginic Acid and Metal Alginate from Algae and their Comparative Study

Alginic acid and metal alginates are prepared from fresh algae using extraction method. A FTIR spectrum indicates that alginic acid is converted into the metal alginate. Comparing calcium and cobalt alginates, asymmetric stretching of free carboxyl group of calcium alginate at 1630 cm⁻¹ is shifted to 1585 cm⁻¹ in cobalt alginate, due to the change of charge density, radius and atomic weight of the cation, creating a new environment around the carbonyl group. The strong exothermic peak of alginic acid in DSC thermogram indicates the decomposition of biopolymer, whereas strong exothermic peak of metal alginate in DSC thermogram attributed to the decomposition of biopolymer and formation of respective carbonate. Based on DSC study, the decomposition of cobalt alginate occurs at higher temperature comparing to those of sodium and calcium alginate, which may conclude into the higher stability of cobalt alginate. TGA results reveal that, cobalt alginate is more stable than calcium and sodium alginate at 300 °C temperature. Surface morphology (at same magnification), as well as porosity (%) and pore size distribution results change with metals present in different metal alginates.     

Formulation and Characterization of Biodegradable Packaging Film Derived from Potato Starch &; LDPE Grafted with Maleic Anhydride—LDPE Composition

There is a paradigm shift from non renewal resources to renewable resources in view of problems of disposal of plastic products after their life cycle. This paper deals with the approach, preparation and product properties of polymer prepared by using polysaccharide based biodegradable polymer. Basic material has been prepared by mixing LDPE, LDPE-g-mA (LDPE grafted with (0.5%) maleic anhydride (1:1)) containing a polar group in the LDPE backbone. Prepared basic material has been compounded in twin screw extruder with 0, 2.5, 5.0, 7.5, 10.0, 12.5 & 15% of Potato Starch. Thereafter, after conditioning blown film samples were prepared using extrusion film blowing technique, under temperature profile ranging from 120 to 160 °C. Packaging films have been prepared with maximum 15% potato starch contents and have been characterized by FTIR, DSC, TGA, and XRD techniques to ascertain its impact on some structural and thermal properties like thermal stability, flexibility, crystallinity, crystal size etc.     

Qualitative and Quantitative Analysis of Lignin Produced from Beech Wood by Different Conditions of the Organosolv Process

Lignins in general have been extensively studied, while beech wood lignin in particular is rarely researched. In the present work, Organosolv isolated lignin from beech wood (OBL) has been characterized. The isolation was done by two methods: (a) by using sulfuric acid at 170 °C and a reaction time of 120 min and (b) at a temperature of 180 °C for 240 min. A range of analytical methods were applied including elemental analysis, FT-IR, UV–Vis, ³¹P NMR, SEC, Pyrolysis-GC/MS and HPLC to gain information about establish the purity, structure, molecular weight, thermal behavior and to determine carbohydrate residues according to the NREL protocol. FT-IR and UV–Vis spectra of OBL revealed expected typical absorptions for lignins. NREL analysis presented a carbohydrate-free lignin fraction which has not been achieved to date. TGA and DSC are used to study the thermal behavior of the isolated lignins and showed a relatively low glass transition temperatures (T_g: 123 °C) and decomposition temperatures of 348 and 381 °C. The pyrograms generated from the pyrolysis–GC/MS at 550 °C consisted mainly of fragments of syringyl, guaiacyl and hydroxyphenyl units, thereby confirming the results of the NMR analysis. Our findings support Organolsolv as an efficient method to isolate pure lignin fractions from beech wood with practical value in industry.     

Characterization of dried sewage sludge for co-firing in coal power plant by using thermal gravimetric analysis

This research studied the characteristics of dried sewage sludge using TGA to co-fire dried sewage sludge with coal in power plants. The sewage sludges that were discharged from Daejeon, Korea were dried and examined fundamental properties to use them as a fuel. Also, the properties of bituminous coal and wood pellet, which are used in domestic coal power plants, were analyzed and compared with them of sewage sludges and non-isothermal analyses of dried sewage sludges were performed at the heating rates of 5, 10, 20, and 30C /min using TG analyzer to investigate the basic combustion characteristics. As a results of these TGA/DTG analyses, sewage sludges showed its primary peak at the temperature of 250–500?°C, which overlapped with main peak of wood and secondary peak at around 500–600?°C, which overlapped with main peak of coals. Also for the interpretation by Friedman method, the activation energies in the section of highest weight loss were 525.16 kJ/mole for dried digested sewage sludge, 544.88 kJ/mole for dried excess sewage sludge, 203.86 kJ/mole for wood pellet and 146.4585 kJ/mole for bituminous coal. The reaction orders for dried digested excess sewage sludge, dried excess sewage sludge, wood pellet and bituminous coal were 28.775, 24.319, 18.398 and 9.1005, respectively, and the frequency factors were 5.89?\(\times \hspace{0.17em}\)10²⁸, 1.65?\(\times \hspace{0.17em}\)10^24,, 9.59?\(\times \hspace{0.17em}\)10¹⁶ and 1.77?\(\times \hspace{0.17em}\)10⁸ for each, respectively.     

Novel Bioactive Chiral Poly(amide–imide)s Containing Different Amino Acids Linkages: Studies on Synthesis, Characterization and Biodegradability

In this paper chiral bioactive poly(amide–imide)s (PAI)s were synthesized from four different diacids containing chiral amino acids with 4,4′-methylene bis(3-chloro 2,6-diethylaniline) as a diamine via direct polycondensation reaction in a system of tetra-n-butylammonium bromide and triphenyl phosphite as a condensing agent. The structures of these polymers were confirmed by FT-IR, ¹H-NMR, specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA showed that the 10 % weight loss temperature in a nitrogen atmosphere was more than 378 °C, which indicates that the resulting PAIs have a good thermal stability. The biodegradability of the monomers and prepared polymers was investigated in culture media and soil burial test for assessment of the susceptibility of these compounds to microbial degradation. The results showed that the synthesized monomers and theirs derived polymers are biologically active and nontoxic to microbial growth.     

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.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

Effect of Poly(Vinyl Acetate) on Mechanical Properties and Characteristics of Poly(Lactic Acid)/Natural Rubber Blends

Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10–20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan δ of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71 °C (pure PLA) to 63 °C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.     

Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

Investigation of Biosurfactant Activity and Asphaltene Biodegradation by <Emphasis Type="Italic">Bacillus cereus</Emphasis>

In this research, a biosurfactant-producing bacterium with capability of asphaltene degradation was isolated from oil-contaminated soil samples, and identified as Bacillus cereus. This strain produced an effective biosurfactant in the presence of molasses and the surface tension was reduced to the level of 36.4 mN/m after 48 h under optimum conditions. The optimum values of carbon-to-nitrogen ratio (C:N), pH, and temperature for biosurfactant production were determined as 30:1, 7.3 and 29 °C, respectively, using response surface methodology. The maximum emulsification activity in the culture broth was 53 % after 48 h using kerosene at 25 °C. The goodness of fit of four growth kinetic models including Tessier, Contois, Logistic and Westerhoff was compared for the bacterial growth and molasses utilization of B. cereus in 5-L batch bioreactor during 120 h. Conducted kinetic study showed that biosurfactant production had a good fit with the Contois growth kinetic model (R² = 0.962) and the maximum specific growth rate (µ _max ), saturation constant (K _s ) and the yield of biomass per substrate (Y _x/s ) were determined to be 0.145 h^?1, 1.83 g/L and 0.428 g/g, respectively. The asphaltene biodegradation in flask was evaluated by FTIR analysis and quantified by a spectrophotometer. This bacterium was able to degrade up to 40 % of asphaltene as a sole carbon and energy source after 60 days at 28 °C. The resulting surface tension of 30.2 mN/m with the critical micelle concentration of 23.4 mg/L indicated good efficiency of the biosurfactant.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.     

Increased 3HV Concentration in the Bacterial Production of 3-Hydroxybutyrate (3HB) and 3-Hydroxyvalerate (3HV) Copolymer with Acid-Digested Rice Straw Waste

Bacterial synthesis of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) copolymer [P(3HB-co-3HV)] using the hydrolysate of rice straw waste as a carbon source was affected by the composition of the hydrolysate, which depends highly on the rice straw pretreatment condition. Acid digestion with 2 % sulfuric acid generated larger production of P(3HB-co-3HV) than 6 % sulfuric acid, but 3HV concentration in the copolymer produced with 2 % acid hydrolysate was only 8.8 % compared to 18.1 % with 6 % acid hydrolysate. To obtain a higher 3HV mole fraction for enhanced flexibility of the copolymer, an additional heating was conducted with the 2 % acid hydrolysate after removal of residual rice straw. As the additional heating time increased a higher concentration of levulinic acid was generated, and consequently, the mole fraction of 3HV in P(3HB-co-3HV) increased. Among the conditions tested (i.e., 20-, 40-, 60-min), 60-min additional heating following 2 % sulfuric acid digestion achieved the highest 3HV mole fraction of 22.9 %. However, a longer heating time decreased the P(3HB-co-3HV) productivity, probably due to the increased intermediates concentrations acting as inhibitors in the hydrolysates. Therefore, the use of additional heating needs to consider both the increase in the 3HV mole fraction and the decrease in the P(3HB-co-3HV) productivity.     

Thermal and FT-IR Characterization of Gigantochloa levis and Gigantochloa scortechinii Bamboo, a Naturally Occurring Polymeric Composite

This research presents, thermal (TGA, Kinetics, DSC) analysis and FT-IR characterization of two bamboo species viz. Gigantochloa levis and Gigantochloa scortechinii at different position and locations (Internode and node). The internodes and nodes of Gigantochloa levis and Gigantochloa scortechinii exhibited similar thermal stability, observed up to 200 °C. The decomposition of cellulose and hemicelluloses component of the bamboo species occurred between 220 and 390 °C, while the degradation of lignin was observed above 400 °C. The kinetic studies revealed that Gigantochloa levis is more sensitive to degradation as compared to Gigantochloa scortechinii. The FT-IR studies were carried to assign the functional groups available at different positions and locations.     

Improving Water Resistance of Soy-Based Adhesive by Vegetable Tannin

In this research tannic acid was used to prepare soy-based adhesives for making plywood and fiber board. The different resin formulations were analyzed by Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and its derivative as a function of temperature (DTG) and Fourier Transform Infra-red (FTIR) spectroscopy. The results showed that the addition of tannic acid to soy-based adhesive decreased soy-based adhesive viscosity and its pH. The DSC analysis showed that the denaturation temperature of soy-based adhesives decrease by adding tannic acid. The TGA and DTG curves showed that the thermal degradation of soy flour starts above 146 °C. The FTIR spectroscopy results also showed that the soy flour amino acids appeared to react well with tannic acid. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannic acid-modified adhesive. The mechanical and physical properties such as MOR, MOE, IB, and water resistance of fiberboard were improved, by adding tannic acid to the soy-based adhesive.     

The potential of SO2 for reducing corrosion in WtE plants

Due to the high-temperature boiler corrosion induced by chloride-rich fly ash deposits, steam generation in today’s Waste-to-Energy (WtE) plants is typically designed only for 40 bar/400 °C as an economic compromise between acceptable corrosion rate and maximum power generation. The high-corrosive metal chlorides in the fly ash can react with SO₂ forming low-corrosive sulfates. The sulfation efficiency is enhanced by high SO₂ levels and sufficient residence time of the flue gas at high-temperatures (700–900 °C). The fly ash sulfation was tested in full scale in a Swedish WtE plant by applying the economic sulfur recirculation method. Probes of several alloys (16Mo3, Inconel 625, Sanicro 28) were exposed for 1000 h at controlled material temperatures in the superheater position, at normal and during sulfating operation respectively. Analyses of the fly ash showed that the molar Cl/S was decreased to values well below 1 and the corresponding corrosion rates of the individual material samples were less than half when sulfur recirculation was in operation. These positive findings demonstrate that the sulfur recirculation process has high potential for low-corrosive high-temperature steam generation (T ≈ 500 °C) and improved electricity production. Further steam superheating can be realized by staged superheating using small amounts of secondary fuel.     

Synthesis and Characterization of Biodegradable Starch-Polyacrylamide Graft Copolymers Using Starches with Different Microstructures

The effects of starch structures, in particular amylose content, on grafting reactions were investigated using thermal gravimetric analysis (TGA), nuclear magnetic resonance, X-ray diffraction (XRD). As a model system, corn starches with different amylose contents (0, 26, 50 and 80 %) were grafted onto acrylamide to produce superabsorbent polymers (SAPs). The weight loss measured by TGA at different temperature was used to analyze the grafting ratio in quantity. In general, the grafting ratio increased (about 10 %) with increasing starch amylose content, and graft chain segment lengths were much lower for the amylopectin-rich (waxy) starch. The high molecular weight and branched structure of the amylopectin reduced the mobility of the polymer chains and increased viscosity, which resulted in resistance to chain growth. The water absorption capability was increased with increasing amylose content for the starch-based SAPs. XRD detection showed that the crystalline structure of all starches was destroyed after grafting reactions. The thermal stability of the polyacrylamide grafted onto the starches increased by about 10 °C, which could be explained by the strong bonding between the grafted polymer chains and the starch matrices.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.