Optimization of Microwave-Assisted and Conventional Heating Comparative Synthesis of Poly(lactic acid) by Direct Melt Polycondensation from Agroindustrial Banana (Musa AAA Cavendish) and Pineapple (Ananas comosus) Fermented Wastes

In Costa Rica, a lot of pineapple (Ananas comosus) and banana (Musa AAA) agroindustrial residues are generated each year. These residues can be used to obtain l-lactic acid by fermentation, ultrafiltration and electrodialysis. Poly(l-lactic acid) (PLLA) is a biodegradable and renewable polyester with many industrial and biomedical applications. There is a growing interest to improve the energetic efficiency of the synthesis of PLLA, because the main issue to produce this polymer is the high productive cost compared with petrochemical traditional commodities. In this research, the synthesis of PLLA through two different techniques was compared: microwave-assisted and conventional heating. On microwave synthesis the best results were obtained using lower temperatures and lower reaction times than the conventional heated synthesis. The reaction time was reduced from 15 h by conventional heating to 4.5 h using microwave-assisted synthesis.     

Thermal Solid State Reactions of Potato Starch with α-Hydroxy Acids

The numerous applications of dextrins resulting from the heating of potato starch with α-amino acids prompted me to check the thermal reactions of starch with hydroxy acids and their lactones, such as citric acid, lactic acid, tartaric acid, and coumarine. The course of reactions was observed by means of Simultaneous TG/DSC Thermal Analyser. The thermal reactions were carried out on convectional and microwave heating. The course of reactions under such conditions was compared and properties of resulting dextrins were recognized. The structure and properties of products were obtained from FTIR spectra, water solubility tests, and pH measurements. It was found, that hydroxy acids and/or products of their thermal transformations reacted with starch and/or resulting dextrins producing esters or crosslinking esterification of dextrins took place. The properties of new dextrins were presented in order to check, in further studies, their application for selective flotation of complex metal ores and their suitability as prebiotics.     

Modification of Aliphatic Polyesters and Their Reactive Blends with Starch

Modified polycaprolactone was synthesized by melt reaction of PCL and reactive monomers such as glycidyl methacrylate (GMA) and maleic anhydride (MAH) in the presence of benzoyl peroxide in Brabender mixer. MAH showed a different grafting phenomenon compared to GMA. The reaction mechanism was discussed with different reactive monomers. Reactive blends of the PCL-g-GMA and the gelatinized starch with glycerin were prepared and their mechanical properties and biodegradabilities were investigated. Reactive blends of PCL-g-GMA and starch showed well-dispersed starch domain in the matrix and better mechanical strength than the unmodified PCL/starch blend. However, the reaction between PCL-g-GMA and starch induced a crosslinking during the reactive blending and this crosslinking in the blend lowered the biodegradation of the blend during the composting test. The biodegradability was investigated by the weight loss and surface morphology change of the blend in the composting medium.     

Solid State Reactions of Potato Starch with Urea and Biuret

Reaction of granular potato starch with urea and biuret resulted in the formation of products, which were soluble neither in cold nor boiling water. The net reaction was a monosubstitution of the hydrogen atom in one hydroxyl group in each D-glucose unit of starch with the either CO–NH₂ or CO–NH–CO–NH₂ moiety, respectively. Properties of the products, particularly these with urea, depended on the mode of reaction. Reactions were carried out in the microwave oven as well as with convection heating. The products retained the granular form of starch but a vast majority of granules were damaged. -Amylolysis of those materials revealed that their susceptibility to the enzyme increasing in the order: starch-amylolysis with simultaneous insolubility in water make these products suitable as ruminant fodder and, eventually, biodegradable material.     

Preparation of activated carbon from coconut shell chars in pilot-scale microwave heating equipment at 60 kW

Experiments to prepare activated carbon by microwave heating indicated that microwave energy can decrease reaction temperature, save the energy and shorten processing time remarkably compared to conventional heating, owing to its internal and volumetric heating effects. The above results were based on the laboratory-scale experiments. It is desirable to develop a pilot-scale microwave heating equipment and investigate the parameters with the aim of technological industrialization. In the present study, the components and features of the self-invented equipment were introduced. The temperature rise curves of the chars were obtained. Iodine numbers of the activated carbons all exceed the state standard of China under the following conditions: 25 kg/h charging rate, 0.42 rev/min turning rate of ceramic tube, flow rate of steam at pressure of 0.01 MPa and 40 kW microwave heating power after 60 kW pre-activation for 30 min. Pore structure of the sample obtained at a time point of 46 h, which contained BET surface area, and pore size distributions of micropores and total pores, was tested by nitrogen adsorption at 77K.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Characterization of Chemically Modified Potato Starch Films Through Enzymatic Degradation

The present investigation was undertaken to characterize the biodegradation pattern of chemically modified starch films. Chemically modified starch films obtained by esterification of the hydroxyl groups of the polysaccharide have shown lower water sorption than native starch films, being therefore more attractive for a number of processing applications. However, no systematic study characterizing their biodegradation behavior and comparing it with the degradation pattern of native starch films has still been published. In the current contribution we characterized the enzymatic degradation pattern of three derivatized starch films by use of a commercial α-amylase from Bacillus licheniformis. Optimum degradation conditions were chosen upon assaying the effect of enzyme load and temperature on the reaction course of native starch films. Under the conditions selected, comparison of different derivatization procedures revealed that the starch film modified with octanoyl chloride was enzymatically hydrolyzed at a much higher rate than native starch film. Maleated starch films also showed higher susceptibility to α-amylolytic hydrolysis than native starch, whereas acetylated starch showed a hydrolysis pattern similar to that of native starch. Differences in degradation rates of chemically modified films were explained in terms of their amylose content which promotes dense networks that hinder the access of starch-degrading enzymes.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

Dechlorination of polyvinyl chloride in NaOH/ethylene glycol solution by microwave heating

This study investigated the dehydrochlorination of flexible polyvinyl chloride (PVC) containing 59.2% PVC, 29.7% dioctyl phthalate (DOP), and approximately 12% stabilizers. Flexible PVC was treated with NaOH/ethylene glycol (NaOH/EG) solutions at NaOH concentrations in the range 0.5–4 mol/l and was heated in a microwave heater at a temperature between 100° and 160°C for 0–30 min. All chlorides were completely eliminated by internal heating at 160°C using microwaves for 10 min in a 1 mol/l NaOH/EG solution, and the residue was made up of hydrocarbons. The weight loss rate reached a maximum of 74.7% at a temperature of 160°C. It was discovered that the use of microwaves significantly shortened the reaction time compared to using conventional electric heaters or other external heating systems and also allowed the use of lower concentrations of NaOH. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Synthesis of Succinylated Starches and Their Application as Adsorbents for the Removal of Phenol

Journal of Polymers and the Environment - Succinylated starches (SS) were prepared by the reaction of normal starch (NS) and porous starch (PS) with succinic anhydride (SA) in the presence of DMF...     

Accessibility of starch to enzymatic degradation in injection-molded starch-plastic composites

Most of the starch in starch-polyethylene-co-acrylic acid (EAA)-polyethylene (PE) composites prepared by injection molding was not accessible to starch-hydrolyzing enzymes. Even when these composites were treated with enzyme in the presence of Triton X-100 for 96 h, little starch hydrolysis was observed. However, when the starch-plastic material was pulverized, both the extent and the rate of starch hydrolysis increased dramatically, with about 70% hydrolysis of the starch within 18 h. Reactions carried out for up to 96 h showed that, while the enzyme was active, the reaction reached a plateau, achieving a total of 80% starch hydrolysis. Fourier transform infrared (FTIR) spectroscopy revealed that only starch, and not EAA or PE, was affected by enzyme in pulverized samples. Results indicated that while 80% of the starch in these composites was transiently inaccessible, perhaps due to EAA and PE forming an impermeable barrier to the enzyme, the other 20% remained inaccessible to enzymes. Also, the rate of starch digestion as determined by solubilized reducing sugar correlated with the particle size of the pulverized material, suggesting that a large available surface area is critical for rapid starch degradation in such composites.The mention of firms names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over the firms or similar products not mentioned. All programs and services of the U.S. Department of Agriculture are offered on a nondiscriminatory basis without regard to race, color, national origin, religion, sex, marital status, or handicap.     

Utilization of Waste Sorghum Grain for Producing Superabsorbent for Personal Care Products

Modification of useful starch extracted from waste sorghum grains was carried out for production of superabsorbent materials which can be used in personal care products. Starch was extracted using alkali steeping method. It was characterized for swelling power, percentage transmittance and iodine binding values. The extracted starch was modified via graft copolymerization of acrylic acid and acrylamide onto starch to produce biodegradable absorbent material. The changes in modified starch structure were assessed using TGA, FTIR and SEM. The evaluation of enhancement in the properties was done by performing absorption tests. The reaction parameters were optimized to achieve higher graft add-on level and water absorption capacity. The absorbent product was further subjected to saponification for further enhancing its water absorption capacity (368.8 g/g). The product prepared by using optimized parameters of reaction was made highly porous by introducing sodium bicarbonate during the reaction. It showed a significant increase in the rate of water absorption and enhancement in water absorption capacity (380.9 g/g).The modified product showed 101.1 and 77.0 g/g absorption of artificial blood and artificial urine, respectively. This modified product was infused in commercially available sanitary napkin and baby diaper. Further, it was tested for fluid absorption and centrifuge retention capacity and it performed distinctly better than the commercial products. This superabsorbent material showed 12% weight loss after 28 days when biodegradability test by soil burial method was carried out.     

Microwave-Assisted Solvent-Free or Aqueous-Based Synthesis of Biodegradable Polymers

Microwave radiation was used as the energy source for various types of chemical derivatizations of polysaccharides and for the synthesis of biodegradable polyesters in solvent-free or aqueous-based reaction systems. A medium to high degree of substitution was obtained for starch acetates, starch succinates, carboxymethyl konjac, aminated starch, and aminated chitosan. Ring-opening polymerization of lactide and -caprolactone proceeded rapidly even at low power output in the presence of tin octanoate catalyst. Complete monomer conversion and high molecular weight were achieved in less than 6 minutes under nonisothermal conditions. The yield rapidly increased with increasing power output and showed no significant change in a wide range of batch sizes. Polycaprolactone was successfully grafted from starch and konjac acetate in 3 minutes, yielding as high as 24% grafting efficiency and 25% grafting degree.     

Biodegradability of Starch Based Self-Supporting Antimicrobial Film and Its Effect on Soil Quality

Alarming environmental pollution from petroleum based non-biodegradable disposable packaging films has generated concern for development of alternatives from natural polymers such as starch. In the present work, the biodegradability of a self-supporting film made from starch and polyvinyl alcohol (PVA) (starch:PVA?=?9:1 as the polymer) together with glutaraldehyde as crosslinker and sodium propionate (SP) as antimicrobial was investigated by soil burial method. The changes in soil composition namely pH, organic carbon, available and total nitrogen, and water holding capacity as a result of biodegradation were also estimated. The film underwent ≈?90% biodegradation within a period of 28 days, with simultaneous increase in soil nutrients. Moreover, the pH remained in the accepted limit for plant growth. Thus, antimicrobial in the film did not hamper its biodegradation, rather disposal of the film in soil might facilitate plant growth.     

Predicting the heating value of MSW with a feed forward neural network

The influence of the heating value of municipal solid waste (MSW) is very important on the combustion efficiency of MSW incinerators. The heating value of MSW is determined by the elementary chemical composition of its various components. Commonly, calorimetric measurement and empirical methods are available for this determination. In this analysis, the relationship between the physical composition and the low heating value (LHV) was studied. A feed forward neural network (FFNN) can be very helpful in predicting the heating value of MSW from its physical composition. The results of this analysis show that the prediction of LHV of MSW with FFNN is much better than conventional models.     

Characterization of Biodegradable Polymer Blends of Acetylated and Hydroxypropylated Sago Starch and Natural Rubber

Development of biodegradable polymers from absolute environmental friendly materials has attracted increasing research interest due to public awareness of waste disposal problems caused by low degradable conventional plastics. In this study, the potential of incorporating natural rubber latex (NRL) into chemically modified sago starch for the making biodegradable polymer blends was assessed. Native sago starch was acetylated and hydroxypropylated before gelatinization in preparing starch thermoplastic using glycerol. They were than casted with NRL into biopolymer films according to the ratios of 100.00/0.00, 99.75/1.25, 98.50/2.50, 95.00/5.00, 90.00/10.00 and 80.00/20.00 wt/wt, via solution spreading technique. Water absorption, thermal, mechanical, morphological and biodegradable properties of the product films were evaluated by differential scanning calorimetry (DSC), universal testing machine (UTM), scanning electron microscopy (SEM) and fourier transform infrared spectroscopy. Results showed that acetylation promoted the incorporating behavior of NRL in sago starch by demonstrating a good adhesion characteristic and giving a uniform, homogenous micro-structured surface under SEM observation. However, the thin biopolymer films did not exhibit any remarkable trend in their DSC thermal profile and UTM mechanical properties. The occurrence of NRL suppressed water adsorption capacity and delayed the biodegradability of the biopolymer films in the natural environment. Despite the depletion in water adsorption capacity, all of the product films degraded 50 % within 12 weeks. This study concluded that biopolymers with desirable properties could be formulated by choosing an appropriate casting ratio of the sago starch to NRL with suitable chemical substitution modes.     

Conventional and fast pyrolysis of automobile shredder residues (ASR)

This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature.     

Pyrolysis kinetics behavior of solid tire wastes available in Bangladesh

Pyrolysis kinetics of available bicycle/rickshaw, motorcycle and truck tire wastes in Bangladesh have been investigated thermogravimetrically in a nitrogen atmosphere at heating rates of 10 and 60 degrees C/min over a temperature range of 30-800 degrees C. The three tire wastes exhibited similar behaviors in that, when heating rate was increased, the initial reaction temperature decreased but the reaction range and reaction rate increased. The percentage of total weight loss was higher for truck tire waste and lower for bicycle/rickshaw tire waste. The pyrolysis of truck tire waste was found to be easier than that of bicycle/rickshaw and motorcycle tire wastes while it was comparatively more difficult for motorcycle tire waste. The overall rate equation for the three tire wastes has been modeled satisfactorily by one simplified equation from which the kinetic parameters of unreacted materials based on the Arrhenius form can be determined. The predicted rate equation compares fairly well with the measured TG and DTG data. DTA curves for all of the samples show that the degradation reactions are three main exotherms and one endotherm.     

Effect of Glycerin and Starch Crosslinking on Molecular Compatibility of Biodegradable Poly(lactic acid)-Starch Composites

Poly(lactic acid) (PLA) is a biodegradable material. However, PLA is relatively cost effective. Blending starch with PLA is one of the promising efforts because starch is a widely distributed and inexpensive product. PLA and starch were blended using a rheometer to form composites in this report. Glycerin was added into the blends to make the mixture molecular compatible and more homogeneous. The starch was crosslinked using epichlorohydrin to improve the compatibility of starch with PLA. Two series of composite were fabricated. One was PLA and the crosslinked starch containing 32 wt% glycerin. In this group, the crosslinking degree of the modified starch was varied. The second group was PLA and non-crosslinked starch with varied amount of glycerin added. Micro-structure of the blending composites was observed using a SEM to view the homogeneity of the mixture. The SEM pictures indicated that the compatibility of PLA and starch molecules was poor. The addition of glycerin can change the compatibility of PLA and starch. The higher the glycerin content in the composites, the better the compatibility between PLA and starch. Furthermore, when the starch was crosslinked by epichlorohydrin, the compatibility of PLA and starch can be greatly improved. The compatibility increases with the increase of crosslinking degree. This is due to the change of hydrophilicity of starch because the hydroxyl groups on the starch molecules were crosslinked into ether groups by the epichlorohydrin molecules.     

Thermodynamic and Diffusion Properties of Biodegradable Systems Based on Starch and Cellulose Derivatives

The interval sorption and diffusion of water vapor were studied for two systems: methylcellulose (MC)/starch and carboxymethylcellulose (CMC)/starch. The diffusion coefficient of water vapor and the Gibbs free energy of swelling of these blends in water were estimated. The Gibbs free energy of mixing starch with the cellulose derivatives was determined using the thermodynamic cycle. CMC/starch was shown to be more compatible than MC/starch. Biodegradation of these systems in the water–soil environment was measured and found to increase with the concentration of starch in its blends with cellulose derivatives.