Physical,Mechanical, and Morphological Characteristics of Extruded Starch Acetate Foams

Starch acetates with degrees of substitution (DS) of 0.57, 1.11, 1.68, and 2.23 were prepared and extruded with either water or ethanol. The microstructure, physical properties (radial expansion ratio [RER] and unit density), mechanical properties (spring index [SI] and compressibility), and crystalline structure of the foams were investigated. The functional properties were a function of DS and blowing agent type. When water was used as the blowing agent and DS increased, the foams were pale yellow, with rough and uneven surfaces. The cells were dense, with thick cell walls. Lower RER and SI, with higher DS, were associated with high unit density and compressibility. When ethanol was used as the blowing agent, contrary results were observed. The snow-white foams had smooth surfaces, uniform cells, and smooth cell walls. High RER and SI, and low unit density and compressibility were observed. The changes in SI and compressibility with RER also were examined and found to depend on the type of solvent. A crystalline pattern was observed because of the formation of well-ordered structures during extrusion.     

Humidity- and Age-Tolerant Starch-Based Sponge for Loose-Fill Packaging

Loose-fill packaging sponges were extruded from mixtures of 54–62% hydroxypropylated (HP 5%) amylomaize V (50% amylose) and wheat starches, 17–24% synthetic polymer, 13% water, 7% blowing agent(s), and 0.5% nucleating agent. One product made from 28% HP wheat starch, 28% HP amylomaize V starch, 12% ethylene vinyl alcohol (EVOH) copolymer, 8% polystyrene (PS), and 3% polystyrene maleic anhydride (PSMA) copolymer, plus the other raw materials, had a compressibility and resilience that matched those of expanded polystyrene (EPS), although its bulk density was four times higher. The starchy sponge showed 16% shrinkage in volume at 90% relative humidity and was 2% soluble in excess water, both at 25°C. After aging for 18 months near 25°C, the HP starchy sponge gave only a trace of fines in a simulated shipping test, compared to 20% fines from a biodegradable, starch-based, loose-fill sponge of commerce.     

Functional Properties of Extruded Starch Acetate Blends

Starch acetate, with degree of substitution of 2, was blended with 0, 7.5 and 15% polylactic acid (PLA), Eastar Bio Copolyester 14766 (EBC) or Mater-Bi ZF03U (MBI) and 10%, 13%, or 16% (d.b.) ethanol and twin-screw extruded at 160°C barrel temperature. Physical characteristics of the extrudates, such as radial expansion ratio, unit and bulk densities, and of the mechanical properties, including unit spring index and bulk spring index, were measured. Type of polymer, polymer content, and ethanol content significantly affected the physical characteristics and mechanical properties. The sample extruded with 7.5% PLA and 13% ethanol had the highest expansion ratio and bulk spring index. The sample with 15% MBI and 16% ethanol had the lowest unit density, while the sample with 7.5% PLA and 16% ethanol had lowest bulk denisty. The highest unit spring index was expressed in the sample containing 7.5% PLA and 10% ethanol.     

Biobased Contents of Organic Fillers and Polycaprolactone Composites with Cellulose Fillers Measured by Accelerator Mass Spectrometry Based on ASTM D6866

The biobased contents of raw materials such as starches, sugar, chitin, or wood powders for biomass plastics were measured using Accelerator Mass Spectrometry (AMS) based on ASTM D6866. AMS measures the isotope carbon ratio of ¹⁴C to ¹²C and ¹³C in graphite derived from sample powders. The biobased contents of starches, sugar or chitin were almost 100% which means that they are fully biobased. The biobased contents of the wood powders were over 140% due to the effect of the post 1950s ¹⁴C injection due to nuclear testing. Poly(ε-caprolactone) (PCL) composite samples were prepared using the polymerization and direct molding method. The starting compound was the ε-caprolactone monomer liquid combined with cellulose and inorganic fillers using aluminum triflate as a catalyst at 80 °C for 6 or 24 h. PCL cylinder-shaped composite samples with a homogeneously dispersed cellulose filler were prepared with M_n = 4,600 (M_w/M_n = 2.9). The biobased content of the PCL composite with 50 wt% cellulose filler (51.67%) measured using AMS was slightly higher than the carbon ratio of cellulose in the starting powder samples (41.3 mol%). This is due to the higher biobased content (112.70%) of the cellulose filler used in this study. The biobased content of the polymer composite powders by AMS was found not to be affected by the presence of inorganic fillers, such as talc.     

Preparation of Cellulose/Xanthan Gum Composite Films and Hydrogels Using Ionic Liquid

This paper reports the preparation of cellulose/xanthan gum composite films and hydrogels through gelation with an ionic liquid. Mixtures of cellulose and xanthan gum in desired weight ratios with an ionic liquid, 1-butyl-3-methylimidazolium chloride (BMIMCl), were thinly placed on a Petri dish and heated at 100 °C for 9 h to obtain the solutions. Then, the solutions were left standing at room temperature for 1 day for the progress of gelation. The resulting ion gels were subjected to Soxhlet extraction with ethanol to remove BMIMCl, followed by drying under ambient conditions to obtain the composite films. The crystalline structures of the polysaccharides and the mechanical properties were evaluated by powder X-ray diffraction measurement and tensile testing of the films, respectively. The ion gels in various cellulose/xanthan gum weight ratios, which were prepared in a test tube by the same procedure, were immersed in water for the exchange of disperse media to obtain the cellulose/xanthan gum composite hydrogels. Water contents of all the materials were higher than 90 %. The mechanical properties of the hydrogels were evaluated by compressive testing.     

Predicting the compressibility behaviour of tire shred samples for landfill applications

Tire shreds have been used as an alternative to crushed stones (gravel) as drainage media in landfill leachate collection systems. The highly compressible nature of tire shreds (25-47% axial strain on vertical stress applications of 20-700 kPa) may reduce the thickness of the tire shred drainage layer to less than 300 mm (minimum design requirement) during the life of the municipal solid waste landfill. There hence exists a need to predict axial strains of tire shred samples in response to vertical stress applications so that the initial thickness of the tire shred drainage layer can be corrected for compression. The present study performs one-dimensional compressibility tests on four tire shred samples and compares the results with stress/strain curves from other studies. The stress/strain curves are developed into charts for choosing the correct initial thickness of tire shred layers that maintain the minimum thickness of 300 mm throughout the life of the landfill. The charts are developed for a range of vertical stresses based on the design height of municipal waste cell and bulk unit weight of municipal waste. Experimental results also showed that despite experiencing large axial strains, the average permeability of the tire shred sample consistently remained two to three orders of magnitude higher than the design performance criterion of 0.01cm/s for landfill drainage layers. Laboratory experiments, however, need to verify whether long-term chemical and bio-chemical reactions between landfill leachate and the tire shred layer will deteriorate their mechanical functions (hydraulic conductivity, compressibility, strength) beyond permissible limits for geotechnical applications.     

Geotechnical properties of fresh municipal solid waste at Orchard Hills Landfill, USA

This paper presents the results of a laboratory investigation to determine the geotechnical properties of fresh municipal solid waste (MSW) collected from the working phase of Orchard Hills Landfill located in Davis Junction (Illinois, USA). Laboratory testing was conducted on shredded MSW to determine the compaction, hydraulic conductivity, compressibility, and shear strength properties at in-situ gravimetric moisture content of 44%. In addition, the effect of increased moisture content during leachate recirculation on compressibility and shear strength of MSW was also investigated by testing samples with variable gravimetric moisture contents ranging from 44% to 100%. Based on Standard Proctor tests, a maximum dry density of 420 kg/m(3) was observed at 70% optimum moisture content. The hydraulic conductivity varied in a wide range of 10(-8)-10(-4)m/s and decreased with increase in dry density. Compression ratio values varied in a close range of 0.24-0.33 with no specific trend with the increase in moisture content. Based on direct shear tests, drained cohesion varied from 31 to 64 kPa and the drained friction angle ranged from 26 to 30 degrees. Neither cohesion nor friction angle demonstrated any correlation with the moisture content, within the range of moisture contents tested. The consolidated undrained triaxial shear tests on saturated MSW showed the total strength parameters (c and phi) to be 32 kPa and 12 degrees, and the effective strength parameters (c' and phi') to be 38 kPa and 16 degrees. The angle of friction (phi) decreased and cohesion (c) value increased with the increase in strain. The effective cohesion (c') increased with increase in strain; however, the effective angle of friction (phi') decreased first and then increased with the increase in strain. Such strain-dependent shear strength properties should be properly accounted in the stability analysis of bioreactor landfills.     

The Role Played by Acetyl Group Distribution Patterns in Substituted Starch Toward Enzymatic De-acetylation and Chain Fragmentation

The nature and distribution of the acetylated groups were evaluated by ¹³C-NMR and ¹H-NMR. The starch substrate with a DS of 1.5 comprises only two patterns: -(14)-d-glucopyranose and 2,3,6-tri-O-acetyl--(14)-d-glucopyranose. The starch with a DS of 3.0 also comprises two patterns: 2,3,4,6-tetra-O-acetyl--(14)-d-glucopyranose and 2,3,6-tri-O-acetyl--(14)-d-glucopyranose; whereas starch (DS = 1.9) contains 4 patterns: 2,3,6-tri-O-acetyl--(14)-d-glucopyranose, 2,3,4,6-tetra-O-acetyl--(14)-d-glucopyranose terminal, 2,6-di-O-acetyl--(14)-d-glucopyranose, and 3,6-di-O-acetyl--(14)-d-glucopyranose. Using esterase from Viscozyme, it has been possible to hydrolyze up to 7% of the DS 3.0 starch. An -amylase (Fungamyl 800) was then added to these acetylesterases. With a 2.4 FAU/mL fraction of -amylase and 2.4 U/mL from the Viscozyme's acetylesterase, 28% of the acetylated end groups were hydrolyzed for the starch substrates with DS 3.0. Moreover, a synergic action between -amylase and acetylesterase was noticed, allowing fragmentation of 32% for DS 1.5, 30% for DS 1.9, and 11% for DS 3.0.     

Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers Using Various Starches

Graft copolymers of polyacrylamide and various substrates were prepared by reactive extrusion in a twin screw extruder using ammonium persulfate as initiator. Substrates included unmodified starches (corn, waxy maize, wheat, and potato), cationic starches, dextrin, dextran, and polyvinyl alcohol (PVOH). The feed ratio of substrate to monomer was 2:1. Average conversion of monomer to polymer was 88.9% (±5.1%). Graft contents for the starch substrates were approximately 25% with grafting efficiencies of about 70%. Polyacrylamide graft molecular weights ranged from 317,000 to 769,000. Absorbencies at pH 7 for saponified graft copolymers prepared with unmodified starches were approximately 200 g/g and approximately 150 g/g for the cationic starches, dextran, and PVOH. In electrolyte solution (0.9% NaCl), absorbencies were in the range of 26–59 g/g, depending on substrate type. Saponified dextrin copolymers were essentially soluble with absorbencies of 6 g/g in water and 12 g/g in 0.9% NaCl.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

New Multi-Scale Hybrid System Based on Maple Wood Flour and Nano Crystalline Cellulose: Morphological,Mechanical and Physical Study

In the first part of this work, composites based on polypropylene (PP) and maple wood flour (MF) were prepared by melt compounding using twin-screw extrusion followed by compression molding. The morphological and mechanical properties of the composites were analyzed for three samples: PP, MF/PP and MF/PP containing maleic anhydride grafted polypropylene (MAPP) as coupling agent. The results showed that MF/PP composites have improved mechanical properties, especially tensile modulus (+33 %), with only 8 % increase in density. The addition of MAPP further improved the mechanical properties, in particular tensile modulus (up to 51 %), which could be related to better fiber/matrix adhesion. In the second step, nano crystalline cellulose (NCC) was added to all samples to produce NCC-MF/PP hybrid composites. From the mechanical analysis performed, the hybrid composites with MAPP have improved properties, especially tensile (+53 %) and flexural (+40 %) moduli. These results confirmed that multi-scale hybrid NCC-MF composites can substantially improve the mechanical properties of polyolefins with limited increase in density (14 %) leading to high specific properties.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

Facile Preparation of Chitin/Cellulose Composite Films Using Ionic Liquids

In this study, we performed the facile preparation of chitin/cellulose composite films using two ionic liquids, 1-allyl-3-methylimidazolium bromide (AMIMBr) and 1-butyl-3-methylimidazolium chloride (BMIMCl); the former dissolves chitin and the latter dissolves cellulose. First, solutions of chitin in AMIMBr and cellulose in BMIMCl were individually prepared by heating each mixture at 100 °C for 24 h. Then, the homogeneous mixture of the two solutions was thinly casted on a glass plate, followed by standing at room temperature for 2 h. After the material was subjected to successive Soxhlet extractions with ethanol for 12 h and with water for 12 h, the residue was dried at room temperature to give a composite film. The crystalline structures of the polysaccharides were evaluated by the X-ray diffraction measurement. Furthermore, the thermal stability and mechanical property of the resulting composite film were estimated by the thermal gravimetric analysis measurement and tensile testing, respectively.     

Enzymatic Degradation of Cellulose-Based Materials

The biodegradability of cellulose-based materials was compared in the standard Sturm test and by enzymatic hydrolysis. Trichoderma reesei culture filtrate, the purified enzymes endoglucanase I and II from T. reesei, and -glucosidase from Aspergillus niger were used in the experiments. The unpurified Trichoderma reesei culture filtrate was found to contain a mixture of enzymes suitable for cellulose degradation. However, when purified enzymes were used the right balance of the individual enzymes was necessary. The addition of -glucosidase enhanced the enzymatic hydrolysis of cellulose materials when both culture filtrate and purified enzymes were used. In the Sturm test the biodegradability of most of the cellulose materials exceeded 70% carbon dioxide generation, but, in contrast, the biodegradability of the highly substituted aminated cellulose and cellulose acetate was below 10%. The results concerning enzymatic hydrolysis and biodegradability were in good agreement for kraft paper, sausage casing, aminated cellulose, and cellulose acetate. However, diverging results were obtained with cotton fabric, probably as a result of its high crystallinity.     

Physicochemical and thermal characterization of nonedible oilseed residual waste as sustainable solid biofuel

The present study aims to investigate the potential of nonedible oilseed Jatropha (Jatropha curcas) and Karanja (Pongamia pinnata) defatted residual biomasses (whole seed, kernel, and hull), as solid biofuel. These biomasses showed good carbon contents (39.8–44.5%), whereas, fewer amounts were observed for sulfur (0.15–0.90%), chlorine (0.64–1.76%), nitrogen (0.9–7.2%) and ash contents (4.0–8.7%). Their volatile matter (60.23–81.6%) and calorific values (17.68–19.98 MJ/kg) were found to be comparable to coal. FT-IR and chemical analyses supported the presence of good amount of cellulose, hemicellulose and lower lignin. The pellets prepared without any additional binder, showed better compaction ratio, bulk density and compressive strength. XRF analysis carried out for determination of slagging–fouling indices, suggested their ash deposition tendencies in boilers, which can be overcome significantly with the optimization of the blower operations and control of ash depositions. Thus, overall various chemical, physical properties, thermal decomposition, surface morphological studies and their high biofuel reactivity indicated that residual biomasses of Jatropha and Karanja seeds have high potential to be utilized as a solid biofuel.     

Investigation of the Aerobic Biodegradability of Several Types of Cyclodextrins in a Laboratory-Controlled Composting Test

The biodegradation of several types of cyclodextrins (CDs) under laboratory-controlled composting conditions was investigated. CDs are used in a broad range of applications in food, pharmaceutical, medical, chemical, and textile industries because of their specific chemical characteristics related to their hydrophobic interior and hydrophilic exterior. The three naturally occurring cyclodextrins -CD, -CD, and -CD proved to be completely and readily biodegradable. Chemical modification of these basic compounds can have a major impact on the biodegradation rate and final biodegradation percentage. Fully acetylated -CD and -CD were found to be nonbiodegradable during 45 days of composting. Reducing the degree of acetylation had a positive effect on the biodegradation. Complete biodegradation was obtained for partially acetylated -CD with a degree of substitution (DS) of 7. The methylation (DS = 13) of -CD resulted in an undegradable compound during the 47 days composting, while (2-hydroxy)propyl--CD reached a plateau in biodegradation at a percentage of 20%. The incorporation of the antimicrobial agents imazalil and allyl-isothiocyanate into -CD had no negative impact on biodegradation, which makes these antimicrobial agents/CD complexes suitable for incorporation into biodegradable active packaging.     

Postconsumer polyethylene terephthalate (PET)/polyolefin blends through reactive processing

Increasing awareness of environmental and energy problems has promoted greater governmental interest in selected waste collection and consequently has attracted the interest of several research groups to the challenge of converting recovered plastics into useful materials. The reactive blending of postconsumer polyethylene terephthalate (PET) with different polyolefins (PO) was studied in attempts to obtain a new material with enhanced properties with respect to the starting materials. The success of the project depends mainly on the possibility of obtaining a compatibilized blend between two starting polymers that, from chemical and thermomechanical viewpoints, are very different. This was approached by employing polyolefins bearing functional groups capable of specific interaction or chemical reaction with PET end groups. Ternary blends of very low density polyethylene (VLDPE)/PET/functionalized polyolefin (FPO) in a weight composition of 70/20/10 and binary blends of FPO/PET in a weight composition of 90/10 were prepared and studied to obtain reinforced polyolefin thermoplastic materials. Reactive blending was achieved in a Brabender Plastograph with a mixing chamber of 30 or 50cm³, at 250°C, and 40rpm for 10min. Differential scanning calorimetry, scanning electron microscopy, and tensile tests were used to investigate the phase behavior, the efficiency of compatibilization, and the mechanical properties of the blends.     

Effect of Starch Granule Size on Viscosity of Starch-Filled Poly(hydroxy ester ether) Composites

The effect of starch granule size on the viscosity of starch-filled poly(hydroxy ester ether) (PHEE) composites was characterized using size-fractionated potato starch, as well as unfractionated starches (rice, corn, wheat, and potato). Potato starch was separated using an air classifier into four particle size fractions: <18 m, 18-24 m, 24-30 m, and >30 m. The starch was dried to a moisture content of 0.5% to minimize moisture effects on composite rheology. PHEE and potato starch were extruded with starch volume fractions of 0.46 and 0.66. Stress relaxation, frequency and strain sweep, and temperature-dependence measurements were carried out. Although small variations in viscosity were seen with the different potato starch fractions, differences were not significant at a volume fraction of 0.46. Viscosity differences between the different particle size fractions were more pronounced at a volume fraction of 0.66. The temperature dependence could be described by an Arrhenius relation, with an apparent activation energy of 84 kJ/mole. At a volume fraction of 0.46, the starch/PHEE viscosities increased in the order potato starch < wheat starch corn starch < rice starch.     

Reusability of sewage sludge in clay bricks

Bricks produced from sewage sludge in different compositions were investigated. Results of the tests indicated that the sludge proportion is a key factor in determining the brick quality. Increasing the sludge content results in a decrease in brick shrinkage, bulk density, and compressive strength. Brick weight loss on ignition was mainly due to the contribution of the contained organic matter from the sludge being burnt off during the firing process, as well as inorganic substances found in both clay and sludge. The physical, mechanical, and chemical properties of the bricks that were supplemented with various proportions of dried sludge from 10 to 40wt% and generally complied with the General Specification for Brick as per the Malaysian Standard MS 7.6:1972, which dictates the requirements for clay bricks used in walling in general. A standard leaching test method also showed that the leaching of metals from the bricks is very low.     

On East Asian Sand and Duststorms and Associated Significant Dustfall Observed from January to May 2001

Monitoring of dust pollution at the western shore of Tae-ahn Peninsula (TAP) and in the Chongju area of central Korea was carried out from January to May 2001. It was found that in Koreathere were 9 cases of sand and duststorms (DS) and 16 associatedsignificant dustfall (SD) days. Observed maximum concentrations of DS and SD coming from NW China and Mongolia were in the rangeof 300–920 for TSP, 200–690 for PM₁₀ and 100–170 g m^-3 for PM_2.5.Satellite measurements clearly showed the formation and subsequent movement of DS to the Korean Peninsula and onward to the Korea East Sea, Japan and the Gulf of Alaska. According to satellite image analysis of dust clouds there were abundant coarse particles, measuring in size of 11.0 m. Medium-sizedparticles measuring in the range of 3.5–7.0 were also prevalent,while fine particles of less than 2.0 m were less distinctive in reflectivity. Measured values of PM_2.5 were alsorelatively low with SD events.The measured average pH values of dusty precipitation associatedwith DS were 7.24. Alkaline precipitation can play a `temporary'role in the neutralization of acidified soil until the subsequentevent of acidic rain. The new selection criteria of SD days from PM_2.5 at 85 g m^-3, PM₁₀ 190 g m^-3 and TSP 250 g m^-3 are recommended on dust pollution occurring from the invasion of a DS elsewhere.     

Validation of an Automated Multiunit Composting System

Biodegradable packaging has high potential to help solve the crisis of non-biodegradable plastic waste causing an increase in the footprint of landfills. However, more research needs to be executed to develop a larger assortment of biodegradable plastics for numerous applications and to make them more economical to manufacture. This paper discusses the design and validation of an automated composting system (AMUCS) that fits the requirements of the American Society for Testing and Materials (ASTM) 5338-11 standard. The results of the experiments show that the AMUCS was able to create and maintain the conditions for biodegradation of biodegradable polymers in compost using microcrystalline cellulose. The biodegradation caused by the composting environment was observed visually with the naked eye and on the micro scale with an environmental scanning electron microscope. The magnitude of biodegradation was measured by calculating the carbon metabolized from the samples. The carbon metabolized from the three compost replicates was consistent and linear, and there was only an 8 % difference between the non-biodegradable low density polyethylene and the compost. For the biodegradation study according to ASTM D 5338-11, the experiment was validated with the use of cellulose as a reference material. Under controlled composting conditions, the mineralization of microcrystalline cellulose yielded 72.05 %, which is slightly higher than the 70 % mineralization requirement.