Biodegradable Complex Polymers from Casein and Potato Starch

Potato starch was blended with defatted milk in proportions providing a 4:1, 3:1, 2:1, 1:1, 1,:2, 1:3, and 1:4 starch/casein ratio. Precipitation was achieved by addition of either hydrochloric acid or leaven. Composition of precipitated products was determined based on elemental analysis for nitrogen. Generally, differences between attempted and achieved casein-to-starch proportions did not exceed 10%. Products coprecipitated with hydrochloric acid were slightly richer in casein than products obtained with leaven. Aqueous solubility, water binding capacity, IR spectra, and thermal analysis (thermogravimetry, TG, and differential thermogravimetry, DTG) were recorded for the precipitates. Analyses revealed that the precipitates were not simple physical mixtures of the components. Partial insolubility in 7 M aqueous urea showed that casein and potato starch are chemically bound. Comparison of the spectra and thermograms suggested that complexes of the 1:1 composition were formed constituting a nucleus of the aggregates carrying excessive amounts of either starch or casein.     

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

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

Degradation studies of novel degradable starch-polyethylene plastics containing oxidized polyethylene and prooxidant

Linear low-density polyethylene films were prepared that contained native corn starch (7, 14, or 28%), low or high molecular weight oxidized polyethylene (15%), and a prooxidant mixture (18% POLYCLEAN II) that contains manganese and vegetable oil. For each mixture all components were first mixed at high temperatures in a twin-screw extruder and pelletized. The pellets were cast into films using a single-screw extruder. Oxidized-polyethylene addition did not impair the transparency and thickness of the films and did not reduce the percentage elongation, whereas significant reductions in film mechanical properties were observed. Thermal and photodegradation properties of each film were evaluated by 70°C forced-air oven treatment (20 days), by high-temperature, high-humidity treatment in a steam chamber (20 days), and by exposure to ultraviolet light (365 nm; 4 weeks). Changes in the mechanical properties of the films were determined by an Instron Universal Test Machine; in the carbonyl index, Fourier transform infrared spectroscopy; and in molecular weight, by high-temperature gel-permeation chromatography (HT-GPC). The addition of oxidized polyethylene, especially high molecular weight oxidized polyethylene, and up to 14% starch to the films significantly increased the rate of thermal and photodegradation.Journal Paper No. J-15363 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project No. 0178 and 2889.     

Spectral Characterization of Four Kinds of Biodegradable Plastics: Poly (Lactic Acid), Poly (Butylenes Adipate-Co-Terephthalate), Poly (Hydroxybutyrate-Co-Hydroxyvalerate) and Poly (Butylenes Succinate) with FTIR and Raman Spectroscopy

Fourier transform infrared microscope and confocal Raman spectroscope were employed in this study to investigate four kinds of biodegradable plastics: poly(lactic acid),poly(butylenes adipate-co-terephthalate), poly(butylenes succinate) and poly(hydroxybutyrate-co-hydroxyvalerate), which are used more and more popularly in everyday life but can not be identified easily with other instruments. Infrared and Raman spectra of the plastics were tentatively interpreted. The indicative peaks to characterize the four polymers were also summarized. The result in this study can help the forensic scientists discriminate the plastics accurately when they occurred as trace evidences in cases, it also offers the producer and environment scientists an effective, non-invasive and fast method to characterize and identify these four polymers.     

Action of soil microorganisms on PCL and PHBV blend and films

Poly(hydroxybutyrate-co-valerate) (PHBV) and poly(ε-caprolactone) (PCL) PCL/PHBV (4:1) blend films were prepared by melt-pressing. The biodegradation of the films in response to burial in soil for 30 days was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The PHBV film was the most susceptible to microbial attack, since it was rapidly biodegraded via surface erosion in 15 days and completely degraded in 30 days. The PCL film also degraded but more slowly than PHBV. The degradation of the PCL/PHBV blend occurred in the PHBV phase, inducing changes in the PCL phases (interphase) and resulting in an increase of its crystalline fraction.     

Poly(vinyl alcohol-co-lactic acid)/Hydroxyapatite Composites: Synthesis and Characterization

There is a wide range of applications where calcium phosphate and hydroxyapatite (HA) are used as biomaterials, e.g. as synthetic bone grafts, coating on metal prostheses (like hip endoprostheses or dental implants) and drug carriers. In the study, the design and synthesis of composites based on poly(vinyl alcohol-co-lactic acid)/hydroxyapatite (PVA-co-LA/HA) with potential for biomedical applications, they are presented. The hydroxyapatite particles were surface-grafted with l(+)-lactic acid in the presence of manganese acetate as catalyst, resulting in modified hydroxyapatite (HA_m) with improved capacity of bonding, respectively for the preparation of the composite based on PVA-co-LA/HA_m. FT-IR spectra further confirmed the existence of PLA polymer on the surface of HA particles. In synthesis of PVA-co-LA copolymer the different molar ratios PVA/LA (2/1, 1/1, 1/2), toluene/water: 1/2 (as azeotrope solvent mixture) and manganese acetate as catalyst, were used. The composite materials were synthesized in situ with 10 wt% HA, and respectively HA_m (reported to PVA and lactic acid components). The composite materials were characterized by FTIR spectroscopy, thermal analyses (DSC, DTG), ¹H-NMR spectroscopy, particle size distribution and zeta potential.     

The mild hydrothermal synthesis of hydrogrossular from coal ash

In this study, an attempt was made to synthesize hydrogrossular, a group of garnet minerals, under hydrothermal conditions at temperatures below 180°C, using coal ash, which is the solid waste from thermal power plants, as a starting material. A single phase corresponding to hydrogrossular was found at around 120°C, and the hydrogrossular coexisted with 11-Å tobermorite above 140°C. The hydrogrossular phase decreased with increasing reaction temperature, while that of 11-Å tobermorite increased concurrently. The physicochemical properties of the hydrogrossular obtained from the hydrothermal synthesis was characterized by X-ray diffraction thermogravimetry/differential thermal, analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy. Received: September 4, 2000 / Accepted: March 7, 2001     

Preparation and Characterization of Three Different Derivatized Potato Starches

The use of native starch as a thermoplastic polymer is limited by its fragility and high water absorption. Due to the presence of several hydroxyl groups in its structure, water acts as a natural plasticizer of starch, modifying its properties. It is necessary to chemically modify starch molecules by replacing hydroxyl groups with other functional groups to reduce water absorption. Chemical modification of starch granules also alters its swelling and gelatinization behavior. In this contribution we describe the chemical modification of starch and its influence on its hydrophilicity and heat resistance. Acetic acid, maleic anhydride and octanoyl chloride were used as derivatizing reagents. The effectiveness of the treatments was evaluated by means of infrared spectroscopy. Different tests were conducted in order to evaluate the influence of the different chemical modifications on starch structure and properties. Results showed that the treatments effectively reduced starch moisture susceptibility, while substantially altering other properties such as amylose content, swelling power, solubility, and heat resistance. Finally, films were prepared from native and derivatized starch and their surface polarity was evaluated.     

Biodegradation by Composting of Surface Modified Starch and PVA Blended Films

Several starch/PVA/glycerol polymer blends were prepared by a solution casting technique and examined for biodegradation by composting over 45 days. Within this time frame, the starch and glycerol components were fully degraded, leaving the PVA component essentially intact. The lowest PVA content film (20%) was selected as a polymer with enough PVA to impart important physical characteristics, but also enough starch to be considered biodegradable. The film characteristics were further improved by surface modification with chitosan. This modification did not interfere with the biodegradation of the starch component. Furthermore, there was slight evidence that PVA biodegradation had been initiated in composted, surface modified starch/PVA blends.     

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.     

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.     

Thermal and Flame Retardancy Behavior of Oil Palm Based Epoxy Nanocomposites

The aim of present study was to investigate the thermal properties and flame retardancy behavior of flame retardant (FR) epoxy nanocomposites from chemically treated (bromine water and tin chloride) oil palm empty fruit bunch (OPEFB) nano filler at different filler loading (1, 3, 5%). Thermal properties were evaluated through thermogravimetry analyzer, derivative thermogravimetry and differential scanning calorimetry. FR properties of nanocomposites are evaluated through UL-94 vertical burning test and limiting oxygen index (LOI). The functional group analysis of all composites was made by FTIR spectroscopy. Thermal analysis shows that degradation temperature of epoxy composites shifts from 370 to 410 °C and char yield also increases for 3% loading. Furthermore LOI value of 29% and UL-94 rating of V-0 with no flame dripping and cotton ignition, revealed that 3% oil palm nano filler filled epoxy nanocomposites display satisfactory flame retardancy. The superior flame retardancy of epoxy nanocomposites are attributed to the chemical reactions occurred in the gaseous phases and the profound synergistic flame retardation effect of tin with bromine in the treated nano OPEFB filler. All the epoxy nanocomposites displayed almost similar FTIR spectra with the characteristics metal-halogen bond supporting the synergism. Homogeneous dispersion of 3% oil palm nano filler act as highly effective combustion chain terminating agent compared with 1 and 5% nano OPEFB/epoxy nanocomposites.     

Biodegradation Properties of Poly-ε-caprolactone,Starch and Cellulose Acetate Butyrate Composites

Blending starches with polymers such as poly-ε-caprolactone (PCL) has been used as a route to biodegradable plastics. The addition of starch has a significant effect on all physical properties including toughness, elongation at break. On blending cellulose acetate butyrate (CAB) with starch and PCL, improvements in most physical and mechanical properties were observed. This is may be due to CAB acts as a compatibilizer between PCL and starch due to the presence of both hydroxyl groups (in starch and CAB) and ester carbonyls (in PCL and CAB). The presence of different compounds affects the way in which other components degrade. For example the structure of CAB within a starch and PCL combination might make the degradation rate different to that when starch was only mixed with PCL. To check whether this was the case, three combinations of different blends were used to calculate the rate of degradation of each of them separately. These degradation rate constants were then used to predict the theoretical degradation which was checked against the experimental value for other different combinations.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Infrared and nuclear magnetic resonance evidence of degradation in thermoplastics based on forest products

The degradation of lignin-(1-phenylethylene) graft copolymers (lignin-styrene graft copolymers) by white rot basidiomycete fungi was followed by monitoring aromatic absorption bands by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The FTIR of the graft copolymers shows a series of characteristic absorbance peaks from multi-substituted aromatic rings and a strong poly(1-phenylethylene) (polystyrene) absorbance peak from monosubstituted aromatic rings. Subtraction of copolymer spectra taken before incubation from spectra taken after 50 days of incubation with the four tested fungi shows the loss of functional groups from the copolymer. NMR spectra also show reduction of aromatic ring resonances from the copolymer and incorporation of peaks from fungi as a result of incubation with fungi. The biodegradation tests were run on lignin-(1-phenylethylene) graft copolymers which contained 10.3, 32.2, and 50.4% of lignin. The polymer samples were incubated with the white rot fungiPleurotus ostreatus, Phanerochaete chrysosporium, andTrametes versicolor, and the brown rot fungusGleophyllum trabeum. White rot fungi degraded the plastic samples at a rate that increased with increasing lignin content in the copolymer sample. Both poly(1-phenylethylene) and lignin components of the copolymer were readily degraded. Observation by scanning electron microscopy of incubated copolymers showed a deterioration of the plastic surface. The brown rot fungus did not affect any of these plastics, nor did any of the fungi degrade pure poly(1-phenylethylene).Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.     

Storage stability of injection-molded starch-zein plastics under dry and humid conditions

Corn starch and zein mixtures (4 : 1 dry weight) were extruded and injection-molded in the presence of plasticizers (glycerol and water). Tensile strength and percentage elongation of the molded plastics were measured before and after 1 week of storage under a dry or humid condition (11 or 93% RH). With 10–12% glycerol and 6–8% water, injection-molded plastics had relatively good tensile properties (20- to 25-MPa tensile strength and 3.5–4.7% elongation). But while exposed to dry conditions (11% RH), the molded plastics lost weight (0.5–1.5% in 7 days) and became very brittle, with significant decreases in tensile strength and elongation. Partial replacement (5–10%) of starch with a maltodextrin (average DE 5) reduced the glass transition and melting temperatures of the starch-zein mixture as well as the dry storage stability. Using potato starch instead of corn starch significantly improved the dry storage stability of the injection-molded starch-zein plastics (18- vs 11-MPa tensile strength). Anionic corn starches with a maleate or succinate group (DS<0.01) produced injection-molded plastics with improved tensile properties and storage stability. Plastics prepared from the starch maleate and zein mixture retained the strength during 1 week of dry storage without a significant change (26-MPa tensile strength and 3.7% elongation after 1 week of storage).Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Journal paper No. J-15561 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa, Project No. 2863.     

Dialdehyde starch and zein plastic: Mechanical properties and biodegradability

Dialdehyde starch (DAS) and zein, a hydrophobic corn protein, were investigated to produce biodegradable plastics with improved water resistance and mechanical properties. In the study, dialdehyde starch and zein ratio, plasticizers, and degree of starch oxidation were examined. Increased molding temperature and level of starch oxidation decreased water absorption of the plastic. Tensile strength and Young's modulus increased with starch oxidation. The biodegradation of starting materials and ground plastic specimens was studied in aerobic soil reactors maintained at 25°C for 180 days. Biodegradation of corn starch, zein, and dialdehyde starch for 180 days produced CO₂ equivalent to 64, 63, and 10% of theoretical carbon, respectively. Specimens of molded DAS and zein (3 : 1) plastic showed accelerated CO₂ evolution compared to DAS and other raw materials alone. By 180 days, specimens made with starch of low oxidation (1 and 5% oxidized) demonstrated a 60% biodegradation, and specimens with highly oxidized starch (90% oxidized) achieved 37% biodegradation.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Journal Paper J-15927 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 3258.     

Combustion characteristics of coal and refuse from passenger trains

Refuse from passenger trains is becoming a significant issue with the development of the Chinese railway. Co-firing is regarded as a promising thermal technology, both environmentally and economically, in reducing the quantity of refuse. The co-firing property of passenger train refuse with coal, however, may differ due to the differences in the composition of the refuse. In the present study, combustion properties of refuse from passenger train samples and the mixture of refuse with coal were studied in a tube furnace. Thermo analysis methods, such as thermogravimetry (TG), differential scanning calorimetry (DSC), differential thermal analysis (DTA) and derivative thermogravimetry (DTG) analyses were employed to evaluate combustion performance. We found that the mixture of passenger train refuse and coal at a ratio of 1:1 has a lower ignition and burnout temperature than the coal-only sample. Moreover, refuse from railway passenger trains has more reactive combustion properties than the coal-only sample, and the addition of railway passenger train refuse to coal can promote the reactivity of coal.     

Classification of waste materials using Fourier transform infrared spectroscopy and soft independent modeling of class analogy

Fourier transform infrared (FTIR) spectroscopy combined with multivariate data analysis is under development as a method to classify waste materials. The chemical composition of the sample is reflected by a series of regions of the infrared spectrum which are used as variables for multivariate data analysis. In this study, separated biowaste collection, mechanically-biologically treated waste (MBT-waste), and old landfill materials were collected to provide materials representing different stages of decomposition. A total of 819 FTIR absorbance spectra were recorded. Principal component analyses (PCA) were performed followed by soft independent modeling of class analogy (SIMCA) for classification of waste materials. Strong classification occurred for an analysis where spectral carbonate regions were included, and for another analysis when they were not. The SIMCA model enabled the differentiation and the classification of unknown samples according to the three categories in both cases. The classification methods developed here provide an assessment tool that regulatory authorities may wish to explore when assessing whether a treated waste from an uncertain process can be classed as compost or MBT-waste.