Sie sind auf Seite 1von 3

Studies on biodegradation of PET Sharon and Sharon, 2012 - chemical changes of polymeric chains detected by Xray photoelectron spectroscopy

y (XPS) - specific microbial media was used to isolate and identify bacteria - Scanning electron microscopy (SEM): degradation impacts on crystalline structure and presence of microbes - record of weight loss and tensile strength - Esterase was found to be involved in biodegradation, slow and weak - microbe involved: Nocardia species BACKGROUND: - PET: endocrine disruptor - thermal degradation generates toxic gases (CO2 and dioxin), release heavy metals (Cd, Pb) - several strains are written here - a roll of transparency sheet kept in a closed container untouched for nearly a YEAR was found to be degrading -sheet was brittle, white coloured microbes growing with foul smell METHODS, RESULTS: - visual: remarkable brownish white discolouration, very brittle and crumbled at places, distinct foul smell, white powder like substances - optical microscope: disorientation of PET crystals, gram +/- observed (presence of bacteria) - SEM: showed crystals of degraded products, presence of abundant colonies of branched mycelium - XRD studies: nondegraded sheets have 2 broad peaks, degraded shows many peaks terepolymer, different - Growth of fungi: none - media for bacterial growth: Actinomycetes Isolation Agar (AIA), Brain Heart Infusing Agar (BHIA), Glycerol Asparagine Agar Base (GAAB), Alternate Thioglycolate Broth (ATGB), Bushnell and Hass Broth (BHB), Alkaline Czapeck Broth (ACB), Luria-Bertani medium (LB plates) and Luria Bertani media containing Tributyrin (LBT). - Growth of bacteria: microbes grew on all, 35degC as suitable temp, dark environment. Each media confirms and identify the type of bacteria - BHB: nocardia species - weight loss, tensile strength changes: BHB>ATGB>GAAB>AIA; no weight loss for BHIA medium - titrimetric estimation of acid: ATGB and BHB have higher amount of acid, BHB 2-fold higher - esterase analysis: nocardia colony confirms esterases A TECHNOLOGY REVIEW OF WOOD PLASTIC COMPOSITES Wolcott and Englund, 33rd International Particleboard/Composite Materials Symposium - late 1980s: investigate high filler levels, coupling agents

- promise of improved moisture performance, recycled and waste material utilization, efficiency in product and process design - the science focused primarily on chemical interaction between dissimilar material components - material and product development has progressed on two fronts: property and process improvements PROPERTY ADVANTAGES - susceptibility to water adsorption, thickness swell, biodeterioration has limited use in exposed environments - hygroscopic nature of wood: limit hydrogen bonding sites, plastic overlays to chemical treatments can also provide resistance to thickness swell BUT, limited effectiveness! -biodeterioration: impregnating fungicides and insecticides -addition of thermoplastic to wood composites has a significant influence on the water adsorption of the material - however little research has addressed the ability for material and product design to influence the durability of wood based materials -increased levels of wood fillers: strength and stiffness, natural resistance to UV degradation, increase melt and softening temperature of the thermoplastic (expanded serviceability) PROCESSING ADVANTAGES - traditional wood composite products are flat pressed to produce prismatic elements -wood fiber: sufficient reinforcement, lower cost, lower composite product density - synthetic and mineral filler: higher machine wear and damage of processing equipment -wood: reduced fiber damage, allows recycling of production waste without compromising quality GENERAL DISADVANTAGES - higher water adsorption and thickness swelling - limited interfacial adhesion, requires coupling agents or surface activating methods -generally for many other types of fillers, dispersing fibers throughout the matrix can be difficult -> dispersing agents and proper mixing techniques RAW MATERIALS Wood: particulate and fibrous fillers; short fiber, particle, or flour the specie selection appears to be influenced more by availability than engineering Thermoplastic: must have a melting and softening temp less than thermal degradation of wood (210 deg C) LDPE, HDPE, PP, PS, PVC; either virgin or recycled; low cost recovered products are often difficult to control

USE OF ADVANCED OXIDATION PROCESSES TO IMPROVE THE BIODEGRADABILITY OF MATURE LANDFILL LEACHATES Morais and Zamora, 2005 - Use of (Fe2+/H2O2/UV and H2O2/UV) as pretreatment of landfiil leachate TiO2 ASSISTED PHOTOCATALYSIS DEGRADATION PROCESS OF DYE CHEMICALS Fang Bai, Guo Bang, et al. 2001 -Use of TiO2 suspension irradiated by high pressure mercury lamp for determination of photocatalytic degredation pathway and degredation products THERMO- AND PHOTO-DEGRADATION OF LDPE AND PP FILMS USING METAL OXIDES AS CATALYSTS Shawaphun, Manangan, and Wacharawichanant - Fe2O3, CuxO, ZnO, and TiO2 at various particle sizes, as catalysts in both thermo- and photo-oxidation of plastic films with oxygen followed by photolytic process - carbonyl index (CI) increased under the shortwave ultraviolet (254nm) significantly greater than under the longer wave (366nm) due to its greater energy and highly absorbed by the prooxidants generating more free radical concentration which could then be photolysed into carbonyl compounds. - The pro-oxidant blended PE and PP films under ultraviolet (254nm) irradiation showed the carbonyl index elevation at the beginning and then reducing to a constant level similarly in most cases. carbonyl primarily formed and degraded into other free radicals. - Under shortwave ultraviolet irradiation for 72 hours, the LDPE films containing nano-sized rutile-TiO2 and nanosized anatase-TiO2 (1%w/w) were able to reduce the film tensile strength by 32% and 55%, respectively. - The film containing micron-sized commercial TiO2 lower the film tensile strength only by 7-10%. - However, the tensile strength of the TiO2 blended PP films tends to increase possibly because the rate of cross linkage exceeds the rate of scission. BACKGROUND -possible degradation pathway is shown - The powders of Fe2O3, ZnO, CuO, TiO2 (63m) and TiO2 (rutile, 200nm) were separately mixed with hexane at 1, 2, 3, and 5% w/v - exposed under a 20-watt shortwave ultraviolet lamp (254nm) and a 20-watt long wave ultraviolet lamp (366nm) at 30 cm in distance - carbonyl index using a Perkin Elmer spectrum 2000 FTIR spectrometer - thermo-catalytic oxidation of the plastic films during processing were then determined via carbonyl index using a Perkin Elmer spectrum 2000 FTIR spectrometer and

tensile strength using a Universal testing machine (Tensile H5K-T; Calserve Thailand) THERMAL DEGRADATION STUDIES OF LDPE CONTAINING COBALT STEARATE AS PROOXIDANT - non-isothermal thermogravimetric analysis (TGA) in both nitrogen and air atmosphere - thermal stability, degradation kinetics, lifetime of LDPE - derivative thermogravimetric (DTG) curves = decomposition process single stage (N2), multistage (air) - kinetic parameters of degradation = Flynn-Wall-Ozawa iso-conversion technique - lifetime of LDPE (time for 5% mass loss) = 8.2 x 1026 min in nitrogen; decrease dramatically with increase in the concentration of cobalt stearate pro-oxidative ability BACKGROUND: - transition metal salts with higher fatty acids - polyethylene containing cobalt carboxylates exhibit a higher susceptibility to both photo as well as thermooxidative degradation - kinetics of degradation can generate parameters, which can be subsequently used to deduce the lifetime of polymers at different temperatures - LDPE contains short butyl branches, which can act as weak links causing initiation to occur adjacent to these sites - almost impossible to obtain the exact kinetic parameters for each reaction involved in the polymer; apparent kinetic parameters are often used to represent the behaviour of polymer decomposition in general MATERIALS AND PROCEDURE: - LDPE/3.7/920/prooxidant mix; proxidant mix = cobalt acetate, sodium hydroxide, stearic acid - Film with 70 micron thickness, 0.05-0.20% w/w cobalt stearate; blow-up ratio for film = 5.5:1; extruder barrel temps = 120 and 130OC, die head section = 135OC - non isothermal thermogravimetric analysis: Perkin Elmer Diamond Simultaneous TGA-DTA-DSC; conducted under flowing atmosphere of nitrogen and air atmosphere at a purge rate of 200 ml/min - sample: 3.50.3 mg, 701 m thickness - TGA analysis: equilibrated to 200C before being heated to 550C at different heating rates (310C/min); actual heating rate = from temperature measurements - DSC analysis: heated from 50C to 200C at 3C/min - Thermooxidative tests: extruded films of F1 and FCS10 in an air oven at two different temperatures (70C and 100C) for extended periods - Changes in mechanical properties: (tensile strength, ASTM 882-85) Samples with a gauge length of 100 mm and width of 10 mm, 100mm/min testing speed; 20C room temp, RH of 65%

-Structural changes: (Carbonyl index, baseline method) FTIR spectroscopy CI = absorption at 1740cm-1 / absorption at 2020cm-1 - Melt flow indices: before and after exposure, at 190C ASTM D1238, 2.16 kg dead weight RESULTS: - peak of the endothermic melting transition (DSC trace): ~110OC, unaltered even with cobalt blend - thermogravimetric (TG), derivative thermogravimetric traces: all the samples exhibit single step decomposition in nitrogen atmosphere; In inert atmosphere, random scission has been reported to be the primary pathway for degradation in polyethylene. However, this is also accompanied by polymer branching. - The degradation temperature was found to increase with increase in the heating rate (), which corresponds to the time temperature superposition principle. A shorter time is required for the sample to reach a given temperature at a faster heating rate. - It was observed that Tonset shifts to lower temperatures with increase in the concentration of cobalt stearate, which also results in larger T (difference of Tonset and Tend). This also indicates that the degradation require relatively longer time periods. - In air atmosphere, a slight increase in the weight due to heating till 160200C, and this has been attributed to the formation of polymeric oxides. It is apparent that the samples start losing weight from the inception of the experiment after 200C. - It is well known that the degradation of polyethylene in air occurs via reaction with oxygen [10], which results in the degradation becoming exothermic at around ~400C. This leads to an unsteady degradation process, which does not show any systematic temperature shifts with heating rate and occurs rather randomly at this temperature (~400C). Contrary to the behavior in nitrogen atmosphere, the degradation temperature was not found to increase with increase in the heating rate () in air. - the degradation occurs at much lower temperatures in air than in nitrogen atmosphere. Addition of cobalt stearate to polyethylene leads to further lowering of these characteristic temperatures, which indicate its prooxidative nature.

Das könnte Ihnen auch gefallen