The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.While this work was in progress, Robert Gardner was struck with cancer and died on June 6, 1995. This paper is dedicated to his memory and to his contributions as a friend and colleague.     

琉基纤维素对水中Cr(VI)离子的吸附研究

制备了巯基纤维素并用其对含Cr(VI)离子的溶液进行了静态吸附实验.研究了pH值、吸附时间、反应温度、吸附剂用量等因素对吸附性能的影响.结果表明:在pH值为2、Cr(VI)浓度为50 mg/L和吸附剂为0.5 g时,常温条件下吸附6h后,Cr(VI)去除率达到99.2%,吸附反应符合Langmuir和Freundlic...     

Synthesis of cellulose-fatty acid esters for use as biodegradable plastics

Long-chain fatty acid carbohydrate esters (FACE) were synthesized by the acid chloride-pyridine reaction to different degrees of substitution (DS). The hydrolyzed soybean oil was used as the source of unsaturated fatty acids. High molecular weight FACE polymers are insoluble in common solvents, such as benzene, toluene, THF, etc., and are highly water resistant. However, FACE polymers of hydrolyzed cellulose (MW 180 kD) are soluble/swellable in toluene and can be cast into tough, flexible films. FACE polymer properties of tensile strength and clasticity vary with degree of substitution and polymer size.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

Investigation of physico-chemical properties and microbial community during poultry manure co-composting process

Co-composting of poultry manure and rubber wood sawdust was performed with the ratio of 2:1(V/V) for a period of 60 days. An investigation was carried out to study the extracellular enzymatic activities and structural degradation utilizing Fourier transform infrared spectroscopy(FT-IR), thermogravimetry and differential thermal analysis(TG/DTA)and scanning electron microscopy(SEM). The microbial succession was also determined by using denaturing gel gradient electrophoresis(DGGE). The compost was able to reach its highest temperature of 71°C at day 3 and stabilized between 30 and 40°C for 8 weeks.CMCase, FPase and β-glucosidase acted synergistically in order to degrade the cellulosic substrate. The xylanase activities increased gradually during the composting and reached the peak value of 11.637 U/g on day 35, followed by a sharp decline. Both Li P and Mn P activities reached their peak values on day 35 with 0.431 and 0.132 U/g respectively. The FT-IR spectra revealed an increase in aromaticity and a decrease in aliphatic compounds such as carbohydrates as decomposition proceeded. TGA/DTG data exhibited significant changes in weight loss in compost samples, indicating degradation of organic matter. SEM micrographs showed higher amounts of parenchyma exposed on the surface of rubber wood sawdust at day 60, showing significant degradation. DGGE and 16 S r DNA analyses showed that Burkholderia sp., Pandoraea sp., and Pseudomonas sp. were present throughout the composting process. Ornithinibacillus sp. and Castellaniella ginsengisoli were only found in the initial stage of the composting, while different strains of Burkholderia sp. also occurred in the later stage of composting.     

Nanocomposites of Cellulose Acetate Butyrate Reinforced with Cellulose Nanocrystals

Nanocrystals were prepared by acid hydrolysis of bacterial cellulose microfibrils. These were topochemically trimethylsilylated, in an attempt to reduce their hydrophilicity. Composites were made by dispersing either native or silylated crystals in cellulose acetatebutyrate matrixes and solution casting of the dispersions. Particles were characterized by transmission electron microscopy. The composites were characterized by differential scanning calorimetry and dynamic mechanical analysis. The unmodified cellulose crystals exhibited better reinforcement characteristics than the trimethylsilated crystals.     

Seasonal variations of Rn concentrations in the air of a tunnel located in Nagano city

The seasonal variation of 222Rn concentrations in the air of tunnels constructed during World War II at Nagano City has been investigated. The determination of 222Rn concentrations in tunnel air was performed using a solid-state nuclear track detector technique. The monthly radon concentrations changed smoothly, decreasing towards winter and increasing towards summer, and it was found that the concentrations strongly correlate with the temperature difference between the inside and the outside of the tunnel. In the innermost areas of the tunnel, the maximum concentration was observed in July, its value being about 6500 Bq m (-3). The concentrations of radon in the tunnel air decrease exponentially towards the openings of the tunnel, which indicates that the radon concentration in the tunnel is basically governed by diffusion and mixing of radon gas with air. These observations lead to the conclusion that the seasonal variation of the radon concentration in the tunnel air is mainly caused by a convection current due to a stack effect induced by the temperature difference between the tunnel air and the outside air.     

Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

Biodegradation and bioconversion of cellulose wastes using bacterial and fungal cells immobilized in radiopolymerized hydrogels

Annually, great amounts of cellulose wastes, which could be measured in many billions of tons, are produced worldwide as residues from agricultural activities and industrial food processing. Consequently, the use of microorganisms in order to remove, reduce or ameliorate these potential polluting materials is a real environmental challenge, which could be solved by a focused research concerning efficient methods applied in biological degradation processes. In this respect, the scope of this chapter is to present the state of the art concerning the biodegradation of redundant cellulose wastes from agriculture and food processing by continuous enzymatic activities of immobilized bacterial and fungal cells as improved biotechnological tools and, also, to report on our recent research concerning cellulose wastes biocomposting to produce natural organic fertilizers and, respectively, cellulose bioconversion into useful products, such as: ‘single-cell protein’ (SCP) or ‘protein-rich feed’ (PRF). In addition, there are shown some new methods to immobilize microorganisms on polymeric hydrogels such as: poly-acrylamide (PAA), collagen-poly-acrylamide (CPAA), elastin-poly-acrylamide (EPAA), gelatin-poly-acrylamide (GPAA), and poly-hydroxy-ethyl-methacrylate (PHEMA), which were achieved by gamma polymerization techniques. Unlike many other biodegradation processes, these methods were performed to preserve the whole viability of fungal and bacterial cells during long term bioprocesses and their efficiency of metabolic activities. The immobilization methods of viable microorganisms were achieved by cellular adherence mechanisms inside hydrogels used as immobilization matrices which control cellular growth by: reticulation size, porosity degree, hydration rate in different colloidal solutions, organic and inorganic compounds, etc. The preparative procedures applied to immobilize bacterial and fungal viable cells in or on radiopolymerized hydrogels and, also, their use in cellulose wastes biodegradation are discussed in detail. In all such performed experiments were used pure cell cultures of the following cellulolytic microorganisms: Bacillus subtilis and Bacillus licheniformis from bacteria, and Pleurotus ostreatus, Pleurotus florida, and Trichoderma viride from fungi. These species of microorganisms were isolated from natural habitats, then purified by microbiological methods, and finally, tested for their cellulolytic potential. The cellulose biodegradation, induced especially by fungal cultures, used as immobilized cells in continuous systems, was investigated by enzymatic assays and the bioconversion into protein-rich biomass was determined by mycelial protein content, during such long time processes. The specific changes in cellular development of immobilized bacterial and fungal cells in PAA hydrogels emphasize the importance of physical structure and chemical properties of such polymeric matrices used for efficient preservation of their metabolic activity, especially to perform in situ environmental applications involving cellulose biodegradation by using immobilized microorganisms as long-term viable biocatalysts.     

改性植被混凝土基材力学与植生试验研究

为探明羧甲基纤维素钠(CMC)与麦秸秆纤维对植被混凝土基材力学与植生性能的影响,通过直剪试验、植生试验研究了改性后植被混凝土基材(简称改性基材)的抗剪性能与黑麦草生长性能.结果 表明:①改性基材的剪切强度随CMC掺量的增加呈先增后减的变化趋势,0.5％CMC掺量时基材的剪切强度出现峰值,而随纤维掺量的增加改性基材剪切强...     

Effect of environmental parameters on the degradability of polymer films in laboratory-scale composting reactors

Previous research in our laboratory reported a convenient laboratory-scale composting test method to study the weight loss of polymer films in aerobic thermophilic (53°C) reactors maintained at a 60% moisture content. The laboratory-scale compost reactors contained the following synthetic compost mixture (percentage on dry-weight basis): tree leaves (45.0), shredded paper (16.5), food (6.7), meat (5.8), cow manure (17.5), sawdust (1.9), aluminum and steel shavings (2.4), glass beads (1.3), urea (1.9), and a compost seed (1.0) which is designated Mix-1 in this work. To simplify the laboratory-scale compost weight loss test method and better understand how compost mixture compositions and environmental parameters affect the rate of plastic degradation, a systematic variation of the synthetic mixture composition as well as the moisture content was carried out. Cellulose acetate (CA) with a degree of substitution (DS) value of 1.7 and cellophane films were chosen as test polymer substrates for this work. The extent of CA DS-1.7 and cellophane weight loss as a function of the exposure time remained unchanged when the metal and glass components of the mixture were excluded in Mix-2. Further study showed that large variations in the mixture composition such as the replacement of tree leaves, food, meat, and sawdust with steam-exploded wood and alfalfa (forming Mix-C) could be made with little or no change in the time dependence of CA DS-1.7 film weight loss. In contrast, substituting tree leaves, food, meat, cow manure, and sawdust with steam-exploded wood in combination with either Rabbit Choice (Mix-D) or starch and urea (Mix-E) resulted in a significant time increase (from 7 to 12 days) for the complete disappearance of CA DS-1.7 films. Interestingly, in this work no direct correlation was observed between the C/N ratio (which ranged from 13.9 to 61.4) and the CA DS-1.7 film weight loss. Decreasing moisture contents of the compost Mix-2 from 60 and 50 and 40% resulted in dramatic changes in polymer degradation such that CA DS-1.7 showed an increase in the time period for a complete disappearance of polymer films from 6 to 16 and 30 days, respectively.Guest Editor: Dr. Graham Swift, Rohm & Haas.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.