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1.
The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10−4mol/L) and H2O2 (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10−9−6.083 × 10−9 mol1.7 L s−1. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H2O2 was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.  相似文献   

2.
The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of Tg (glass transition temperature), Tm (melting point temperature), and Tmax (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.  相似文献   

3.
In this work, a product distribution study from thermal degradation of low-density polyethylene (LDPE) is presented. Thermal degradation of the polymer was investigated under dynamic condition in an inert environment using a thermo-gravimetric analyzer (TGA) coupled with evolved products’ analysis using a gas chromatograph (GC). Fractions evolved at nine different temperatures from 200 to 600 °C were injected into GC for a detailed product analysis. The main objective of the present investigation is to highlight the species-specific evolution profiles of LDPE pyrolyzates (C5–C44) at different stages of its degradation under an inert environment. Pyrograms have been analyzed in terms of amount of different products evolved at various pyrolysis temperatures. Volatile pyrolyzates essentially remain low at low decomposition temperature (200–300 °C) of the polymer, which gradually increase to attain a maximum at maximum decomposition temperature (470 °C) and finally level off at 600 °C. In the mechanistic approach adopted to understand the decomposition mechanism of LDPE, the following reaction types were considered: (a) main chain cleavage to form chain-terminus radicals; (b) intramolecular hydrogen transfer to generate internal radicals; (c) intermolecular hydrogen transfer to form both volatile products and radicals; and (d) β-scission to form both volatiles and terminally unsaturated polymer.  相似文献   

4.
The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C5–C32 yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.  相似文献   

5.
This paper describes the chemical degradation of waste poly(ethylene terephthalate) (PET) with polyamines or triethanolamine, the characteristics of the products, and a search for ways to use these products. Solvolysis of the polymer ester bonds was caused by diethylenetriamine, triethylenetetramine, and their mixtures, as well as mixtures of triethylenetetramine and p-phenylenediamine or triethanolamine. Products of aminolysis or aminoglycolysis of PET obtained in reactions performed at 200–210°C (with a molar ratio of the recurrent polymer unit to amine of 1 : 2) have been characterized using nuclear magnetic resonance (NMR). Viscosity and hydroxyl number measurements have been done for PET/triethanolamine products. Substances from aminolytical reactions with polyamines were tested as hardeners for liquid epoxy resins, and the product of polymer aminoglycolysis with triethanolamine was tested as an epoxy resin hardener, e.g., for water-borne paints, and a polyol component for rigid polyurethane foams. The compositions of epoxy resin hardeners have been characterized using DSC and rheometry. Comparative analyses of the hardened epoxy materials have been done on the basis of glass temperature and mechanical properties data, as well as some specific properties of the coating materials and rigid polyurethane foams. Received: September 15, 2000 / Accepted: September 21, 2000  相似文献   

6.
Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by 1H NMR, quantitative 13C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.  相似文献   

7.
Linseed oil-based polymers have been synthesized via cationic and thermal polymerization and characterized through various techniques, such as SEM, DMA, DSC and TGA. The morphology of the polymer samples after extraction reveals the smooth structure of the polymer matrix. With an increase in oil content, the morphology is observed to be more loosely bound. With an increase in linseed oil content in the samples, the room temperature storage modulus (E′) varies from 10.4 × 107 to 1.8 × 107 Pa. The glass transition temperatures measured through DMA of the cationic samples ranges from 70 to −6 °C and the crosslink densities range from 18.4 × 103 to 3.4 × 103 mol/m3. The glass transition temperatures of the thermal samples range from 106 to −4 °C and the crosslink densities range from 7.7 × 103 to 2.4 × 103 mol/m3. The TGA results show three stages of degradation of the polymer samples and it is also revealed that these polymers are stable up to 200 °C, showing negligible decomposition.  相似文献   

8.
Chitosan as a biopolymer, biodegradable, safe, non-toxic and widely abundant in nature was grafted with poly(2-hydroxyaniline) (P2-HA) through aqueous chemical oxidative copolymerization using ammonium persulphate in acetic acid medium. The grafting conditions were studied by varying grafting parameters. The effect of oxidant, 2-hydroxyaniline (2-HA) and acetic acid concentrations on the rate of copolymerization was studied. The synthesized graft characterized using UV–Vis, FTIR, TGA, XRD, and scanning electron microscope and compared with chitosan and P2-HA. The grafting enhances the thermal properties of chitosan. The effect of temperature on the rate of grafting copolymerization reaction was studied. The apparent activation energy (Ea) of the copolymerization reaction found to be 21.1116 kJ/mol. Also, ΔH* and ΔS*, were calculated and found to 22.8630 kJ/mol and ?109.4290 J/mol K respectively. The mechanism of the grafting copolymerization reaction discussed. Chitosan, P2-HA and chitosan-graft-P2-HA used for the removal of Cr, Fe, Mn, Cu and Zn divalent ions from a contaminated water samples. The adsorption isotherm parameters are given.  相似文献   

9.
Degradation of Cellulose Acetate-Based Materials: A Review   总被引:1,自引:0,他引:1  
Cellulose acetate polymer is used to make a variety of consumer products including textiles, plastic films, and cigarette filters. A review of degradation mechanisms, and the possible approaches to diminish the environmental persistence of these materials, will clarify the current and potential degradation rates of these products after disposal. Various studies have been conducted on the biodegradability of cellulose acetate, but no review has been compiled which includes biological, chemical, and photo chemical degradation mechanisms. Cellulose acetate is prepared by acetylating cellulose, the most abundant natural polymer. Cellulose is readily biodegraded by organisms that utilize cellulase enzymes, but due to the additional acetyl groups cellulose acetate requires the presence of esterases for the first step in biodegradation. Once partial deacetylation has been accomplished either by enzymes, or by partial chemical hydrolysis, the polymer’s cellulose backbone is readily biodegraded. Cellulose acetate is photo chemically degraded by UV wavelengths shorter than 280 nm, but has limited photo degradability in sunlight due to the lack of chromophores for absorbing ultraviolet light. Photo degradability can be significantly enhanced by the addition of titanium dioxide, which is used as a whitening agent in many consumer products. Photo degradation with TiO2 causes surface pitting, thus increasing a material’s surface area which enhances biodegradation. The combination of both photo and biodegradation allows a synergy that enhances the overall degradation rate. The physical design of a consumer product can also facilitate enhanced degradation rate, since rates are highly influenced by the exposure to environmental conditions. The patent literature contains an abundance of ideas for designing consumer products that are less persistent in the outdoors environment, and this review will include insights into enhanced degradability designs.  相似文献   

10.
An epoxy-based thermoplastic polyester, poly(hydroxy ester ether), was incubated under aerobic conditions in a laboratory-scale compost system for 168 days to evaluate its potential for biodegradation. Radiolabeled test polymer [uniformly 14C ring-labeled, poly(hydroxy ester ether)] was incorporated into a mature compost and a sludge-amended compost at a loading of 3 mg test polymer/g compost. 14C-Cellulose was used as the positive control and a biologically inhibited control reactor was used to assess abiotic degradation of the test polymer. Degradation of the test polymer was assessed by measuring the amount of 14C-CO2 from each of the test reactors. In addition, at selected time intervals subsamples of the compost were collected and serially extracted with water, methanol, and dimethylformamide to monitor degradation of the 14C-test polymer and provide a partial characterization of the degradation intermediates. Extensive degradation of 14C-poly(hydroxy ester ether) was observed in the test reactors with degradation half-life of the parent polymer (t 1/2) of approximately 32 days. By the end of the study, only 2% of the total 14C activity in the test reactors was attributed to intact polymer, with most of the measurable 14C activity converted to either 14C-CO2 (26% of total 14C activity) or nonextractable products (accounting for 60% of the total activity). In contrast to the test reactors, only 3% of the 14C-poly(hydroxy ester ether) added to the biologically inhibited control reactor was mineralized to 14C-CO2. The results obtained from the microbially active and biologically inhibited compost systems indicate that the poly(hydroxy ester ether) polymer was degraded, at least in part, by a biologically mediated process.  相似文献   

11.
The mechanical–thermal properties and volatile organic compound (VOC) emissions of natural-flour-filled, biodegradable polymer bio-composites were investigated according to variation in porous inorganic filler types. At a porous inorganic filler content of 3%, the tensile and flexural strengths of the hybrid bio-composites were not significant changed. However, the coefficient of thermal expansion and thermal expansion of the bio-composites were slightly decreased. Furthermore, the incorporation of the porous inorganic materials into bio-composites slightly increased the E’ values of the hybrid bio-composites over the entire temperature range, although the tan δmax temperature (T g) of the hybrid bio-composites was not significantly changed. At a porous inorganic filler content of 3%, the various odor and VOC emissions of the hybrid bio-composites were significantly decreased because the various oxidation and thermal degradation gases of the natural flour and matrix were absorbed in the pore structures of the porous inorganic fillers and thereby prevented the migration into the final products.  相似文献   

12.
One of the major concerns of mining companies is the safety of their tailing dams. Among the cares required to operate such a dam, a proper treatment of the effluent composing its waste stands out, since that, waste must be treated before returned to the environment. In the process of bauxite beneficiation, the effluent level of turbidity is the discard parameter that deserves attention. In this work, quaternized chitosan (TMCCl?) derivative with cationic charge was synthetized and investigated to be used as coagulant in bauxite treatment for tailing dam effluent. The chitosan (CHT) was quaternized by methylation reaction. The quaternized chitosan structure was characterized by the following techniques: FTIR Spectroscopy and 1H nuclear magnetic resonance (NMR). Its thermal stability was analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis. After quaternized chitosan was obtained, analysis with aluminum sulfate, protonated and quaternized chitosan were executed in jar-test apparatus. The tests were conducted in order to find the optimum pH, velocity gradient, coagulant and alkalizer dosages, as well as coagulation, flocculation and decantation time. The studied coagulants showed good results and reduced the effluent turbidity to levels below determined by legislation. By comparing the coagulants, it was possible to state that quaternized chitosan presented higher reduction of effluent turbidity levels; the tests were performed in the same conditions.  相似文献   

13.
In the present work the photo-degradation of polychloroprene (PCP) in toluene solution catalyzed by FeCl3·6H2O and polychromatic light was investigated based on FTIR and 13C NMR spectroscopies, on conductivity measurements and DSC technique. The band in the 1700–1790 cm−1 range in the FTIR spectrum characterized the presence of carbonyl products due to the degradation of the PCP on the solution exposed to polychromatic light. The formation of carbonyl on degraded PCP was confirmed by the presence of signal on 13C NMR at δ 203.5. Products of PCP degradation, such as acid chlorides, generated in the toluene solution migrate to the aqueous phase (in contact with toluene phase) and the conductivity of aqueous phase increased as the time is elapsed. The area related to the PCP melting-peak on the DSC (film casted after the PCP-FeCl3·6H2O toluene solution has been exposed to polychromatic light) significantly decreased in comparison to that in the DSC of the raw PCP cast film.  相似文献   

14.
The crosslinking of chitosan with cyanoguanidine shows some advantages, such as the improved the stability in acid solutions and the decrease of adsorbent cost. In this work, cyanoguanidine-crosslinked chitosan and pure chitosan were prepared to apply in the adsorption of Food Yellow 4 (FY4) and Food Blue 2 (FB2), in single and binary systems. Effects of pH and deacetylation degree (DD) of chitosan in adsorption were evaluated. The adsorbents were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The kinetic data were analyzed by pseudo-first order, pseudo-second order and Avrami models. The conditions of pH 3 and DD 95% were the more suitable to reach the highest adsorption capacities in all experimental assays. Under these conditions, the adsorption capacities for FY4 were approximately of 392 and 200 mg g?1 and, for FB2 were approximately of 370 and 184 mg g?1, respectively, in the single and binary systems. The Avrami model was suitable to represent the kinetic curves in all conditions, and the highest adsorption capacities were found for FY4 in binary aqueous system, being for the pure chitosan of 229 mg g?1 and crosslinked chitosan of 218 mg g?1. The Langmuir and extended Langmuir models presented a good fit to the equilibrium data in both systems. It was found that, the chitosan crosslinked with cyanoguanidine improved the chemical stability of chitosan as adsorbent.  相似文献   

15.
Graft copolymerization of cellulosic biopolymers with synthetic polymers is of enormous interest because of its application in biofiltration, biosorption, biomedical, biocomposites and various other eco-friendly materials. Synthesis of graft copolymers of methyl acrylate onto mercerized Grewia optiva biofibers using ferrous ammonium sulfate–potassium per sulfate as redox initiator in air was carried out. Different reaction parameters such as amount of solvent, monomer concentration, initiator molar ratio, reaction time and reaction temperature were optimized to get the maximum percentage of grafting. The graft copolymers thus formed were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and differential thermogravimetric techniques. A plausible mechanism for explanation of the graft copolymerization reactions pattern shown is offered. The effect of grafting percentage on the physico–chemical properties of raw as well as grafted Grewia optiva biofibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. Green polymer composites were also successfully prepared through compression molding technique by using grafted Grewia optiva biofibers as reinforcement.  相似文献   

16.
Chitosan (0.1–1%, w/w), dissolved in 2% acetic acid solution, was added into 1% methylcellulose (MC)-based formulation containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween?80. Films were prepared by casting. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient and water vapour permeability (WVP) of the films were measured. The PS value of 312 N/mm was observed for MC-based films containing 0.25% chitosan. Values of PD, viscoelasticity coefficient and WVP of these films were 5.0 mm, 44.1%, and 6.0 g mm/m2 day kPa, respectively. The MC-based films containing 0.25% chitosan were also exposed to gamma radiation (0.5–50 kGy). The PS of the treated films decreased significantly from 312 at 0 kGy to 201 N/mm when treated at a dose of 50 kGy. However, WVP values were not affected by increasing irradiation the dose used. The Fourier Transform Infrared spectroscopy supported the molecular interactions due to addition of chitosan in MC-based films. Thermo gravimetric analysis and differential scanning calorimetric experiments showed that thermal properties of the films were significantly improved by chitosan loading. Surface topography of the films was studied by scanning electron microscopy and found rougher due to chitosan addition.  相似文献   

17.
Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm−1 and ca. 1050 cm−1 for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.  相似文献   

18.
Biodegradable copolymers of l-lactide(l-LA) and p-dioxanone(PDO) were synthesized in supercritical carbon dioxide (scCO2) with stannous octoate as the ring-opening catalyst and a fluorocarbon polymer surfactant as an stabilizer. Fine powderous products were achieved when more than 90% (w/w) l-LA was fed. Scanning electron micrographic images and laser diffraction particle size analysis of the products showed the mean diameter of particles greatly increased as the content of PDO increased. The obtained polymers had the number-average molecular weights ranging from 15,000 to 26,000 g mol−1 (polydispersity index ranging from 1.3 to 2.1) according to the gel permeation chromatography measurements. The polymer structure was characterized by NMR spectroscopy, indicating the formation of copolymers. Thermal properties of the obtained polymers investigated using differential scanning calorimetry showed that the morphology of products was directly relevant to the crystallinity of the copolymers. The polymerization of l-LA and PDO copolymers in scCO2 is also proposed as a novel production technique for high-purity, biodegradable polymers.  相似文献   

19.
The biodegradation behavior of PCL film with high molecular weight (80,000 Da) in presence of bacterium Alcaligenes faecalis and the analysis of degraded polymer film have been carried out. Thin Films of PCL were prepared by means of solution casting method and the bacterial degradation behavior was carried in basal medium, in presence of bacteria with time variation after UV treatment. It was observed that after UV treatment the degradation of polymer film was increased and the degradation rate followed a three steps degradation mechanism. The degraded polymer film was analyzed by means of Differential Scanning Calorimeter (DSC), Thermo Gravimetric Analyzer (TGA) and Fourier Transform Infrared Spectroscope (FTIR). DSC results revealed that at the initial stages of the degradation up to 15–20 days, the bacterium preferentially degrades the amorphous parts of the polymer film over the crystalline zone. Thermo gravimetric analysis highlighted the low temperature stability of degraded films with extent of degradation. FTIR results showed the chain scission mechanism of the polymer chains and also supported the preferential degradation of amorphous phase over crystalline phase in the initial stages of the degradation.  相似文献   

20.
Degradation of a model polymer mixture (PVC/PS/PE) and a waste polymer mixture in the presence of HCl fixators (Red Mud, precipitated CaCO3 and dolamite) was studied using thermal gravimetric analysis (TGA) and a cycled-spheres-reactor. The experiments in cycled-spheres reactor model were performed by stepwise pyrolysis. Liquid products and HCl from each step were collected separately. For the model polymer mixture, the precipitated CaCO3 showed the best effect on the fixation of evolved HCl and the reduction of chlorine content in the liquid products whereas RM yielded the best result for the waste polymer mixture. In addition, using HCl fixator also affected the degradation of both types of polymer mixture, leading to the formation of more gaseous and less residue.  相似文献   

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