壳聚糖改性凹凸棒土对重金属离子的吸附

采用浸渍法将壳聚糖负载在凹凸棒土上,制备了改性的凹凸棒土。用该吸附剂吸附溶液中Pb^2＋,Cd^2＋的实验结果表明：未负载壳聚糖时,凹凸棒土对Cd^2＋的吸附率为55%;当负载壳聚糖的质量分数为0.04时,凹凸棒土对Cd^2＋的吸附率达最大值（为91%）,对Pb2＋的吸附率也达最大值（为75%）。其吸附行为符合Langmuir等温吸附方程和Freundlich等温吸附方程。该吸附剂可重复使用。     

Alkali Treated 3D Chitosan Scaffolds with Enhanced Strength and Stability

Journal of Polymers and the Environment - 3D chitosan scaffolds treated with alkali showed enhanced mechanical properties and stability in aqueous conditions. Chitosan is a preferred polymer for...     

Properties of Low Molecular Weight Chitosan Obtained by Catalytic Degradation Using Lanthanum(III)/Halloysite Nanotube Catalysts

Journal of Polymers and the Environment - The catalytic degradation of chitosan (CS) using halloysite nanotubes-supported lanthanum(III) (HNT-La3+) catalysts have been studied. The HNT-La3+...     

Dynamic Mechanical Behavior and Thermal Characterization of Biofilms Based on Starch Modified by Fungi Isolates

Starches modified by Ophiostoma spp. have been investigated to develop bio-materials with enhanced mechanical and physical properties for thermoplastic applications. In this study, glass transition temperature (T_g) of modified starches was investigated in both dynamic mechanical analyzer (DMA) and differential scanning calorimeter (DSC) to detect molecular changes in the starch’s structure. Overall, two thermal transitions were observed in modified starches, as opposed to one in their native counterparts. Scanning electron microscopy of granular modified starch indicated visible damages and internal structural perturbations in addition to occlusion of granular pores by extraneous materials owing to possible enzymatic degradation and production of secondary metabolites. Modified starches registered two-fold improvement in storage modulus as compared to that of native starches. From the study of second derivative of the mass loss against temperature, two thermal transitions were also identified in modified starches. X-ray diffraction analyses showed that crystalline regions of the starch granules remained intact after the modification. It is proposed that the second phase transition potentially corresponds to modified amylose fractions and/or exopolysaccharides produced by the fungi.     

Characterization of Chemically Modified Potato Starch Films Through Enzymatic Degradation

The present investigation was undertaken to characterize the biodegradation pattern of chemically modified starch films. Chemically modified starch films obtained by esterification of the hydroxyl groups of the polysaccharide have shown lower water sorption than native starch films, being therefore more attractive for a number of processing applications. However, no systematic study characterizing their biodegradation behavior and comparing it with the degradation pattern of native starch films has still been published. In the current contribution we characterized the enzymatic degradation pattern of three derivatized starch films by use of a commercial α-amylase from Bacillus licheniformis. Optimum degradation conditions were chosen upon assaying the effect of enzyme load and temperature on the reaction course of native starch films. Under the conditions selected, comparison of different derivatization procedures revealed that the starch film modified with octanoyl chloride was enzymatically hydrolyzed at a much higher rate than native starch film. Maleated starch films also showed higher susceptibility to α-amylolytic hydrolysis than native starch, whereas acetylated starch showed a hydrolysis pattern similar to that of native starch. Differences in degradation rates of chemically modified films were explained in terms of their amylose content which promotes dense networks that hinder the access of starch-degrading enzymes.     

Determination of Kinetic Parameters for the Degradation of Chitosan/Silica Hybrid Nano Composites

The thermal degradation behavior of chitosan (CS) and chitosan–silica (CS–Si) nanocomposites were studied using a differential kinetic model. The influence of the heating rate in the non-isothermal degradation kinetics of CS and CS–Si nanocomposites are presented. Kinetic parameters, such as the activation energy (E) and pre-exponential factor (A), and thermodynamic parameters, such as the Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were determined using the modified Arrhenius equation. It was shown that the rate constant for degradation (k), activation energy and pre-exponential factor depend on the heating rates. The order of reaction was found to be one. The isothermal stability of CS and CS–Si was determined from non-isothermal kinetics and was also found to be dependent on the heating rate. Thermogravimetric studies revealed that neat CS was less thermally stable than the CS–Si nanocomposites.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

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.     

Competitive Adsorption of Pb(II) and Phenol Onto Modified Chitosan/Vermiculite Adsorbents

Journal of Polymers and the Environment - Many industrial wastewaters are contaminated with both heavy metal ions and organic compounds, posing a major threat to public health and the ecosystem. In...     

Thermal Degradation Mechanism of Low-Density Polyethylene Plastic Wastes in Cyclohexane

The thermal LDPE degradation mechanism harnessing a high-pressure autoclave surrounded by a furnace was investigated in this work. Rates of formation of gas, liquid, and solid during degradation of PE plastic wastes in cyclohexane as solvent at 400 and 425°C have been experimentally determined. Four reaction mechanisms have been proposed and tested to estimates of gas, liquid, and solid. Proposed mechanisms are based on the assumption that the reactions are pseudo-first-order with respect to the reacting species. Pseudo-first-order rate constants for each of the indicated mechanistic steps have been calculated by nonlinear regression analysis. The best fit was obtained by model 2 (pure parallel reaction mechanism), and its activation energy was determined.     

Mechanical and Thermal Properties of PLLA/PCL Modified Clay Nanocomposites

Poly(l-lactic acid) (PLLA)/poly(caprolactone) (PCL) and two types of organoclay (OMMT) including a fatty amide and ocatdecylamine montmorillonite (FA-MMT and ODA-MMT) were employed to produce polymer nanocomposites by melt blending. Materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties were also investigated for these nanocomposites. The nanocomposites showed increasing mechanical properties and thermal stability. XRD results indicated that the materials formed nanocomposites. SEM morphology showed that increasing content of OMMT reduced the domain size of phase separated particles. TEM outcomes have confirmed the intercalated type of nanocomposite. Additionally, a solution casting process has been used to prepare these nanocomposites and characterized to compare these results with the above process.     

Thermal and Environmentally Induced Degradation Behaviors of Amorphous and Semicrystalline PLAs Through Rheological Analysis

Journal of Polymers and the Environment - The degradation behaviors of an amorphous and a semicrystalline PLA (i.e., aPLA and cPLA) with similar molecular weights are compared at elevated...     

Rheological and Thermal Properties of the PLA Modified by Electron Beam Irradiation in the Presence of Functional Monomer

Polylactic acid (PLA) has been modified by electron beam radiation in the presence of glycidyl methacrylate (GMA) to enhance the melt strength of PLA. The modified PLA was prepared by varying both the amount of GMA and the irradiation dose and was characterized by observing the thermal properties, the melt viscoelastic properties and the gel fraction. For comparison, virgin PLA was also irradiated. All irradiated virgin PLA had a lower complex viscosity and a storage modulus compared to virgin PLA due to irradiation-induced chain scission. However, these properties were remarkably improved due to formation of long chain branching and retarding chain scission if GMA was introduced in this system. The increase in melt viscoelastic property was much dependent on the irradiation dose. At optimum doses of radiation, it showed maximum complex viscosity and storage modulus. The PLA irradiated with 20 kGy in the presence of 3 phr GMA showed a complex viscosity of about 10 times higher and a storage modulus of 100 times higher than those of virgin PLA at 0.1 rad/s. Gel fraction measurement revealed that chain scission and branching was more dominant than crosslinking. The biodegradability of irradiated PLA was slightly decreased by the presence of GMA.     

改性Y沸石催化降解聚苯乙烯的研究

用热重分析方法研究了HY沸石与改性Y沸石(UHY)作为催化降解聚苯乙烯的催化剂对聚苯乙烯催化降解的作用及影响,对聚苯乙烯的催化降解与热降解反应产物进行了比较。结果表明,催化剂的存在能显著地降低聚苯乙烯的降解温度,催化剂的酸量和孔结构对聚苯乙烯的降解温度、活化能、积炭的生成量及裂解产物有很大的影响。     

Study of Thermal Decomposition Kinetics of Palm Oleic Acid-Based Alkyds and Effect of Oil Length on Thermal Stability

Thermal decomposition kinetics of three palm oleic acid-based alkyds with different oil lengths and having different molecular weights were studied using TGA measurements under non-isothermal conditions. Activation energies were obtained from Kissinger and Ozawa, Flynn and Wall (OFW) methods and subsequently the pre-exponential factor, A, degradation rate constant, k, for all the alkyds were also determined. From kinetic analysis of the thermal decomposition using the OFW method, it was found that degradation of all the alkyds has taken place in more than two stages, corresponding to different mechanisms. As shown from Ozawa and Kissinger methods, the chemical composition of the alkyds influenced the thermal degradation; increasing the phthalic anhydride and glycerol, and decreasing the oleic acid increased the thermal stabilities of the alkyds.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

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 mol^1.7 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.     

Transcrystal,Polymorphism, Thermal Stability and Biodegradation of Poly(1,4-butylene adipate) Modulated by a Nucleobase

Journal of Polymers and the Environment - In this work, we reported the interesting transcrystals of the poly(1,4-butylene adipate) (PBA) with loading of the bio-derived additive. The overlapped...     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

Highly Efficient Removal of Uranium(VI) From Aqueous Solution Using the Polyethyleneimine Modified Magnetic Chitosan

Journal of Polymers and the Environment - In this study, Polyethyleneimine modified magnetic chitosan (MCS-PEI) was synthesized by grafting polyethyleneimine onto chitosan and adding magnetic Fe3O4...     

Degradation of Polylactide by Commercial Proteases

Fifty-six commercially available proteases were tested for polylactide-degrading activity. Little or no activity was found in acid and neutral proteases, while some alkaline proteases formed appreciable amounts of lactic acid from polylactide. These polylactide-degrading proteases were derived from Bacillus species and had catalytic activity even under neutral, as well as alkaline, conditions. Savinase (Novo Nordisk) degraded polylactide the fastest among the enzymes tested and its specific activity corresponded to about one-half of proteinase K. Polylactide-degrading activity was not always present in the enzymes that affected keratin, while polylactide-degrading proteases commonly hydrolyzed keratin. A significant correlation was observed between degrading activities of polylactide and keratin in alkaline proteases.