Quaternized Chitosan for Ecological Treatment of Bauxite Mining Effluents

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 (TMC_Cl^?) 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.     

The Shape Memory Properties of Biodegradable Chitosan/Poly(l-lactide) Composites

The shape memory behavior of PLLA (poly(l-lactide)) and chitosan/PLLA composites was studied. PLLA and chitosan were compounded to fabricate novel materials which may have biodegradability and biocompatibility. Chitosan does not significantly affect the glass and melting transition temperature of the PLLA. Both the pure PLLA and chitosan/PLLA composites showed shape memory effect arising from the viscoelastic properties of PLLA comprised of semi crystalline structures. The shape recovery ratio of the chitosan/PLLA composites decreased significantly with increasing chitosan contents due to the incompatibility between PLLA and chitosan. Phase separation structures of the composites were observed by using atomic force microscopy. To obtain good shape memory effect, the chitosan content should be below 15 wt%.     

壳聚糖的絮凝性能及其在废水脱色处理中的应用

介绍了壳聚糖的理化性质及其作为絮凝剂的优点,探讨了壳聚糖的絮凝机理,分析了壳聚糖絮凝效果的影响因素(包括废水p H、絮凝温度、搅拌转速及时间、壳聚糖投加量、壳聚糖脱乙酰度及相对分子质量、废水浊度),总结了壳聚糖改性和复合后在废水脱色处理中的应用。指出:未来还需更深入地研究絮凝机理,同时也需进一步研究影响絮凝效果的因素;新型壳聚糖絮凝剂将向更高效、成本更低且环境友好的方向发展。     

Mechanical and Barrier Properties of Biodegradable Films Made from Chitosan and Poly (Lactic Acid) Blends

Biodegradable film blends of chitosan with poly(lactic acid) (PLA) were prepared by solution mixing and film casting. The main goal of these blends is to improve the water vapor barrier of chitosan by blending it with a hydrophobic biodegradable polymer from renewable resources. Mechanical properties of obtained films were assessed by tensile test. Thermal properties, water barrier properties, and water sensitivity were studied by differential scanning calorimeter analysis, water vapor permeability measurements, and surface-angle contact tests, respectively. The incorporation of PLA to chitosan improved the water barrier properties and decreased the water sensitivity of chitosan film. However, the tensile strength and elastic modulus of chitosan decreased with the addition of PLA. Mechanical and thermal properties revealed that chitosan and PLA blends are incompatible, consistent with the results of Fourier transform infrared (FTIR) analysis that showed the absence of specific interaction between chitosan and PLA.     

Fabrication of Nano Zero valent Iron/Biopolymer Composite with Antibacterial Properties for Simultaneous Removal of Nitrate and Humic Acid: Kinetics and Isotherm Studies

Journal of Polymers and the Environment - This investigation compared the adsorption behavior of humic acid (HA) on cellulose, chitosan and nano zerovalent iron/chitosan (nZVI/chitosan). Results...     

Renewable Resources and Enzymatic Processes to Create Functional Polymers: Adapting Materials and Reactions from Food Processing

We are exploiting materials and concepts from food science to create functionalized, environmentally friendly derivatives of the biopolymer chitosan, a byproduct of seafood processing. Functional groups are grafted onto chitosan using tyrosinase, the enzyme responsible for food browning. The functionalizing groups studied include low-molecular-weight phenols derived from natural sources and high-molecular-weight proteins. The approach of using low-molecular-weight phenols to functionalize chitosan is illustrated with arbutin, a natural phenol found in pears. Results demonstrate that tyrosinase initiates reactions that lead to the conversion of arbutin–chitosan solutions into gels. These gels can be rapidly broken by treatment with the chitosan-hydrolyzing enzyme chitosanase, demonstrating that the chitosan derivatives remain biodegradable. We briefly review other studies in which low-molecular-weight natural phenols are enzymatically grafted onto chitosan to confer functional properties. The creation of co-polymers is illustrated by results in which tyrosinase is used to couple gelatin onto chitosan. Gelatin is a proteinaceous byproduct of meat production. The tyrosinase-generated gelatin–chitosan conjugates have been observed to offer interesting rheological and thermal properties. These results demonstrate the potential for using renewable resources and enzymatic processing to create environmentally friendly polymers with useful functional properties.     

Fabrication of Polypyrrole/Chitosan Nanocomposite Aerogel Monolith for Removal of Cr(VI)

Three-dimensional polypyrrole/chitosan nanocomposite monoliths are fabricated by polymerization of pyrrole in chitosan aqueous solution. The static polymerization of pyrrole monomer and the cross-linking of chitosan by glutaraldehyde occur simultaneously, resulting in the self-assembly of polypyrrole/chitosan nanocomposite aerogel monolith. The addition of methyl orange and glutaraldehyde and the static reaction play key roles in the formation of the self-standing aerogel monolith. The as-prepared monolith with larger specific surface area exhibits much better adsorption capability for Cr(VI) removal in comparison with that prepared without the addition of glutaraldehyde. The adsorption process and adsorption isotherms are found to well follow the pseudo-second-order and Langmuir models, respectively. Furthermore, this polypyrrole/chitosan nanocomposite monolith is stable and recyclable. About 73.5% of the initial adsorption capability is kept after eight adsorption–desorption cycles. The polypyrrole/chitosan nanocomposite monolith can be a promising candidate for the efficient removal of Cr(VI).     

交联壳聚糖/沸石复合吸附剂的制备及性能

用沸石负载由缩水甘油基三乙基氯化铵交联的壳聚糖,制得了性能良好的交联壳聚糖/沸石复合吸附剂。研究了该吸附剂应用性能的影响因素,探讨了该吸附剂的吸附性、沉降性和重复使用性,利用FTIR仪和高倍透射电子显微镜对该吸附剂的结构进行了表征。实验结果表明:壳聚糖的交联度为0.93、交联壳聚糖与沸石的质量比为0.045时,制得的交联壳聚糖/沸石复合吸附剂对腐殖酸的去除率可达81.4%,吸附量为4.07mg/g;交联壳聚糖/沸石复合吸附剂对腐殖酸的吸附性能较沸石有显著提高,沉降时间较交联壳聚糖明显缩短;经二次洗脱后腐殖酸去除率仍可达80.2%,腐殖酸吸附量为4.01mg/g。     

Adsorption Kinetics of Dyes in Single and Binary Systems Using Cyanoguanidine-Crosslinked Chitosan of Different Deacetylation Degrees

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.     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Influence of the Concentrations of Chitosan and Glycerol on Edible Film Properties Showed by Response Surface Methodology

The individual and interactive effects of glycerol and chitosan concentrations on edible film properties were investigated using response surface methodology. The results of ANOVA indicated that all the independent variables exhibited significant effect on the film properties. Chitosan concentration had a positive effect on CO₂ permeability and negative effect on O₂ while the glycerol concentration had a positive effect on permeability to both gases. Regarding water vapor permeability, the chitosan concentration had a negative effect, whereas the glycerol had no influence. Moreover, both chitosan and glycerol concentration influenced the elongation at break point (%A), and only glycerol concentration had a significant effect on tensile strength. Optimization by desirability approach was carried out on the independent variables to get the optimum levels within the experimental conditions. It was found that 1.5 % of chitosan and 25 % of glycerol (wt/wt of chitosan) retarded respiration and showed a strong permeability to water vapor.     

Recovery of gold by chicken egg shell membrane-conjugated chitosan beads

We have successfully prepared a bead-type adsorbent from two materials with different adsorption characteristics. Heavy metals were removed by greatly swollen egg shell membrane-conjugated chitosan beads. The egg shell membrane accumulated and removed precious metal ions from a dilute aqueous solution with a high affinity in a short contact time. Experiments suggested that chitosan beads could take up gold ions with great capacity and selectivity by conjugation with egg shell membrane. Under certain conditions, the selective removal of gold and copper in a mixture of gold and copper ions by egg shell membrane-conjugated chitosan beads was 100% and 2%, respectively. Egg shell membrane-conjugated chitosan beads can be seen as a promising material to recover gold in wastewater from various industries, such as electroplating.     

Improvement of Physico-mechanical Properties of Chitosan Films by Photocuring with Acrylic Monomers

Natural polymer, chitosan was obtained from dried prawn shell waste through the preparation of chitin and was characterized. Thin film of chitosan was prepared by casting method from its 2% chitosan solution. Mechanical properties like tensile strength (TS), elongation at break (Eb) of chitosan film were studied. Five formulations were developed with 2-ethyl-2-hydroxy methyl-1,3-propandiol trimethacrylate (EHMPTMA), a trifunctional monomer and 2-ethylhexyl acrylate (EHA), a monofunctional monomer in the presence of photoinitiator Darocur-1664 (2%). The film was soaked in those monomer formulations in dissimilar soaking times and irradiated under UV-radiation at different radiation intensities for the improvement of the properties of chitosan film. The cured films were then subjected to various characterization tests like TS, Eb, polymer loading (PL), water absorbency, gel content etc. The formulation, containing 25% EHMPTMA and 73% EHA showed the best performance at 10th UV passes of UV radiation for 4 min soaking time.     

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

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 T_g (glass transition temperature), T_m (melting point temperature), and T_max (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.     

Clean Preparation Process of Chitosan Oligomers in Gly Series Ionic Liquids Homogeneous System

Chitosan oligomers because of its water solubility has some special physiological functions, such as binding lipid, affecting the mitogenic response, restraining the growth of tumors, and was widely used in cosmetics and health. H₂O₂/Gly (Glycine) series ionic liquids system, a new solvable-catalytic system, was an efficient clean process for preparation of chitosan oligomers. The effects of the anions of Gly series ionic liquids on the solubility and degradation for chitosan were investigated, and the results showed that [Gly]Cl aqueous solution was of good solubility and assistant degradation for chitosan. In additional, the mechanism for oxidative degradation of chitosan in ionic liquids (ILs) was studied. The effect on the property of chitosan oligomers catalyzed by H₂O₂, in two different kinds of solvents (HAc and [Gly]Cl) were compared. It was found that the performance of moisture absorption and retention of chitosan oligomers using ionic liquid aqueous solution as solvent was better than that using HAc aqueous solution as solvent, and even superior to that of hyaluronic acid. Furthermore, [Gly]Cl could be easily separated from the product and reused with only slight loss. It could provide an efficient and environmental friendly method for the preparation of chitosan oligomers in H₂O₂/ILs system.     

Synthesis,Characterization, and Evaluation of Degussa P25/Chitosan Composites for the Photocatalytic Removal of Sertraline and Acid Red 18 from Water

Journal of Polymers and the Environment - Degussa P25 titanium dioxide/chitosan composites (P25/CS) were prepared using three different methods and two different chitosan materials. The obtained...     

Thermal Stability and Degradation of Chitosan Modified by Acetophenone

N-(Methylphenylmethylidenyl) chitosan (MPMC) polymer was synthesized by chemical modification of chitosan. The chemical structure of the modified polymer was characterized by IR, ¹H NMR and elemental analysis. Thermogravimetric reveals that the thermal stability of chitosan polymer is greater than MPMC polymer. The activation energies of thermal degradation of chitosan and MPMC polymers determined using Arrhenius relationship. Thermal degradation of MPMC polymer was studied and the products of degradation were identified by GC–MS technique. It seems that the mechanism of degradation of MPMC polymer is characterized by elimination of low-molecular weight radicals. Combination or recombination of H^· or OH⁻ with these radicals and random scission mechanism along the backbone chain are the main source of the degradation products.     

Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films

Poly(lactic acid) (PLA) is a biodegradable polymer that exhibits high elastic modulus, high mechanical strength, and feasible processability. However, high cost and fragility hinder the application of PLA in food packaging. Therefore, this study aimed to develop flexible PLA/acetate and PLA/chitosan films with improved thermal and mechanical properties without the addition of a plasticizer and additive to yield extruder compositions with melt temperatures above those of acetate and chitosan. PLA blends with 10, 20, and 30 wt% of chitosan or cellulose acetate were processed in a twin-screw extruder, and grain pellets were then pressed to form films. PLA/acetate films showed an increase of 30 °C in initial degradation temperature and an increase of 3.9 % in elongation at break. On the other hand, PLA/chitosan films showed improvements in mechanical properties as an increase of 4.7 % in elongation at break. PLA/chitosan film which presented the greatest increase in elongation at break proved to be the best candidate for application in packaging.     

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。     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.