Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers Using Various Starches

Graft copolymers of polyacrylamide and various substrates were prepared by reactive extrusion in a twin screw extruder using ammonium persulfate as initiator. Substrates included unmodified starches (corn, waxy maize, wheat, and potato), cationic starches, dextrin, dextran, and polyvinyl alcohol (PVOH). The feed ratio of substrate to monomer was 2:1. Average conversion of monomer to polymer was 88.9% (±5.1%). Graft contents for the starch substrates were approximately 25% with grafting efficiencies of about 70%. Polyacrylamide graft molecular weights ranged from 317,000 to 769,000. Absorbencies at pH 7 for saponified graft copolymers prepared with unmodified starches were approximately 200 g/g and approximately 150 g/g for the cationic starches, dextran, and PVOH. In electrolyte solution (0.9% NaCl), absorbencies were in the range of 26–59 g/g, depending on substrate type. Saponified dextrin copolymers were essentially soluble with absorbencies of 6 g/g in water and 12 g/g in 0.9% NaCl.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Effect of Additives on the Improvement of Mechanical and Degradable Properties of Photografted Jute Yarn with Acrylamide

The jute yarn was grafted with acrylamide monomer (AA) under ultraviolet (UV) radiation to modify its mechanical and degradable properties. A number of AA solutions of different concentrations in methanol (MeOH) along with photoinitiator Irgacure 907 [2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone-1] were prepared. The monomer concentration and irradiation time were optimized. Jute yarn grafted with 30% AA under UV radiation for 60 min showed of the highest polymer loading (PL) value of 22% with a enhanced tensile strength (TS) value of 195% and elongation at break (Eb) value of 256% compared to untreated jute yarn. To further improve the properties of jute yarn, a number of additives (1%) such as urea, polyvinylpyrrolidone, urethane acrylate, and urethane diacrylate were used in the AA (30%) solution. Among all the additives used, urea significantly influenced the PL (27%), TS (230%), and Eb (264%) values of the treated jute yarns. Water uptake and the degradation properties of treated and untreated jute yarn caused by simulated weathering and in soil (25% water) were also studied. The rate of degradation of grafted sample is lower then that of untreated sample. DSC studies showed the thermal stability of the AA plus urea grafted sample.     

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.     

废锂电池放电及正极片分离回收处理

研究了废锂电池放电及正极片分离回收处理工艺。实验结果表明:经质量浓度30 g/L NaCl溶液浸泡9.0 h可实现电池放电,残余电压在0.5 V以下;在60℃恒温水浴振荡、NaOH质量浓度40 g/L、废锂电池质量与NaOH溶液体积的比为15 g/L的优化条件下,集流体完全与活性物质分离,回收得到的黑色粉末为LiCoO2活性材料,未见铝杂质的特征峰;通过硫酸中和的方法回收碱浸溶液中的铝,当体系pH为10.0时,可获得最大量的Al(OH)3沉淀,沉淀物颗粒表面光滑,粒径大小不一。     

Itaconic Acid Grafted Starch Hydrogels as Metal Remover: Capacity,Selectivity and Adsorption Kinetics

Hydrogels were synthesized by free radical graft copolymerization of itaconic acid (IA) onto corn starch (S-g-IA). For this purpose, potassium permanganate (KMnO₄)-sodium bisulfite (NaHSO₃) was used as redox initiation system. The formation of grafted starches was confirmed by Fourier transform infrared spectroscopy, wide angle X-ray scattering, thermogravimetric analysis and scanning electron microscopy. The effect of monomer concentration, neutralization, addition of crosslinking agent, N,N-bismetilenacrilamide (MBAm), and initiator concentration on grafting efficiency and adsorption capacity of the starch hydrogels was investigated. It was demonstrated that the introduction of carboxyl and carbonyl groups promoted starch hydration and swelling. Grafting degree increased with the decrease of monomer concentration, increase of initiator concentration, grade of neutralization and the addition of MBAm without neutralization. Remarkably the resulting materials exhibited water absorption capacities between 258 and 1878% and the ability to adsorb metal ions. It was experimentally confirmed the metal uptake, obtaining the higher adsorption capacity (q _e  = 35 mg/g) for the product prepared with the pre-oxidation and lower initiator concentration. The removal capacity order was Pb²⁺>Ni²⁺>Zn²⁺>Cd²⁺. Moreover, the experimental kinetic and the equilibrium adsorption data for Ni²⁺ and Pb²⁺ were best fitted to the pseudo-second order and Freundlich isotherm models, respectively. This work describes for the first time the preparation of metal removal hydrogels based on starch and itaconic acid using the pair redox system KMnO₄/NaHSO₃, which avoids the starch hydrolysis and allows itaconic acid grafting incorporation without the requirement of more reactive comonomers.     

Some Investigations on the Nylon 6/Zn Composite Material Obtained by Simultaneous Anionic Polymerization-Molding Process

This study is concerned with the behavior of samples based on nylon 6/zinc (Ny6/Zn) composite material in high salinity water that contains NaCl (3.5 wt%) and in aqueous solution of HCl (0.5 N and 1 N). The samples were obtained from parts prepared by in situ anionic ring-opening polymerization of ?-caprolactam (CL) in the presence of zinc (Zn), as filler (15 wt%) using the rotational molding technique. This type of composite was evaluated by the testing of swelling degree, structural modifications, evolution of hydrogen and electrochemical behavior. The properties of Ny6/Zn composite material have ascertained through the combined use of more analysis methods: attenuated total reflectance Fourier transform infrared spectroscopy, wide-angle X-ray diffraction technique, scanning electron microscopy, swelling and electrochemical measurements. It was revealed that regarding swelling behavior the Ny6 matrix has an important role while Zn filler contributes especially to the (electro)chemical corrosion.     

酸化碱渣对氨氮的吸附和解吸性能

研究了氨氮质量浓度、体系温度、时间、酸化碱渣溶液的pH等对酸化碱渣吸附氨氮性能的影响,比较了作为解吸剂的蒸馏水和NaCl溶液对氨氮的解吸效果。在选定的实验条件下,酸化碱渣对氨氮的最大吸附量可达13．9mg／g。氨氮吸附量随其质量浓度的增加而增大、随体系温度的升高而降低,酸化碱渣溶液的pH对吸附性能的影响可以忽略。酸化碱渣表面吸附作用力主要为偶极间力和氢键力,吸附过程可用一级动力学方程模拟。NaCl溶液对氨氮的解吸效果好于蒸馏水,最大解吸率为25．7％。     

Desiccation of contaminant barrier materials amended with aqueous carboxymethyl cellulose solution

The stabilization potential of negatively charged sodium carboxymethyl cellulose (CMC) solution was assessed through investigation of its retention on clays under environmental conditions that promote soil desiccation. Sodium montmorillonite and kaolinite, commonly used in clayey soils, were mixed with aqueous CMC solutions in concentrations ranging from 0 to 10 g/L. These samples were dried in a specially-designed desiccation chamber which was operated at a temperature of 25°C and relative humidity of 30%. The results show an inverse proportionality between liquid loss and CMC concentration. Liquid loss from clayey soil follows the first-order reaction with a rate constant in the range of 4.6–6.7 mg/h. CMC half-lives on sodium montmorillonite during desiccation ranged from 103 to 181 h for an aqueous concentration range of 0.5–10 g/L compared to 108 h for distilled water. For kaolinite, more liquid was retained at 10 g/L CMC concentration than at other concentrations, but liquid retention was generally insignificant. These conclusions are valid for a desiccation duration of 890 h, a time that is reasonably simulative of the duration of exposures of bare ground surfaces to weather elements. The experimental results are explained in terms of the role of CMC molecular interactions with clay minerals in controlling fluid flow to desiccating clay surfaces.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.     

Cement‐based solidification/stabilization of phenol‐contaminated soil by bentonite and organophilic clay

The performance of ordinary and organophilic clays in the solidification and stabilization process was investigated with respect to the unconfined compressive strength (UCS) and leaching of phenol‐contaminated soil. The samples contained 2,000 mg/kg of phenol. White cement (15 and 30 percent by weight [wt%]) was used as binder, while ordinary and organophilic clays (8, 15, and 30 wt%) were applied as additives for reducing the harmful effects of phenol interference in cement hydration with a 28‐day curing time. The results revealed that the UCS is reduced by increasing the amount of clays. The values of UCS of all samples met the minimum standards specified for disposal in sanitary landfills determined by developed countries. The leaching test demonstrated that the degree of leaching diminished with increased clay content in all samples of both clay types. This reduction was observed to be greater in samples containing organophilic clay than in bentonite clay samples. Furthermore, the best composition of the materials tested was determined to be 30 wt% white cement plus 13.3 wt% organophilic clay with a compressive strength of 3,839 kPa, phenol removal percentage of 80 percent, and a cost of $67 per ton of contaminated soil.     

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8–1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20 wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1 day, accordingly to EN 12457 regulation and extended to 7 days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.     

非离子型聚丙烯酰胺絮凝剂的制备及其絮凝性能

以丙烯酰胺（AM）和烷基酚聚醚（APAP）为单体,采用反相乳液聚合法制备了流动性好的非离子型聚丙烯酰胺絮凝剂（PAM-APAP）。考察了乳化剂和引发剂的种类、单体总质量分数、单体配比和反应温度等因素对聚合反应的影响。实验结果表明,制备PAM-APAP的最佳工艺条件为：单体总质量分数35%、m（AM）∶m（APAP）=9.0∶1.0、Span80+Tween80复配乳化剂加入量为油水总质量的7%、m（Span80）∶m（Tween80）=7.0∶1.5、V50加入量为单体总质量的1.5‰、反应温度50℃。PAM-APAP具有较好的絮凝效果,与其他絮凝剂相比用量较少,在加入量为100mg/L时,对聚合物驱油中产生的含聚合物污水的浊度去除率为87.9%,去油率为89.5%,且絮体不黏壁。     

O3氧化法和O3-H2O2氧化法去除水中聚丙烯酰胺

采用O3氧化法和O3-H2O2氧化法去除水中的聚丙烯酰胺（PAM）,分别考察了反应时间、O3质量浓度、n（H2O2）∶n（O3）和溶液pH对PAM去除效果的影响。实验结果表明：O3氧化的最佳操作条件为反应时间30 min、O3质量浓度22.6 mg/L、溶液pH 8.5,O3-H2O2氧化的最佳操作条件为反应时间10 min、O3质量浓度22.6 mg/L、n（H2O2）∶n（O3）=0.1、溶液pH 8.5;在最佳操作条件下,O3氧化和O3-H2O2氧化均可有效降低PAM溶液的黏度和PAM质量浓度,但对COD的去除效果不佳,黏度可降至和蒸馏水相近,PAM的去除率可达80%以上,而COD的去除率分别约为15%和28%;O3-H2O2氧化后的PAM比O3氧化后的PAM更容易被微生物利用,两种氧化预处理方法均有利于后续的生化处理。     

Synthesis of Gum Acacia Capped Polyaniline-Based Nanocomposite Hydrogel for the Removal of Methylene Blue Dye

In this research work, a novel gum acacia capped polyaniline-based nanocomposite hydrogel (GPA NCHs) was developed and evaluated for the adsorptive removal of cationic methylene blue dye (MB) from aqueous solutions. Firstly, Gum acacia (GA) capped Polyaniline (PANI) dispersion was synthesized by using dispersion polymerization. Then, a water-swellable hydrogel network consisting of GA-PANI and acrylamide (AM) was obtained by using N,N′ -methylene-bisacrylamide (MBA) as a cross-linker, and ammonium persulphate/N,N,N′,N′-tetramethylethylenediamine (APS/TMEDA) as an initiating system. The developed materials were characterized by UV–visible, FTIR, XRD, SEM–EDX and TEM techniques. The microscopy studies revealed that GA-PANI nanoparticles have a granular morphological surface with an average size of?~?40–100 nm. Removal of MB dye from aqueous system was performed by adsorption studies in batch equilibrium mode with different dosage of GA-PANI, MB concentration, pH and temperatures. The adsorption data revealed that the absorption capacity of GPA NCHs highly depends on the dosage of GA-PANI, pH and concentration of the MB dye. The maximum percentage of MB removal onto GPA 1.0 NCHs was found to be 89% at pH 10 with a dye concentration of 10 mg L^?1. The equilibrium adsorption data were also analyzed by different models to understand the adsorption process. The results revealed that the adsorption process followed the pseudo-second-order kinetics and it fit well in Langmuir and Freundlich adsorption isotherms with a maximum adsorption capacity of 35.41 mg g^?1. These studies demonstrate that the GPA NCHs could be a promising adsorbent material for the removal of MB dye from contaminated aqueous systems.

     

中和—絮凝法回收硝酸型退锡废水中的锡

将传统的中和法和絮凝法相结合,采用中和—絮凝法回收硝酸型褪锡废水中的锡,考察了反应终点体系pH、碱液浓度、絮凝剂浓度等因素对锡回收效果的影响。实验结果表明,在NaOH溶液浓度为6 mol/L、反应终点体系pH为0.8、聚丙烯酰胺溶液质量浓度为3 g/L的工艺条件下,可得到干基锡含量54.6%（w）的高品位锡泥。与传统的单一中和/絮凝法相比,采用中和—絮凝法不仅可以有效提高生产效率,而且减少了碱液和絮凝剂用量,回收锡之后体系中大量的硝酸可进一步回收利用。     

Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion

Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.     

Recycling of waste tyre rubber into oil absorbent

The abundant and indiscriminant disposal of waste tyres has caused both health and environmental problems. In this work, we provide a new way to dispose off waste tyres by reusing the waste tyre rubber (WTR) for oil absorptive material production. To investigate this feasibility, a series of absorbents were prepared by graft copolymerization-blending method, using waste tyre rubber and 4-tert-butylstyrene (tBS) as monomers. Divinylbenzene (DVB) and benzoyl peroxide (BPO) were employed as crosslinker and initiator, respectively. The existence of graft-blends (WTR-g-tBS) was determined by FTIR spectrometry and verified using thin-layer chromatography (TLC). In addition, the thermal properties of WTR-g-tBS were confirmed by a thermogravimetric analyzer (TGA). Oil absorbency of the grafted-blends increased with increases in either feed ratio of WTR to tBS or DVB concentration. This absorbency reached a maximum of 24.0gg(-1) as the feed ratio and DVB concentration were 60/40 and 1wt%, respectively, after which it decreased. At other ratios and concentrations the absorbency decreased. The gel fraction of grafted-blends increased with increasing concentration of DVB. Oil-absorption processes in pure toluene and crude oil diluted with toluene were found to adhere to first-order absorption kinetics. Furthermore, the oil-absorption rate in diluted crude oil was observed to be lower than pure toluene.     

Synthesis and Characterization of a Thin-Film Composite Nanofiltration Membrane Based on Polyamide-Cellulose Acetate: Application for Water Purification

Membrane separation has been widely used for various applications including microfiltration (MF), ultrafiltration (UF), and nanofiltration (NF) processes in the fields of biomedicine, food, and water purification. In this work, a facile synthesis of new polyamide thin-film composite nanofiltration membranes (NF-TFC) for water purification was described. The polyamide thin film was deposed over a synthetic cellulose acetate (CA) support by interfacial polymerization method. 1,3 cyclohexane bis (methylamine) (CHMA) and trimesoyl chloride (TMC) were used as monomers. The membranes were characterized using Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FT-IR), water uptake, porosity, contact angle, water permeability and rejection towards specific salt and dye molecules. The effect of the variation of the CHMA concentration (0.2–2 wt.%) on the morphology, porosity, water permeation and rejection properties of the prepared membranes was studied. SEM results displayed the growth of the membrane thickness when the CHMA concentration increased from 0.2 to 2 wt.%. The strong adhesion between the cellulose acetate substrate and the polyamide layer explained by the formation of the polyamide film in the substrate surface and inside the pores. The water permeability varied from 36.02 to 17.09 L h^?1 m^?2 bar^?1. The salt rejection of Na₂SO₄ and NaCl increased from 9 to 68% and from 38.41% to 89.4%, respectively, when the CHMA concentration was changed from 0.2 to 2 wt.%. The prepared membranes were further applied successfully for the removal of malachite green and congo red. The results indicated that the maximum rejection reached 89% and 85% for malachite green and congo red, respectively.

     

Cell-recycle fed-batch production of a highly unsaturated polyhydroxyalkanoate from 1,3-butanediol byPseudomonas sp. A33

The recently isolatedPseudomonas sp. A33 was investigated for the production of a highly unsaturated polyhydroxyalkanoate (PHA) containing various alkyl and alkenyl pendent groups from 1,3-butanediol in a cell-recycle fed-batch production mode. The monomer composition and degree of unsaturation in PHA were dependent on the environmental conditions. The production temperature markedly influenced the content, composition, and degree of unsaturation of PHA. As the production temperature decreased from 30 to 10°C, the degree of unsaturation and content of PHA were increased, while the mole percentage of 3-hydroxybutyrate (3HB) was decreased. These temperature effects on the composition of PHA imply that the production can be used as a control variable for the biosynthesis of a highly unsaturated PHA and for the specific regulation of the composition of PHA. The biosynthetic pathway for a highly unsaturated PHA which is based on de novo fatty acid biosynthetic pathway is proposed. For the enhanced production of this functional PHA, a high cell density was achieved by cell-recycle continuous culture at 30°C, and then a large amount of PHA was accumulated at 15°C by fed-batch addition of the feeding solution containing excess 1,3-butanediol. The structures of monomer constituents of polymer were confirmed by gas chromatography—mass spectrometric analysis of trimethylsiyl derivatives of 3-hydroxyalkanoic acids methyl esters.     

Rheology of Concentrated Cellulose Solutions in 1-Butyl-3-methylimidazolium Chloride

Rheological behavior of the concentrated cellulose/1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solutions was investigated. As polymeric fluid, solutions of cellulose in [BMIM]Cl display a marked elastic behavior under shear flow. The dependence of the shear viscosity η, and of the dynamic modulus, on concentration, average degree of polymerization (DP) and temperature is discussed. At lower concentrations and degrees of polymerization (DP), cellulose solutions show viscous, inelastic behavior at low frequencies and low shear rate. At higher concentration and DP, cellulose solutions are more elastic at higher frequencies and shear rate. Such solutions also have some usual rheological properties. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions at high deformation rate. Plotting storage modulus G′ against loss modulus G″ gave almost a master curve which is independent of temperature and concentration, with the slope of about 1.651 for 10 wt% cellulose solutions. This value indicates the existence of microheterogeneity in the solution system.