聚氨酯材料表面微波辅助接枝聚乙二醇的研究

采用微波辐照辅助技术在聚氨酯膜的表面接枝聚乙二醇,并与传统加热反应接枝聚乙二醇的方法进行对比。结果表明,微波辅助反应能明显加快聚氨酯表面接枝PEG的速度,其接枝效果受微波功率、反应时间以及投料比的影响。在实验条件下,微波功率为100W,反应物的质量分数为5%,反应时间为10min时,微波辅助表面接枝反应效果以及效益最好。SEM和AFM表面分析表明,与传统加热反应方法相比,微波辅助反应对膜表面的破坏程度更小,膜表面更加光滑平整。水接触角的结果也表明,微波辅助反应接枝PEG所得膜表面具有良好的亲水性能。     

Biobased polymeric flocculants for industrial effluent treatment

Water is a scare commodity now. Recycling of municipal wastewater, industrial and mineral processing effluents require treatment with the inorganic or organic flocculants. Inorganic flocculants are used in large quantities, leave large amount of sludge and are very much affected by pH changes. Other polymeric flocculants are used in a very minute quantity, form large cohesive floc and are inert to pH changes. Both natural and synthetic polymers are used as flocculants. Natural polymers are biodegradable and are effective at very large dosages but are very shear stable. The synthetic polymers are highly effective flocculants at very small dosages and have high tailorability, but have poor shear stability. In the authors laboratory, a new class of flocculants has been developed by grafting polyacrylamide branches onto polysaccharide such as guargum, hydroxypropyl guargum, starch, amylopectin and sodium alginate. These grafted polysaccharides exhibit synergistic flocculation characteristics, shear stability and controlled biodegradability. Out of all the grafted polysaccharides, amylopectin grafted polysaccharides out performs most of the commercially available flocculants. The polacrylamide branches grafted on high molecular weight branched amylopectin have larger approachability to contaminants in the industrial effluents [1, 2].     

Sequential separation of lanthanides, thorium and uranium using novel solid phase extraction method from high acidic nuclear wastes

A novel grafted polymer for selective extraction and sequential separation of lanthanides, thorium and uranium from high acidic wastes has been developed by grafting Merrifield chloromethylated (MCM) resin with octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) (MCM-CMPO). The grafting process is well characterized using FT-IR spectroscopy, (31)P and (13)C CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNPS elemental analysis. The influence of various physico-chemical parameters during metal ion extraction by the resin phase are studied and optimized by both static and dynamic methods. The resin shows very high sorption capacity values of 0.960mmolg(-1) for U(VI), 0.984mmolg(-1) for Th(IV), 0.488mmolg(-1) for La(III) and 0.502mmolg(-1) for Nd(III) under optimum HNO(3) medium, respectively. The grafted polymer shows faster rate exchange kinetics (<5min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, sequential separation of the analytes is possible with varying eluting agents. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. All the analytical data is based on triplicate analysis and measurements are within 3.5% rsd reflecting the reproducibility and reliability of the developed method.     

淀粉接枝丙烯酰胺制备絮凝剂的研究方法

对淀粉接枝丙炮酰胺的制备方法,分离提纯方法,接枝产物的表征方法及絮凝实验方法进行了综述。     

Graft copolymerization of 2-vinyl pyridine and styrene onto isotactic polypropylene powder by the preirradiation method

Preirradiated isotactic polypropylene (IPP) powder has been modified by grafting 2-vinyl pyridine (2-VP) and styrene (Sty) in an aqueous medium. The graft copolymerization reaction was studied under different experimental conditions such as total dose, monomer concentration, amount of the solvent, time of reaction and temperature to determine the optimum conditions for affording maximum percentage of grafting (P_g). Maximum grafting percent of 2-VP (180%) and styrene (117%) was obtained under optimum conditions. The rate of grafting (R_g) of 2-VP and styrene has also been determined as a function of total dose, initial monomer concentration and the reaction temperature. From maximum P_g and different R_g values of 2-VP and Sty, 2-VP is more reactive towards grafting as compared to styrene under optimum conditions. Characterization of the graft copolymers is based on differential scanning calorimetric (DSC) analysis. Isolation of the grafted poly(2-VP) and poly(styrene) chains from the grafted samples provides an additional evidence of formation of the graft copolymer.     

Microwave assisted template synthesis of silver nanoparticles

Easier, less time consuming, green processes, which yield silver nanoparticles of uniform size, shape and morphology are of interest. Various methods for synthesis, such as conventional temperature assisted process, controlled reaction at elevated temperatures, and microwave assisted process have been evaluated for the kind of silver nanoparticles synthesized. Starch has been employed as a template and reducing agent. Electron microscopy, photon correlation spectroscopy and surface plasmon resonance have been employed to characterize the silver nanoparticles synthesized. Compared to conventional methods, microwave assisted synthesis was faster and provided particles with an average particle size of 12 nm. Further, the starch functions as template, preventing the aggregation of silver nanoparticles.     

聚乙烯表面亲水化改性及其血液相容性改进

以过氧化苯甲酰（BPO）为引发剂,在聚乙烯（PE）膜表面接枝丙烯酸（AA）以改善其亲水性。系统地讨论了引发剂浓度、单体浓度、反应温度以及反应时间等各影响因素对接枝率的影响,并通过傅立叶变换红外（FT-IR）、表面水接触角等物理手段来表征接枝膜的表面结构、亲水性等性能。实验结果表明BPO能成功引发丙烯酸接枝PE膜,接枝改性后PE膜亲水性有了明显的提高。采用了3种比较直观的常规评价方法对PE膜接枝改性前后的血液相容性进行初步的评价。研究结果表明表面接枝AA后的PE膜与血细胞的相互作用较弱,对血细胞的破坏程度明显减小,其抗凝血性比未接枝改性膜有显著提高。     

Synthesis and characterisation of styrene butadiene styrene-g-N-vinyl-2-pyrrolidinone for use in biomedical applications

The current contribution investigates the potential use of styrene butadiene styrene (SBS) block copolymer grafted with N-vinyl-2-pyrrolidinone (NVP) for use as a novel biomaterial. SBS-g-NVP was synthesised using UV polymerisation and analytical techniques such as differential scanning calorimetry (DSC), attenuated total reflectance infrared Fourier transform spectrometry (ATR-FTIR), dynamic thermal mechanical analysis (DMTA) and goniometry were used to characterise the grafted copolymers. The ATR-FTIR spectrum for grafted SBS-g-NVP copolymer exhibits a shoulder at 1714 cm^?1, which is associated with carbonyl stretching of NVP. DSC analysis showed the grafted copolymers had broader thermographs within the butadiene rich domain resulting in increased T_g values, suggesting that grafting occurred. Confirmation of this was established by the use of DMTA, where the T_g (?90 °C) which represents the butadiene domain increased to ?76 °C, thus proving grafting. The surface chemistries of the grafted copolymers have also been altered which is reflected in the goniometry results which show a dramatic reduction in contact angles (113° to 7°), which is a desired property for biomedical polymers.     

Microwave assisted synthesis of nanocrystalline YAG

Using nitrate precursors, a novel microwave assisted citrate gel process for the preparation of nanocrystalline yttrium aluminium garnet (YAG) phase has been developed. Synthesis of single phase polycrystalline YAG was achieved at temperatures as low as 600 °C using the microwave methodology whilst conventional approaches currently available require ≥1000 °C. The microwave prepared YAG powder was characterised using X-ray diffraction, FTIR spectroscopy, TEM and EDAX. The microwave method was found to yield YAG particles of ∼40 nm diameter, whilst the conventional route yielded 150 nm particles. Also substantial morphological differences were observed between the YAG particles and their agglomerates produced by the different processing methods.     

Treatment of pulp and paper mill wastewater by polyacrylamide (PAM) in polymer induced flocculation

The flocculation performances of nine cationic and anionic polyacrylamides with different molecular weights and different charge densities in the treatment of pulp and paper mill wastewater have been studied. The experiments were carried out in jar tests with the polyacrylamide dosages range of 0.5-15 mg l(-1), rapid mixing at 200 rpm for 2 min, followed by slow mixing at 40 rpm for 15 min and settling time of 30 min. The effectiveness of the polyacrylamides was measured based on the reduction of turbidity, the removal of total suspended solids (TSS) and the reduction of chemical oxygen demand (COD). Cationic polyacrlyamide Organopol 5415 with very high molecular weight and low charge density is found to give the highest flocculation efficiency in the treatment of the paper mill wastewater. It can achieve 95% of turbidity reduction, 98% of TSS removal, 93% of COD reduction and sludge volume index (SVI) of 14 ml g(-1) at the optimum dosage of 5 mg l(-1). SVI values of less than 70 m lg(-1) are found for all polyacrylamide at their respective optimum dosage. Based on the cost evaluation, the use of the polyacrylamides is economically feasible to treat the pulp and paper mill wastewaters. This result suggests that single-polymer system can be used alone in the coagulation-flocculation process due to the efficiency of the polyacrylamide. Sedimentation of the sludge by gravity thickening with settling time of 30 min is possible based on the settling characteristics of the sludge produced by Organopol 5415 that can achieve 91% water recovery and 99% TSS removal after 30 min settling.     

Microwave-mediated synthesis for improved morphology and pseudocapacitance performance of nickel oxide

Synthetic methods greatly control the structural and functional characteristics of the materials. In this article, porous NiO samples were prepared in conventional-reflux and microwave assisted heating method under homogeneous precipitation conditions. The NiO samples synthesized in conventional reflux method showed flakelike morphology, whereas the sample synthesized in microwave methods showed hierarchical porous ball like surface morphology with uniform ripple-shaped pores. The NiO samples characterized using BET method were found to bear characteristic meso- and macroporosity due to differently crystallized Ni(OH)(2) precursors under various heating conditions. Thermogravimety analysis showed morphology dependent decomposition of Ni(OH)(2) precursors. The microwave synthesized porous NiO sample with unique morphology and pore size distribution showed significantly improved charge storage and electrochemical stability than the flaky NiO sample synthesized by employing conventional reflux method. The cyclic voltammetry measurements on microwave synthesized NiO sample showed considerably high capacitance and better electrochemical reversibility. The charge-discharge measurements made at a discharge current of 2 A/g showed higher rate specific capacitance (370 F/g) for the NiO sample synthesized by microwave method than the sample synthesized by reflux method (101 F/g). The impedance study illustrates lower electronic and ionic resistance of rippled-shaped porous NiO due to its superior surface properties for enhanced electrode-electrolyte contact during the Faradaic redox reactions. It has been further established from the Ragone plot that the microwave synthesized NiO sample shows higher energy and power densities than the reflux synthesized NiO sample. Broadly, this study reveals that microwave-mediated synthesis approach is significantly a better strategy for the synthesis of porous NiO suitable to electrochemical supercapacitor applications.     

Single step synthesis of indium tin oxide by ultrasonic spray and microwave assisted pyrolysis

Ultrafine indium tin oxide (ITO) powders were successfully synthesised by the combined methods of ultrasonic spray and microwave assisted pyrolysis, which is a single step, facile, rapid and continuous method without post-heating treatment. Crystallinity, morphology and microstructure of the samples were investigated by X-ray diffractometer, scanning electron microscope, transmission electron microscope, energy dispersive X-ray spectroscope, selected area electron diffraction pattern and laser grain size analyser. Results indicate that pure solid solution ITO ultrafine powders with homogeneous and narrow size distribution, highly dense and smooth surface morphology can be obtained under optimum conditions. Each uniform spherical particle consisted of many smaller crystallites with diameter of <10 nm.     

Modification in Surface Chemistry of the Polyetrafluoroethylene Through Chemical Graft Copolymerization for Potential Oil Contamination Control

In the present study, an attempt has been made to design an oleophobic surface through chemical graft copolymerization of methyl methacrylate (MMA) onto polytetrafluroethylene (PTFE) film. The PTFE films were grafted with MMA resulting in PTFE-g-MMA grafts using benzoyl peroxide (BPO) as initiator in aqueous media. Optimum conditions pertaining to maximum percentage of grafting were evaluated by varying time, temperature, initiator, and monomer concentration. The maximum graft yield 9.47% was obtained at [BPO] = 0.03 M, [MMA] = 10%V/V, [reaction temperature] = 50°C and [reaction time] = 120 min. Methyl iodide was used to measure the contact angle, which revealed the oleophobic nature of grafted PTFE-g-MMA film. Maximum contact angle 95.5° of PTFE-g-MMA film was observed at optimum grafting conditions. The surface morphology of PTFE-g-MMA films was studied by Field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD) analysis confirmed the change in structure of PTFE after MMA grafting.     

微波辅助酸化蒙脱土催化合成乳酸正丁酯的研究

采用微波辐照法对钠基蒙脱土进行了酸化改性,制备出了酸化蒙脱土(H-MMT)固体酸催化剂,并利用X射线衍射、低温物理吸附等技术对催化剂性质进行了表征,结果表明,经微波辐照酸改性的催化剂层状结构没有被破坏,层间距略有下降,结晶度降低;比表面积和孔径都增大,形成了较好的介孔结构;表面酸量增加.这些特性使得催化剂表现出良好的催化活性.而后,以H-MMT为催化剂,系统研究了乳酸正丁酯的微波辅助合成方法,考查了催化剂用量、微波功率以及微波辐照时间对酯化率的影响.结果表明,微波功率200W、辐照15min、催化剂用量6.0%(占乳酸和正丁醇总质量)为最优的酯化条件,在此条件下,酯化率可达72.4%.最后,探讨了微波辅助H-MMT催化合成乳酸正丁酯的机制,发现H-MMT与微波具有协同作用.微波辅助H-MMT催化合成乳酸正丁酯是一种高效、节能、环境友好的方法,具有市场推广前景.     

Microwave assisted semi-solvothermal synthesis of nanocrystalline barium titanate

In an endeavor to synthesize tetragonal nanocrystallites of BaTiO3 at much reduced reaction time, we explored the possibility of performing microwave assisted semi-solvothermal reaction by using Ba(OH)2 . 8H2O and amorphous titanium hydrous gel as precursors and 1,4-butanediol and water as solvent. Typically, such a microwave assisted reaction was accomplished within 2 hrs at 220 degrees C as against 12 hrs required in conventional approach. The crystallized BaTiO3 powders (microwave assisted as well as conventionally processed for reference) were characterized by X-ray diffraction, thermal analysis, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. We have detected metastable cubic phase by XRD while locally symmetric tetragonal phase by Raman spectroscopy in case of conventional semi-solvothermal processing. On the contrary, we could detect co-existence of tetragonal and cubic phases by XRD and only tetragonal phase by Raman spectroscopy in case of microwave assisted semi-solvothermal processing. The TEM analysis indicates typical particle size distribution in the range of approximately 20 to 80 nm for conventionally processed powder while that in the range of approximately 20 to 50 nm for microwave processed powder. HRTEM images evince the distortion from an ideal cubic structure in case of microwave processed powder which can be correlated with anisotropic lattice contraction during the microwave induced heating. AFM analysis exhibited relatively less aggregation of nanoparticles for microwave assisted process.     

Feasibility investigation of oily wastewater treatment by combination of zinc and PAM in coagulation/flocculation

Poly-zinc silicate (PZSS) is a new type of coagulant with cationic polymer synthesized by polysilicic acid and zinc sulfate. It has been used in several sorts of wastewaters treatment, but not used in oily wastewater treatment. In this study, we investigated the coagulation/flocculation of oil and suspended solids in heavy oil wastewater (HOW) by PZSS and anion polyacrylamide (A-PAM). The properties of PZSS cooperated with A-PAM were compared with PAC and PFS in dosages, PAMs amount, settling time, pH value and flocs morphology. The results showed that PZSS was more efficient than PAC and PFS. Under the optimum experimental conditions of coagulation/flocculation (dosage: 100mg/L, A-PAM dosage: 1.0mg/L, settling time time: 40min and pH 6.5-9.5), more than 99% of oil was removed and suspended solid value less than 5mg/L by using PZSS cooperated with A-PAM, which could satisfy the demands of the pre-treatment process for HOW to be reused in the steam boiler or recycled into the injecting well.     

Humidity sensor using microporous film of polyethylene-graft-poly-(2-hydroxy-3-methacryloxypropyl trimethyl-ammonium chloride)

An hydrophilic monomer, 2-hydroxy-3-methacryloxypropyl trimethylammonium chloride, was graft-polymerized in a microporous polyethylene film using three different initiation methods, that is, with benzyl peroxide, pre-U.V. irradiation and mutual photo-initiation. Humidity dependence of the impedance was measured for the grafted microporous polyethylene films. Among the three graft polymers, the one prepared by pre photo-irradiation seems to have the most homogeneously grafted layer. The impedance increases as the grafting percentage increases except in the low grafting percentage region. The response time for the abrupt change of humidity becomes longer as the grafting percentage increases. The activation energy for conductivity has a maximum at 40% relative humidity in the plot of activation energy against humidity.     

Novel thermosensitive flocculanting agent based on pullulan

New thermosensitive polysaccharide (P-g-pNIPAAm) was synthesized by graft-polymerization of p(N-isopropylacrylamide) (pNIPAAm) onto pullulan (P) using Ce(IV) ion as initiator. The grafted polysaccharide was characterized by FT-IR and ¹H NMR spectroscopy and elemental analysis. Its flocculation efficiency was studied in a clay suspension, in comparison with p(NIPAAm) homopolymer, as a function of the polymer dose, temperature and settling time. The thermosensitive polysaccharide could induce clay particle flocculation both below and above the lower critical solution temperature (LCST), but the process was more effective above the LCST. A lower value of the residual turbidity at the optimum polymer dose and a wider flocculation window were recorded at temperature above the LCST. The floc size distribution and surface morphology revealed bigger size flocs when the flocculation was performed above the LCST. The re-dispersion effect was negligible for the flocs obtained in the presence of P-g-pNIPAAm.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Selective flocculation of iron oxide-kaolin mixtures using a modified polyacrylamide flocculant

High molecular weight polyacrylamides were synthesized and successfully modified to contain up to 8·3% hydroxamate functional groups. The selective flocculation tests carried out on 1:1 iron oxide/kaolin mixtures using parent polyacrylamide, polyacrylic acid and the modified polyacrylamide, confirm the possibility of enhancing selectivity through introduction of iron chelating functional groups in commercially available polymers. Starting with a feed grade of 35% iron, 92% recovery with acceptable grade of 60% iron has been achieved using the modified polyacrylamide. NCL communication No. 4415