Complexation studies of Eu(III) with alumina-bound polymaleic acid: effect of organic polymer loading and metal ion concentration

To contribute to the comprehension of the metal ion sorption properties in mixed mineral-organic matter systems, interaction studies between Eu(III) and polymaleic acid (PMA)-coated alumina colloids were carried out at pH 5 in 0.1 M NaClO4. The studied parameters were the metal ion concentration (1 x 10(-10) to 1 x 10(-4) M) and PMA loading on alumina (gamma = 10-70 mg/g). The data were described by a surface complexation model. The constant capacitance model was used to account for electrostatic interactions. The results showed thattwo sites were necessary to explain the sorption data. At high Eu loading, Eu is surrounded by one carboxylate group and one aluminol group. The existence of this ternary surface site was in agreement with time-resolved laser-induced fluorescence spectroscopy measurements. At low metal ion concentrations, a surface site corresponding to a 1:1 Eu/COO-stoichiometry was deduced from modeling. Spectroscopic data did not corroborate the existence of this latter site. This discrepancy was explained by postadsorption kinetic phenomenon: a migration of the metal ion within the adsorbed organic layer.     

Phospholipids and poly(glutamic acid)/hydrolysed gluten: Interaction and kinetics

The effect of poly(glutamic acid) (PGA) and hydrolysed wheat gluten (HG) on the thermal and kinetics properties of lysophosphatidylcholine (LPC) was determined using DSC. A model system containing PGA or HG was added to 40% LPC aqueous suspension. The results from the study showed reduced ΔH values as a function of PGA molecular weight, which signified some kind of penetration of PGA or HG into the LPC bi-layer but not enough to minimise the order of LPC vesicle structure. The ability of LPC molecules to rearrange itself into a bi-layer again was evident in the emergence of crystallisation profiles in the course of the cooling cycle. The calculated activation energy (E_a) of pure LPC vesicle disruption (heating) and formation (cooling) was 696.6 and 520.4 kJ/mol, respectively. Overall, the trend of lower E_a as a function of PGA molecular weight was apparent during both heating and cooling cycles. Although, both PGA and HG reduced the E_a, HG was less effective in reducing E_a. The purported molecular interaction between phospholipids and gluten has been confirmed using FT-IR spectroscopy. The FT-IR results indicated that interactions occurred in LPC/HG blends and in model mixtures consisting of LPC/PGA with different molecular weight.     

Uptake of Cm(III) and Eu(III) by calcium silicate hydrates: a solution chemistry and time-resolved laser fluorescence spectroscopy study

The interaction of the two chemical homologues [Cm(III) and Eu(III)] with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6 +/- 3) x 10(5) L kg(-1). Three different Cm(III) species have been identified: A nonfluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH-sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 and 620.9 nm and fluorescence emission lifetimes of 289 +/- 11 and 1482 +/- 200 micros, respectively. From the fluorescence lifetimes, it was calculated that the two fluorescing Cm(III) species have one or two and no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.     

纺粘非织造用聚乳酸/聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)的可纺性

为获得高质量的聚乳酸/聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)(PLA/PHBV)双组分生物降解纺粘非织造材料,对PLA/PHBV母粒的相对分子质量及分布、熔体指数、热力学、结晶和流变性能进行了研究,并对PLA/PHBV纺粘纤维的热力学和结晶性能进行了探讨。结果表明:PLA/PHBV母粒重均分子质量约为120 000,分布指数为1.99;热失重起始热分解温度为285℃,适宜纺粘非织造挤出加工,合适的纺粘加工温度约为210℃。PLA/PHBV熔体在剪切速率小于1 000 rad/s时,表观黏度对剪切速率变化敏感;熔体对温度的敏感程度随着剪切速率的增大而降低。纺粘加工工艺对PLA/PHBV原料的热力学和结晶性能影响显著。与PLA/PHBV母粒相比,纺粘纤维结晶度下降明显,但非晶区取向程度提高。     

生物可降解聚（3-羟基丁酸-co-3-羟基戊酸共聚酯）/聚乳酸共混物的相容性和结晶性

针对聚（3-羟基丁酸-co-3-羟基戊酸共聚酯）（PHBV）热稳定性差、易分解的问题,通过与聚乳酸（PLA）采用熔融共混的方法制备了不同混合比例的的PHBV/PLA共混物,借助差示扫描量热仪、热重分析仪、动态热机械分析仪和X射线衍射仪研究了PHBV/PLA共混物的相容性、热学性能和结晶性等,并用热台偏光显微镜观察了PHBV/PLA共混物的动态热结晶过程。结果表明：PHBV/PLA共混物呈现分离的熔融温度和玻璃化转变温度,X射线衍射曲线上没有出现新的衍射峰,说明PHBV和PLA的相容性较差;PLA的加入提高了PHBV的热稳定性能,拓宽了PHBV的熔融加工窗口;随着共混物中PLA比例的增加,共混物的结晶相由“海-岛”相逐渐变成两聚合物分别连续成相。     

A spectroscopic characterization and quantification of m(III)/clay mineral outer-sphere complexes

For the long-term safety assessment of deep radioactive waste repositories an understanding of the interactions of actinides with mineral surfaces at a molecular level is necessary. The retention/mobility of the released radionuclides is strongly dependent on sorption/desorption reactions at mineral surfaces. Thus, a quantitative understanding of the uptake mechanisms of actinides on clay minerals will make an important contribution to long-term safety assessments. Using time-resolved laser fluorescence spectroscopy (TRLFS), it was possible to differentiate between nonsorbed aquo ions and outer-sphere sorbed Cm(III) onto different montmorillonites. In addition, Cm(III)/clay outer-sphere complexation at different ionic strengths using NaCI as the background electrolyte is quantified. Finally, the results are verified by sorption model calculations.     

衣康酸/丙烯酸与聚酯织物接枝共聚性能

研究了在水溶液中以过氧化苯甲酰为引发剂,衣康酸/丙烯酸为单体与碱处理后的三叶形聚酯(PET)平纹织物接枝共聚;对共聚条件如聚合温度、时间、引发剂浓度、单体物质的量比等进行研究,得出最佳聚合条件。电子扫描电镜照片和傅里叶红外变换光谱显示衣康酸/丙烯酸共聚到聚酯大分子上。研究结果表明随着接枝率的上升,织物吸湿快干性能提高;阳离子染料上染率大幅度提高,织物色光鲜艳。     

Arsenate sorption on lithium/ aluminum layered double hydroxide intercalated by chloride and on gibbsite: sorption isotherms, envelopes, and spectroscopic studies

The objective of this study was to provide fundamental knowledge of arsenate sorption on lithium/aluminum layered double hydroxide intercalated by chloride (Li/Al LDH-Cl) and further to reveal the contribution of exposed positive charge surface of Li/Al LDH-CI created by intercalating LiCl into Al(OH)3 layers to arsenate sorption. Therefore, sorption isotherms, envelopes and extended X-ray absorption fine structure (EXAFS) technique were employed to examine the reaction of arsenate on Li/Al LDH-Cl and on gibbsite. Based on an isotherm study, the sorption maximum of Li/Al LDH-Cl for arsenate was approximately six times higher than that of gibbsite. Sorption envelopes of arsenate on Li/Al LDH-Cl displayed a pH-sensitive behavior from pH 4.0 to 7.0, but it was insensitive to pH above pH 7.0, approaching to the pHpzc of Li/Al LDH-Cl (7.22). This transformation with shifted pHs illustrated that there were two types of reaction sites within Li/Al LDH-Cl that participate in arsenate sorption; one is pH-sensitive and the other is not. From EXAFS analysis, arsenate sorbed on Li/Al LDH, reacted not only with Al in the edges of Al-(OH)3 layers, but also with Li located in the vacant octahedral sites within Al(OH)3 layers; however, the decreasing intensity of As(V)-Al shells with increasing pH represented there were fewer As(V)-Al complex existed at higher pH, i.e., the complex between arsenate and Al is pH-sensitive. The superior sorption capability of Li/Al LDH-Cl to that of gibbsite could be attributed to the intercalated Li cations which served as the permanent sorption sites and made the surface of Al(OH)3 have high affinity to arsenate.     

抗菌和防紫外线双效功能聚乳酸/ZnO纤维的制备及其性能

为赋予聚乳酸(PLA)纤维高效的防紫外线性能和抗菌性能,以ZnO为功能粒子,采用熔融共混法制备了不同质量配比的PLA/ZnO共混物,对共混物的形貌结构、热性能、防紫外线性能和抗菌性能进行表征,选用最佳质量配比的共混物进行熔融纺丝制备PLA/ZnO纤维。结果表明:当ZnO母粒质量分数为5％时(ZnO质量分数为0.85％),ZnO粒子在PLA基体中分布均匀,PLA/ZnO共混物热稳定性较好,防紫外线和抗菌性能优异,紫外线防护系数达到663,且对大肠杆菌和金黄色葡萄球菌的抑菌率在99％以上;该比例的共混物具有良好的可纺性,制得的PLA/ZnO纤维的结晶度达30％以上,纤维的强度符合织造要求,制备的PLA/ZnO织物紫外线透过率低于30％,对大肠杆菌和金黄色葡萄球菌的抑菌率也高达99％,且织物水洗10次后抑菌率不变。     

熔喷非织造用聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)/聚乳酸双组分生物降解材料的可纺性能

采用熔融共混法制备了质量比为100/0、75/25、50/50、25/75、0/100的熔喷非织造用PHBV/PLA共混材料,分别采用热重分析法（TG）、熔融指数法（MFI）、热台偏光镜法（POM）和毛细管流变法对共混材料的可纺性能进行了研究,并对其初生纤维的纺丝性能给予了初步评价。研究表明：PHBV的热稳定性差、加工窗口窄且熔体流动性差,PHBV/PLA共混材料的热稳定性和熔体流动性明显改善;PHBV结晶速率快, PLA对PHBV的结晶具有稀释作用;PHBV/PLA共混物为典型的切力变稀型流体,PHBV对温度和剪切速率变化敏感度高,PHBV/PLA共混材料的表观粘度随着PLA含量的提高而有所增大,但均小于纯PLA;PHBV纤维发粘现象严重,纺丝困难,随着共混材料中PLA含量的提高,纺丝性能提高,初生纤维表面变得光滑。     

Reduction of aqueous chromate by Fe(II)/Fe(III) carbonate green rust: kinetic and mechanistic studies

This work describes the heterogeneous reaction between FeII in carbonate green rust and aqueous chromate, in NaHCO3 solutions at 25 degrees C, and at pH values of 9.3-9.6. Evidence for reduction of CrVI to CrIII and concomitant solid-state oxidation of lattice FeII to FeIII was found from FeII titration and from structural analysis of the solids using FTIR, XRD, SEM, and XPS methods. Results indicate the formation of ferric oxyhydroxycarbonate and the concomitant precipitation of CrIII monolayers at the surface of the iron compound that induce passivation effects and progressive rate limitations. The number of CrIII monolayers formed at the completion of the reaction depends on [FeII]t=0, the molar concentration of FeII(solid) at t=0; on [n(o)]t=0, the molar concentration of reaction sites present at the surface of the solid phase at t=0; and on [CrVI]t=0, the molar concentration of CrVI at t=0. Kinetic data were modeled using a model based on the formation of successive CrIII monolayers, -(d[CrVI]/dt) = sigma(1)j k(i)[S] [CrVI]([n(i - 1)] - [n(i)]) with k(i)[S] (in s(-1) L mol(-1)), the rate coefficient of formation of CrIII monolayer i, and [n(i)] and [n(i - 1)], the molar concentration of CrIII precipitated in monolayer i and monolayer i - 1, respectively. Good matching curves were obtained with kinetic coefficients: k(1)[S] = 5-8 x 10(-4), k(2)[S] = 0.5-3 x 10(-5), and k(3)[S] about 1.7 x 10(-6) s(-1) m(-2) L. The CrVI removal efficiency progressively decreases along with the accumulation of CrIII monolayers at the surface of carbonate green rust particles. In the case of thick green rust particles resulting from the corrosion of iron in permeable reactive barriers, the quantity of FeII readily accessible for efficient CrVI removal should be rather low.     

Obtention and characterization of poly(3-hydroxybutyricacid-co-hydroxyvaleric acid)/mcl-PHA based blends

The aim of this work was to evaluate the physical–chemical properties of blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and a medium-chain-length polyhydroxyalkanoate (LA). Blends were obtained by casting film-solution on leveled trays. Morphological analysis showed compatibility between the two polymers up to 5 g/100 g of LA polymer was added and phase separation in the polymeric system for compositions containing more than 5 g/100 g of LA polymer. TGA data and glass transition temperatures revealed some compatibility of the polymers. Moreover, there is a significant decrease of melting temperature and elasticity modulus for PHBV–LA blends with composition. Films containing 5 g/100 g of LA polymer showed an improvement of 50% in elongation to break (SB) when compared with pure PHBV. For other samples the SB decreased most likely due to the lack of adhesion between the two polymeric phases.     

Sorption of Eu(III) on humic acid or fulvic acid bound to hydrous alumina studied by SEM-EDS, XPS, TRLFS, and batch techniques

To identify the effect of humic acid (HA) and fulvic acid (FA) on the sorption mechanism of Eu(III) on organic--inorganic colloids in the environment at a molecular level, surface adsorbed/ complexed Eu(III) on hydrous alumina, HA-, and FA-hydrous alumina hybrids were characterized by using X-ray photoelectron spectroscopy (XPS) and time-resolved laser fluorescence spectroscopy (TRLFS). The experiments were performed in 0.1 mol/L KNO3 or 0.1 mol/L NaClO4 under ambient conditions. The pH values were varied between 2 and 11 at a fixed Eu(III) concentration of 6.0 x 10(-7) mol/L and 4.3 x 10(-5) mol/L. The different Eu(III)/FA(HA)/hydrous alumina complexes were characterized by their fluorescence emission spectra ((5D0-F1)/ (5D0 --> 7F2)) and binding energy of Eu(III). Inner-sphere surface complexation may contribute mainly to Eu(III) sorption on hydrous alumina, and a ternary surface complex is formed at the HA/ FA-hydrous alumina hybrid surfaces. The sorption and species of Eu(III) in ternary Eu-HA/FA-hydrous alumina systems are not dominated by either HA/FA or hydrous alumina, but are dominated by both HA/FA and hydrous alumina. The results are important for understanding the sorption mechanisms and the nature of surface adsorbed Eu(III) species and trivalent chemical homologues of Eu(III) in the natural environment.     

Incorporation of Eu(III) into hydrotalcite: a TRLFS and EXAFS study

The behavior of radionuclides in the environment (geo-, hydro-, and biosphere) is determined by interface reactions like adsorption, ion exchange, and incorporation processes. Presently, operational gross parameters for the distribution between solution and minerals are available. For predictive modeling of the radionuclide mobility in such systems, however, individual reactions and processes need to be localized, characterized, and quantified. A prerequisite for localization and clarification of the concerned processes is the use of modern advanced analytical and speciation methods, especially spectroscopy. In this study, Eu(III) was chosen as an analogue for trivalent actinides to identify the different species that occur by the Ln(III)/hydrotalcite interaction. Therefore, Eu(III) doped Mg-Al-Cl-hydrotalcite was synthesized and investigated by TRLFS, EXAFS, and XRD measurements. Two different Eu/hydrotalcite species were obtained. The minor part of the lanthanide is found to be inner-sphere sorbed onto the mineral surface, while the dominating Eu/hydrotalcite species consists of Eu(III) that is incorporated into the hydrotalcite lattice. Both Eu/hydrotalcite species have been characterized by their fluorescence emission spectra and lifetimes. Structural parameters of the incorporated Eu(III) species determined by EXAFS indicate a coordination number of 6.6 +/- 1.3 and distances of 2.41 +/- 0.02 A for the first Eu-OH shell.     

Bridging the gap between macroscopic and spectroscopic studies of metal ion sorption at the oxide/water interface: Sr(II), Co(II), and Pb(II) sorption to quartz

Metal sorption mechanisms were investigated for strontium, cobalt, and lead using sodium chloride, sodium nitrate, and sodium perchlorate as background electrolytes and quartz as the adsorbent. Spectroscopic analyses of concentrated sorption samples were evaluated for their ability to provide insight into the controlling sorption process for more dilute systems. For strontium, outer-sphere complexes identified using X-ray absorption spectroscopy (XAS) of concentrated samples were consistent with macroscopic sorption data collected in more dilute systems. XAS results indicated that cobalt formed a new solid phase upon sorption to silica. Macroscopic studies of cobalt sorption supported the spectroscopic data for total cobalt concentrations of 10(-5) M, regardless of the background electrolyte composition or concentration. At a lower total cobalt concentration (10(-7) M), adsorption appeared to be the prevailing mechanism of cobalt removal. Spectroscopic results suggested that lead adsorbed as an inner-sphere complex on silica. The decrease of lead removal with increasing chloride concentration was attributed to competition with aqueous lead-chloride complexes, based on thermodynamic calculations.     

Preparation,characterization, and adsorption application of poly (lactic acid)/tea polyphenols porous composite nanofiber membranes

In this study, high surface area poly (lactic acid) (PLA)/tea polyphenols (TPs) porous composite nanofiber membranes (CNFMs) were prepared successfully by electrospinning and applied to adsorption of silver ions. The morphology and properties of the electrospun PLA/TPs CNFMs before and after adsorption of silver ions were investigated by scanning electron microscopy (SEM), energy dispersive spectrometer test (EDS), universal testing machine, etc. In addition, the adsorption capacities of PLA/TPs CNFMs for silver ions were determined by atomic absorption spectrophotometer. Adsorption tests showed that the electrospun PLA/TPs CNFMs exhibited good adsorption properties of silver ions, and the porous structure could promote the adsorption of silver ions.     

Preparation and textile application of poly(methyl methacrylate-co-methacrylic acid)/n-octadecane and n-eicosane microcapsules

In this study, a series of microencapsulated phase change materials with poly(methyl methacrylate-co-methacrylic acid) P(MMA-co-MAA) shell and n-octadecane or n-eicosane core were synthesized by emulsion polymerization method. The aim was to produce microencapsulated n-alkanes having functional groups on their outer surface, so that functional groups would help increasing physical interactions between microcapsules and fiber surface. Therefore, methyl methacrylate (MMA), ethylene glycoldimethacrylate (EGDM), and methacrylic acid (MAA) were copolymerized in oil phase of n-alkane. FT-IR results proved the successful synthesis of P(MMA-co-MAA) shell of microencapsulated n-alkanes. The DSC results indicated that the microencapsulated n-alkanes have considerable latent heat storage capacity in a range of 58–145 J/g. The average melting and freezing temperatures of the microencapsulated n-alkanes were measured as 27 and 26 °C for n-octadecane and 36 and 35 °C for n-eicosane, respectively. The microcapsules were of spherical and compact shape with particle sizes between 15 and 32 μm. The microcapsules on the cotton fabric applied by pad-dry-cure method were found highly durable and they showed sufficient stability upon several washings and rub fastness. Thermo-regulating properties of the fabrics were declared as a result of thermal history measurements.     

Fabrication of highly electrical synthetic leather with polyurethane/poly(3,4-ethylene dioxythiophene)/poly(styrene sulfonate)

Poly(ethylene-3,4-dioxythiophene)/poly(styrene sulfonic acid)(PEDOT/PSS) water dispersions are commercially available, and various coating formulations for substrates, such as glass, plastics, and ceramics, have been suggested. Recently, it was found that the addition of a small amount of organic solvent, such as ethylene glycol (EG) and dimethylsulfoxide (DMSO), to the aqueous dispersion of PEDOT/PSS increases the conductivity significantly. This study examined how a combination of solvent addition affects the PEDOT/PSS conductivity of artificial leather (napping fabric with short fur). In addition, the sustainability of the PEDOT/PSS conductivity for the common use of artificial leather was investigated using abrasion and tension cycle tests. The electric conductivity of the leather increased in the order of EG < DMSO < EG + DMSO. The sustainability of the PEDOT/PSS conductivity in the case of EG + DMSO was superior to that of the EG or DMSO solvents. The padding process was found to be a more effective method for achieving durability against abrasion and tension cycle with a lower deposit weight than when using the coating process. The mechanical properties of the synthetic leather using the padding process also showed high performance compared to the coating process.     

Cr(VI)/Cr(III) and As(V)/As(III) ratio assessments in Jordanian spent oil shale produced by aerobic combustion and Anaerobic Pyrolysis

With the increase in the awareness of the public in the environmental impact of oil shale utilization, it is of interest to reveal the mobility of potentially toxic trace elements in spent oil shale. Therefore, the Cr and As oxidation state in a representative Jordanian oil shale sample from the El-Lajjoun area were investigated upon different lab-scale furnace treatments. The anaerobic pyrolysis was performed in a retort flushed by nitrogen gas at temperatures in between 600 and 800 °C (pyrolytic oil shale, POS). The aerobic combustion was simply performed in porcelain cups heated in a muffle furnace for 4 h at temperatures in between 700 and 1000 °C (burned oil shale, BOS). The high loss-on-ignition in the BOS samples of up to 370 g kg(-1) results from both calcium carbonate and organic carbon degradation. The LOI leads to enrichment in the Cr concentrations from 480 mg kg(-1) in the original oil shale up to 675 mg kg(-1) in the ≥ 850 °C BOS samples. Arsenic concentrations were not much elevated beyond that in the average shale standard (13 mg kg(-1)). Synchrotron-based X-ray absorption near-edge structure (XANES) analysis revealed that within the original oil shale the oxidation states of Cr and As were lower than after its aerobic combustion. Cr(VI) increased from 0% in the untreated or pyrolyzed oil shale up to 60% in the BOS ash combusted at 850 °C, while As(V) increased from 64% in the original oil shale up to 100% in the BOS ash at 700 °C. No Cr was released from original oil shale and POS products by the European compliance leaching test CEN/TC 292 EN 12457-1 (1:2 solid/water ratio, 24 h shaking), whereas leachates from BOS samples showed Cr release in the order of one mmol L(-1). The leachable Cr content is dominated by chromate as revealed by catalytic adsorptive stripping voltammetry (CAdSV) which could cause harmful contamination of surface and groundwater in the semiarid environment of Jordan.