紫外脉冲荧光法测定微量铀的研究

紫外脉冲荧光法是一种通过液体激光来直接测定微量铀的方法。在采用紫外脉冲荧光法分析面包酵母吸附放射性核素铀后溶液剩余铀浓度之前,研究了荧光增强剂、pH 值、以及温度对微量铀浓度工作曲线的影响。结果表明:当pH > 3时,400 μL 荧光增强剂可以充分缓冲溶液,不同pH 值下测得的荧光计数基本保持恒定,即待测溶液pH值不会影响铀浓度的测量;随着温度的升高,荧光计数近似线性下降,并在室温23.6℃时得到了铀质量浓度范围为0:120 μg/L 的工作曲线。在此基础上研究了酵母菌对放射性核素铀的吸附作用,为使吸附剂达到最高效利用,对溶液pH 值、吸附速率进行了批次实验,并通过紫外脉冲荧光分析法进行测量, 发现达到吸附平衡所需的最短时间为180 min,吸附的最佳溶液pH 值为5.8 左右。The method of pulse ultraviolet fluorescence was employed to analyze the concentration of radioactive nuclide uranium after adsorbed by baker’s yeast. Influences of fluorescent enhance reagent, pH value, and temperature on measurement of the concentration of trace uranium were investigated. The results showed that 400 μL fluorescent enhance reagent was greatly enough to buffer the solution when pH > 3 and the counts of fluorescence kept constant with the variation of pH, which indicates that the pH of solutions doesn’t affect the determination of uranium concentration, moreover, the counts of fluorescence declined linearly as the increase of the temperature. In addition, the working curve of the determination of uranium concentration within 0.1 20 μg/L was obtained when the temperature was 23.6 ℃. On this basis, the adsorption of uranium by baker’s yeast was studied. For the adsorption of radioactive nuclides of uranium by baker’s yeast to achieve the best use, the batch experiments were carried out on the rate of adsorption and pH of solutions. The method of pulse ultraviolet fluorescence was used to measure and found that the minimum time required to reach adsorption equilibrium was 180 min and the optimum pH value of solutions was about 5.8.     

Research of measurement errors caused by salt solution temperature drift in surface plasmon resonance sensors

Influence of temperature on measurement of surface plasmon resonance (SPR) sensor was investigated. Samples with various concentrations of NaCl were tested at different temperatures. It was shown that if the affection of temperature could be neglected, measurement precision of salt solution was 0.028 wt.-%. But measurement error of salinity ca,used by temperature was 0.53 wt.-% in average when the temperature drift was 1 ℃. To reduce the error, a double-cell SPR sensor with salt solution and distilled water flowing respectively and at the same temperature was implemented.     

Research of measurement errors caused by salt solution temperature drift in surface plasmon resonance sensors

Influence of temperature on measurement of surface plasmon resonance (SPR) sensor was investigated.Samples with various concentrations of NaCI were tested at different temperatures. It was shown that if the affection of temperature could be neglected, measurement precision of salt solution was 0.028 wt.-%.But measurement error of salinity caused by temperature was 0.53 wt.-% in average when the temperature drift was 1 ℃. To reduce the error, a double-cell SPR sensor with salt solution and distilled water flowing respectively and at the same temperature was implemented.     

Measurement and analysis of fission rates in a spherical mockup of uranium and polyethylene

Measurements of the reaction rate distribution were carried out using two kinds of Plate Micro Fission Chamber （PMFC）. The first is a depleted uranium chamber and the second an enriched uranium chamber. The material in the depleted uranium chamber is strictly the same as the material in the uranium assembly. With the equation solution to conduct the isotope contribution correction, the fission rate of 238U and 235U were obtained from the fission rate of depleted uranium and enriched uranium. Then, the fission count of 238U and 235U in an individual uranium shell was obtained. In this work, MCNP5 and continuous energy cross sections ENDF/BV.0 were used for the analysis of fission rate distribution and fission count. The calculated results were compared with the experimental ones. The calculation of fission rate of DU and EU were found to agree with the measured ones within 10% except at the positions in polyethylene region and the two positions near the outer surface. Because the fission chamber was not considered in the calculation of the fission counts of 238U and 235U, the calculated results did not agree well with the experimental ones.     

Large-mode-area neodymium-doped all-solid double-cladding silicate photonic bandgap fiber with an index step of ～0.5%

A large-mode-area neodymium-doped silicate photonic bandgap fiber was theoretically designed and experimentally demonstrated. The relative index step between the high-index rods and the background glass was ～0.5%,which is the lowest cladding index difference reported on rare-earth-doped all-solid photonic bandgap fibers to our knowledge. An output power of 3.6 W with a slope efficiency of 31% was obtained for a 100-cm-long fiber.     

Piezoelectric film electro-deposition for optical fiber sensor with ZnO coating

The piezoelectric film electro-deposition for optical fiber sensor with ZnO coating is studied.The zinc oxide plating film is made on the copper surface directly by cathodic electro-deposition in the Zn(NO_3)_2 single salt aqueous solution systems.The influences of main experimental conditions on the properties of ZnO thin film in the electro-deposition processes are analyzed and a stable,practical and economic technique is obtained.     

175-W continuous-wave master oscillator power amplifier structure ytterbium-doped all-fiber laser

We report on hundred watts range ytterbium-doped all-fiber laser assembly based on the master oscillator power amplifier structure.It consisted of an oscillator and an amplifier with all-fiber components.And fiber fusion splice made the laser be an integrated fiber system.It generated up to 175.5 W of continuous- wave (CW) output power at 1085 nm with more than 75% extraction efficiency in the amplifier when the total coupled pump power into the double clad fiber was 270 W.     

Characteristics of stable L-band SFS using dual-forward synchronous pumping technique

We investigate the characteristics of the dual-forward synchronously pumped L-band erbium-doped su- perfiuorescent fiber source （SFS）. The effects of pump ratio and fiber length arrangements on the output characteristics of the L-band SFS in terms of mean wavelength, spectral linewidth, and output power are analyzed. It is shown that the optimized pump ratio and fiber length arrangements provide broadening spectral linewidth and enhanced pumping efficiency, while the synchronous pump ensures stable mean wavelength operation. A new single-forward pumping scheme with a section of unpumped fiber is pro- posed to achieve a mean wavelength stable L-band SFS with a broadening linewidth of 50.4 nm and a pumping efficiency of 33.5%.     

Energy law preserving continuous finite element schemes for a gas metal arc welding system

In this paper a modifed continuous energy law was explored to investigate transport behavior in a gas metal arc welding(GMAW)system.The energy law equality at a discrete level for the GMAW system was derived by using the finite element scheme.The mass conservation and current density continuous equation with the penalty scheme was applied 10 improve the stability.According to the phase-field model coupled with the energy law preserving method,the GMAW model was discretized and a metal transfer process with a pulse current was simulated.It was found that the numerical solution agrees well with the data of the metal transfer process obtained by high-speed photography.Compared with the numerical solution of the volume of fuid model,which was widely studied in the GMAW system based on the finite element method Euler scheme,the energy law preserving method can provide better accuracy in predicting the shape evolution of the droplet and with a greater computing efficiency.     

Optical properties of ytterbium-doped tandem-pumped fiber oscillatorOptical properties of ytterbium-doped tandem-pumped fiber oscillatorOptical properties of ytterbium-doped tandem-pumped fiber oscillator

With the rapid development of ytterbium-doped fiber lasers, some obtrusive limitations on power scaling appeared. In order to avoid these problems, a scheme called tandem pumping is introduced into the fiber laser field. In this paper, the optical properties of an ytterbium-doped tandem-pumped fiber oscillator are presented. According to the oscillator profile, the proper gain fiber type and pump wavelength range are picked out, under the comprehensive consideration of laser conversion efficiency and beam quality. In addition, the photodarkening performances of tandem pumping lasers and conventional ones are compared based on practical application, with all possible impact parameters taken into account. Moreover, an all-fibered tandem-pumped oscillator centered at 1079.5 nm is built, in the way of clad pumping by a 1030-rim fiber laser. The laser power of the oscillator reaches 7 W, with an opto-optic efficiency of 82.4%.     

ICP-OES研究活性炭无纺布对镉的吸附

重金属污染是一个相当严重的环境问题。镉具有很强的生物毒性和不可降解性,对生态环境和人体健康有极大威胁,被列为优先控制污染物。环境中镉的主要污染源是电镀、采矿和化学工业等部门的废水,如何简单高效去除水中的镉,有重要的社会意义和经济意义。目前,水中重金属的去除方法有化学沉淀、膜分离、离子交换、吸附、电解等,其中吸附法因简单高效而广泛应用。活性炭纤维是一种新型活性炭,孔径小且均匀,表面官能团发达,吸附性能好,逐步应用于水处理领域。以电感耦合等离子体光谱为检测手段,佐以比表面积分析,X射线衍射,元素分析和傅里叶变换红外光谱,研究比较了三种活性炭纤维(纤维炭网、活性炭无纺布、活性炭纤维毡)的结构特点及其对水中镉的吸附性能。三种活性炭纤维结构基本类似,具有较发达的孔隙结构。活性炭无纺布极性较强,表面有丰富的羟基、羧基、醛基等含氧官能团,对水中镉的吸附作用最大。因此,选择活性炭无纺布为吸附剂进行后续实验。研究了活性炭无纺布吸附镉的影响因素,如溶液pH,吸附时间等。溶液pH影响吸附剂表面电荷及水中镉的存在状态。水中镉的去除效率随溶液初始pH的增大而增大,在较低pH时,吸附剂与Cd2+间存在静电斥力,同时H+和Cd2+存在竞争吸附,pH>9时,镉的去除是吸附与沉淀协同作用的结果,选择pH为6～7。在吸附的初始阶段,活性炭无纺布对Cd2+的吸附量迅速增加,10 min时,吸附率达到72%。随着吸附位点逐渐被Cd2+所填充,吸附速率逐渐变慢,300 min时,吸附容量基本无变化,吸附趋于平衡。优化了镉的吸附条件后,进行等温吸附实验和动力学实验。结果表明,25 ℃时,吸附时间为300 min,pH 6.0条件下,当镉的平衡浓度在20.00 mg·L-1时,活性炭无纺布对镉的单位质量吸附量和单位比表面积吸附量分别是3.04 mg·g-1和0.035 mg·m-2。用Langmuir方程(R2=0.997, K_L =1.796 L·mg-1)和Freundich方程(R2=0.895, K_F=0.918 L·mg-1, n=2.12)拟合活性炭无纺布对镉的等温吸附数据,Langmuir方程计算的理论吸附量为3.07 mg·g-1,与实验值相当,并且线性系数更高,说明该体系的吸附符合Langmuir方程,主要为单分子层吸附。Langmuir分离因子介于0和1之间,表明活性炭无纺布对镉的吸附容易进行。用准一级动力学方程、准二级动力学方程、颗粒内扩散方程和Elovich方程四种动力学模型拟合吸附过程。在吸附的前5 min,镉在活性炭无纺布上的吸附符合颗粒内扩散方程(R2=0.985),吸附主要受颗粒内扩散控制。在吸附的5～300 min,颗粒内扩散方程拟合较差。整个吸附过程符合准二级动力学方程(R2=0.999,k₂=0.367 g·mg-1·min-1),Elovich方程(R2=0.981,a=0.271 mg·g-1, b=0.083 mg·g-1·(lg min)-1)和准一级动力学方程(R2=0.927,k₁=0.008 8 min-1)次之,颗粒内扩散方程(R2=0.785)最差。活性炭无纺布对镉的吸附过程是一种化学作用为主的吸附过程。对5.00 mg·L-1含镉水样,活性炭无纺布投放量为10 g·L-1时,吸附后水中镉的浓度小于0.10 mg·L-1,符合《污水综合排放标准》(GB 8978-1996)。活性炭无纺布可同时吸附镉,铜,铅,铬等重金属离子,选择性较差。但在电镀、采矿等实际废水中重金属种类复杂,适当提高吸附剂投放量,可同时去除多种重金属。利用活性炭无纺布吸附处理含镉水样,处理效果好、操作简单,可以作为去除水中镉的吸附剂,为含镉废水的处理提供了技术支持和理论基础。     

Synthesis of Tapioca Cellulose-based Poly(amidoxime) Ligand for Removal of Heavy Metal Ions

Poly(acrylonitrile)/cellulose block copolymer (PAN-b-cell) was prepared by using a free radical initiating process and then the nitrile functional groups of the PAN blocks of the copolymers were transformed into amidoxime ligands. The resulting poly(amidoxime) ligands could complex with heavy metal ions; for example, the reflectance spectra of the [Cu -ligand]ⁿ⁺ was found to be at the highest absorbance, about 94%, at pH 6. The pH was the key parameter for metal ions sensing by the ligand. The adsorption capacity for copper was very good, 272 mg g^?1, with a fast adsorption rate (t_1/2 = 10 min). The adsorption capacities for other heavy metal ions such as Fe³⁺, Cr³⁺, Co³⁺ and Ni²⁺ were also good, being 242, 219, 201 and 195 mg g^?1, respectively, at pH 6. The heavy metal ions removal efficiency from water was 98% at low concentration. The data proved that the heavy metal ions adsorption onto the polymer ligands were well fitted with the Langmuir isotherm model (R²>0.99), which suggests that the cellulose-based adsorbent surface namely the poly(amidoxime) ligand, was homogenous and a monolayer. The reusability was examined by a sorption/desorption process for six cycles and the extraction efficiency was determined. This new adsorbent could be reused for 6 cycles without any significant loss in its original removal function.     

Tris‐amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X‐ray absorption spectroscopy and density functional theory methods

The present study sheds some light on the long‐standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X‐ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl–amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO₂²⁺ and the amidoxime ligand is η² coordination with tris‐amidoximate species. In such a uranyl–amidoximate complex with η² binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single‐crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.     

基于光谱学分析探讨磷的释放促进酿酒酵母菌生物矿化铀的研究

磷作为生物体必需的化学元素之一,在微生物矿化铀的过程中发挥重要作用。以酿酒酵母菌为吸附剂,利用等离子体发射光谱仪和等离子体发射光谱-质谱仪考察了铀酰离子、pH值和磷的释放在生物吸附铀过程中的相互作用和影响;结合光谱学和介观分析手段探讨了酿酒酵母菌与铀作用过程中生物体释放磷的行为与铀生物矿化的关系,进而推测出酿酒酵母菌生物矿化铀的机理。结果表明：酿酒酵母菌可以有效去除水体的U(Ⅵ),且生物体在与U(Ⅵ)作用过程中释放的磷有效促进了酿酒酵母菌生物矿化铀。在溶液初始pH 3.0时,酿酒酵母菌对U(Ⅵ)的去除效果最好;随着吸附体系中U(Ⅵ)浓度的降低,溶液pH值升高,磷的消耗量增大,说明溶液中的H+和酿酒酵母菌释放的磷参与了酿酒酵母菌去除U(Ⅵ)的过程。酿酒酵母菌对U(Ⅵ)的吸附不受反应温度的影响,是自发的、吸热行为。通过FTIR,SEM,XPS和XRD测试分析,推测酿酒酵母菌生物矿化铀的机理为：最初在静电引力作用下,U(Ⅵ)被迅速吸附到酿酒酵母菌细胞表面,随后以配位的形式被菌体表面的磷酸盐、羟基和酰胺等官能团络合;溶液中的H+和酿酒酵母菌释放的无机磷酸盐可作为菌体与U(Ⅵ)结合的沉淀配体,继续矿化形成鳞片状的晶体物质H₂(UO₂)₂(PO₄)₂·8H₂O而被固定在酿酒酵母菌细胞外表面。此外,还有少量的U(Ⅵ)被菌体释放的物质还原成U(Ⅳ)形成CaU(PO₄)₂沉降下来。综上所述,磷是引起酿酒酵母菌生物矿化铀的主要功能元素。开展磷参与的铀的生物矿化机制研究对于铀污染的生物原位修复和深入理解放射性核素铀在自然界中的活化和固定化具有重要的意义。     

Optimum complexation of uranyl with amidoxime in aqueous solution under different pH levels: density functional theory calculations

This study aims to understand the complexation of uranyl with amidoxime in aqueous solution under different pH levels using density functional theory calculations. The geometries, relative stabilities of complexes, and changes in Gibbs free energies for different complexing reactions were investigated. Amidoximate ions were gradually added to the equatorial plane of uranyl to understand the complexation process. We modelled the effect of pH by varying the number of OH^? and H₂O ligands accompanying amidoximate ions in the equatorial plane of uranyl. The ?² binding motif was the most favourable form, regardless of the uranyl/amidoximate ratio and the pH level. Compared with low and high pH, neutral pH condition was more beneficial to the complexation of uranyl with amidoxime.     

双水相体系中Cu(Ⅱ),La(Ⅲ),U(Ⅵ),Ce(Ⅳ)光谱行为及萃取分离

利用聚乙二醇2000(PEG)-(NH)2SO4-萃取剂(铜试剂)双水相体系,采用液-液萃取的方法,研究了PEG相、单纯水相中金属离子络合物及萃取剂的光谱行为,探讨了金属离子络合物在PEG相中存在形态及萃取机理。同时实验了在不同酸度,不同盐用量,不同萃取剂用量,以及在不同表面活性剂的影响下,铜、镧、铀、铈的萃取率,通过控制一定条件,实现了Cu(Ⅱ)与La(Ⅲ),Cu(Ⅱ)与Ce(Ⅳ)之间的定量萃取分离。     

Oil absorption capacity of bare and PDMS-coated PET non-woven fabric; dependency of fiber strand thickness and oil viscosity

Water and oil absorption behaviors of the bare and PDMS (polydimethylsiloxane)-coated PET (polyethylene terephthalate) fabrics with two different fiber strand thicknesses were investigated. PET fabrics were superhydrophobically modified by PDMS-coating via a thermal vapor deposition process. The modification greatly enhanced the selectivity of PET fabric to oil absorption from oil/water mixture, making the PDMS-coated fabric a promising candidate as an absorbent of oil spills. We have also studied oil sorption behaviors of PDMS-coated PET fabric as a function of fiber strand thicknesses and oil viscosities. In general, fabric with a thinner fiber strand thickness showed a higher maximum oil absorption capacity, whereas uptake of the oil in thicker-fiber-absorbent was faster. Based on our results, we suggest that different absorbent structures with various fiber strand thicknesses can be chosen to maximize the efficiency of oil removal, depending on oil viscosity and available oil absorption time.     

纳米氧化铁对铀(Ⅵ)吸附性能的研究

用可见分光光度法研究了新型吸附剂纳米氧化铁对水中铀的静态吸附行为,考察了溶液pH值、吸附时间、离子强度和铀初始浓度等对吸附率的影响.结果表明,溶液pH对吸附率的影响较明显,在pH为6时,吸附率达最大,吸附5min后达到吸附平衡,且吸附率达95%以上;随铀酰离子浓度的增加,吸附率呈下降趋势,而吸附容量逐渐上升;铀在纳米氧...     

偕胺肟纤维与Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cd(Ⅱ),Hg(Ⅱ)配合物的红外光谱研究

用聚丙烯腈纤维 (PAN)改性制备的偕胺肟纤维 (AOCF)分别与三氯化铁、氯化钴、氯化镍、氯化镉和氯化汞在酸性介质中反应 ,制备偕胺肟 铁 (Ⅲ )、偕胺肟 钴 (Ⅱ )、偕胺肟 镍 (Ⅱ )、偕胺肟 镉 (Ⅱ )和偕胺肟 汞 (Ⅱ ) 5种偕胺肟 重金属配合物 (用通式M AOCF表示 )。用红外分光光度计分别对偕胺肟纤维和 5种配合物在 4 0 0 0～ 4 0 0cm- 1 范围进行傅里叶变换红外吸收 ,对各M AOCF的FTIR主要吸收峰做了经验归属 ,并将各M AOCF的特征吸收峰与AOCF的相应吸收峰作对比分析 ,结果表明 :配合物中C—N ,CN ,N—O等键的吸收峰位置均向高波数方向移动 ,且峰的强度增加。说明纤维材料中的偕胺肟基团与重金属离子在酸性介质中进行了配位反应 ,偕胺肟基团与重金属离子之间形成了配位键。