最优化算法与纯元素谱剥离相结合的能量色散X射线荧光谱解谱方法

在进行能量色散X射线荧光光谱(EDXRF)解谱时,如果给定样品的元素构成,采用纯元素谱图剥离的方式会更加合理,但由于每个元素的谱线都不止一条,如果仅仅针对主线对齐做剥离,会导致结果的严重失真,同时剥离次序对解谱结果有较大影响。介绍了一种最优化算法与纯元素谱剥离相结合的EDXRF解谱方法,该方法以多个纯元素谱的强度大小和峰位漂移道数作为变量构建残差方程,并用最优化计算的方法去调整,直至残差达到极小。实验采用强度顺序剥离、能量顺序剥离和最优化算法拟合3种方法分别对谱线重叠较为严重的La-Ce-Pr-Nd混合液样品的L系谱线进行了解析,结果表明最优化计算方法拟合的谱图与原始谱的残差 (1415.0)比另两种方法(166094.0和3192.7)大幅度缩小,拟合谱与原始谱更为吻合,并且方法在实现时对初值不敏感,解谱精度也不依赖于剥离次序。     

Introduction to crystallographic refinement of macromolecular atomic models

Refinement of atomic models is a necessary step in solving the macromolecular structure by X-ray diffraction methods. Nowadays, high automation and well-developed interfaces give a possibility to use the most popular refinement programs as black boxes. Nevertheless, working with complex objects requires an understanding of the internal structure and principles of operation of these programs and critical assessment of the results of refinement. In this review, we discuss the basic principles of the organization of refinement programs and the history of their improvement and development, as the studied objects became more and more complicated. The discussions are kept at the level of basic mathematic knowledge avoiding unnecessary formalism and too detailed expressions.     

Effect of nonlinear thermal radiation on 3D magneto slip flow of Eyring-Powell nanofluid flow over a slendering sheet with binary chemical reaction and Arrhenius activation energy

An analysis is performed to study the combined effects of nonlinear thermal radiation, Arrhenius activation energy, chemical reaction and heat generation/absorption on the steady three-dimensional magnetohydrodynamic flow of Eyring-Powell nanofluid flow over a slendering stretchable sheet with velocity, thermal and solutal slips. The prevailing partial differential equations are transmuted into coupled non-linear ordinary differential equations via with the suitable similarity transformations. The resultant non-linear coupled differential equations are solved numerically by using the R-K 4^th order method along with shooting scheme. The results are calculated to measure the influence of sundry parameters on velocity, temperature, concentration, shear stress, temperature gradient and concentration gradient are presented graphically and in tabular form. It is noticed that the temperature is more impactable for higher values of radiative heat transport. The local Sherwood number decays exponentially for all the values of the chemical reaction parameter. We compared the present results for the limiting cases with previously published results, which has shown reliability and efficiency.     

机械力化学制备锡酸锌及其在PVC中的阻燃应用

以二氧化锡（SnO₂）和氧化锌（ZnO）为原料,通过机械力化学湿法球磨,制备了锡酸锌（ZS）,再与水滑石按一定比例研磨得到锡酸锌改性的水滑石（ZS/HT）。通过扫描电子显微镜、X射线衍射、透射电子显微镜对合成的ZS与ZS/HT做了表征。将制得的ZS/HT应用于PVC制得阻燃PVC样品,当加入10%（ZS与水滑石的质量比）ZS/HT时材料的极限氧指数比纯PVC样品高3.5%,同时材料的力学性能有所增加。热重分析结果表明,ZS/HT的加入促使PVC提前分解成炭,有效提高PVC材料的残炭量。     

电感耦合等离子体原子发射光谱法测定辛酸铑催化剂中铂钯铅铁铜铝镍

准确测定辛酸铑催化剂中杂质元素含量,是判定产品是否合格的重要指标之一。以往常采用直流电弧发射光谱法(摄谱法)进行检测,但测定周期长,且重复性较差。用电感耦合等离子体原子发射光谱法(ICP-AES)测定辛酸铑催化剂中微量杂质元素时,辛酸铑催化剂样品中含有的大量有机组分和铑基体会对测定有严重干扰。实验采用反复滴加硝酸消解样品中有机组分,再用王水溶解盐类,选用合适背景点扣除的方式消除铑基体的干扰,建立了使用ICP-AES测定辛酸铑催化剂中0.001%~0.1%(质量分数)Pt、Pd、Pb、Fe、Cu、Al、Ni等7种微量杂质元素的方法。各元素在0.10~10.00μg/mL范围内与其发射强度呈线性关系,相关系数均大于0.9999;方法检出限(μg/mL)为0.075(Pt)、0.0033(Pd)、0.015(Pb)、0.0036(Fe)、0.010(Cu)、0.001(Al)、0.012(Ni)。实验方法用于测定辛酸铑催化剂样品中Pt、Pd、Pb、Fe、Cu、Al、Ni,结果的相对标准偏差为(RSD,n=7)为1.4%~9.6%。按照实验方法测定辛酸铑催化剂中Pt、Pd、Pb、Fe、Cu、Al、Ni,并与直流电弧发射光谱法的测定结果进行比对,结果相一致。     

高分辨连续光源原子吸收光谱法测定铀铌铅多金属矿中痕量银

铀铌铅多金属矿组成成分复杂,准确有效的测定其中的痕量银,有利于银的回收利用。采用HCl-HNO₃-HF-HClO₄处理铀铌铅多金属矿样品,以HCl(1+4)-2g/L酒石酸为测定介质,以λ_Ag=328.068nm为分析谱线,建立了高分辨连续光源原子吸收光谱法(HR-CS-AAS)测定铀铌铅多金属矿样品中痕量银的新方法。对仪器参数进行了优化,确定采用迭代基线校正(IBC)背景校正方式,CCD检测器有效像素点选择5个;由银的平均吸收光谱图和吸光度-波长-时间三维吸收光谱图可知,银的CCD检测器分辨率为0.0020nm/pixel,λ_Ag=328.068nm在327.86~328.27nm范围内没有受到溶液中其他共存元素的谱线干扰。在优化的实验条件下,银的吸光度与其质量浓度在0.40~1.60μg/mL范围内运用二次方程最小二乘法拟合校准曲线,相关系数为0.9999,特征浓度为0.0148μg/mL,方法检出限为0.0013μg/mL。将HR-CS-AAS测定样品中银的参数与空心阴极灯原子吸收光谱法(HCL-AAS)相比,其检出限更低,特征浓度更低,标准溶液系列的吸光度更高。按照实验方法对铀铌铅多金属矿样品中的银进行测定,结果与电感耦合等离子体质谱法基本一致,相对标准偏差(RSD,n=9)为0.63%~3.3%。按实验方法在铀铌铅多金属矿样品中加入银标准溶液进行加标回收试验,回收率为97%~104%,满足国家地质矿产行业标准DZ/T 0130—2006的要求。     

竹材液化墙体泡沫材料的阻燃改性

为提高竹材液化产物所制备的高轻发泡墙体材料的防火性能，分别采用材料内部添加和表面浸泡的方法进行阻燃改性，并评价不同阻燃剂及其添加量对发泡材料阻燃性能的影响。实验结果表明：在材料内部或表面添加选择的阻燃剂不会对材料自身形貌或组分产生明显影响，对材料的力学性能亦不会造成破坏，在材料内部添加3 g膨胀型凝胶-二氧化硅/聚磷酸铵核壳阻燃剂（MCAPP）后压缩强度达到了0.37 MPa，在材料表面浸泡聚硅氧烷后压缩强度达到了0.58 MPa，同时能提高材料的阻燃性能，在材料内部添加聚磷酸铵（M-APP）后极限氧指数提高到33.2%，比改性前提高3%。在材料表面浸泡膨胀型壳聚糖-蒙脱土-聚磷酸铵（CMAp）后点燃时间明显延长，极限氧指数最高达到了31.5%。     

Measurements and modeling of absorptive partitioning of volatile organic compounds to painted surfaces

Partitioning to surfaces is an important sink for volatile organic compounds (VOCs) indoors, but the mechanisms are not well understood or quantified. Here, a mass spectrometer was coupled to a portable surface reactor and a flow tube to measure partitioning of VOCs into paint films coated onto glass or wallboard, and their subsequent diffusion. A model was developed to extract values of the effective absorbing organic mass concentration of the film, C_w, which is a measure of absorption capacity, and VOC diffusion coefficients, D_f, from VOC time profiles measured during film passivation and depassivation. Values of C_w agreed well with the value estimated from the paint film mass and flow tube air volume, and D_f values (also measured using attenuated total reflectance-Fourier transform infrared spectroscopy) correlated well with VOC vapor saturation concentrations, C*, estimated using a group contribution method. The value of these relationships for estimating key parameters that control VOC partitioning into paint and the fate of VOCs indoors was demonstrated using a house model, which indicated that >50% of VOCs with C* ≤10⁸ μg/m³ (C* of octane, hexanone, and propanol) that contacted a paint film of typical thickness fully permeated the film regardless of emission duration.