Evolution of past enamel technology and metal conservation issues: the case of two Byzantine style bindings

The results of a Raman spectroscopic study of the cloisonne’ and basse‐taille enamels, which beautify two Byzantine style bindings from the Marciana Library (Venice), namely the Lat. III,111 and the MsGR.I.53 codexes, are presented in this work. The first binding dates back to the 13th century and was subject to an early restoration work in the 14th century, when new enamels substituted four originals. The second binding, from the 15th century, shows a lower number of enamels, all originals, and with a larger color palette. The white and yellow enamels of both codexes were successfully characterized and the red ones, where hematite was not used. Interestingly the white and yellow color of the 13th century enamels of the Lat. III,111 codex has been obtained by an ancient technique of the glass technology, which was already obsolete in the 13th century, and is based on the use of calcium antimonate and Naples yellow. The white color in the other binding's enamels have been instead obtained by using cassiterite, according to the tradition of the time. Cassiterite was also mixed to Naples yellow in the enamels of the MsGR.I.53 codex, to change the yellow hue. The identification of agents determining some colors is instead uncertain or not feasible by Raman spectroscopy. The transparency of the 14th century enamels of the Lat. III,111 codex has allowed the comparison of metal degradation below the enamels and in regions exposed to the atmosphere. Copyright © 2012 John Wiley & Sons, Ltd.     

ICP-OES法测定穿心莲药材中6种重金属元素溶出特性的研究

以电感耦合等离子体发射光谱法(ICP-OES)同时测定了中药穿心莲中的As,Ba,Cd,Cr,Cu,Pb等6种重金属元素,方法相对标准偏差2.1%~4.6%,回收率92.0%~103.2%,灵敏度高、简单、准确可靠。考察了采用热回流提取、浸泡提取、超声辅助提取等不同提取方法和提取溶剂时,上述6种元素的溶出情况。结果表明,实验所用穿心莲药材中Ba的含量最高,其次为Cu和Cr,而As,Pb,Cd在药材中含量相对较低。随着提取溶剂中乙醇含量升高,Ba的溶出减少,而Cu、Cr的溶出增加,Cd在酸性溶液中溶出最多;提取方法则以冷浸法溶出重金属元素最少,使用纯水和碱水的热回流提取重金属元素溶出相对较多。以上差异可能与这些元素在药材中的存在形态有关。     

Many-electron effect in the Fe L3-M4,5M4,5 Auger electron spectrum of ultrathin Fe films grown on Cu(1 0 0)

D’Addato et al. [S. D’Addato, P. Luches, R. Gotter, L. Floreano, D. Cvetko, A. Morgante, A. Newton, D. Martin, P. Unsworth, P. Weightman, Surf. Rev. Lett. 9 (2002) 709] studied the variation with Fe coverages in the relative Fe L₃-M_4,5M_4,5 Auger electron spectroscopy (AES) spectral satellite intensity of ultrathin Fe films grown on Cu(1 0 0) by sweeping photon excitation energy through the Fe L₂-level ionization threshold. They interpreted that the M_4,5 hole in the L₃M_4,5 double-hole state created by the L₂-L₃M_4,5 Coster–Kronig (CK) decay remains localized for longer than the L₃-hole lifetime for the 0.3 and 10 ML coverages but has a lifetime comparable to the L₃-hole lifetime for the 1 ML coverages. The present many-body theory shows that when the M_4,5 hole created either by the CK decay or by the L₃M_4,5 shakeoff hops away from the ionized atomic site and becomes completely screened out prior to the L₃-hole decay, the Fe L₂-L₃M_4,5-L₃-M_4,5M_4,5 AES main line as well as the Fe L₃ M_4,5 (satellite)-L₃-M_4,5M_4,5 one, both of which are identical in line shape to the Fe L₃-M_4,5M_4,5 one, dominate in the Fe CK preceded AES spectrum. The present analysis shows that the delocalization time of the M_4,5 hole created in the 1 ML Fe/Cu(1 0 0) system by the L₂-L₃M_4,5 CK decay is much shorter than the L₃-hole lifetime so that the Fe L₃-M_4,5M_4,5 AES spectral line shape hardly changes, except for the presence of a very weak spectator L₂-L₃M_4,5-M_4,5M_4,5M_4,5 AES satellite, when the photon excitation energy is swept through the Fe L₂-level ionization threshold. For the 0.3 ML coverages the M_4,5-hole delocalization time is still shorter than the L₃-hole lifetime.     

N‐Methylbenzoazacrown ethers with the nitrogen atom conjugated with the benzene ring: the improved synthesis and the reasons for the high stability of complexes with metal and ammonium cations

An improved method for the synthesis of formyl derivatives of N‐methylbenzoazacrown ethers is proposed. They are prepared in up to 68% yields over fewer steps and with a much shorter time required for the last step. The stability constants of complexes formed by N‐methylbenzoazacrown ethers and their structural analogs with alkali metal, alkaline‐earth metal and ammonium cations were determined by ¹H NMR titration in CD₃CN. High stability of complexes of N‐methyl derivatives of benzoazacrown ethers is demonstrated, comparable with or even exceeding the stability of benzocrown‐ether complexes and markedly exceeding the stability of complexes of phenylazacrown ethers with the same macrocycle size. The structures of azacrown ethers and their complexes with Ba(ClO₄)₂ were studied by X‐ray diffraction. A high degree of pre‐organization of N‐methylbenzoazacrown ethers toward the formation of complexes with metal and ammonium cations was noted, which is due to the clear‐cut pyramidal geometry of the nitrogen atom and the orientation of the lone electron pairs (LEPs) of most heteroatoms towards the centre of the macroheterocycle. Copyright © 2009 John Wiley & Sons, Ltd.     

基于超声红外技术对金属管内壁缺陷的检测

为提高管道的运送效率,及时检测排除管道内壁的缺陷非常重要。提出利用超声红外无损检测方法对管道内部进行检测。超声主动热激励试件,高频红外热像仪记录试件表面温度变化,结合了超声摩擦生热和红外热成像的优点。对壁厚约为3.3mm检测难度较大的金属管内壁缺陷进行了检测。通过对采集数据和热图的处理分析,准确快速地确定缺陷所在的位置。实物对比分析表明：超声热激励红外无损检测技术可以对金属管道内壁缺陷进行准确检测定位。     

可迁移的土壤重金属污染高光谱定性分类方法研究

现有基于高光谱遥感的土壤重金属污染定性分类模型,大多采用同一地区室内光谱测定训练样本数据进行模型构建与测试。但室内光谱测定需要复杂的处理过程,成本高,效率低,且无法快速获得目标区域空间上连续的光谱信息。考虑到实际应用需求,模型在相同实验区和不同试验区野外光谱数据是否具有较好的迁移推广能力是目前迫切需要回答的问题。为回答这一问题,选取湖南省郴州市和衡阳市两铅锌矿区作为实验研究区,选用支持向量机（SVM）作为分类器,将郴州实验区室内采样的83个样本数据和衡阳实验区室内采样的46个样本数据分别用于分类器训练,将衡阳地区野外采样的46个样本数据用于分类测试。并首先通过基于联合分布适配（JDA）的迁移学习方法进行光谱变换以缩小两地室内外测定光谱分布差异,然后进行不同区域室内外土壤重金属污染定性分类模型迁移。实验结果表明：（1）由于野外测得的光谱数据会受到太阳辐射、提取的土壤成分差异等因素的干扰导致室内外光谱数据存在显著的分布差异,难以直接将基于室内采样数据训练得到的土壤重金属污染定性分类模型迁移到同一地区测定的野外高光谱数据上。但通过JDA变换缩小室内外分布差异后,模型迁移能力得到显著提升,砷（As）、铅（Pb）和锌（Zn）三种重金属含量是否超标的分类精度都达到了84%以上,Zn元素含量是否超标的分类精度甚至达到了89%以上。（2）由于季节性影响、地区成分的干扰和光谱噪声的增加,不同地区光谱数据存在着更为显著的分布差异,加大了不同地区土壤重金属污染监测的难度,难以将基于室内采样光谱数据所建立的土壤重金属定性分类模型直接迁移到其他地区野外采样数据上（平均分类精度仅在50%左右）。经过JDA迁移学习方法进行室内外光谱变换处理后,模型迁移能力得到保证,因此,室外光谱采样可直接用于研究不同试验区域重金属（As,Pb和Zn）的污染情况。     

Attaching tweezers like ionophore to a proton crane: theoretical design of new tautomeric sensors

ABSTRACT

The tautomeric optical sensors based on 4-(phenyldiazenyl)naphthalen-1-ol exist in their pure enol tautomeric form as free ligands, while the addition of metal ion fully shifts the equilibrium towards the keto tautomer allowing a red shift in the measured absorbance. This effect is achieved when a side ionophore group is connected to a tautomeric backbone by a spacer in a way that stabilizes the enol form via hydrogen boding. When the ionophore captures the metal ion the keto form is stabilized due to C─O tautomeric group participation in the complex. In the current study, we model theoretically the effect of symmetric tweezer like ionophores (RCOXCOR, where X, being CH or N, is the linker to the tautomeric backbone) on the tautomeric state and complexation ability of 4-(phenyldiazenyl)naphthalen-1-ol containing ligands. It was found that enol form stabilisation is achieved when R?=?NMe₂, independing on the linker. Both ligands are unsuitable for capturing alkali metal ions. The calculations predict that the complexation with alkali earth metal ions could lead to a full shift of the tautomeric equilibrium towards keto tautomer.     

重金属碲酸盐玻璃中Ho~(3+)的红外辐射特性

制备了高折射率Ho3+单掺和Ho3+/Yb3+共掺低声子能量重金属碲酸盐玻璃.根据Judd-Ofelt理论对吸收光谱进行拟合,求得Ho3+强度参数Ωt(t=2,4,6)分别为4.373×10-20,1.906×10-20和1.451×10-20cm2,并进一步计算了Ho3+在红外区各能级跃迁的振子强度、自发辐射跃迁概率、辐射寿命和荧光分支比等光谱参数.982 nm激发下,铋碲酸盐玻璃中Yb3+直接敏化Ho3+,在红外区产生有效红外发射.Ho3+吸收与发射截面在1.95和2.05μm处分别高达5.63×10-21和6.24×10-21cm2,大于Ho3+掺杂磷酸盐和氟化物玻璃,这有利于降低激光抽运阈值,实现高效Ho3+激光输出.较低的声子能量和较大的发射截面表明,Ho3+/Yb3+共掺杂铋碲酸盐玻璃有望成为良好的红外激光工作物质.     

Reviews

Abstract

Biological Effects of Radiations Daniel S. Grosch Blaisdell Publishing Co., New York, 1965, 293 pages. $3.50

Ion Bombardment of Solids G. Carter and J. S. Colligon American Elsevier Publishing Company, Inc., New York, 1968, 446 pages. $40.00     

Bifurcation Instability of sheet metal during spring-back

In automotive and home appliance industries, there are many complex-shaped sheet metal components which need to be fabricated in multiple stamping operations. For example, the manufacturing of an outer case of washing machine consists of stamping followed by a bending operation. After the first stage of the stamping process, a large amount of spring-back takes place, and therefore, it is difficult to proceed to the next stage of the bending process. In the stamping process of that kind of sheet component with low geometric constraint, the forming area is large compared to the forming depth. Therefore, the formed part is in an unstable state and is less geometrically constrained, which causes a large amount of spring-back. To investigate this phenomenon, finite element analyses are carried out. During a spring-back analysis after forming, bifurcation takes place and the finite element solution procedure using the Newton–Raphson scheme becomes unstable. To get a stable post-bifurcation solution, a bifurcation algorithm is introduced at the bifurcation point. The deformed shapes obtained from finite element analyses are in good agreement with the experimental data. From this study, it is shown that the bifurcation behaviour enlarges the spring-back and the degree of dimensional error. To obtain additional possible post-bifurcation solutions, non-bifurcation analyses using initial guesses obtained in a modal analysis are carried. For the initial guesses, lowed four eigenmodes are utilized. Finally, the post-bifurcation behaviour and spring-back amount are investigated for various process parameters including the forming depth, punch width and corner radius.