Investigation of the tarnish on the surface of a panda gold coin

In natural environment, tarnish was observed on the surface of historic and contemporary gold coins in several countries. Few years after the emergence of panda gold coins, several red spots were appeared on the surface. To identify the stains and to examine the spots, optical microscope （OM）, scanning electron microscope （SEM）, electron microprobe analysis （EMPA）, X-ray photoelectron spectroscopy （XPS）, and X-ray diffraction （XRD） were used. It was found by microscopic observation that the stain has a dark blue central area surrounded by a large area with a nuance of colors from brown to red. Red spots usually contain holes in the center, which are distributed along the forging stress zones formed in the struck process. From the surface analyses using EMPA, sulfur and silver are detected besides gold, and the contents of Ag and S at the tarnish part are higher than those at the other part. Furthermore, distributions of Ag and S are correlated with the morphology of stains. XPS shows that components of stains are Ag2S and Ag2SO4 and the former is much predominant. These results are confirmed using XRD analysis. Accelerated tarnish test of gold in an atmosphere containing sulfur compound proves that the similar phenomenon appears when a small amount of silver is present on the surface of gold. It can be concluded that the occurrence of tarnish stains is caused by the presence of Ag and S.

Anti-tarnish property of sterling silver alloy with yttrium addition

It has been demonstrated that sterling silver alloy is a widely used material in the jewelry industry. The anti-tarnish property is one of the most important properties of this material. In this work, the effect of yttrium on the corrosion resistance, and tarnish resistance properties of sterling silver alloy were investigated with the use of CIE-LAB uniform color scale, which gained acceptance as an effective way to assess color. To better understand the mechanism of the effect, the distribution of yttrium in the alloy was analyzed by mainly segregating in gaps among dendrite crystals and grain boundary. An increase in yttrium content in sterling silver alloy resulted in a decrease in the amount of eutectic structure. The tarnish and corrosion resistance of sterling silver were improved with yttrium content increase. However, too high yttrium content will lead to poor anti-tarnish properties.

Effect of Sn on the Color and Tarnishing of Cu-Mn-Zn Alloys

The effect of Sn on the color and tarnishing of Cu-Mn-Zn alloys is investigated quantitatively. Using the CIE LAB color system, color parameters such as L*, a* and V are selected to describe the surface color of atloys while the color difference (AB*) is used to evaluate the color stability. The results show that with the increase of Sn, the color change of Cu-Mn-Zn alloys is greatly reduced and the corrosion resistance in the synthetic sweat is improved dramatically. However, up to 4.4 wt pct Sn does not change the color of Cu-Mn-Zn alloys much. XPS and AES are employed to analyze the tarnished surface. It is proved that a Sn enriched film is formed and Sn takes the form of Sn oxide. This thin and protective oxide film can prevent alloy from further tarnishing.

Tarnish Testing of Copper-Based Alloys Coated with SiO_2-Like Films by PECVD

The tarnishing test in the presence of hydrogen sulfide（H2S） vapors has been used to investigate the tarnish resistance capability of copper-based alloys coated with Si02-like films by means of plasma-enhanced chemical vapor deposition（PECVD） fed with a tetraethoxysilane/oxygen mixture.The chemical and morphological properties of the films have been characterized by using infrared absorption spectroscopy（IR） and scanning electron microscopy（SEM）with energy disperse spectroscopy（EDS）.The corrosion products of the samples after the tarnishing test have been identified by X-ray diffraction analysis（XRD）.It has been found that SiO2-like films formed via PECVD with a high O2 flow rate could protect copper-based alloys from H2S vapor tarnishing.The alloys coated at the O2 flow rate of 20 sccm remain uncorroded after 54days of H2S vapor tarnish testing.The corrosion products for the alloys deposited at a low O2flow rate after 54 days of tarnish testing are mainly composed of brochantite.

Role of copper in tarnishing process of silver alloys in sulphide media

Silver and silver alloys usually tarnish,which causes some changes in their aesthetic appearance and electrical properties,due to their exposure to sulphide environments(H2S),and this is a problem in the field of corrosion and conservation of cultural heritage metallic artefacts.In this study,the role of copper content in the tarnishing process of 0.925,0.800 and 0.720 silver alloys in a 0.07 vol.%ammonium sulphide solution for different immersion periods was analyzed by electrochemical impedance spectroscopy(EIS)and scanning electron microscopy(SEM).The polarisation curves showed that the copper content and sulphide increased the corrosion current density and delayed the passivation of silver alloys.The impedance spectra collected at the open circuit potential(OCP)showed a single capacitive,incomplete and depressed loop,indicating that the charge transfer resistance decreased as the copper content increased in the alloys.In contrast,the double-layer capacitance increased as the copper content increased.The SEM-EDS analysis confirmed that the copper-rich phase in the silver alloys was selectively dissolved due to the preference of S to react with Cu,resulting in a localised attack,thus delaying the formation of a passive film.A marked localised attack was observed in alloys with lower copper content.The mechanism for the tarnishing of silver alloys in sulphide media was dependent on the nature of the alloy and the greater affinity of copper for sulphur.The dissolution of Ag and Cu to form corrosion products was proposed as the rate determining step.

Laser Ablation of Silver Artifacts in Vacuum： Solution to Silver Tarnishing Problem

This work is a study of effect of laser ablation in different medium on silver artifacts. The effectiveness of laser ablation cleanness methods was evaluated in air, water and vacuum condition. The samples were subjected to HC1 treatment for several hours to simulate the formation of chloride patina on marine archeological artifacts. Laser ablation removes the patina in all medium, reducing its thickness from 300 to few microns in air and water and eliminating completely the chlorine in vacuum conditions. However, it was observed the formation, during cleanness of a white patina in air and water and an increasing of oxygen amount on surface. This indicate that in ambient reach in oxygen laser ablation favorite the oxygen absorbance on surface and the formation of a thin layer of AgO which dulls the surface. This hypothesis is confirmed by the results of laser ablation in vacuum conditions where surface tarnishing was not observed. So, laser ablation in vacuum condition was indicated as the most effective procedure to clean silver artifacts.

Resistance risk assessment of six pyrethroids and acephate toward the resistant adult tarnished plant bug,Lygus lineolaris

Due to rapidly developed resistance,pest management relies less on pyrethroids to control economically damaging infestations of the tarnished plant bug(TPB),Lygus lineolaris(Palisot de Beauvois)in cotton fields of Mississippi.Yet,pyrethroid resistance remains prevalent in TPB populations.This study assessed the resistance levels in adult TPB to six common pyrethroids and acephate.Resistant TBPs were collected from wild host plants in late October after harvest in the Mississippi Delta region of the United States.Based on LCso values,the field-resistant TPBs displayed higher resistance to permethrin,esfenvalerate,and bifenthrin(approximately 30 fold)and moderate resistance toα-cyhalothrin,β-cyfluthrin,5-cypermethrin,and acephate(approximately 15 fold).Further investigations showed that the inhibitors of three detoxification enzyme,triphenyl phosphate(TPP),diethyl maleate(DEM),and piperonyl butoxide(PBO)had synergistic effects on permethrin,γ-cyhalothrin,and bifenthrin in resistant TPBs.Furthermore,elevated esterase,GST,and P450 activities were significantly expressed in fieldresistant TPBs.Additionally,GST and esterase were reduced after 48 h exposure to certain pyrethroids at LCso dose.The synergistic and biochemical assays consistently indicated that P450 and esterase were involved in pyrethroid detoxification in TPBs.This study provides valuable information for the continued use of pyrethroids and acephate in controlling TPBs in cotton fields in the Mississippi Delta region of the United States.

磁控溅射玫瑰金膜层的颜色及抗变色性能

[目的]玫瑰金因其优雅浪漫的颜色而被广泛用于装饰镀膜,但现有玫瑰金镀膜基本采用电镀工艺制备,存在严重的环境污染问题,需要寻求绿色环保的镀膜新工艺。[方法]采用磁控溅射镀膜工艺在316L不锈钢表面沉积Au85玫瑰金膜层。研究了溅射时间、靶电流和基体表面状态对膜层颜色的影响。检测了较佳工艺下所得膜层的抗变色性能。[结果]溅射时间在30 min以内变化时膜层颜色基本不受影响。靶电流从0.5 A增大至1.0 A时,膜层晶粒变粗,亮度下降,色度增大。基体表面状态会影响膜层颜色及不同方向的色差。在靶电流1.0 A下对镜面抛光的316L不锈钢磁控溅射15 min可获得较明亮的红色膜层,该膜层在模拟太阳光照射和人工模拟汗液浸泡试验中都表现出较好的抗变色性能。[结论]磁控溅射Au85玫瑰金镀膜工艺满足绿色环保和工艺饰品表面装饰要求,应用前景良好。

TARNISH AND PROTECTION OF SILVER DEPOSIT——MECHANISM AND METHOD

The mechanism of tarnish caused by exposure to light and Na_2S solution treatment on silver-electroplated deposit and the antitarnish effects of various antitarnish agents have been investigated in this paper. The results showed that 1-phenyl-5-mercaptotetrazole (PMTA) has excellent antitarnish effect for UV light and H_2S tests.The studies of XPS and AES and UV absorption spectra showed that PMTA can absorb effectively UV light and form a dense surface film which can prevent effectively the reactions between silver deposit with corrosive media.Antitarnish surface film could be composed of a polynuclear coordination polymeric compound with structure unit approximate to [Ag_3(PMTA)]. according to the depth dependence of percent component (C%) and sputtering time.

锈蚀钢材力学性能试验及等效本构模型研究

为准确描述锈蚀钢材在循环荷载下的本构关系,对经人工加速腐蚀的16组Q355钢锈蚀试件进行单调拉伸及循环加载试验,得到锈蚀钢材的力学性能参数及其退化规律.分析锈蚀对钢材试件滞回性能的影响,基于Giuffre-Menegotto-Pinto(GMP)模型建立了锈蚀钢材的循环本构模型.结果表明:钢材的屈服强度、极限强度及对应的屈服应变、极限应变等力学性能随着锈蚀程度的增加呈线性退化趋势;锈蚀会削弱钢材的耗能能力,使得结构在往复荷载下的安全性难以保证;建立的锈蚀钢材的循环本构模型与试验结果吻合较好,可为腐蚀环境下的钢构件及结构的抗震性能评估提供支撑.

Metapopulation approach for landscape level management of western tarnished plant bug,Lygus hesperus,in Texas( Hemiptera,Miridae)

Insect source-sink dynamics are vital to ecologically intensive pest management. Maintaining sink plant hosts,or "trap crops",and destroying alternate hosts or breeding places adjacent to the field crop are effective pest management strategies for some arthropods. However,determining whether a host acts as a source or a sink is challenging, especially when the pest species is highly mobile and polyphagous. The western tarnished plant bug,Lygus hesperus,is highly polyphagous,and can utilize >300 hosts. Its presence has been documented in 26 roadside weed hosts in the Texas High Plains.Previous studies demonstrated that L. hesperus prefer alfalfa over cotton and several alternate weed hosts.A four-year project involved surveying and sampling for L. hesperus in the agricultural landscapes of several sub-regions of the southwestern United States,including the Texas High Plains. In Texas,geographic information of the landscape vegetation complex was compiled from a 150 km radius in the Texas High Plains. In one study,fifty irrigated cotton fields representing the crop diversity within this region were sampled via sweep-net for 10 weeks. This effort also included sampling of up to six noncotton insect habitats within a 3 km radius of each field. Seasonal average L. hesperus abundance data were regressed with 27 field characteristics( variables),including habitat-specific land cover,distance between focal cotton fields and non-cotton habitats,longitude,latitude,elevation,habitat heterogeneity index,and several environmental / ecological variables. Significant variables were selected using a stepwise regression at 15% probability rate. A 10-parameter linear model explained 93% of the variation in the data. Major parameters contributing significantly to variation in L. hesperus abundance in cotton were corn and sunflower acreages,focal cotton field distances from several non-cotton hosts,and habitat heterogeneity index. In addition,field marking-and-capture studies were conducted using protein markers and enzyme-linked immunosorbent assays to characterize L. hesperus intercrop movement behavior. The field marking-and-capture approach can be used to study the effects of various crop management practices on L. hesperus intercrop movement and can potentially be applied to other pests and cropping systems.

燃气-蒸汽联合循环机组余热锅炉尾部受热面锈蚀对烟道阻力的影响

在某燃气 蒸汽联合循环机组长期停机备用期间,针对其余热锅炉尾部受热面开齿螺旋鳍片管锈蚀导致烟气流动阻力升高,影响燃气轮机带负荷的问题,通过现场数据监测、数值模拟及小型试验台试验,研究鳍片管表面锈蚀状态对流动阻力特性的影响。结果表明:余热锅炉尾部模块5、模块6的阻力上升明显;鳍片管背风侧的锈蚀堆积不会导致流动阻力的上升,两侧锈蚀厚度增加是流动阻力上升的主要原因;鳍片管除锈后鳍片减薄,流通截面积增大,阻力特性优于新鳍片管。

纯银饰品抗变色的研究

银具有光亮的外表,但是它长期暴露在空气中易氧化硫化变色,影响美感。为了提高银的抗氧化能力,本文介绍了一种抗变色银材料的制备方法。该方法是通过在银表面覆盖一层透明无机陶瓷膜,避免银与外界物质接触,来达到抗变色的目的。该无机陶瓷膜的原料是正硅酸四乙酯、水、聚乙二醇、硼酸、偏铝酸钠,其最佳配比是92∶1000∶160∶3∶4,最佳搅拌时间是60分钟。该方法制备的抗氧化银材料比纯银抗变色能力强近500倍。

铜基镀银引线框架抗化学腐蚀工艺过程影响研究

铜基镀银引线框架作为半导体封装的主要材料之一,其铜面和镀银区易受空气影响造成化学腐蚀,随着时间的变长,此种化学腐蚀程度会不断增加。由于化学腐蚀过度会造成引线框架表面的可焊性降低,最终造成焊线脱落和封装后分层问题,故铜面和镀银区的表面状态对半导体的可靠性有重要影响。本文介绍了铜基镀银引线框架生产过程中不同电镀工艺和铜保护剂类型的差异性,提出了铜基镀银引线框架生产过程中抗化学腐蚀性实现的关键控制点,为引线框架产品可靠性的提升预防提供数据支持。

超声辅助对铜表面无氰电镀银的影响

采用由硝酸银15 g/L、烟酸50 g/L、乙酸铵40 g/L、碳酸钾40 g/L和氢氧化钾15 g/L组成的镀液(pH=9)在铜基体表面电镀Ag。对比了无超声辅助和超声辅助电镀所得Ag镀层的表面形貌、晶相结构、结合强度、抗变色能力和耐腐蚀性能,并研究了超声功率对沉积速率和Ag镀层抗拉强度的影响。结果表明:在超声波辅助下,Ag镀层变得更加细致,晶面择优取向由(311)转变为(220),结合力、抗变色能力和耐腐蚀能力均有所提高。随着超声功率增大,沉积速率和Ag镀层的抗拉强度均先增大后减小,在90 W时均达到最大,分别为9.5μm/h和260 MPa。

925Ag75Cu和925Ag40Cu35Zn合金在人造汗液和H_2S气氛中的腐蚀与变色行为(英文)

采用静态腐蚀、XRD、SEM、EDS和XPS,研究了250℃时效4h和70%冷变形+200℃时效4h两种硬化状态下的925Ag75Cu与925Ag40Cu35Zn合金在37℃人造汗液和室温H2S气氛中的腐蚀与变色行为。结果表明,这两种925银合金在37℃人造汗液中的腐蚀变色是由Cl-和OH-离子引起的,但925Ag40Cu35Zn合金的变色过程明显比925Ag75Cu合金缓慢,腐蚀过程中产生的白色AgCl和灰黑色Ag2O难以在其表面沉积而形成灰黑色腐蚀膜。这两种925银合金在室温H2S气氛中的腐蚀变色是由S2-引起的,但925Ag40Cu35Zn合金的腐蚀变色过程明显比925Ag75Cu合金缓慢,这是由于腐蚀过程中白色ZnS最先形成,从而延缓了灰黑色Ag2S和黑色Cu2S的形成。

含氟牙膏对纯钛铸件表面形态、光泽和色彩的影响

以无氟牙膏为对照,研究含氟牙膏刷洗钛铸件对其表面形态、光泽和色彩的影响。结果表明:钛铸件用含氟牙膏刷洗后表面形态有较大的改变,而用无氟牙膏刷洗后表面形态无明显变化;两组钛铸件刷洗后均出现了失泽和变色,色彩偏蓝、偏绿,变得晦暗,但两组的色差无显著性差异。因此使用含氟牙膏刷洗对钛铸件表面形态的影响大于无氟牙膏,2种牙膏对钛铸件的色彩均有一定影响,但二者之间无显著性差异。

银器的变色和防护技术

分析了银器表面在硫化物、硫氧化物等腐蚀性气体环境中变色的机理和影响因素,讨论了银器表面处理防变色(贵金属或合金的涂层、阳极化钝化、阴极电泳、化学钝化、自组装单分子膜的防腐蚀等)的方法和加工技术,并提出了包装贮存材料处理防银器变色的新途径。

防止银器文物变色的唑系复合缓蚀剂——II.SERS法研究唑系缓蚀剂防银变色的作用机理

测定了 PMTA、MBO、MBI的普通拉曼光谱 ( NRS) ,利用表面增强拉曼散射光谱( SERS)研究了几种唑系缓蚀剂防止银器文物变色的表面成膜过程 ,复合缓蚀剂组分与银的相互作用 ,并讨论了其防变色作用的机理。实验结果表明 ,PMTA、MBI和 MBO与银表面存在着较强的相互作用 ,由于杂环结构的差异 ,不同缓蚀剂在银表面上呈现不同的吸附取向 ,形成了更为致密的防变色保护膜。在成膜溶液中 ,p H值较小时有利于缓蚀剂吸附 ,处理时间应不少于 1 2 0 min。成膜溶液和含缓蚀剂的硫化钠溶液中 ,银电极阴极极化时 (外加阴极电位≤ 60 0 m V的测试范围内 ) ,复合缓蚀剂的 SERS响应均随电位负移而增强 。

银的变色及抗变色研究

讨论了大气中各种腐蚀性气体对银变色的影响,以及变色膜中各种腐蚀产物的成分及状态,以硫化氢气体和硫化银为主要对象进行阐述,侧重介绍了最近30年的研究结果。总结了近年来各种银的抗变色的方法。