Corrosion behaviors of thermally grown oxide films on Fe-based bulk metallic glasses

Oxide films formed on the surfaces of Fe-based bulk metallic glasses in the temperature range between 373 K and 573 K were characterized and their effects on the corrosion behaviors were investigated by microstructural and electrochemical analysis. The oxide film formed at 573 K is iron-rich oxide and it exhibits an n-type semiconductor at a higher potential than 0.35 V and a p-type semiconductor at a lower potential than 0.35 V. Capacitance measurements show that the donor density decreases with the increase in oxidation temperature, while the thickness of the space charge layer increases with the oxidation temperature rising. The result of immersion tests shows that the mass loss rate increases with the oxidation temperature rising. Therefore, the correlation between microstructure and corrosion resistance needs to be proposed because the corrosion resistance is deteriorated with the development of the oxide films.

Influence of Zr(50)Cu(50) thin film metallic glass as buffer layer on the structural and optoelectrical properties of AZO films

Aluminum-doped ZnO(AZO) thin films with thin film metallic glass of Zr(50)Cu(50) as buffer are prepared on glass substrates by the pulsed laser deposition. The influence of buffer thickness and substrate temperature on structural, optical, and electrical properties of AZO thin film are investigated. Increasing the thickness of buffer layer and substrate temperature can both promote the transformation of AZO from amorphous to crystalline structure, while they show(100)and(002) unique preferential orientations, respectively. After inserting Zr(50)Cu(50) layer between the glass substrate and AZO film, the sheet resistance and visible transmittance decrease, but the infrared transmittance increases. With substrate temperature increasing from 25℃ to 520℃, the sheet resistance of AZO(100 nm)/Zr(50)Cu(50)(4 nm) film first increases and then decreases, and the infrared transmittance is improved. The AZO(100 nm)/Zr(50)Cu(50)(4 nm) film deposited at a substrate temperature of 360℃ exhibits a low sheet resistance of 26.7 ?/, high transmittance of 82.1% in the visible light region, 81.6% in near-infrared region, and low surface roughness of 0.85 nm, which are useful properties for their potential applications in tandem solar cell and infrared technology.

Second phase effect on corrosion of nanostructured Mg-Zn-Ca dual-phase metallic glasses

Dual-phase metallic glasses(DP-MGs),a special member of the MGs family,often reveal unusual strength and ductility,yet,their corrosion behaviors are not understood.Here,we developed a nanostructured Mg_(57)Zn_(36)Ca_(7)(at.%)DP-MG and uncovered its corrosion mechanism in simulated body fluid(SBF)at the near-atomic scale utilizing transmission electron microscope(TEM)and atom probe tomography(APT).The 10-nm-wide Ca-rich amorphous phases allow oxygen propagation into the DP-MG,resulting in a micrometer thick hydroxides/oxides layer.This dense corrosion layer protects the DP-MG from further corrosion,enabling a corrosion rate that is 77%lower than that of Mg(99.99%purity).

电子束与电阻复合法制备Cu-Ti金属玻璃薄膜及性能测试

文章采用电子束与电阻复合热蒸发的方法,在衬底盘无冷却水条件下成功制备了Cu-Ti二元金属玻璃薄膜。通过X射线衍射仪(X-ray diffraction, XRD)、差示扫描量热仪(differential scanning calorimetry, DSC)和场发射透射电子显微镜(field emission transmission electron microscope, FE-TEM)表征了该二元合金薄膜的非晶态结构。此外,利用升温XRD方法研究了升温速率对玻璃转变温度和晶化温度的影响作用。另外,在紫外光和可见光辐照下,偏压分别为+0.2 V和-0.2 V时均有光电流响应,结果表明,该方法制备的Cu-Ti金属玻璃薄膜在紫外光和可见光区域具有光电响应特性,且表现出典型的N型光电流特性。

超薄金属基电磁屏蔽玻璃研究进展

电磁屏蔽玻璃是国防、民生等领域的重要应用材料,但是电磁性能和光学性能往往难以兼顾提升。超薄金属基透明电磁屏蔽薄膜是电磁屏蔽玻璃领域常用的功能性材料。本文对超薄金属基电磁屏蔽玻璃的屏蔽设计原理进行了详细阐述,重点综述了降低超薄金属薄膜阈值厚度的方法,回顾了近年来不同结构的超薄金属基电磁屏蔽玻璃的光学及电磁屏蔽性能,并对电磁屏蔽玻璃的未来发展趋势进行了讨论。

Enhanced pitting corrosion resistance of a Zr-based metallic glass by ultraviolet light irradiation

The influence of ultraviolet light irradiation on the pitting corrosion performance of a Zr_(2)Ni metallic glass was examined using electrochemical methods and immersion test in 0.05 mol/L NaCl solution.From the results of potentiostatic polarization,the pitting potential of the ultraviolet light-irradiated sample shifted positively with a value of~300 mV,revealing the enhanced pitting corrosion resistance of the samples.The corrosion morphology after the immersion test also demonstrated lower degree of corrosion damage and improved pitting resistance of the sample with ultraviolet light irradiation.X-ray photoelectron spectroscopy analysis revealed more zirconium enrichment in the passive film and no chloride ions adsorption for the samples with ultraviolet irradiation,accounting for the suppression of the pit generation and growth.Our findings indicate that ultraviolet light irradiation improves the pitting corrosion resistance of the Zr-based metallic glasses,which are promising structural materials to be used in corrosion environments with high ultraviolet irradiation.

Tailoring mechanical heterogeneity,nanoscale creep deformation and optical properties of nanostructured Zr-based metallic glass

Metallic glasses are spatially heterogeneous at the nanometer scale.However,the effects of external excitation on their structural and mechanical heterogeneity and the correlation to their properties are still unresolved.Nanoindentation,atomic force microscopy(AFM) and high-resolution transmis sion elec tron micro scopy(HRTEM) were carried out to explore the effects of cryogenic thermal cycling(CTC) on mechanical/structural heterogeneity,nano sc ale creep deformation and optical properties of nano structured metallic glass thin films(MGTFs).The results indicate that CTC treatment alters the distribution fluctuations of hardness/modulus and energy dissipation and results in an increase-then-decrease variation in mechanical heterogeneity.By applying Maxwell-Voigt model,it can be shown that CTC treatment results in a remarkable activation of more defects with longer relaxation time in soft regions but has only a slight effect on defects in hard regions.In addition,CTC treatment increases the transition time from primary-state stage to steady-state stage during creep deformation.The enhanced optical reflectivity of the MGTFs after 15 thermal cycles can be attributed to increased aggregation of Cu and Ni elements.The results of this study shed new light on understanding mechanical/structural heterogeneity and its influence on nanoscale creep deformation and optical characteristics of nanostructured MGTFs,and facilitate the design of high-performance nanostructured MGTFs.

Facile fabrication of ultrathin freestanding nanoporous Cu and Cu-Ag films with high SERS sensitivity by dealloying Mg-Cu(Ag)-Gd metallic glasses

Nanoporous metals prepared by dealloying have attracted increasing attention due to their interesting size-dependent physical,chemical,and biological properties.However,facile fabrication of metallic ultrathin freestanding nanoporous films(UF-NPFs)by dealloying is still challenging.Herein,we report a novel strategy of facile preparation of flexible Cu,Cu_(3)Ag,and CuAg UF-NPFs by dealloying thick Mg-Cu(Ag)-Gd metallic glass ribbons.During dealloying,the local reaction latent heat-induced glass transition of the precursor ribbons leads to the formation of a solid/liquid interface between the initially dealloyed nanoporous layer and the underlying supercooled liquid layer.Due to the bulging effect of in situ generated H2 on the solid/liquid interface,Cu,Cu_(3)Ag,and CuAg UF-NPFs with thicknesses of~200 nm can self-peel off from the outer surface of the dealloying ribbons.Moreover,it was found that the surfaceenhanced Raman scattering(SERS)detection limit of Rhodamine 6G(R6G)on the Cu and CuAg UF-NPF substrates are 10^(-6)M and 10^(-11)M,respectively,which are lower than most of the Cu and Cu-Ag substrates prepared by other methods.This work presents a reliable simple strategy to synthesize a variety of cost effective and flexible metallic UF-NPFs for functional applications.

Coating behavior and surface hardening of Pd_(77)Cu_6Si_(17) thin film metallic glass on AZ31 magnesium alloy

Pd77Cu6Si17(PCS) thin film metallic glasses(TFMGs) with high glass forming ability and hardness were selected as a hard coating for improving the surface hardness of AZ31 magnesium alloy. Both microindentation and nanoindentation tests were conducted on specimens with various PCS film thicknesses from 30 to 2000 nm. The apparent hardness and the relative indentation depth(β) were integrated using a quantitative model. The interaction parameters involved and relative hardness values were extracted from iterative calculations. According to the results, surface hardness can be enhanced greatly by PCS TFMGs in the shallow region, followed by gradual decrease with increasing β ratio. In addition, specimens with thinner coatings(e.g., 200nm) showed greater substrate-film interaction and those with thick coatings(e.g., 2000nm) became prone to film cracking. The optimum TFMG coating thickness in this study was estimated to be around 200 nm.

Synthesis of Ag-Cr thin film metallic glasses with enhanced sulfide-resistance

The thin film glass forming region of the immiscible Ag-Cr binary system was explored by combinatorial sputtering.The electrochemical behavior of Ag-Cr alloy films with different Cr content in different corrosive environments containing S^2-or Cl-were investigated in comparison with those of pure silver.The Ag-Cr thin film metallic glasses(TFMG)exhibit much enhanced corrosion resistance in 0.01 M K2S solution,comparing with that of the bulk silver,the Ag50 Cr50 TFMG exhibits much higher corrosion potential as well as two orders of magnitude lower corrosion current density.Nevertheless,no obvious improvement of the corrosion resistance can be found for the glassy films in 0.1 M NaCl solution.

Corrosion behavior of bulk metallic glasses in different aqueous solutions

The corrosion behavior of as-cast fully amorphous, structural relaxed amorphous and crystallized Fe65.5Cr4Mo4Ga4P12C5B5.5 bulk metallic glasses (BMGs) in NaCl, HCl and NaOH solutions was investigated by electrochemical polarization and immersion methods. X-ray photoelectron spectroscopy measurements was used to analyze the changes of the elements on the alloy surface before and after immersion in various solutions. The corrosion resistance of the Fe65.5Cr4Mo4Ga4P12C5B5.5 BMG was better than its structural relaxation/crystallization counterparts and common alloys (such as stainless steel, carbonized steel, and steel) in the selected aqueous solutions. The high corrosion resistance of this alloy in corrosive solutions leads to the formation of Fe-, Cr- and Mo-enriched protective thin surface films.

Preparation of hydroxyapatite layer on Ti-based bulk metallic glasses by acid and alkali pre-treatment

In this paper, a thin calcium phosphate layer was prepared on the surface of Ti4oZr10Cu36Pd14 bulk metallic glasses （BMGs）. All samples were dipped in HNO3 aqueous solution and boiled in 1.2 mol-L-I NaOH aqueous solution. After the two preliminary treatment steps, they were soaked in simulated body fluid （SBF） to form an apatite layer on the surface. After immersion for 12 days, a coating composed mainly of Ca-P particles was rapidly deposited on the surface of Ti40Zr10Cu36Pd14 bulk metallic glasses. The surfaces of chemically treated sam- ples and the samples after immersion in SBF were char- acterized by X-ray diffraction （XRD）, X-ray photoemission spectroscopy （XPS）, field emission scanning electron microscopy （FESEM）, and energy dispersive spectroscopy （EDS）. Analysis results indicate that this apatite coating consists of Ca-P particles with different diameters. In addition, the Ca/P ratio of the apatite coatings immersed for 14 days is 1.62, which is close to that of hydroxyapatite （HA）.

中高硼硅药用玻璃窑炉废气环保治理方法研究

通过分析中高硼硅药用玻璃窑炉烟气主要成分,找出了环保治理难点,指出目前常见物理方法治理氧化硼存在的不足,提出了采用化学方法治理氧化硼的技术措施及采用金属膜过滤器为过滤器件去除颗粒物。该技术路线能够充分回收利用废气热能,在满足环保要求和系统运行稳定的前提下,可有效降低系统建设成本和运行成本。

Role of late transition metals on pitting resistance of Zr-Ti-(Cu, Ni,Co)-Al bulk metallic glasses in 0.6 M NaCl aqueous solution

Four quanternary Zr-based bulk metallic glasses（BMGs）were selected,including the Zr_（46）Ti_2Cu_（45）Al_7,Zr_（61）Ti_2Cu_（25）Al_（12）,Zr_（55）Ti_4Ni_（22）Al_（19）and Zr_（55）Ti_2Co_（28）Al_（15）,due to their robust glass-forming ability and containing a single species of late transition metal（LTM）in compositions.Their pitting resistances in 0.6 M Na Cl aqueous solution were investigated to examine the role of LTM elements in the alloys,with electrochemical measurements,surface morphology observation and x-ray photoelectron spectrometry analysis.It is shown that in comparision with two Cu-bearing BMGs,Zr_（55）Ti_4Ni_（22）Al_（19）and Zr_（55）Ti_2Co_（28）Al_（15）BMGs exhibited significantly superior resistance to pitting.Zr_（61）Ti_2Cu_（25）Al_（12）,Zr_（55）Ti_4Ni_（22）Al_（19）and Zr_（55）Ti_2Co_（28）Al_（15）BMGs manifested distinct passivation behaviour,because of the formation of surface passive film mainly comprising of Zr O_2,Ti O_2and Al_2O_3.However,no significant differences in the electrochemical resistive properties and thicknesses of passive films were found between Zr_（61）Ti_2Cu_（25）Al_（12）and Zr_（55）Ti_4Ni_（22）Al_（19）BMGs.Nevertheless,at the passive film/metal interface,copper enrichment took place in Zr_（61）Ti_2Cu_（25）Al_（12）,whereas the nickel was slightly deficient at the interface in Zr_（55）Ti_4Ni_（22）Al_（19）.During pitting propagation,selective dissolution of the zirconium,titanium and aluminum over the copper took place in Zr_（61）Ti_2Cu_（25）Al_（12）,but it was not the case in Zr_（55）Ti_4Ni_（22）Al_（19）.For the two Cu-bearing BMGs,reduction of passive base metal elements in composition resulted in local selective dissolution,even absence of the passivation.

玻璃-金属封接技术

玻璃 金属封接按玻璃与金属两者间的膨胀系数差异 (即Δα)分为匹配封接和压力封接 ,它广泛应用于电池、电子、汽车、医疗、照明等行业。不同类型的玻璃 金属封接对金属材料及玻璃的要求将被讨论。对匹配封接 ,两者间的膨胀系数之差应小于 10 % ,而压力封接则要求细而薄的弹性金属。封接材料的选择及相应工艺参数的匹配对玻璃 金属封接件的质量好坏起着很重要的作用。封接工艺包括对温度、封接时间、氧化膜的厚度、保护气氛等的控制。

FeCoCrMoCBY块体非晶合金在强酸介质中的耐蚀性能

采用静态浸泡法研究了Fe43.7Co7.3Cr14.7Mo12.6C15.5B4.3Y1.9块体非晶合金(BMG)在浓HCl、浓H2SO4、浓HNO3以及王水中的腐蚀行为。研究表明该合金在强酸介质中具有优异的耐蚀性,在王水中浸泡236h的平均腐蚀速率仅为不锈钢的1/130。利用扫描电子显微镜(SEM)和X射线光电子能谱(XPS)分别对非晶合金在王水中腐蚀后的形貌和表面钝化膜的成分进行了分析。结果表明,合金的非晶态结构促使腐蚀过程中发生均匀腐蚀以及Cr元素在钝化膜中的富集是其具有强耐蚀能力的主要原因。

用于第一镜表面的金属玻璃薄膜研究

为解决大口径非晶金属第一镜实现难题,在研究块体金属玻璃Co61.2B26.2Si7.8Ta4.8材料基础上,采用金属玻璃块体材料制作拼接成溅射靶材,通过非平衡磁控溅射镀膜方法,实现了Co61.2B26.2Si7.8Ta4.8非晶金属薄膜第一镜。研究结果表明:通过成分设计及合成靶材的设计,能够实现与块体金属玻璃具有相同光学特性的非晶薄膜第一镜;通过Cr成分改进,能够进一步提高非晶金属薄膜第一镜在可见光波段的光谱反射率。

添加微量Mo对铜基块体非晶合金耐蚀性的影响

采用动电位极化和交流阻抗谱技术(EIS)研究了(Cu47Zr11Ti34Ni8)100-xMox(x=0,2)块体非晶合金在mol／L H2SO4溶液中的室温电化学行为．结果表明, x=2的钝化膜破裂电位(Eb)显著上升,致钝化电位(E0)与维钝电流密度(ip)明显减小．这主要是由于在稳定的钝化区内,微量Mo的添加增加了基体合金中的“氧空位”和表面活性,抑制了阴离子空位在金属／表面膜(M／F)界面上的形成,促使元素Zr和Ti在M／F界面上快速形成相应的氧化物,并增加了钝化层中氧化层的厚度和稳定性．根据该体系在电解质中的电化学反应,基于点缺陷模型(PDM)建立了简单的动力学模型．利用该模型,结合EIS数据,分析了微合金化提高铜基块体非晶合金耐蚀性能的机理．

金属膜电极层对Na_2O-PbO-Nb_2O_5-SiO_2玻璃陶瓷电容器电性能的影响

玻璃陶瓷电容器内电极结构及界面形貌对电性能有重要影响.采用磁控溅射法在介质层与银浆料电极间分别制备了Pt、Au、Cu和Ag金属膜内电极层,研究此电极层对Na2O-PbO-Nb2O5-SiO2玻璃陶瓷电容器电性能的影响.与单层浆料的电极结构相比,引入Pt、Au金属膜可以更有效地改善电性能:等效电容值增加25%,漏电流降低一个数量级.由SEM结果可知:Pt、Au、Cu膜与玻璃陶瓷紧密的界面接触能够抑制银向介质中扩散;然而,采用单层银浆料或引入Ag金属膜的样品界面多孔且银扩散严重.以上分析表明:Pt、Au金属膜电极层能够改善玻璃陶瓷电容器界面微观结构,有效抑制银的扩散,提高整体电性能.

中空玻璃镀膜层化学变性的研究

金属铜镀膜层在空气层中的水、氧气和二氧化碳的作用下转变为碱式碳酸铜,进一步与来自多硫聚合物的二氧化硫作用,生成亚硫酸铜,最后被空气中的氧气氧化为硫酸铜,造成腐蚀,使镀层化学性能发生变化。这是一个中空玻璃金属镀膜层化学变性的实例。