一种双靶磁控溅射制备的Mg掺杂的NiO薄膜

采用磁控溅射“共溅射”方法,将Ar气作为溅射气体,高纯NiO和MgO双陶瓷靶作为溅射靶材。当控制NiO和MgO靶的溅射功率分别为190 W和580 W,溅射真空度为2 Pa,衬底温度为300℃时,得到了Mg掺杂的NiO(Ni_(0.61)Mg_(0.39)O)薄膜。该薄膜是一种具有(200)择优取向的晶态薄膜。薄膜表面比较平整,晶粒分布致密,晶粒尺寸约46.9 nm。(200)衍射峰位置相对未掺杂的NiO薄膜向小角度偏移约0.2°。合金薄膜在可见光波段具有较大的透过率,而在300 nm附近透过率陡然下降,其光学带隙向高能方向移动到了3.95 eV。该研究为采用磁控溅射制备高质量的Mg掺杂的NiO薄膜提供了技术支撑。

An overview of progress in Mg-based hydrogen storage films

Mg-based hydrogen storage materials are considered to be one of the most promising solid-state hydrogen storage materials due to their large hydrogen storage capacity and low cost. However, slow hydrogen absorption/desorption rate and excessive hydrogen absorption/desorption temperature limit the application of Mg-based hydrogen storage materials.The present paper reviews the advances in the research of Mg-based hydrogen storage film in recent years, including the advantage of the film, the function theory of fabricating method and its functional theory, and the influencing factors in the technological process. The research status worldwide is introduced in detail. By comparing pure Mg, Pd-caped Mg, nonpalladium capped Mg, and Mg alloy hydrogen storage films, an ideal tendency for producing Mg-based film is pointed out,for example, looking for a cheap metal element to replace the high-priced Pd, compositing Mg film with other hydrogen storage alloy of catalytic elements, and so on.

Effect of Mg-Film Thickness on the Formation of Semiconductor Mg_2Si Films Prepared by Resistive Thermal Evaporation Method

Mg films of various thicknesses were deposited on Si（111） substrates at room temperature by resistive thermal evaporation method, and then the Mg/Si samples were annealed at 40 ℃ for 4 h. The effects of Mg film thickness on the formation and structure of Mg2Si films were investigated. The results showed that the crystallization quality of Mg2Si films was strongly influenced by the thickness of Mg film. The XRD peak intensity of Mg2Si （220） gradually increased initially and then decreased with increasing Mg film thickness. The XRD peak intensity of Mg2Si （220） reached its maximum when the Mg film of 380 um was used. The thickness of the Mg2Si film annealed at 400℃ for 4 h was approximately 3 times of the Mg film.

Comparison on corrosion resistance and surface film of pure Mg and Mg−14Li alloy

To study different corrosion resistances and surface film types of hexagonal close-packed(HCP)pure Mg and body-centered cubic(BCC)Mg−14wt.%Li alloy in 0.1 mol/L NaCl,a series of experiments were conducted,including hydrogen evolution,mass loss,in-situ electrochemical testing combined with Raman spectroscopy and microstructural observation.The results indicate that the corrosion resistance of pure Mg is superior to that of Mg−14Li,and the protective function of the surface films on both magnesium systems is elevated within 16 h of immersion in 0.1 mol/L NaCl.An articulated,thick,and needle-like surface film containing Li2CO3 on Mg−14Li,different from the typically thin,flaky Mg(OH)2 film on pure Mg,is confirmed via scanning electron microscopy(SEM).However,both surface films can be broken down at a high anodic over-potential.Thus,different corrosion resistances of the two Mg systems are ascribed to various protective films forming on their surfaces.

Effect of solution concentration on sealing treatment of Mg-Al hydrotalcite film on AZ91D Mg alloy

Cerium-based sealing treatment was developed for Mg-Al hydrotalcite film on AZ91D Mg alloy,and the influence of cerium salt solution was investigated to modify the surface integrity and corrosion resistance.Scanning electron microscope(SEM)and X-ray diffraction(XRD)measurements were carried out to analyze the surface morphology and phase composition.The corrosion resistance of Mg-Al hydrotalcite film after sealing treatment was evaluated by the polarization curve and electrochemical impedance spectroscopy(EIS)tests.The results showed that lower concentration of Ce-containing solution was beneficial to seal the micro-cracks on Mg-Al hydrotalcite film,and improve the surface integrity and corrosion resistance;higher concentration of Ce-containing solution could seal fewer micro-cracks,and the corrosion resistance was decreased owing to the disintegration of Mg-Al hydrotalcite film.

Formation mechanism of pulse current anodized film on AZ91D Mg alloy

The kinetics of forming process of pulse current anodized film on AZ91D Mg alloy was studied by the voltage-time and thickness-time curves.The surface morphology,structure,elemental constitution and valences of the anodic films were analyzed by SEM,EDS,XPS and XRD respectively.The results show that the film-forming process can be divided into four stages.Formation of a dense layer before sparking is the first stage.Formation of a porous layer accompanied with slight sparking is the second stage.The third stage is characterized by fast growth of the porous layer accompanied with more intensive sparking.The fourth stage starts after the sparking process becomes even more vigorous and the pores become large.

Preparation of Mg-Yb alloy film by electrolysis in the molten LiCl-KCl-YbCl_3 system at low temperature

The electrochemical behavior of Yb3+ and electrodeposition of Mg-Yb alloy film at solid magnesium cathode in the molten LiCl-KCl-YbCl3(2 wt.%) system at 773 K was investigated.Transient electrochemical techniques,such as cyclic voltammetry,chronopotentiometry and chronoamperometry were used in order to explore the deposition mechanism of Yb.The reduction process of Yb3+ is stepwise reactions which are single-electron and double-electron reversible charge transfer reactions.The speed control step was a diffu...

Influence of second phase precipitates on mechanical and in-vitro corrosion behaviour of Mg-4Zn-0.5Ca-0.8Mn alloy in optimum homogenized conditions

The present study investigates the mechanical and in-vitro corrosion behavior of Mg-4Zn-0.5Ca-0.8Mn alloy in optimum homogenized conditions.The optimization of the homogenization parameters has been carried out employing thermodynamic calculations and kinetic modeling.The model utilizes the inter-diffusivity of the solute elements and predicts that∼6–24 h of homogenization at 633 K effectively redistributes the elements in the Mg matrix.Based on the insights obtained from the simulations,the as-cast Mg-4Zn-0.5Ca-0.8Mn alloy was subjected to homogenization heat treatment process for 6–24h.The microstructural study through optical microscopy and scanning electron microscopy(SEM)revealed that the interconnected network of second phase precipitates substantially dissolve within 24 h,implying adequate homogenization.Moreover,fine Mg-Zn based precipitates with varied morphology and phase fractions also evolved during homogenization treatment,as confirmed through SEM and transmission electron microscopy.In the 12 h homogenized specimen,the highest fraction of uniformly dispersed fine precipitates resulted in the highest strength(∼225 MPa).On the other hand,a substantial disruption in coarse precipitate network and lower aspect ratio of fine Mg-Zn precipitates led to the highest ductility(∼8%)in this specimen.In the 24 h homogenized specimen,the ductility reduced marginally owing to higher aspect ratio of fine precipitates.The immersion and electrochemical tests(viz.,potentiodynamic polarization and electrochemical impedance spectroscopy)carried out in Hank’s solution revealed that the 24 h homogenized specimen exhibits the best corrosion properties.The least fraction of Ca_(2)Mg_(6)Zn_(3)phase with maximum disruption in interconnectivity,in combination with a small fraction of fine equilibrium MgZn_(2)precipitates,resulted in suppression of localized corrosion in this specimen.This promotes the formation of the most stable and compact product layer over the specimen,resulting in the highest corrosion resistance.

Improved electrochemical hydrogen storage properties of Mg-Y thin films as a function of substrate temperature

Pd-capped Mg78Y22 thin films have been prepared by direct current magnetron co-sputtering system at different substrate temperatures and their electrochemical hydrogen storage properties have been investigated.It is found that rising substrate temperature to 60 ℃ can coarsen the surface of thin film,thus facilitating the diffusion of hydrogen atoms and then enhancing its discharge capacity to 1725 mAh·g-1.Simultaneously,the cyclic stability is effectively improved due to the increased adhesion force between film and substrate as a function of temperature.In addition,the specimen exhibits a very long and flat discharge plateau at about —0.67 V,at which nearly 60%of capacity is maintained.The property is favorable for the application in metal hydride/nickel secondary batteries.The results indicate that rising optimal substrate temperature has a beneficial effect on the electrochemical hydrogen storage of Mg-Y thin films.

含金属Mg相的Mg_(2)(Sn,Si)薄膜的微观结构与热电性能

利用高真空磁控溅射设备,采用Mg-Sn-Si合金靶材和纯Mg靶进行顺序沉积,在表面含有500 nm厚氧化硅的单晶Si(100)衬底上制备了不同Mg含量的Mg-Sn-Si薄膜。沉积Mg-Sn-Si薄膜的相组成、化学成分、表面和横截面形貌和热电性能被系统的测量、观察和分析。结果表明,制备的Mg-Sn-Si薄膜由Mg_(2)(Sn,Si)固溶体和金属Mg相组成。随着金属Mg相含量的增多,沉积薄膜载流子浓度升高,迁移率降低。沉积薄膜的电导率随着金属Mg相含量的增多而增大,而Seebeck系数降低。沉积薄膜的金属Mg相含量增加,虽然电导率增加,但因Seebeck系数急剧下降,最终导致功率因子下降。在所研究的金属Mg含量范围内,Mg_(2)(Sn,Si)固溶体薄膜含有部分金属Mg相,对提高复合薄膜的功率因子是不利的。

Nucleation and growth behavior of coating film on Mg–Al–Zn alloy with different surface topographies via plasma electrolytic oxidation

This work was made to investigate how nucleation and growth behavior of the coating film were affected by surface topographies of Mg–Al–Zn alloy substrate during the initial stage of plasma electrolytic oxidation(PEO).To satisfy this end,a single substrate was prepared by mechanical treatment exhibiting rough and smooth regions with an equal area on the surface.The rough region with prominent hills and grooves induced the breakdown of passive film,which was indicated by an early appearance of plasma discharge on the rough region since nucleation of coating film occurred preferentially around the hills.However,the coating film grown on the grooves was somewhat thicker and more porous than the film grown on the hills and smooth regions.This was due to the fact that the growth of the coating film was found to be localized in the presence of rough region,which was in line with the discharge activities.Herein,the nucleation and growth behavior during the initial stage of PEO will be discussed schematically on the basis of microstructural interpretation.

Hydrogen storage properties of preferentially orientated Mg-Ni multilayer film prepared by magnetron sputtering

Mg-Ni multi-layer thin film was deposited on (001) Si wafer by magnetron sputtering with dual-target. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis reveal that the microstructure of the Mg-Ni multilayer thin film is composed of fine-crystalline Ni layer and crystalline [001] Mg layer. Hydrogenation process of the films were carried out by using the automatic gas reaction controller. The films undergone hydrogenation for different time were analyzed by XRD. The results show that hydrogenation properties of Mg with different preferential orientations are different. (002) diffraction peak of Mg disappears in compensating the appearing of the peaks of Mg2NiH4 and MgH2 in hydrogenation at 533 K, while the (101) peak still remains. The result reveals that the Mg film with (001) preferential orientation absorbs hydrogen at certain temperature easier than that of the Mg film with (101) orientation. This phenomenon can be explained in the view point of the energy change for the nucleation and growth of hydride in different crystal plane.

Mg-Ni THIN FILM-A POTENTIAL NEGATIVE ELECTRODE FOR NIKEL-METAL HYDRIDE BATTERY

Mg-Ni thin films for nickel-metal hydride (Ni-MH) battery negative electrode were prepared on three different substrates by using magnetron sputtering with compacted Ni and Mg mixture powder. The microstructure of Mg-Ni thin films deposited on the glass and the Ni foil substrate respectively was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the Mg-Ni thin films were in amorphous structure and the composition of the thin film was homogeneous. Electrochemical measurement show the discharge capacity of the thin film negative electrode deposited on the foam Ni substrate was 284.8mAh/g in 6M alkaline electrolyte and the internal resistance was much lower than that of the electrode prepared by the ball-milled powder during the charge-discharge cycle.

The transverse laser induced thermoelectric voltages in step flow growth (1-x)Pb(Mg_(1/3)Nb_(2/3))O_(3-x)PbTiO_3 thin films

This paper reports that the transverse laser induced thermoelectric voltages （LITV） axe observed for the first time in the step flow growth （1- x）PD（Mg1/3Nb2/3）O3-xPbTiO3 （PMN-PT, x = 0.20, 0.33, 0.50） thin films deposited on vicinal-cut strontium titanate single crystal substrates. Because lead magnesium niobate-lead titanate is a solid solution of lead magnesium niobate （PMN） and lead titanate （PT）, there are two types of signals. One is wide with a time response of a microsecond, and the other superimposed with the wide signal is narrow with a time response of a nanosecond. The transverse LITV signals depend on the ratio of PMN to PT drastically. Under the irradiation of 28-ns pulsed KrF excimer laser with the 248-nm wavelength, the largest induced voltage is observed in the 0.50Pb（Mg1/3Nb2/3）O3-0.50 PbTiO3 films. Moreover, the effects of film thickness, substrates, and tilt angles of substrates are also investigated.

Effect of Al addition on corrosion behavior of high-purity Mg in terms of processing history

In this study,the effects of Al addition on the corrosion behavior of pure Mg with controlled impurity contents were systematically analyzed according to the processing history.The results revealed that the corrosion behavior of high-purity Mg-Al alloys is strongly related to changes in the microstructure,including theβphase and Al-Mn or Al-Fe phases,and the protectiveness of the surface film according to the Al content and processing history.In the as-cast alloys,the corrosion rate increased due to the increase ofβphase as the Al content increased,but in the as-extruded alloys,the corrosion rate,which was high due to intermetallic compounds caused by impurities in the low Al alloy,decreased as the Al content increased,and then increased again.This is due to the combined effect of the increase of theβphase and decrease of the impurity effect,and the increase of the dissolved Al content.The results suggest that it is necessary to analyze the effect of alloying elements on the corrosion behavior of pure Mg with information concerning the impurity content and processing history.

环保型陶化膜的研究进展及其在镁合金上的应用

陶化膜作为替代磷化的预处理工艺,操作简单,无需加热,能耗低,成膜时间短,不排放有害物质和残渣,解决了磷化膜的成本和环保问题。目前陶化膜已经在钢铁、铝合金等基材上实现了工业化应用,但在镁合金表面的研究还比较少。本文结合国内外陶化膜的研究进展,总结了陶化膜的发展历史,成膜机制,陶化膜的溶液组成及工艺参数的影响(包括成膜剂、成膜液中的添加剂、成膜液的pH、成膜时间、成膜温度、成膜液的搅拌、基体材料的影响),同时介绍了镁合金表面陶化膜的研究现状,并对未来镁合金陶化膜的研究重点进行了总结和展望。为了尽早实现陶化膜在镁合金部件的批量应用,膜层的均匀性、致密性、与漆膜的结合力等方面尚需深入研究,成膜液的维护,操作规范的制定,废水处理等这些问题尚待解决。

热蒸发法制备Mg和Mg-Ni薄膜及其氢化性能

采用热蒸发法制备了纯Mg膜及Mg_(78)Ni_(22)合金膜,研究了薄膜的结构及其氢化性能。Mg膜具有典型的柱状晶结构,择优取向生长趋势明显;Mg_(78)Ni_(22)薄膜由纳米晶Mg_2Ni,Mg及少量非晶组成,Mg_2Ni相沿着平行于薄膜表面的(001)方向择优生长。纯Mg膜的吸放氢温度分别为593和653 K,其吸氢过程遵循形核长大机制。Mg_(78)Ni_(22)薄膜的压力一组成等温曲线存在低压和高压两个平台区,分别对应Mg和Mg_2Ni的氢化反应,薄膜内Mg的吸放氢温度可分别降至473和503 K,薄膜的最大吸氢量(质量分数)达到5.7％。Mg的氢化性能改善与薄膜中纳米晶Mg_2Ni和非晶相起到的催化作用有关。

Mg-Gd-Y-Zr合金表面含硫硅烷薄膜的结构与耐蚀性能

采用分子自组装的方法在Mg-Gd-Y-Zr合金表面制备双-(γ-三乙氧基硅丙基)四硫化物硅烷薄膜。通过傅立叶变换红外光谱研究薄膜结构特性,用扫描电镜观察薄膜表面形貌,并用电化学极化曲线和交流阻抗测试研究薄膜的耐蚀性能。结果表明,镁合金表面薄膜通过SiOSi链接形成网状结构,并可能通过形成SiOMg界面相结构与镁合金表面连接;晶界上薄膜厚度小于其他各处;薄膜将腐蚀电流密度降低2个数量级以上,明显提高了盐水浸泡过程中的阻抗值。

PVA/Mg(NO_3)_2复合膜的制备及性能

采用溶液成膜的方法制备了不同Mg(NO3)2含量的聚乙烯醇(PVA)/Mg(NO3)2复合薄膜。考察了PVA/Mg(NO3)2复合薄膜在相对湿度为54%时的含水量。采用X射线衍射(XRD),差示扫描量热(DSC),动态力学性能(DMA)和力学性能测试方法研究了Mg(NO3)2对PVA膜的结构和性能的影响。结果表明,Mg(NO3)2与PVA的相容性非常好,所制备的PVA/Mg(NO3)2复合膜的透明性好。Mg(NO3)2的加入能显著破坏PVA中的氢键作用,增加PVA膜中的水含量,降低PVA的结晶度,使复合膜的玻璃化温度明显降低。拉伸实验表明,PVA/Mg(NO3)2具有比纯PVA膜更低的拉伸强度和更高的断裂伸长率。

含稀土元素的Mg-Al合金在NaCl溶液中腐蚀产物膜的研究

利用多种表面分析手段比较研究了纯Mg和Mg - 8Al、Mg - 8Al-RE等镁铝合金在Mg(OH) 2 饱和的 3 5 %NaCl溶液中的腐蚀产物膜的形貌及结构 .发现Al元素的加入使镁合金表面形成含Mg、Al的复杂氧化物 ,有利于提高镁合金耐腐蚀性 .稀土元素RE的加入有利于提高Al元素在氧化膜中的含量 ,形成具有三层结构的产物膜 ,进一步提高了Mg