纳米反应多层膜的制备及应用

纳米反应多层膜是指两种或两种以上不同材料按一定厚度在衬底上交替沉积形成的薄膜材料。纳米反应多层膜是一种新结构形式的纳米含能材料,可在较低的能量刺激下发生放热反应,产生的热量足以使反应区以特定的速度自持传播,具有反应瞬间完成、放热量大等特点。由于结构可自行设计以及不同于单层膜的特殊性能,纳米反应多层膜可广泛应用于微电子器件、微机械系统(MEMS)等领域。对近年来国内外纳米反应多层膜的制备方法、反应机理以及在器件应用等方面的研究进行了综述,主要分析讨论了机械加工、蒸发镀膜和磁控溅射3种制备方法的优缺点,并对今后纳米反应多层膜的研究方向及研究重点进行了展望。     

退火处理工艺在纳米多层膜材料研究中的应用进展

与传统块状材料相比,纳米多层膜因其小尺寸效应、表面效应、量子尺寸效应和宏观量子隧道效应,表现出独特的光、磁、电、力学和热学性能,可作为光电材料、光吸收材料、电磁波吸收材料、磁记录材料和低温连接材料,被广泛应用于光学器件、半导体、电磁防护、加工制造、表面防护以及电子封装等领域。纳米多层膜的微观结构与宏观物理力学性能具有强烈的尺度效应。由于受制备工艺所限,纳米多层膜内部存在的空位、位错等缺陷导致其在复杂服役环境中难以完全满足耐热、耐磨和耐腐蚀等要求,限制了纳米多层膜的发展。而在集成电路和芯片制造领域,纳米多层膜器件常处于偏离常温的苛刻工作环境中,具有较高表面自由能的亚稳态纳米多层膜在受热情况下会通过两相互扩散、层内脱离和界面结构变化等方式,趋向达到低能量的稳定结构,从而破坏了多层膜内部的微观结构,导致其熔点降低、超硬等特性消失或减弱。因此,研究纳米多层膜的微观结构演化、热稳定性及其失效机理,直接关系到纳米多层膜体系的服役寿命和可靠性。退火工艺作为一种常见的热处理手段,被广泛应用于消除金属内部的缺陷,从而达到改善材料性能的目的。对于在高温条件下工作的纳米多层膜,退火工艺也是延长其使用寿命的有效手段。目前退火工艺在纳米多层膜研究中的主要应用方向有:(1)通过改变退火温度、保温时间和冷却速度,改善纳米多层膜的性能;(2)通过提高退火上限温度,研究退火温度对纳米多层膜热稳定性的影响,获得保持微观结构稳定的临界温度。研究发现,适当的退火工艺可以细化纳米多层膜的晶粒结构,增加致密度,降低缺陷密度,诱导产生特殊结构,增强原子与位错的交互作用,从而提高薄膜的透光率,改善薄膜光学性能或磁学、电学和力学性能;(3)在一定温度区间内对纳米多层膜进行退火,通过TEM、XRD等手段观察多层膜内部界面的结构变化、原子扩散情况及新的物相生成情况,从而研究了纳米多层膜的结构稳定性、化学稳定性和力学稳定性。本文综述了退火工艺在纳米多层膜改性以及热稳定性研究中的应用进展,讨论了退火工艺对纳米多层膜性能(光学性能、磁学性能、电学性能、力学性能)的影响。重点介绍了退火处理温度对不互溶纳米多层膜体系热稳定性和组织演变的影响机理。最后指出了退火工艺在纳米多层膜研究中的进一步应用方向,以期对高强度、高热稳定性纳米多层膜的设计制备及在材料焊接/连接、集成电路、切削刀具、吸波涂层等领域的广泛应用提供重要的理论和应用价值。     

陶瓷硬质纳米多层膜研究进展

陶瓷纳米多层膜因具超硬效应而成为近年的研究热点.本文对这类人工材料的研究进展和存在的不足进行了评述,并展望了进一步研究的方向.二十年来,陶瓷纳米多层膜的实验研究已取得明显进展:在微结构特征方面,两调制层形成共格外延生长结构是纳米多层膜产生超硬效应的必要微结构条件已成为共识;材料组合方面,由于模板效应,不同结构类型的材料,甚至非晶材料都可在纳米多层膜中形成共格外延生长结构,高硬度纳米多层膜材料体系已得到大大的拓展.与此相比较,对纳米多层膜强化机制和设计准则的研究相对滞后,仍停留在以金属纳米多层膜基于位错运动受阻于界面的理论解释上.因而,建立适合于陶瓷纳米多层膜的强化机制和设计准则;拓展纳米多层膜的材料组合,开发以碳化物、硼化物甚至氧化物为基的纳米多层膜将成为进一步研究的方向.     

纳米多层膜的研究现状

纳米多层膜是在单层膜与复合膜的基础上发展起来的一种新型薄膜,它被广泛应用于机械加工、航空航天、能源等领域,作为结构材料或功能材料都具有良好的发展前景。介绍了近十几年纳米多层膜的研究状况,主要从多层膜体系、制备技术、多层膜的性能以及多层膜的表征方法4个方面对纳米多层膜进行了综述,同时对纳米多层膜的超硬机制、纳米多层膜未来的研究方向和应用前景进行了分析。     

具有纳米调制结构的AlTiN/AlCrN复合涂层在干摩擦条件下的摩擦磨损性能研究

目的 研究干摩擦条件下不同AlTiN/AlCrN多层膜纳米调制结构对摩擦磨损行为的影响。方法 将处理过的合金工具钢和单晶硅片作为膜层生长的基底材料,在膜层制备之前,先对基底材料进行预处理,然后使用多靶磁控溅射纳米膜层系统沉积一系列不同调制周期和调制比的AlTiN/AlCrN纳米多层膜。通过控制涂层总厚度不变,在调制比为1︰1时,设计不同的调制周期,择优选出磨损量最小、耐磨性最好的调制周期,并以此为恒定值,进而设计不同调制比的试样。采用X射线衍射仪(XRD)、摩擦磨损试验机分析与表征纳米多层膜的微观结构和性能,研究调制周期和调制比对AlTiN/AlCrN纳米多层膜微观结构和干摩擦条件下摩擦磨损性能的影响。结果 AlTiN/AlCrN纳米多层膜主体均为面心立方结构,且在(111)、(200)和(220)晶面择优取向。调制结构对多层膜的磨损特性影响较大,当调制周期为14.4 nm时,在干摩擦条件下AlTiN/AlCrN纳米多层膜的摩擦磨损量最小;在调制周期恒定为14.4 nm情况下,当调制比为3︰1时,在干摩擦条件下AlTiN/AlCrN纳米多层膜的耐磨性能最好;AlTiN/AlCrN纳米多层膜的磨损机理主要以磨粒磨损和黏附磨损为主。结论 优化的AlTiN/AlCrN多层膜纳米调制结构技术可应用在切削刀具的表面再制造领域,从而延长刀具工作寿命,通过涂层良好的耐磨性能提升设备的加工效率。     

Zr基氮化物／金属Cu纳米多层膜的强韧化研究

多层结构可以提高材料的强度、弹性模量和韧性。当尺寸减小到纳米量级时,性能将产生飞跃变化。首先探讨了多层结构提高强度、弹性模量和韧性等性能的基本原理,然后阐明了纳米尺度效应及理论,重点以过渡族金属氮化物ZrN纳米多层膜为例,研究了氮化物／金属（ZrN／Cu）纳米多层膜、ZrAIN纳米复合膜以及ZrAIN／Cu纳米多层膜的强韧化性能。结果表明,ZrN／Cu纳米多层膜的断裂韧性约是二元ZrN薄膜的2倍。当纳米多层膜的Cu单层厚度为2013131时,多层膜的K1C值最高。ZrAIN复合膜的断裂韧性与Al含量密切相关,当Al原子分数为23％时,薄膜的KIc值达3．17MPa·m^1/2,其硬度〉40Gpa,Al原子分数为47％的薄膜的K1C值则降低到1．13MPa·m…。,其硬度降低至17．1GPa。与z州／cu纳米多层膜和ZrAlN复合膜相比,以ZrAIN层和cu层为调制结构制备的ZrAlN／Cu纳米多层膜具有最高的硬度和最好的韧性。     

TiAlN/TiN纳米多层膜的微结构与力学性能

采用多靶反应磁控溅射制备了一系列TiAlN层厚固定,TiN层厚在一定范围内连续变化的不同调制结构的TiAlN/TiN纳米多层膜,并使用X射线衍射分析、扫描电子显微镜、纳米压痕仪和CETR-UMT-3型多功能摩擦磨损试验机对多层膜的微观结构和力学性能进行了表征和分析。研究结果表明:TiAlN/TiN纳米多层膜形成了周期性良好的成分调制结构,其中TiN层的插入并没有打断TiAlN层的柱状晶生长。在一定的调制周期下,TiN层和TiAlN层能够形成共格外延生长结构,多层膜呈现硬度异常升高的超硬效应,当TiN层厚约为1.6 nm时多层膜的硬度达到最大值50 GPa,并具有相比于TiAlN单层膜更低的摩擦系数。进一步增加TiN层厚,由于多层膜共格界面结构的破坏,多层膜的硬度随之降低。     

纳米金属多层膜的电化学制备与性能研究的现状

介绍了金属多层膜电化学制备方法的现状,简述了单槽电化学制备多层膜材料的数学模型,比较了纳米金属多层膜与亚纳米金属多层膜不同的力学、电学、磁学、光学和电化学性能,并讨论了巨磁阻多层膜材料的应用前景。     

ZrN/TiSiN纳米多层膜的微观结构和力学性能研究

采用反应磁控溅射的方法,利用Zr靶与TiSi复合靶成功制备了不同TiSiN层厚度的ZrN/TiSiN纳米多层膜。利用X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、扫描电子显微镜(SEM)和纳米压痕仪研究了不同TiSiN层厚度对ZrN/TiSiN纳米多层膜的微观结构和力学性能的影响。结果表明,ZrN/TiSiN纳米多层膜主要由面心立方的ZrN相组成,随着TiSiN层厚度的增加,纳米多层膜的结晶程度先增加后降低,其硬度和弹性模量也先升高后降低。当TiSiN层厚度为0.7nm时,纳米多层膜具有最高的硬度和弹性模量,分别为28.7和301.1GPa,远超过ZrN单层膜。ZrN/TiSiN纳米多层膜的强化效果可由交变应力场和模量差理论进行解释。     

金属纳米多层膜力学性能研究进展

新型功能材料及器件向小型化,集成化和复合化发展的趋势,使得尺寸在纳米尺度的层状材料和柔性多层器件在使用过程中的服役行为成为其发展的关键科学问题。本文结合作者近几年对Ag/M系列和Cu/M系列多层膜力学性能的研究工作,对金属纳米多层膜的微结构特征及其对力学性能的影响进行了回顾和总结,主要包括多层膜的晶粒形貌对其强化机制和塑性变形行为的影响,组元强度错配对多层膜硬化行为的影响,界面结构与其强度极值的关系、不对称界面结构引起的异常弹性模量增强和多层膜的室温蠕变机制及界面结构对蠕变性能的影响等几个方面,并对多层膜的力学性能研究进行了展望。     

Attenuated total internal reflection infrared microscopy of multilayer plastic packaging foils

Multilayer plastic foils are important packaging materials that are used to extend the shelf life of food products and drinks. Fourier transform infrared (FT-IR) spectroscopic imaging using attenuated total internal reflection (ATR) can be used for the identification and localization of different layers in multilayer foils. A new type of ATR crystal was used in combination with a linear array detector through which large sample areas (400 x 400 microm(2)) could be imaged with a pixel size of 1.6 microm. The method was tested on laminated plastic packing materials containing 5 to 12 layers. The results of the identification of the different materials using ATR-FT-IR were compared with differential scanning calorimetry (DSC) and the layer thickness of the individual layers measured by ATR-FT-IR was compared with polarized light microscopy (LM) and scanning electron microscopy (SEM). It has been demonstrated that individual layers with a thickness of about 3 microm could be identified in multilayer foils with a total thickness ranging from 100 to 150 microm. The results show a spatial resolution of about 4 microm (measured at wavenumbers ranging from 1000 to 1730 cm(-1)), which is about a factor of two better than can be obtained using transmission FT-IR imaging. An additional advantage of ATR is the ease of sample preparation. A good correspondence was found between visible and FT-IR images. The results of ATR-FT-IR imaging were in agreement with those obtained by LM, SEM, and DSC. ATR-FT-IR is superior to the combination of these techniques because it delivers both spatial and chemical information.     

Investigation of the joining zone of laser welded and cross wedge rolled hybrid parts

Most of today’s technical parts and components are made of monolithic materials. These mono-material components produced in established production processes reach their limits due to their respective material characteristics. Thus, a significant increase in production quality and efficiency can only be achieved by combining different materials in one part. Bulk forming of previously joined semi-finished products to net shape hybrid components that consist of two different materials is a promising method to produce parts with locally optimized characteristics. This new production process chain offers a number of advantages compared to conventional manufacturing technologies. Examples are the production of specific load-adapted forged parts with a high level of material utilization and an impact on the joining zone caused by the following forming process. This paper describes the production process of serially arranged hybrid steel parts, produced by combining a laser welding process with a subsequent cross wedge rolling process. The presented results are only a first approach in order to get first insights in the forming behaviour of laser welded and cross wedge rolled parts. The investigated material combination is C22 (1.0402) and 20MnCr5 (1.7147). This innovative process chain enables the production of hybrid parts. To evaluate the developed process chain, the weld and the joining zone is analysed before and after cross wedge rolling. Main results are that the joining process using laser welding enables a strong bonding between the two materials with a higher hardness in the joining zone than for the individual materials. After the forming process, the bonding of the joining zone is still present, while the hardness decreased but remains higher than of the materials themselves.     

Nanostructuring polymeric materials by templating strategies

This contribution summarizes efforts in designing, assembling/synthesizing, and structurally and functionally characterizing nanostructured materials using anodized aluminum oxide (AAO) as a thin-film template. Optical waveguide spectroscopy, using a nanoporous template as the guiding structure, is a particularly powerful analytical tool. The layer-by-layer approach for the fabrication of multilayer assemblies is shown to allow the fabrication of nanotube arrays. In addition to using dendrimers as building blocks, semiconducting nanomaterial (e.g., quantum dot) hybrid architectures with very interesting photophysical properties can be assembled. These can be employed, for example, in biosensing applications. Other strategies for using the AAO layers as templates include the growth of polymeric nanorod arrays from different functional monomers, which, after the dissolution of the template, are still able to guide light. This opens up novel concepts for integrated optics platforms with nanostructured materials.     

BONDING OF CERAMICS TO METALS WITH ACTIVATED COATING LAYERS MADE BY PLASMA SPRAYING

Bonding of ceramics to metals was carried out by using thermal sprayed coatings as interlayer materials. This bonding method is referred as the thermal spray bonding. In the present study, Si₃N₄ and Al₂O₃ ceramics were bonded to SS41 mild steel using activated Ti-Cu multilayer coatings plasma-sprayed on the steel in a low pressure atmosphere. The bondability was estimated by SEM/EDX analysis and shear tests of the joints. The results were compared to those obtained using Ti-Cu multilayer foils as interlayers. When using Ti-Cu foils as interlayers, brittle Fe-Ti compound layers were formed in the joint area after long time heating at a bonding temperature of 900°C, which deteriorated the joint strength. In contrast with the activated interlayers made by plasma spraying, the Ti-Cu eutectic reaction took place uniformly at the joint immediately after heating to the bonding temperature. This improved the bondabilrty, and the resultant joints exhibited shear strengths of about 180 MPa.     

Joining Technology in Metal-Ceramic Systems

Metallic alloys and ceramic materials are employed in aggressive and hostile environments, ranging from aerospace to energy production, from offshore to biological applications. Today, production requires materials able to survive for a long time at high temperatures, in highly aggressive atmospheres, both from the chemical and the mechanical points of view. No single material can offer these characteristics, so that “composite” structures (composites, multilayer materials, metal-ceramic joints) are designed and tested under extreme conditions.

In this paper are presented the basic principles underlying joining technologies, a short discussion of the thermodynamic background of wetting processes, recent developments related to non-reactive and reactive wetting, the influence of trace chemical elements (in the solid, liquid and gaseous phases), and some specific aspects of diffusion bonding, brazing and transient liquid phase joining processes.     

Anti‐Eis‐Oberflächenbeschichtungen

Anti‐icing coating — optimization by means of plasma technology Ice on surfaces can significantly limit the function of devices and has to be removed by processes with high energy consumption. E. g., the formation of ice on rotor blades of wind turbines is not desired, on the wings of aircrafts it is even dangerous. With the aid of plasma technology, the Fraunhofer IGB has developed an anti‐icing coating for polymeric surfaces. Water‐repellent micro‐ and nanostructured coatings are applied to polymer foils made of impact‐resistant and shockproof polyurethane. Optimization of various process parameters has made it possible to produce ultra‐thin coatings, which reduces the ice's adhesion by over 90 percent. The new nanostructured foils open a wide range of applications.     

Multifunctional lipid multilayer stamping

Nanostructured lipid multilayers on surfaces are a promising biofunctional nanomaterial. For example, surface-supported lipid multilayer diffraction gratings with optical properties that depend on the microscale spacing of the grating lines and the nanometer thickness of the lipid multilayers have been fabricated previously by dip-pen nanolithography (DPN), with immediate applications as label-free biosensors. The innate biocompatibility of such gratings makes them promising as biological sensor elements, model cellular systems, and construction materials for nanotechnology. Here a method is described that combines the lateral patterning capabilities and scalability of microcontact printing with the topographical control of nanoimprint lithography and the multimaterial integration aspects of dip-pen nanolithography in order to create nanostructured lipid multilayer arrays. This approach is denoted multilayer stamping. The distinguishing characteristic of this method is that it allows control of the lipid multilayer thickness, which is a crucial nanoscale dimension that determines the optical properties of lipid multilayer nanostructures. The ability to integrate multiple lipid materials on the same surface is also demonstrated by multi-ink spotting onto a polydimethoxysilane stamp, as well as higher-throughput patterning (on the order of 2 cm(2) s(-1) for grating fabrication) and the ability to pattern lipid materials that could not previously be patterned with high resolution by lipid DPN, for example, the gel-phase phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) or the steroid cholesterol.     

Welding and Joining of NiTi Shape Memory Alloys: A Review

NiTi is an increasingly applied material in industrial applications. However, the difficulties faced when welding and joining is required, limits its broader use in the production of complex shaped components. The main weldability problems associated with NiTi are: strength reduction, formation of intermetallic compounds, modification of phase transformation and transformation temperatures, as well as, changes in both superelastic and shape memory effects. Additionally, NiTi is envisaged to be joined to other materials, in dissimilar joints with more complex problems depending on the other base material. Thus, intensive research in welding and its effects on the joints performance has been conducted since the early stages of NiTi. This paper presents a detailed review of welding and joining processes applied to NiTi, in similar and dissimilar combinations considering both fusion and solid-state processes. Since laser is the most studied and applied welding process, a special section is devoted to this technique.     

水热碳化法制备碳纳米材料

形态可控的碳纳米材料由于独特的结构和性能而受到研究者的普遍关注,常见的制备方法有化学气相沉积法(CVD)、乳液法和水热碳化法等。水热碳化法是一种重要的碳纳米材料制备方法,具有成本低、反应条件温和、产物粒径均匀且形态可控等特点。综述了近年来以糖类及淀粉等有机物为原料,采用水热碳化法制备各种形态可控碳纳米材料的研究现状,重点介绍了水热碳化工艺条件对合成碳微球、空心碳微球、核壳结构碳复合材料显微形貌的影响,并提出了水热碳化法制备碳纳米材料研究中存在的问题和今后可能的发展方向。