Engineering of micro- and nanostructured surfaces with anisotropic geometries and properties

Widespread approaches to fabricate surfaces with robust micro- and nanostructured topographies have been stimulated by opportunities to enhance interface performance by combining physical and chemical effects. In particular, arrays of asymmetric surface features, such as arrays of grooves, inclined pillars, and helical protrusions, have been shown to impart unique anisotropy in properties including wetting, adhesion, thermal and/or electrical conductivity, optical activity, and capability to direct cell growth. These properties are of wide interest for applications including energy conversion, microelectronics, chemical and biological sensing, and bioengineering. However, fabrication of asymmetric surface features often pushes the limits of traditional etching and deposition techniques, making it challenging to produce the desired surfaces in a scalable and cost-effective manner. We review and classify approaches to fabricate arrays of asymmetric 2D and 3D surface features, in polymers, metals, and ceramics. Analytical and empirical relationships among geometries, materials, and surface properties are discussed, especially in the context of the applications mentioned above. Further, opportunities for new fabrication methods that combine lithography with principles of self-assembly are identified, aiming to establish design principles for fabrication of arbitrary 3D surface textures over large areas. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Handbook of nanoindentation with biological applications

Nanoindentation is ideal for the characterization of inhomogeneous biological materials. However, the use of nanoindentation techniques in biological systems is associated with some distinctively different techniques and challenges. For example, engineering materials used in the microelectronics industry (e.g. ceramics and metals) for which the technique was developed, are relatively stiff and exhibit time-independent mechanical responses. Biological materials, on the other hand, exhibit time-dependent behavior, and can span a range of stiffness regimes from moduli of Pa to GPa - eight to nine orders of magnitude. As such, there are differences in the selection of instrumentation, tip geometry, and data analysis in comparison with the "black box" nanoindentation techniques as sold by commercial manufacturers. The use of scanning probe equipment (atomic force miscroscopy) is also common for small-scale indentation of soft materials in biology. The book is broadly divided into two parts. The first part presents the "basic science" of nanoindentation including the background of contact mechanics underlying indentation technique, and the instrumentation used to gather mechanical data. Both the mechanics background and the instrumentation overview provide perspectives that are optimized for biological applications, including discussions on hydrated materials and adaptations for low-stiffness materials. The second part of the book covers the applications of nanoindentation technique in biological materials. Included in the coverage are mineralized and nonmineralized tissues, wood and plant tissues, tissue-engineering substitute materials, cells and membranes, and cutting-edge applications at molecular level including the use of functionalized tips to probe specific molecular interactions (e.g. the ligand-receptor binding). The book concludes with a concise summary and an insightful forecast of the future highlighting the current challenges. © 2011 by Pan Stanford Publishing Pte. Ltd. All rights reserved.

A highly conductive and transparent solution processed AZO/MWCNT nanocomposite

A solution processed aluminum-doped zinc oxide (AZO)/multi-walled carbon nanotube (MWCNT) nanocomposite thin film has been developed offering simultaneously high optical transparency and low electrical resistivity, with a conductivity figure of merit (σDC/σopt) of ~75-better than PEDOT:PSS and many graphene derivatives. The reduction in sheet resistance of thin films of pristine MWCNTs is attributed to an increase in the conduction pathways within the sol-gel derived AZO matrix and reduced inter-MWCNT contact resistance. Films have been extensively characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffractometry (XRD), photoluminescence (PL), and ultraviolet-visible (UV-vis) spectroscopy. © 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

La2Zr2O7的增韧及陶瓷纤维的制备

La2Zr2O7是一种近年来才提出的新型热障涂层材料，该材料熔点高，在熔点以下不发生相变，热导率低，抗烧结及没有氧传输发生，这些特点使得它作为一种高温下应用的热障涂层材料越来越引起人们的重视。但是，由于该材料的热膨胀系数和断裂韧性比较低，它的实际应用受到了限制。 在本论文中，使用高压烧结的方法获得了致密化的纳米La2Zr2O7块体材料，并对其断裂韧性和热膨胀系数进行了研究。得到的La2Zr2O7纳米材料的断裂韧性和热膨胀系数分别为1.98MPam1/2和9.6×10-6K-1 (200-1000℃)，这些数值明显高于非纳米的La2Zr2O7陶瓷(断裂韧性和热膨胀系数分别为1.40 MPam1/2 和 9.1×10-6 K-1，该结果表明纳米化是一种提高材料断裂韧性和热膨胀系数的有效方法。在La2Zr2O7纳米粉末中加入8YSZ纳米颗粒，高压烧结后使其颗粒充分生长，在得到的复相化合物中观察到形成了类似棒状晶体的自增韧相，使得复合材料的断裂韧性(1.88 MPam1/2)比La2Zr2O7有所提高，甚至超过了同样条件下制备的8YSZ样品的断裂韧性。 La2Zr2O7的断裂韧性也可以通过在基体中添加BaTiO3铁电材料得到明显的提高。当添加BaTiO3的体积含量达到10vol％时，4.5GPa，1450℃高压烧结10min得到的复合材料断裂韧性达1.98 MPam1/2，明显高于同条件下烧结的La2Zr2O7 (1.60MPam1/2)。应力诱导下BaTiO3的电畴转向是主要的增韧原因。随着BaTiO3颗粒添加的体积含量增加，复相化合物的热膨胀系数也明显提高。当掺杂20vol％BaTiO3时，得到的复合材料平均热膨胀系数达到10.2×10-6K-1 (150~1200℃)。 我们通过在4.5GPa, 1650℃高压烧结5min的方法还获得了掺杂YAG纳米颗粒的La2Zr2O7纳米复相陶瓷。在室温下测量了材料的维氏硬度，并通过压痕裂纹长度计算出了材料的断裂韧性。随着YAG纳米颗粒体积含量的增加，纳米复相陶瓷的断裂韧性和维氏硬度都依次增加，当添加20vol％的YAG纳米颗粒时达到最大，分别为1.93 MPam1/2和11.45GPa。断裂韧性增加的机理可归结为以下三点：一是YAG纳米颗粒的添加提高了La2Zr2O7基体的晶界强度，二是基体晶粒尺寸变化的影响，三是YAG纳米颗粒对裂纹的偏转和钉扎作用。添加微米YAG颗粒的复相化合物因为和纳米复相陶瓷具有不同的增韧机制，因此断裂韧性的变化趋势也不相同，在掺入10vol％的YAG微米颗粒时，复合材料的断裂韧性最大，而后降低，当掺入YAG微米粒子的体积含量达到20vol％时，断裂韧性甚至低于La2Zr2O7。 从20世纪90年代开始，电纺作为一种合成纤维的办法越来越吸引人们的注意。其合成的纤维长度长，直径均匀，并且组成范围很广。最初，电纺只是被用来合成一些有机聚合物的纤维，最近，很多研究组开始致力于使用电纺的方法合成复合纤维或者陶瓷纤维。 在本论文中，我们使用电纺的方法获得了La2Zr2O7纳米纤维和SiC单晶纳米线。1000℃煅烧得到的La2Zr2O7纳米纤维具有烧绿石结构，直径在200~500nm之间。同样的温度煅烧时得到的La2Zr2O7纳米纤维的比表面积要明显高于粉末样品的，表明纤维的抗烧结性能比粉末的高。得到的SiC纳米线直径在50~100nm之间，表面有一约5nm厚的无定形的SiO2薄层。 使用电纺的方法，恰当的控制煅烧条件，我们获得了La2Ce2O7， La2(Zr0.745Ce0.386)2O7.524和8YSZ中空纤维。这种中空结构减小了粒子之间的接触面积，提高了材料的抗烧结性能。在扫描电镜分析的基础上，我们总结了这些中空纤维的形成过程。

掺杂压电陶瓷／铁电薄膜的制备和研究

PZT陶瓷粉体的制备和研究。用溶胶一凝胶法制备了错钦酸铅Pb(Zr_(0.52)Ti_(0.48))O_3（PZT），研究了溶剂乙二醇单甲醚和水的比例对PZT的晶化温度和晶粒尺寸的影响，结果表明，随溶剂比例的增大，PZT粉体的晶化温度升高晶粒尺寸增大，当V（C_3H_9O_2）／V（H_2O）＝4.47时，不仅缩短了溶胶-凝胶过程的时间，且得到的PZT粉体晶化温度低（443℃），晶粒的粒径分布集中（60-70nm）。PZT掺杂压电陶瓷的制备和研究。用同一主族元素对PZT进行掺杂改性实验，制备了Ca-PZT，Sr-PZT，Ba-PZT三个系列的压电陶瓷体系，其中每个体系中又包含1％、3％、5％、7％、9％（10％，11%）不同的掺杂量。经过压片，蒸镀电极，极化处理后测定其由，常数，结果表明，Ba离子的半径是最适合掺杂的离子半径。PZT和PbTIO。（PT）稳定溶胶的制备。在溶胶形成过程中，通过调整溶剂乙二醇单甲醚和水的比例，并加入适当量的乙酞丙酮作稳定剂，在有水体系下制备稳定的PZT和PT溶胶前驱体。该方法省略了制备中的蒸馏过程，简化了PZT和PT稳定溶胶的制备工艺。PZT铁电薄膜的制备。用自制的溶胶进行旋涂制膜，制备了膜层厚度不同的PZT和PT-PZT薄膜，在不同的锻烧温度，锻烧时间下处理为晶态膜，并对晶态膜进行表征，证明获得了钙钦矿结构的PZT晶态膜。

Synthesis and characterization of (Zn,Cd)TiO3 by a modified sol-gel method

Ilmenite-type (Zn1-xCdx)TiO3 (0 <= x <= 0.15 and 0.8 <= x <= 1.0) was synthesized by a modified sol-gel route including the Pechini process via two-step heat treatments. The thermal stability of (Zn1-xCdx)TiO3 depended on the amount of cadmium content. The as-synthesized (Zn1-xCdx)TiO3 (0 <= x <= 0.15 and 0.8 <= x <= 1.0) showed higher thermal stability than that of ZnTiO3. The variation of the dielectric constant of all synthesized (Zn1-xCdx)TiO3 samples for all measurement frequencies showed a similar tendency.

La-2(Zr0.7Ce0.3)(2)O-7 - A new oxide ceramic material with high sintering-resistance

Oxide ceramics with high sintering-resistance above 1473 K have very important applications in thermal barrier coatings (TBCs), catalytic combustion and high-temperature structural materials. Lanthanum zirconate (La2Zr2O7, LZ) is an attractive TBC material which has higher sintering-resistance than yttria stabilized zirconia (YSZ), and this property could be further improved by the proper addition of ceria.

Lanthanum zirconate ceramic toughened by BaTiO3 secondary phase

La2Zr2O7 (LZ) is a promising thermal barrier coating material for the high-temperature applications, which could be significantly toughened by the BaTiO3 piezoelectric phase incorporated into the matrix. The composites of xBaTiO(3)/(l-x)LZ (x=5, 10, 15, 20 vol%, LZ-x-BaTiO3) were densified by means of high-pressure sintering (HPS) under a pressure of 4.5 GPa at 1450 degrees C for 10 min, by which a high relative density above 93% could be obtained.

Effects of Y2O3 addition on the phase evolution and thermophysical properties of lanthanum zirconate

Lanthanum zirconate (La2Zr2O7, LZ) powders with the addition of various Y2O3 contents for potential thermal barrier coatings (TBCs) application were synthesized by solid-state reaction. The structure evolution, sintering-resistance and thermophysical properties of the synthesized powders and sintered ceramics were systematically studied. X-ray diffraction (XRD) results indicate that LZ containing 3-12 wt.% Y2O3 mainly keeps a pyrochlore-type structure, and two new phases of LaYO3 and Y0.18Zr0.82O1.91 are also detected. Raman spectra confirm that the higher the Y2O3 content, the easier is the formation of LaYO3.

Preparation and characterization of La2Zr2O7 coating with the addition of Y2O3 by EB-PVD

Thermal barrier coatings (TBCs) of La2Zr2O7 (LZ) with the addition of 3 wt.% Y2O3 (LZ3Y) were deposited by electron beam-physical vapor deposition (EB-PVD). The phase stabilities, thermophysical and mechanical properties, and chemical compositions of these ceramics and coatings were studied in detail. The phase stability and thermal expansion behavior of LZ3Y bulk material are identical to those of LZ bulk material, but the mechanical properties of the former are superior to those of the latter. Elemental analysis and X-ray diffraction indicate that compositional deviation of LZ coating can be optimized after doping by 3 wt.% Y2O3, Y2O3 acts as a dopant as well as a process regulator. The optimal composition of LZ3Y coating could be effectively achieved by the addition of excess Y2O3 into the ingot and by properly controlling the current of electron beam (i.e. similar to 650 mA).

The nanocomposite scaffold of poly(lactide-co-glycolide) and hydroxyapatite surface-grafted with L-lactic acid oligomer for bone repair

Nanohydroxyapatite (op-HA) surface-modified with L-lactic acid oligomer (LAc oligomer) was prepared by LAc oligomer grafted onto the hydroxyapatite (HA) surface. The nanocomposite of op-HA/PLGA with different op-HA contents of 5, 10, 20 and 40 wt.% in the composite was fabricated into three-dimensional scaffolds by the melt-molding and particulate leaching methods. PLGA and the nanocomposite of HA/PLGA with 10 wt.% of ungrafted hydroxyapatite were used as the controls. The scaffolds were highly porous with evenly distributed and interconnected pore structures, and the porosity was around 90%. Besides the macropores of 100-300 mu m created by the leaching of NaCl particles, the micropores (1-50 mu m) in the pore walls increased with increasing content of op-HA in the composites of op-HA/PLGA. The op-HA particles could disperse more uniformly than those of pure HA in PLGA matrix. The 20 wt.% op-HA/PLGA sample exhibited the maximum mechanical strength, including bending strength (4.14 MPa) and compressive strength (2.31 MPa). The cell viability and the areas of the attached osteoblasts on the films of 10 wt.% op-HA/PLGA and 20 wt.% op-HA/PLGA were evidently higher than those on the other composites.

Preparation of bioactive glass ceramic nanoparticles by combination of sol-gel and coprecipitation method

SiO2-CaO-P2O5 ternary bioactive glass ceramic nanoparticles were prepared via the combination of sol-gel and coprecipitation processes. Precursors of silicon and calcium were hydrolyzed in acidic solution and gelated in alkaline condition together with ammonium dibasic phosphate. Gel particles were separated by centrifugation, followed by freeze drying, and calcination procedure to obtain the bioactive glass ceramic nanoparticles. The investigation of the influence of synthesis temperature on the nanopartilce's properties showed that the reaction temperature played an important role in the crystallinity of nanoparticle. The glass ceramic particles synthesized at 55 degrees C included about 15% crystalline phase, while at 25 degrees C and 40 degrees C the entire amorphous nanopowder could be obtained.

Preparation and electrical properties of new oxide ion conductors Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8)

Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8) were synthesized by modified sol-gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 degrees C and 800 degrees C indicated a sharp increase in conductivity for the system containing small amount of Dy2O3. The Ce5.6Dy0.4MoO15-delta detected to be the best conducting phase with the highest conductivity (sigma(t) = 8.93 x 10(-3) S cm(-1)) is higher than that of Ce5.6Sm0.4MoO15-delta (sigma(t) = 2.93 x 10(-3) S cm(-1)) at 800 degrees C, and the corresponding activation energy of Ce5.6Dy0.4MoO15-delta (0.994 eV) is lower than that of Ce5.6Sm0.4MoO15-delta (1.002 eV).

Synthesis of Titanate-Based Nanotubes for One-Dimensionally Confined Electrical Properties

Structural tailoring for dimensionally confined electrical properties is fundamentally important for nanodevices and the relevant technologies. Titanate-based nanotubes were taken as a prototype one-dimensional material to study. First, Na0.96H1.04Ti3O7 center dot 3.42H(2)O nanotubes were prepared by a simple hydrothermal condition, which converted into Na0.036H1.964Ti3O7 center dot 3.52H(2)O nanotubes by a subsequent acidic rinsing. Systematic sample characterization using combined techniques of X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, electron paramagnetic resonance, Fourier transform infrared spectroscopy, elemental analyses, and alternative current impedance indicated that both nanotubes possessed a scrolled trititanate-type structure with the (200) crystal face predominant on the tube surface. With increasing temperature, both nanotubes underwent a continuous dehydration process, which however imposed different impacts oil the structures and electrical properties, depending on the types of the nanotubes