Eletrodeposição de revestimentos funcionais compósitos Cu/partículas de óxidos de alumínio

Revestimentos funcionais compósitos são um atrativo tecnológico crescente, pois possibilitam a combinação de materiais metálicos, poliméricos ou cerâmicos, resultando em propriedades superiores as dos materiais individuais, sendo por este motivo, largamente aplicados na engenharia de materiais. Na presente dissertação, foram produzidos revestimentos compósitos por eletrodeposição através da codeposição de uma matriz metálica de cobre e de partículas de óxidos de alumínio incorporadas (g - Al2O3 ou AlO(OH)), sobre substratos de aço carbono, a partir de diferentes banhos eletrolíticos. Três etapas foram efetuadas, na primeira realizou-se o estudo da influência do modo de agitação e da presença ou não de ligantes (citrato de sódio 1,00 mol/L) nos teores de cobre e alumina nos revestimentos produzidos. Em seguida foi avaliada a ação de complexantes (citrato de sódio 1,00 mol/L e pirofosfato de potássio 0,90 mol/L) usando polarização potenciodinâmica e voltametria cíclica, em conjunto com microbalança eletroquímica de cristal de quartzo (EQCM) e a posterior produção de revestimentos compósitos a partir de banhos contendo CuSO4 0,02 mol/L + pirofosfato de potássio 0,90 mol/L + 20 g/L de alumina, variando a densidade de corrente aplicada (I), a velocidade de agitação do eletrodo rotatório (A) e o do tempo de agitação prévia (t). Por fim, na terceira etapa, fez-se a substituição de alumina por Boehmita e a produção dos revestimentos a partir de banhos contendo CuSO4 0,02 mol/L + pirofosfato de potássio 0,90 mol/L + 20 g/L de Boehmita, empregando um planejamento composto central, em que os parâmetros citados também foram variados. Os resultados mostraram que a presença de um ligante e a agitação prévia e continuada do eletrólito durante o experimento foram fundamentais para a produção dos revestimentos compósitos. Ensaios de EQCM mostraram que o citrato se adsorveu na superfície do eletrodo de ouro, diferentemente do pirofosfato. Os teores de Boehmita e cobre nos revestimentos produzidos, assim como a morfologia, resistência de polarização e densidade de corrente de corrosão dos revestimentos foram influenciados pelos parâmetros avaliados.

Modelagem Numérica da Construção de Aterro Instrumentado na Baixada Fluminense, Rio de Janeiro.

A complexidade na previsão do comportamento de aterros sobre solos compressíveis representa um desafio para os engenheiros geotécnicos, mesmo os mais experientes. As limitações das teorias de análise e a dificuldade na seleção de parâmetros muitas vezes acarretam em estimativas de recalque incoerentes com a observação de campo. O presente trabalho tem como objetivo reproduzir a seqüência construtiva de extenso aterro, instrumentado, executado na Baixada Fluminense, Rio de Janeiro, para implantação da indústria Rio Polímeros, utilizando o programa PLAXIS. Os parâmetros geotécnicos foram definidos a partir de ensaios oedométricos, tendo sido realizado um estudo prévio sobre a qualidade das amostras. Estes parâmetros foram confrontados com a experiência local, que resume mais de 30 anos de investigações na argila mole da Baixada Fluminense, no Rio de Janeiro. Apesar da distância entre os locais de investigações, não houve diferenças significativas entre os parâmetros geotécnicos. As análises numéricas foram realizadas considerando-se diferentes hipóteses para o coeficiente de permeabilidade, de forma a reproduzir adequadamente as leituras de placa de recalque e poropressão registradas no campo. Este parâmetro teve grande influência na resposta da modelagem numérica, tendo sido obtidos bons resultados com valores de permeabilidade variando em função da profundidade.

聚合物膜离子选择性电极的制备与性能研究

聚合物膜离子选择性电极具有选择性高、使用简便、价格低廉等优点，在环境监测中日益受到人们的关注。这类电极的响应特性主要取决于聚合物膜相中起分子识别作用的离子载体的选择性。本文设计合成了一系列对重金属离子具有高选择性的有机配体，并将其作为电中性离子载体应用于银、汞、锌、铬等离子选择性电极中，实现了对重金属离子的高选择性测定。此外，我们对海水中有机物质的紫外线消解进行了研究，优化了消解条件，采用离子选择性电极技术实现了对海水中重金属污染物的快速检测。具体内容如下： 1、以硫氮杂冠醚为离子载体的银离子选择性电极制备及性能研究。 合成了一系列硫氮杂冠醚配体，通过优化反应条件，提高了反应产率，简化了产物处理过程。将此类冠醚作为离子载体用于银离子选择性电极的制备，并讨论了冠醚环大小、冠醚环的韧性以及硫原子个数对电极选择性的影响。在此研究基础上，利用沉淀-溶解平衡法调节内充液主离子浓度，采用冠醚9，10，12，13，24，25-六氢-5H，15H，23H-二苯[b，q][1，7，10，13，19，4，16]五硫二氮二十三环-6，16 (7H，17H)-二酮环作为低检出限银离子选择性电极载体，通过优化电极的内充液和聚合物膜组份，测得最低检出限为2.2×10-10 M，电极电位响应斜率为54.5 mV/dec.，线性范围为1.0×10-9-1.0×10-5 M，电极使用寿命为一个月。采用标准加入法，成功实现了自来水中银离子浓度的测试，并以该电极作为指示电极，以硝酸银溶液为滴定剂，成功滴定了I-、Br-和Cl-离子的混合液。 2、以1，2，4-三唑衍生物为离子载体的汞离子选择性电极的制备及性能表征。 设计合成了一种基于1，2，4-三唑的希夫碱结构化合物，3，5-二(二硫代甲酸苄酯肼基-2-亚甲胺基苯氧甲基)-1-(四氢-2H-吡喃)-1H-1，2，4-三唑，并成功用作中性载体实现对汞离子的测定。在最佳膜组分条件下，以该化合物作为载体的汞离子选择性电极的检出限为2.6×10-7 M Hg2+，电极电位响应斜率为29.3±0.3 mV/dec.，线性范围为1.0×10-6-3.0×10-4 M。该电极使用寿命为2个月，在pH 2.6-5.2范围内测试不受酸度影响。以该电极为指示电极，以EDTA为滴定剂，可准确滴定溶液中汞离子的浓度。 3、以希夫碱结构化合物为离子载体的锌离子选择性电极的制备及性能研究。 本文设计了一种含吡啶杂环的希夫碱结构化合物(E)-N'-(吡啶-2-亚甲胺基)-2-((E)-吡啶-2-亚甲胺基)苯甲酰肼，并成功用作离子载体实现对锌离子的测定。在最佳膜组分条件下，以该化合物为载体的锌离子选择性电极的检出限为7.4×10-7M Zn2+，电极电位响应斜率为25.9 mV/dec.，线性范围为1.0×10-6-1.0×10-3 M。该电极使用寿命为3个月，在pH 3.4-5.8范围内测试不受酸度影响。以该电极为指示电极，以EDTA为滴定剂，可准确滴定溶液中锌离子的浓度。 4、紫外光在线消解技术用于离子选择性电极测试海水中重金属离子的研究。 海水中重金属离子大多以络合物形式存在，而离子选择性电极只对游离态金属离子响应，因此要实现离子选择性电极测试海水中的重金属，首先必须使金属离子从络合物中游离出来。紫外光消解方法相对于其它海水预处理手段是一种清洁的样品预处理方法。我们以模拟海水为考察对象，考察了盐度、酸度、有机物浓度对消解效率的影响，并在优化消解条件的基础上对实际海水进行消解，利用离子选择性电极成功实现了海水中铜离子浓度的测试，测试值与ICP-MS数值一致。 5、合成希夫碱结构罗丹明B衍生物作为载体和分子探针用于Cr3+离子的检测。 设计合成了希夫碱结构罗丹明B衍生物2-亚甲胺基-8-乙酯基喹啉-罗丹明。荧光法显示，在化合物对铬离子(III)有较好的选择性，进而我们将该化合物作为分子探针进行了详细的研究。结果表明，分子探针与铬离子配位比为1:1，铬离子响应的线性范围是8.0×10-7-8.0×10-5 M，检测下限为1.9×10-7 M。电化学测试结果显示，基于该化合物为载体的离子选择性电极对铬离子(III)的选择性较差。

SU8 bio-chemical sensor microarrays

Microfabricated cantilevers have recently attracted considerable attention as novel label-free chemical and biological biosensors which translate surface reactions into nanomechanical bending motion. However these studies have primarily focused on commercially available silicon cantilevers and relatively little work has been performed on cantilevers fabricated from other materials. Polymeric materials, offer significant advantages over silicon by virtue of the low Young's modulus, ease of microfabrication and reduced cost. In this paper, we report a non-vacuum fabrication process to produce arrays of SU8 cantilevers and demonstrate their application as chemical sensors using in situ reference cantilevers. © 2006 Elsevier B.V. All rights reserved.

Friction of sliding surfaces carrying adsorbed lubricant layers

In concentrated contacts the behaviour of lubricants is much modified by the high local pressures: changes can arise both from molecular ordering within the very thin film lubricant layers present at the interface as well as from the deposition on the component surfaces of more solid-like polymeric boundary layers. These 'third bodies' separating the solid surfaces may have rheological or mechanical properties very different from those observed in the bulk. Classical elasto-hydrodynamic theory considers the entrapped lubricant to exhibit a piezo-viscous behaviour while the conventional picture of more solid boundary lubricant layers views their shear strength r as being linearly dependent on local pressure p, so that T = TO + ap where TO and a are constants. If TO is relatively small, then the coefficient of friction \i = T Ip ~ a and so Amonton's laws are recovered. However, the properties of adsorbed or deposited surface films, or indeed other third bodies such as debris layers, may be more complex than this. A preliminary study has looked quantitatively at the influence of the pressure dependence of the shear strength of any surface layer on the overall friction coefficient of a contact which is made up of an array of asperities whose height varies in a Gaussian manner. Individual contact points may be elastic or plastic. The analysis results in plots of coefficient of friction versus the service or load parameter PIH&NRa where P is the nominal pressure on the contact, HS the hardness of the deforming surface, N the asperity density, R the mean radius of curvature of the asperities, and a is the standard deviation of their height distribution. In principle, any variation oft withp can be incorporated into the model; however, in this initial study we have used data on colloidal suspensions from the group at the Ecole Centrale de Lyon as well as examining the effect of functional relationships of somewhat greater complexity than a simple linear form. Results of the analysis indicate that variations in fj. are possible as the load is varied which depend on the statistical spread of behaviour at individual asperity contacts. The value of this analysis is that it attempts to combine the behaviour of films on the molecular scale with the topography of real engineering surfaces and so give an indication of the effects at the full-size or macro-scale that can be achieved by chemical or molecular surface engineering.

Nanoindentation measurements of bone viscoelasticity as a function of hydration state

Bone is an anisotropic material, and its mechanical properties are determined by its microstructure as well as its composition. Mechanical properties of bone are a consequence of the proportions of, and the interactions between, mineral, collagen and water. Water plays an important role in maintaining the mechanical integrity of the composite, but the manner in which water interacts within the ultrastructure is unclear. Dentine being an isotropic two-dimensional structure presents a homogenous composite to examine the dehydration effects. Nanoindentation methods for determining the viscoelastic properties have recently been developed and are a subject of great interest. Here, one method based on elastic-viscoelastic correspondence for 'ramp and hold' creep testing (Oyen, J. Mater. Res., 2005) has been used to analyze viscoelastic behavior of polymeric and biological materials. The method of 'ramp and hold' allows the shear modulus at time zero to be determined from fitting of the displacement during the maximum load hold. Changes in the viscoelastic properties of bone and dentine were examined as the material was systematically dehydrated in a series of water:solvent mixes. Samples of equine dentine were sectioned and cryo-polished. Shear modulus was obtained by nanoindentation using spherical indenters with a maximum load hold of 120s. Samples were tested in different solvent concentrations sequentially, 70% ethanol to 50% ethanol, 70 % ethanol to 100% ethanol, 70% ethanol to 70% methanol to 100% methanol, and 70% ethanol to 100% acetone, after storage in each condition for 24h. By selectively removing and then replacing water from the composite, insights in to the ultrastructure of the tissue can be gained from the corresponding changes in the experimentally determined moduli, as well as an understanding of the complete reversibility of the dehydration process. © 2006 Materials Research Society.

Poroelastic indentation analysis for hydrated biological tissues

Indentation techniques are employed for the measurement of mechanical properties of a wide range of materials. In particular, techniques focused at small length-scales, such as nanoindentation and AFM indentation, allow for local characterization of material properties in heterogeneous materials including natural tissues and biomimetic materials. Typical elastic analysis for spherical indentation is applicable in the absence of time-dependent deformation, but is inappropriate for materials with time-dependent responses. Recent analyses for the viscoelastic indentation problem, based on elastic-viscoelastic correspondence, have begun to address the issue of time-dependent deformation during an indentation test. The viscoelastic analysis has been shown to fit experimental indentation data well, and has been demonstrated as useful for characterization of viscoelasticity in polymeric materials and in hydrated mineralized tissues. However, a viscoelastic analysis is not necessarily sufficient for multi-phase materials with fluid flow. In the current work, a poroelastic analysis-based on fluid motion through a porous elastic network-is used to examine spherical indentation creep responses of hydrated biological materials. Both analytical and finite element approaches are considered for the poroelastic Hertzian indentation problem. Modeling results are compared with experimental data from nanoindentation of hydrated bone immersed in water and polar solvents (ethanol, methanol, acetone). Baseline (water-immersed) bone responses are characterized using the poroelastic model and numerical results are compared with altered hydration states due to polar solvents. © 2007 Materials Research Society.

Perylene-based fluorescent liquid crystal dye guest-host mixtures

We present a study on a series of dye guest-host mixtures using fluorescent perylene-based molecules as the guest dye in an organosiloxane host. These hosts have temperature-independent switching, at room temperature, through 90° for fields of the order of 10 Vrms/μm. Perylene molecules have been grafted onto the organosiloxane moiety via an alkyl spacer producing novel and rugged fluorescent dyes that are readily miscible in the host. Micro-separation of the low molar mass siloxane groups in the mesophases tend to form smectic phases. These planes produce an effective two-dimensional polymer backbonethat engenders the rugged mechanical properties of polymeric liquid crystals onto these low molar mass ferroelectric liquid crystals. In this study we show how the introduction of the dye molecules affects the electro-optic properties of the organosiloxane host. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Fabrication and electromechanical characterization of near-field electrospun composite fibers.

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of multi-walled carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. In particular, we examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates.

Migration of mouse antibody-secreting hybridoma cells from blood to genital tract and its regulation by sex hormones are associated with the differential expression patterns of adhesion molecules and chemokines in the tract rather than in the antibody-secreting cells

To understand better the molecular mechanisms of differential migration of antibody-secreting cells (ASCs) into mouse genital tracts, and regulation by sex hormones, surface markers, hormone receptors and adhesion molecules in mouse SG2 and PA4 hybridoma cells, respectively, secreting IgG2b and polymeric IgA antibody were detected by flow cytometry or RT-PCR. Semiquantitative RT-PCR was also used for measuring mRNA expression of adhesion molecules and chemokines (VCAM-1, ICAM-1, P-selectin, JAM-1 and CXCL12) in genital tracts of various adult mouse groups. The mRNAs of androgen receptor, estrogen receptor beta and CXCR4 were expressed in the ASCs. Sex hormones had no effect on expression of these molecules in ASCs. Except for VCAM-1, mRNA of all examined genes was expressed in normal mouse genital tracts. The mean of relative amounts of ICAM-1 and CXCL12 mRNA in all examined organs of females were higher (2.1- and 1.9-fold) than those in males. After orchiectomy or ovariectomy, the expression of ICAM-1, CXCL12 and P-selectin mRNA in the examined organs increased, except JAM-1 in male and CXCL12 in female. Sex hormone treatment recovered the changes to normal levels of mRNA expression in many examined genital tissues. In combination with our previous work, preferential migration of ASCs into female genital tract and regulation of migration by sex hormones are associated with expression patterns of adhesion molecules and chemokines in genital tract rather than in ASCs. (C) 2006 Elsevier Ireland Ltd. All rights reserved.

Polymer waveguide-based backplanes for board-level optical interconnects

Optical interconnects are increasingly considered for use in high-performance electronic systems. Multimode polymer waveguides are a promising technology for the formation of optical backplane as they enable cost-effective integration of optical links onto standard printed circuit boards. In this paper, two different types of polymer waveguide-based optical backplanes are presented. The first one implements a passive shuffle architecture enabling non-blocking on-board optical interconnection between different cards/modules, while the second one deploys a regenerative bus architecture allowing the interconnection of an arbitrary number of electrical cards over a common optical bus. The polymer materials and the multimode waveguide components used to form the optical backplanes are presented, while details of the interconnection architectures and design of the backplanes are described. Proof-of-principle demonstrators fabricated onto low-cost FR4 substrates, including a 10-card 1 Tb/s-capacity passive shuffle router and 4-channel 3-card polymeric bus modules, are reported and their optical performance characteristics are presented. Low-loss, low-crosstalk on-board interconnection is achieved and error-free (BER10 12) 10 Gb/s communication between different card/module interfaces is demonstrated in both polymeric backplane systems. © 2012 IEEE.

Direct-write conductive fibres for soft electronics

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. We then examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates. © 2012 IEEE.

爪哇伪枝藻胞外多糖诱导皮肤癌细胞(A431)凋亡的研究

为探讨爪哇伪枝藻胞外多糖(Extracellular polymeric substances ofScytonema javanicum,EPS)诱导人表皮癌A431细胞凋亡及其对凋亡相关基因caspase-3、bcl-2和bax表达的影响,本实验利用MTT法检测细胞生长抑制情况;HE染色法及透射电镜进行形态学观察;单细胞凝胶电泳法(SCGE/彗星电泳)分析DNA受损情况;免疫组织化学法检测细胞内caspase-3、bcl-2和bax表达水平。结果显示EPS能显著抑制A431细胞增殖,并呈时间和剂量依赖

失水-吸水过程中微鞘藻光合活性的特性

雨季来临时,干藻重新吸收水分,光合活性恢复,迅速生长。微鞘藻(Microcoleus vaginatus)藻体在失水过程中,光合活性降低;而干藻接种到流沙后,恢复生长,在生长后期,生物量可达27μg/cm2土壤。在重吸水中,离子对光合活性的恢复具有重要作用,相对于去离子水来说,BG-11培养液处理后活性恢复较高;K+和Mg2+的缺失,对光合活性有抑制作用,而Ca2+的缺失,造成光合活性恢复的延缓;较高浓度的胞外多糖(Extracellular polymeric substances,EPS)和热水溶性多

Failure mechanisms in fibrous scaffolds.

Polymeric fibrous scaffolds have been considered as replacements for load-bearing soft tissues, because of their ability to mimic the microstructure of natural tissues. Poor toughness of fibrous materials results in failure, which is an issue of importance to both engineering and medical practice. The toughness of fibrous materials depends on the ability of the microstructure to develop toughening mechanisms. However, such toughening mechanisms are still not well understood, because the detailed evolution at the microscopic level is difficult to visualize. A novel and simple method was developed, namely, a sample-taping technique, to examine the detailed failure mechanisms of fibrous microstructures. This technique was compared with in situ fracture testing by scanning electron microscopy. Examination of three types of fibrous networks showed that two different failure modes occurred in fibrous scaffolds. For brittle cracking in gelatin electrospun scaffolds, the random network morphology around the crack tip remained during crack propagation. For ductile failure in polycaprolactone electrospun scaffolds and nonwoven fabrics, the random network deformed via fiber rearrangement, and a large number of fiber bundles formed across the region in front of the notch tip. These fiber bundles not only accommodated mechanical strain, but also resisted crack propagation and thus toughened the fibrous scaffolds. Such understanding provides insight for the production of fibrous materials with enhanced toughness.