Dynamic characterization of micro-particle systems

Ordered granular systems have been a subject of active research for decades. Due to their rich dynamic response and nonlinearity, ordered granular systems have been suggested for several applications, such as solitary wave focusing, acoustic signals manipulation, and vibration absorption. Most of the fundamental research performed on ordered granular systems has focused on macro-scale examples. However, most engineering applications require these systems to operate at much smaller scales. Very little is known about the response of micro-scale granular systems, primarily because of the difficulties in realizing reliable and quantitative experiments, which originate from the discrete nature of granular materials and their highly nonlinear inter-particle contact forces.

In this work, we investigate the physics of ordered micro-granular systems by designing an innovative experimental platform that allows us to assemble, excite, and characterize ordered micro-granular systems. This new experimental platform employs a laser system to deliver impulses with controlled momentum and incorporates non-contact measurement apparatuses to detect the particles’ displacement and velocity. We demonstrated the capability of the laser system to excite systems of dry (stainless steel particles of radius 150 micrometers) and wet (silica particles of radius 3.69 micrometers, immersed in fluid) micro-particles, after which we analyzed the stress propagation through these systems.

We derived the equations of motion governing the dynamic response of dry and wet particles on a substrate, which we then validated in experiments. We then measured the losses in these systems and characterized the collision and friction between two micro-particles. We studied wave propagation in one-dimensional dry chains of micro-particles as well as in two-dimensional colloidal systems immersed in fluid. We investigated the influence of defects to wave propagation in the one-dimensional systems. Finally, we characterized the wave-attenuation and its relation to the viscosity of the surrounding fluid and performed computer simulations to establish a model that captures the observed response.

The findings of the study offer the first systematic experimental and numerical analysis of wave propagation through ordered systems of micro-particles. The experimental system designed in this work provides the necessary tools for further fundamental studies of wave propagation in both granular and colloidal systems.

Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.

Modified porous silica antireflective coatings with laser damage resistance for Ti:sapphire

Porous SiO2 antireflective (AR) coatings are prepared from the colloidal silica solution modified with methyltriethoxysilane (MTES) based on the sol-gel route. The viscosity of modified silica suspensions changes but their stability keeps when MTES is introduced. The refractive indices of modified coatings vary little after bake treatment from 100 to 150 Celsius. The modified silica coatings on Ti:sapphire crystal, owning good homogeneity, display prominent antireflective effect within the laser output waveband (750-850 nm) of Ti:sapphire lasers, with average transmission above 98.6%, and own laser induced damage thresholds (LIDTs) of more than 2.2 J/cm2 at 800 nm with the pulse duration of 300 ps.

Catalisadores para hidroisomerização de n-hexadecano

No processo de hidrocraqueamento para a produção de lubrificantes ocorre a formação de uma corrente rica em compostos parafínicos que possuem alto ponto de fluidez, apesar dos mesmos apresentarem excelentes desempenhos em termos de estabilidade térmica e oxidativa. A transformação das n-parafinas obtidas nestas correntes em isoparafinas e compostos naftênicos, os quais possuem menores pontos de fluidez, se faz necessária a fim de enquadrar esta propriedade. Uma das rotas catalíticas mais importantes neste sentido é a hidroisodesparafinação ou HIDW (hydroisodewaxing) que consiste na conversão de n-parafinas nas respectivas isoparafinas, onde são empregados catalisadores bifuncionais zeolíticos com a ocorrência de seletividade de forma. No caso dos catalisadores industriais, se faz necessária a dispersão da fase metálica e da zeólita em uma matriz amorfa para viabilizar sua conformação e melhorar a resistência mecânica do catalisador final. Neste cenário, o objetivo deste trabalho foi preparar e analisar o desempenho de uma série de catalisadores à base de zeólita beta inseridos numa matriz de alumina, variando-se o teor de zeólita e o tipo de precursor de Pt utilizado. Os catalisadores foram avaliados na reação de hidroisomerização de um composto modelo, no caso, n-hexadecano. Os testes realizados para avaliação da atividade e seletividade foram conduzidos em um reator de fluxo contínuo em alta pressão e fase líquida em unidade de laboratório. Os catalisadores foram testados em condições operacionais que proporcionassem uma ampla faixa de conversões do n-C16. Verificou-se que as atividades dos catalisadores foram proporcionais ao teor de zeólita no catalisador, indicando que a função ácida, neste catalisador bifuncional, é a etapa limitante do processo. Quanto à natureza do precursor de Pt, o catalisador preparado com ácido cloroplatínico foi sensivelmente mais ativo que os preparados com o complexo aminplatina. No entanto, para todos os catalisadores, a distribuição de produtos em função da conversão foi similar, independente do teor de zeólita e da natureza do precursor de platina. Foi também determinado o ponto de fluidez de uma série de produtos de reação, obtendo-se valores entre 17,5 C (n-hexadecano) e - 41 C (produto com 98% de conversão). Obteve-se uma boa correlação entre o ponto de fluidez e a composição dos produtos, considerando-se a presença de isômeros mono, di e tri-substituídos e compostos de menor peso molecular que C16

Electrical transport in metallic films

On the basis of the Boltzmann equation, the authors propose a model that includes scattering from both film surfaces and grain boundaries, and have studied the quasiclassical electrical transport in metallic films. The in-plane electric conductivity of metallic films is obtained, and the theoretical results are shown to be in good agreement with experimental data. We also give the relation between temperature coefficient of resistivity and thickness of metallic films and make a comparison with experiment. <(C)> 2004 American Institute of Physics.

脉冲激光辐照光学薄膜的缺陷损伤模型

建立了缺陷吸收升温致薄膜激光损伤模型，该模型从热传导方程出发，考虑了缺陷内部的温度分布以及向薄膜的传导过程，通过引入散射系数简化了Mie散射理论得出的吸收截面．对电子束蒸发沉积的ZrO2：Y2O3单层膜进行了激光破坏实验，薄膜样品的损伤是缺陷引起的，通过辉光放电质谱法对薄膜制备材料的纯度分析发现材料中的主要杂质元素为铂，其含量为0．9％．利用缺陷损伤模型对损伤过程进行了模拟，理论模型和实验结果取得了较好的一致性．

纳米孔结构金属多孔材料研究进展

纳米孔结构金属多孔材料(以下简称金属纳米多孔材料)是近年来纳米技术及多孔材料科学领域引人注目的研究对象。本文综述了近年来金属纳米多孔材料的制备方法(粉末烧结法、脱合金法、胶晶模板法、斜入射沉积法等)、表征技术、应用现状以及最新的研究成果。指出了金属纳米多孔材料研究进程中存在的主要问题、发展前景及今后的研究方向。

Estudo da influência da temperatura na desativação de catalisadores automotivos comerciais

Foi estudada a influência da temperatura na desativação de catalisadores automotivos comerciais, à base de Pt/Rh e de Pd/Rh, de diferentes fabricantes. Foram empregadas técnicas de caracterização textural e físico-química como FRX, AAS, fisissorção de N2, TG-ATD, DRX, RTP, quimissorção de H2 e MEV-EDX. Os catalisadores foram avaliados nas reações de oxidação do CO e oxidação do propano, utilizando uma mistura de gases estequiométrica semelhante ao gás de exaustão. Os catalisadores denominados G e V, de Pt/Rh e Pd/Rh, respectivamente, foram envelhecidos a 900C, em condições estequiométricas, e a 1200C, em ar, por períodos de tempo determinados. Em relação ao envelhecimento a 900C, apesar da caracterização apontar melhores resultados para o catalisador G, a comparação com os catalisadores novos indicou que a extensão da desativação sofrida pelo catalisador V foi menor do que aquela sofrida pelo catalisador G. O envelhecimento oxidante a 1200C foi muito prejudicial ao desempenho de ambos os catalisadores. Os difratogramas dos catalisadores envelhecidos nestas condições mostraram fenômenos importantes de transição de fase da alumina, bem como indícios de formação de novas fases a partir do óxido misto de Ce/Zr. Os perfis de RTP mostraram uma grande queda na redutibilidade, tanto para o catalisador G como para o V após este envelhecimento, e as micrografias de MEV-EDX mostraram estruturas muito sinterizadas e vários pontos de Pd aglomerado no catalisador V. Esse catalisador também apresentou partículas de texturas incomuns. Além disso, para ambos foi verificado indícios de perda de material nas amostras calcinadas por 72h a 1200C. Com relação aos resultados de avaliação catalítica, o catalisador G apresentou um desempenho inferior ao do catalisador V. A realização de envelhecimentos em atmosfera oxidante pode justificar esse comportamento uma vez que esse procedimento promove a formação de óxidos de platina, menos ativos que a platina metálica para essas reações. Além disso, este catalisador apresentou um teor de Pt bem abaixo daqueles registrados na literatura para catalisadores automotivos comerciais. Por outro lado, para catalisadores de Pd, o envelhecimento oxidante leva à formação de PdO, mais ativo que o Pd metálico. Outra observação significativa em relação à avaliação catalítica foi o fato de o catalisador G novo ter apresentado uma atividade muito baixa, especialmente para o propano, que tendeu a aumentar com o envelhecimento térmico. Foi sugerido que este catalisador precisaria de uma ativação térmica, a qual o catalisador V parece ter sido submetido durante a fabricação, pois há indícios da ocorrência de certo desgaste térmico neste catalisador novo, como mostrados pelos resultados de fisissorção de N2, DRX, TG-ATD, RTP e MEV-EDX. Foi também mostrado que os resultados de quimisorção de H2, apesar de não poderem ser usados na determinação da dispersão metálica, apresentaram uma tendência de correlação entre o consumo de H2 e o desempenho catalítico expresso como T50 ou T20. Observa-se um aumento na atividade catalítica quando a quantidade de H2 dessorvido (DTP-H2) aumenta. Concluindo, o envelhecimento térmico mostrou ser prejudicial ao desempenho do catalisador comercial, principalmente para situações drásticas como o envelhecimento realizado a 1200C em condições oxidantes

Direct growth of horizontally aligned carbon nanotubes between electrodes and its application to field-effect transistors

This paper presents direct growth of horizontally aligned carbon nanotubes (CNTs) between two predefined various inter-spacing up to tens of microns of electrodes (pads) and its use as CNT field-effect transistors (CNT-FETs). The catalytic metals were prepared, consisting of iron (Fe), aluminum (Al) and platinum (Pt) triple layers, on the thermal silicon oxide substrate (Pt/Al/Fe/SiO2). Scanning electron microscopy measurements of CNT-FETs from the as-grown samples showed that over 80% of the nanotubes are grown across the catalytic electrodes. Moreover, the number of CNTs across the catalytic electrodes is roughly controllable by adjusting the growth condition. The Al, as the upper layer on Fe electrode, not only plays a role as a barrier to prevent vertical growth but also serves as a porous medium that helps in forming smaller nano-sized Fe particles which would be necessary for lateral growth of CNTs. Back-gate field effect transistors were demonstrated with the laterally aligned CNTs. The on/off ratios in all the measured devices are lower than 100 due to the drain leakage current. ©2010 IEEE.

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.

Catalyst-free synthesis of zinc oxide nanostructures by microheaters in the ambient environment

This paper demonstrates a catalyst-free synthesis of ZnO nanostructures using platinum microheaters under ambient environmental conditions. Different morphologies of ZnO nanostructures are synthesized from the oxidization of Zn thin film by local heating. The synthesized ZnO structures are characterized by the SEM, EDX and Raman spectra. The characterization of two shapes of Pt microheaters is investigated and the relationship between the applied heating power and ZnO nanostructures synthesis is investigated under ambient conditions. We observe that the density and morphology of ZnO nanostructures can be controlled through applied heating voltages. Furthermore, a connected composite structural (Zn-ZnO-Zn) layer is synthesized using combinative microheaters. © 2011 IEEE.

Autobrinometer

An instrument developed for the rapid and accurate measurement of brine concentrations during blanching without disturbing the routine blanching operation is described. The concentration is sensed by a platinum electrode conductivity cell and displayed in a moving coil meter after conversion of the electrical signals into D.C. voltage. The instrument can measure in the range 5 to 12% with an accuracy of ± 1%. The errors caused mostly are those due to wide temperature variations of the brine between 95 to 102°C and the unknown quantities of protein.

Preparation and characterization of a novel pyrrole-benzophenone copolymerized silica nanocomposite as a reagent in a visual immunologic-agglutination test.

Biological sensing is explored through novel stable colloidal dispersions of pyrrole-benzophenone and pyrrole copolymerized silica (PPy-SiO(2)-PPyBPh) nanocomposites, which allow covalent linking of biological molecules through light mediation. The mechanism of nanocomposite attachment to a model protein is studied by gold labeled cholera toxin B (CTB) to enhance the contrast in electron microscopy imaging. The biological test itself is carried out without gold labeling, i.e., using CTB only. The protein is shown to be covalently bound through the benzophenone groups. When the reactive PPy-SiO(2)-PPyBPh-CTB nanocomposite is exposed to specific recognition anti-CTB immunoglobulins, a qualitative visual agglutination assay occurs spontaneously, producing as a positive test, PPy-SiO(2)-PPyBPh-CTB-anti-CTB, in less than 1 h, while the control solution of the PPy-SiO(2)-PPyBPh-CTB alone remained well-dispersed during the same period. These dispersions were characterized by cryogenic transmission microscopy (cryo-TEM), scanning electron microscopy (SEM), FTIR and X-ray photoelectron spectroscopy (XPS).

Applying quality control in building energy modelling: Comparative simulation of a high performance building

Quality control is considered from the simulator's perspective through comparative simulation of an ultra energy-efficient building with EE4-DOE2.1E and EnergyPlus. The University of Calgary's Leadership in Energy and Environmental Design Platinum Child Development Centre, with a 66% certified energy cost reduction rating, was the case study building. A Natural Resources Canada incentive program required use of EE4 interface with DOE2.1E simulation engine for energy modelling. As DOE2.1E lacks specific features to simulate advanced systems such as radiant cooling in the CDC, an EnergyPlus model was developed to further evaluate these features. The EE4-DOE2.1E model was used for quality control during development of the base EnergyPlus model and simulation results were compared. Advanced energy systems then added to the EnergyPlus model generated small difference in estimated total annual energy use. The comparative simulation process helped identify the main input errors in the draft EnergyPlus model. The comparative use of less complex simulation programs is recommended for quality control when producing more complex models. © 2009 International Building Performance Simulation Association (IBPSA).

Imbibition dynamics of nano-particulate ink-jet drops on micro-porous media

Ink-jet printing of nano-metallic colloidal fluids on to porous media such as coated papers has become a viable method to produce conductive tracks for low-cost, disposable printed electronic devices. However, the formation of well-defined and functional tracks on an absorbing surface is controlled by the drop imbibition dynamics in addition to the well-studied post-impact drop spreading behavior. This study represents the first investigation of the real-time imbibition of ink-jet deposited nano-Cu colloid drops on to coated paper substrates. In addition, the same ink was deposited on to a non-porous polymer surface as a control substrate. By using high-speed video imaging to capture the deposition of ink-jet drops, the time-scales of drop spreading and imbibition were quantified and compared with model predictions. The influences of the coating pore size on the bulk absorption rate and nano-Cu particle distribution have also been studied.