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Moisture Diffusion in Silica/Clay/Natural Rubber Hybrid Composites 二氧化硅/粘土/天然橡胶混合复合材料中的水分扩散
Pub Date : 2019-05-01 DOI: 10.4028/www.scientific.net/DF.22.9
B. Pajarito, Mark Rigel R. Ali
This study investigated moisture diffusion in natural rubber (NR) hybrid composites filled with silica and bentonite clay. Natural bentonite (BNT) was treated with tetradecyldimethylammonium chloride and coco diethanolamide to produce modified bentonite (M-BNT). Varied proportions of silica, M-BNT, and BNT fillers were added to raw NR according to a third-degree simplex lattice mixture design of experiment. The addition of fillers affects the vulcanization characteristics, mechanical properties, and hardness of NR hybrid composites. Moisture diffusion behavior was studied by monitoring the water uptake of NR composites during immersion in deionized water at 80°C. Data from sorption experiments were fitted on the classical Fickian and Langmuir-type diffusion models. The Fickian model overestimates and underestimates the water uptake of NR composites in the early and later stages of moisture diffusion, respectively. On the other hand, the Langmuir-type model adequately captures the anomalous diffusion behavior of moisture in NR composites. Parameters of the Langmuir model (equilibrium water uptake and diffusion coefficient) vary with the composition of hybrid fillers. Optimum proportions of silica, M-BNT, and BNT in rubber composites were obtained by considering the effect of fillers on mechanical properties and moisture diffusion characteristics of NR.
研究了硅土和膨润土填充的天然橡胶(NR)杂化复合材料中水分的扩散。以天然膨润土为原料,经十四烷基二甲基氯化铵和可可二乙醇酰胺处理,制备改性膨润土(M-BNT)。根据实验的三次单纯点阵混合设计,将不同比例的二氧化硅、M-BNT和BNT填料添加到原料NR中。填料的加入影响了NR混杂复合材料的硫化特性、力学性能和硬度。通过监测NR复合材料在80℃去离子水浸泡过程中的吸水率,研究了其水分扩散行为。吸附实验的数据被拟合到经典的Fickian和langmuir扩散模型上。Fickian模型分别高估和低估了NR复合材料在水分扩散初期和后期的吸水性。另一方面,langmuir型模型充分捕捉了NR复合材料中水分的异常扩散行为。Langmuir模型的参数(平衡吸水和扩散系数)随混合填料的组成而变化。通过考虑填料对NR力学性能和水分扩散特性的影响,得到了二氧化硅、M-BNT和BNT在橡胶复合材料中的最佳配比。
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引用次数: 0
The Vacancy-Wind Factor and the Manning Factor Occurring in Interdiffusion and Ionic Conductivity in Solids 固体中相互扩散和离子电导率中的空风因子和曼宁因子
Pub Date : 2019-05-01 DOI: 10.4028/www.scientific.net/DF.22.170
I. Belova, G. Murch
In crystalline solids, during such processes as chemical interdiffusion in alloys, ionic conductivity and the annealing out of radiation damage there will inevitably be a net flux of vacancies. In most cases, when different species of atoms have different jump rates with vacancies within a net flux of vacancies, the phenomenon of the vacancy-wind effect will occur. This effect was first discovered in the 1960s by the late Dr John Manning. It is a subtle phenomenon that comes about because of the local redistribution of the equilibrium concentration of vacancies with respect to two or more species of drifting atoms in a driving force. The effect is captured in various ‘vacancy-wind factors’ (some of which are now sometimes called Manning factors) which formally arise from non-zero off-diagonal Onsager phenomenological transport coefficients and non-unity values of the tracer correlation factors. In this paper, the effect is reviewed and discussed.
在结晶固体中,在合金中的化学相互扩散、离子电导率和辐射损伤退火等过程中,不可避免地会存在空位的净通量。在大多数情况下,当不同种类的原子在一个空位的净通量内具有不同的空位跳跃率时,就会出现空位风效应的现象。这种效应最早是在20世纪60年代由已故的约翰·曼宁博士发现的。这是一种微妙的现象,由于在驱动力中相对于两种或两种以上漂移原子的空位平衡浓度的局部重新分布而产生。这种效应体现在各种“空风因子”(其中一些现在有时被称为曼宁因子)中,这些因子通常来自非零的非对角线Onsager现象输运系数和示踪相关因子的非单位值。本文对其效果进行了回顾和讨论。
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引用次数: 0
Ion Transport in Glass-Forming Calcium Potassium Nitrate: From Complex Behaviours to Unexpected Simplicities 形成玻璃的硝酸钙钾中的离子传输:从复杂的行为到意想不到的简单性
Pub Date : 2019-05-01 DOI: 10.4028/www.scientific.net/DF.22.140
K. Funke, R. D. Banhatti, M. Ingram
Re-examination of published conductivity spectra for 2Ca (NO3)2∙3KNO3 (CKN) in its molten and glassy states, in terms of the MIGRATION concept, has brought to light new links between elementary processes occurring within one picosecond and their successful outcomes, i.e. those which determine the DC conductivities. The starting point of this analysis is the transition at 378 K, which arises from a change from a decoupled to a coupled transport mechanism. Remarkably, while there is a change in the shape of the conductivity dispersion and a jump in its onset frequency, there is no change in the temperature dependence of DC conductivity. What emerges from the analysis is a surprising continuity in high-frequency behaviour, with the activation energy and volume for elementary displacements, Eed and Ved, remaining constant from 300 K in the glass up to 500 K in the melt. The ratio, Eed/Ved, turns out to be equal to our previously defined DC activation moduli for CKN, given by EDC(T)/VDC(T) and Tg/(dTg/dp) for charge transport in the melt and structural relaxation at Tg, respectively. It seems that, at very short times, molten CKN behaves just like an elastic solid. The importance of elastic forces for ionic transport in CKN is corroborated by the finding that the published value of the high-frequency shear modulus of glassy CKN, G¥, matches those of Eed/Ved and hence of both activation moduli. The detected continuity in the picosecond behaviour of CKN across the glass transition could provide a new link between fragile liquids and glassy materials in general.
根据迁移概念,重新检查已发表的2Ca (NO3)2∙3KNO3 (CKN)熔融和玻璃态的电导率谱,揭示了在一皮秒内发生的基本过程与其成功结果(即决定直流电导率的过程)之间的新联系。本分析的起点是在378 K时的跃迁,这是由从解耦到耦合输运机制的变化引起的。值得注意的是,虽然电导率色散的形状发生了变化,其开始频率也有所上升,但直流电导率的温度依赖性没有变化。从分析中得出的结果是高频行为的惊人连续性,基本位移的活化能和体积,Eed和Ved,从玻璃中的300k到熔体中的500k保持不变。该比值ed/Ved等于我们之前定义的CKN的直流激活模量,分别由熔体中的电荷输运和Tg处的结构弛豫的EDC(T)/VDC(T)和Tg/(dTg/dp)给出。似乎在很短的时间内,熔融的CKN就像弹性固体一样。弹性力对CKN中离子传输的重要性得到了证实,这一发现表明,公布的玻璃态CKN的高频剪切模量g¥与Eed/Ved的高频剪切模量相匹配,因此两者的激活模量也相匹配。在整个玻璃化转变中检测到的CKN皮秒行为的连续性可以在易碎液体和玻璃材料之间提供新的联系。
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引用次数: 0
Hydrogen Distribution in Partly Desorbed MgH2 Samples 部分解吸MgH2样品中氢的分布
Pub Date : 2019-05-01 DOI: 10.4028/www.scientific.net/DF.22.34
S. Lushnikov, T. V. Filippova, I. Bobrikov
The structure of MgH2 samples has been investigated by the neutron diffraction method at room temperature and 5 K. Samples of MgH2 have been prepared with vacuum extraction technique at high temperature. Obtained neutron data demonstrated that samples contain coexisting Mg and MgH2 phases in different rate. The distribution of hydrogen atoms in the structure of the samples is comparable at both temperatures. Collected neutron data and results of X-ray analysis show that microstructure of the samples is different at room and at low temperature. Non-stability of partly desorbed MgH2 samples after low temperature treatment has been discussed on basis of different diffusion of hydrogen atoms in varied microstructure.
用中子衍射法在室温和5k条件下研究了MgH2样品的结构。采用真空萃取技术在高温下制备了MgH2样品。获得的中子数据表明,样品中含有不同速率的Mg和MgH2相共存。在两种温度下,样品结构中氢原子的分布是相似的。收集的中子数据和x射线分析结果表明,样品在室温和低温下的微观结构不同。根据不同微观结构中氢原子扩散的不同,讨论了低温处理后部分脱附MgH2样品的不稳定性。
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引用次数: 0
Investigation of Interdiffusion in High Entropy Alloys: Application of the Random Alloy Model 高熵合金中相互扩散的研究:随机合金模型的应用
Pub Date : 2019-05-01 DOI: 10.4028/www.scientific.net/DF.22.94
M. Afikuzzaman, I. Belova, G. Murch
High entropy alloys (HEAs) are composed of five or more principal elements with equal (or nearly equal) compositions. In this paper, interdiffusion phenomenon in the HEAs is investigated. Two composition dependent (as well as composition independent) interdiffusion matrices have been used for detailed studying of the diffusion behaviour in CoCrFeMnNi HEAs. These matrices are calculated according to the Darken and Manning formalisms and are used in combination with the explicit finite difference method (EFDM) to obtain interdiffusion profiles. First, the interdiffusion profiles are calculated for the case of the terminal binary diffusion couple. A significant difference in the composition profiles is found between predictions according to the Darken and Manning formalisms. Next, the interdiffusion problem in the 5-component alloy is addressed numerically by considering the interdiffusion coefficients as constant, independent of composition, in CoCrFeMnNi alloys for several diffusion couples (mainly quasi-binary and quasi-ternary). The simulated composition profiles are found to be in a very good agreement with the available experimental results [1, 2]. It should be pointed out that the independence on composition of the interdiffusion matrix should be used for diffusion couples under two conditions: relatively small changes in composition, and the non-zero/non-dilute terminal compositions. The composition dependent interdiffusion matrix should be used in the diffusion couple if the composition differences are large and/or zero/dilute terminal compositions. In this paper, the Darken and Manning formalisms are used for modelling the composition dependent interdiffusion matrices. The purpose of this modelling is to systematically investigate interdiffusion in CoCrFeMnNi alloys in diffusion couples with substantial changes in composition. The main application of the present research is in the prediction of possible interdiffusion profiles in the framework of the random alloy model.
高熵合金(HEAs)是由五种或多种成分相等(或几乎相等)的主元素组成的。本文研究了HEAs内的互扩散现象。两种组分依赖(以及不依赖)的互扩散矩阵被用于CoCrFeMnNi HEAs中的扩散行为的详细研究。这些矩阵根据Darken和Manning形式计算,并与显式有限差分法(EFDM)结合使用,以获得相互扩散曲线。首先,计算了末端二元扩散偶的扩散曲线。在根据Darken和Manning形式主义所作的预测中,发现了成分分布的显著差异。接下来,通过考虑CoCrFeMnNi合金中几种扩散对(主要是准二元和准三元)的相互扩散系数为常数,与成分无关,对五组分合金中的相互扩散问题进行了数值求解。模拟的组分分布与现有的实验结果非常吻合[1,2]。应该指出的是,在两种情况下,扩散偶应使用与组成无关的扩散矩阵:组成变化相对较小,以及非零/非稀端组成。如果组分差异较大,且/或末端组分为零/稀,则应在扩散偶中使用组分依赖的互扩散矩阵。在本文中,使用了Darken和Manning形式来模拟成分相关的互扩散矩阵。该模型的目的是系统地研究CoCrFeMnNi合金在成分发生实质性变化的扩散偶中的相互扩散。本研究的主要应用是在随机合金模型框架下预测可能的相互扩散分布。
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引用次数: 5
Mechanisms of Silicide Formation by Reactive Diffusion in Thin Films 薄膜中反应扩散形成硅化物的机理
Pub Date : 2019-03-01 DOI: 10.4028/www.scientific.net/DF.21.1
D. Mangelinck
Silicide formation by reactive diffusion is of interest in numerous applications especially for contact formation and interconnections in microelectronics. Several reviews have been published on this topic and the aim of this chapter is to provide an update of these reviews by focusing on new experiment results. This chapter presents thus some progress in the understanding of the main mechanisms (diffusion/reaction, nucleation, lateral growth…) for thin and very thin films (i.e. comprised between 4 and 50 nm). Recent experimental results on the mechanisms of formation of silicide are presented and compared to models and/or simulation in order to extract physical parameters that are relevant to reactive diffusion. These mechanisms include nucleation, lateral growth, diffusion/interface controlled growth, and the role of a diffusion barrier. The combination of several techniques including in situ techniques (XRD, XRR, XPS, DSC) and high resolution techniques (APT and TEM) is shown to be essential in order to gain understanding in the solid state reaction in thin films and to better control these reaction for making contacts in microelectronics devices or for other application.
反应扩散形成硅化物在许多应用中都很有意义,特别是在微电子领域的接触形成和互连方面。关于这一主题已经发表了几篇综述,本章的目的是通过关注新的实验结果来提供这些综述的更新。因此,本章介绍了在理解薄膜和超薄膜(即由4到50纳米组成)的主要机制(扩散/反应、成核、横向生长……)方面的一些进展。本文介绍了硅化物形成机制的最新实验结果,并将其与模型和/或模拟进行了比较,以便提取与反应扩散相关的物理参数。这些机制包括成核、横向生长、扩散/界面控制生长以及扩散屏障的作用。包括原位技术(XRD, XRR, XPS, DSC)和高分辨率技术(APT和TEM)在内的几种技术的结合被证明是必不可少的,以便了解薄膜中的固态反应,并更好地控制这些反应,以在微电子器件中制造接触或用于其他应用。
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引用次数: 2
Diffusion Rates of Components in Metal-Silicides Depending on Atomic Number of Refractory Metal Component 金属硅化物中组分的扩散速率与难熔金属组分原子序数的关系
Pub Date : 2019-03-01 DOI: 10.4028/www.scientific.net/DF.21.29
A. Paul
Interdiffusion studies conducted in group IVB, VB and VIB metal-silicon systems are discussed in detail to show a pattern in the change of diffusion coefficients with the change in atomic number of the refractory metal (M) component. MSi2 and M5Si3 phases are considered for these discussions. It is shown that integrated diffusion coefficients increase with the increase in atomic number of the refractory component when the data are plotted with respect to the melting point normalized annealing temperature. This indicates the increase in overall defect concentration facilitating the diffusion of components. This is found to be true in both the phases. Additionally, the estimated ratios of tracer diffusion coefficients indicate the change in concentration of antisite defects in certain manner with the change in atomic number of the refractory components.
详细讨论了在IVB、VB和VIB族金属硅体系中进行的相互扩散研究,揭示了扩散系数随难熔金属(M)组分原子序数变化的规律。这些讨论考虑了MSi2和M5Si3相。结果表明,当数据与熔点归一化退火温度相关时,积分扩散系数随耐火材料原子序数的增加而增加。这表明整体缺陷浓度的增加促进了组件的扩散。这在两个阶段都是成立的。此外,示踪剂扩散系数的估计比值表明,对位缺陷的浓度随耐火材料原子序数的变化有一定的变化。
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引用次数: 3
Diffusion-Limited Reactions of Non-Oxide Ceramics with Transition Metals 非氧化物陶瓷与过渡金属的扩散限制反应
Pub Date : 2019-03-01 DOI: 10.4028/www.scientific.net/DF.21.85
A. Kodentsov
Thermodynamic and diffusion models are given to describe morphological evolution of the reaction zone during diffusion-limited interaction between non-oxide Si-containing ceramics (SiC and Si3N4) and transition metals (Cr, Mo, Ti, Ni, Co, Pt). In the case of diffusion-controlled process in the ternary metal-ceramic systems, reaction phenomena can be rationalized using chemical potential diagrams. However, in some cases, a periodic layered morphology is found in the transition zone, which is not fully understood, and it is difficult to predict a priori. Silicide formation in systems based on dense Silicon Nitride and non-nitride forming metals can be explained by assuming a nitrogen pressure build-up at the contact surface. This pressure determines the chemical potential of Silicon at the interface, and hence, the product phases in the diffusion zone. Traces of Oxygen in the ambient atmosphere might affect the interaction in non-oxide ceramic/transition metal systems. The thermodynamic stability of the condensed phases in the systems where volatile species may form can be interpreted using predominant area-type diagrams.
给出了热力学和扩散模型来描述非氧化物含硅陶瓷(SiC和Si3N4)与过渡金属(Cr, Mo, Ti, Ni, Co, Pt)在扩散限制相互作用过程中反应区的形态演变。对于三元金属-陶瓷体系中的扩散控制过程,可以用化学势图来解释反应现象。然而,在某些情况下,在过渡带中发现了周期性的层状形态,这种形态尚不完全清楚,而且很难进行先验预测。在基于致密氮化硅和非氮化金属的系统中,硅化物的形成可以通过假设接触表面的氮压力积聚来解释。这个压力决定了界面上硅的化学势,从而决定了扩散区的产物相。环境大气中痕量的氧可能影响非氧化物陶瓷/过渡金属体系中的相互作用。在可能形成挥发性物质的体系中,凝聚相的热力学稳定性可以用显性面积型图来解释。
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引用次数: 3
Periodic Layer Formation during Multiphase Diffusion in Silicide Systems 硅化物体系多相扩散过程中周期性层的形成
Pub Date : 2019-03-01 DOI: 10.4028/www.scientific.net/DF.21.157
A. Kodentsov, J. Wojewoda-Budka, A. Wierzbicka-Miernik
Periodic layered morphology may occur during displacement solid-state reactions in ternary (and higher-order) silicide and other material systems. This periodic layered structure consists of regularly spaced layers (bands) of particles of one reaction product embedded in a matrix phase of another reaction product. The number of systems that is known to produce the periodic layered structure is rather small but increasing and includes metal/metal and metal/ceramic semi-infinite diffusion couples. The experimental results on different systems, where the periodic pattern formation has been observed are systematized and earlier explanations for this peculiar diffusion phenomenon are discussed. Formation of the reaction zone morphologies periodic in time and space can be considered as a manifestation of the Kirkendall effect accompanying interdiffusion in the solid state. The patterning during multiphase diffusion is attributed to diverging vacancy fluxes within the interaction zone. This can generate multiple Kirkendall planes, which by attracting in situ-formed inclusions of “secondary-formed phase” can result in a highly patterned microstructure.
在三元(和高阶)硅化物和其他材料体系的位移固相反应中可能出现周期性层状形态。这种周期性层状结构由一种反应产物的粒子层(带)嵌入另一种反应产物的基质相组成。已知产生周期性层状结构的系统数量相当少,但正在增加,包括金属/金属和金属/陶瓷半无限扩散偶。对不同系统中观察到周期性图案形成的实验结果进行了系统化,并讨论了对这种特殊扩散现象的早期解释。在时间和空间上具有周期性的反应区形态的形成可以认为是伴随固态相互扩散的Kirkendall效应的一种表现。多相扩散过程中的图案是由相互作用区内的空位通量发散引起的。这可以产生多个Kirkendall面,通过吸引原位形成的“二次形成相”夹杂物,可以产生高度图案化的微观结构。
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引用次数: 2
Oxidation Behavior of Silicides 硅化物的氧化行为
Pub Date : 2019-03-01 DOI: 10.4028/www.scientific.net/DF.21.127
R. Mitra
The oxidation behavior of Mo, Nb, and Ti-silicides has received significant attention in past few decades for their potential to be used as high temperature structural materials. These Si-bearing intermetallic alloys have the ability to form an oxide scale containing SiO2, which is protective if formed as a continuous and impervious layer, so that the ingress of oxygen from atmosphere to the underneath alloy is restricted. To form a continuous and stable SiO2 scale, it is important to have sufficient activity of Si along with thermodynamic and kinetic conditions favoring its growth in comparison to that of oxides of other alloying elements. MoSi2 has superior oxidation resistance compared to that of Mo3Si or Mo5Si3, because of its higher Si content. Furthermore, a continuous film of SiO2 is able to form at temperatures in the range of 800-1700 oC on MoSi2 due to vaporization of MoO3, but not on NbSi2 or TiSi2 due to competitive growth of Nb2O5 or TiO2, respectively. During past two decades, a significant effort has been devoted to development of Mo-Si-B alloys containing Mo-rich solid solution, Mo3Si and Mo5SiB2 as constituent phases, due to their ability to form a protective borosilicate scale. The presence of B2O3 contributes to fluidity of borosilicate scale, thereby contributing to closure of porosities. Efforts have been also made to develop multicomponent Nb-silicide based alloys with optimum combination of mechanical properties and high temperature oxidation resistance with limited success. There have been efforts to develop silicide based coatings for protection oxidation for Mo-rich Mo-Si-B alloys and Nb-Si based ternary or multicomponent alloys with inadequate oxidation resistance. Oxidation behavior of selected silicides with potential for structural application, along with mechanisms for protection against oxidation has been reviewed and discussed.
在过去的几十年里,Mo、Nb和ti硅化物的氧化行为因其作为高温结构材料的潜力而受到了极大的关注。这些含硅金属间合金具有形成含有SiO2的氧化层的能力,如果形成连续的不透水层,则具有保护作用,从而限制氧气从大气进入下面的合金。与其他合金元素的氧化物相比,要形成连续稳定的SiO2结垢,重要的是要有足够的Si活性以及有利于其生长的热力学和动力学条件。与Mo3Si或Mo5Si3相比,MoSi2具有更好的抗氧化性能,这是由于其较高的Si含量。此外,由于MoO3的汽化,在800-1700℃的温度范围内,MoSi2上可以形成连续的SiO2膜,而NbSi2和TiSi2上则分别由于Nb2O5和TiO2的竞争生长而不能形成连续的SiO2膜。在过去的二十年中,由于Mo-Si-B合金具有形成硼硅保护层的能力,人们致力于开发含有富mo固溶体、Mo3Si和Mo5SiB2组成相的Mo-Si-B合金。B2O3的存在有利于硼硅垢的流动性,从而有利于孔隙的闭合。人们也在努力开发具有最佳力学性能和高温抗氧化性组合的多组分铌硅化物基合金,但取得的成功有限。对于抗氧化能力不足的富Mo-Si-B合金和Nb-Si基三元或多组分合金,人们一直在努力开发用于保护氧化的硅化物涂层。综述和讨论了具有结构应用潜力的硅化物的氧化行为及其氧化保护机制。
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引用次数: 4
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Diffusion Foundations
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