307 resultados para PHASE-SEPARATION BEHAVIOR


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A new metal catalysis-free method of fabricating Si or SiO2 nanowires (NWs) compatible with Si CMOS technology was proposed by annealing SiOx (x < 2) films deposited by plasma -enhanced chemical vapor deposition (PECVD). The effects of the Si content (x value) and thickness of SiOx films, the annealing process and flowing gas ambient on the NW growth were studied in detail. The results indicated that the SiOx film of a thickness below 300 rim with x value close to 1 was most favorable for NW growth upon annealing at 1000-1150 degrees C in the flowing gas mixture of N-2 and H-2. NWs of 50-100nm in diameter and tens of micrometers in length were synthesized by this method. The formation mechanism was likely to be related to a new type of oxide assisted growth (OAG) mechanism, with Si nanoclusters in SiOx films after phase separation serving as the nuclei for the growth of NWs in SiOx films > 200nm, and SiO molecules from thin SiO, film decomposition inducing the NW growth in films < 100nm. An effective preliminary method to control NW growth direction was also demonstrated by etching trenches in SiOx films followed by annealing.

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InGaN/GaN heterostructures have been deposited onto (0 0 0 1) sapphire by our home-made low pressure MOVPE with different growth parameters. It has been noted that the indium incorporation depends by a complex way on a number of factors. In this work, the effect of substrate temperature, trimethylindium input flow and V/III ratio on the indium incorporation has been investigated. Finally, by optimizing the growth parameters, we made a series of single-phase InGaN samples with indium content from 10% up to 45%.

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本文提出了将自洽场理论与多相流格子Boltzmann方法相结合的模型,并从该模型出发推导出了描述动量守恒的Navier-Stokes方程和扩散方程,验证了模型理论上的正确性。应用此模型,对聚合物的相分离过程进行了模拟。 首先证实了本模型最终能够得到正确的热力学平衡结果。对于高分子共混物和嵌段共聚物相分离的动力学过程。在分相各个阶段,对高分子共混物和嵌段共聚物都进行了验证。 其次,应用所提出的格子Boltzmann模型,分别对二元聚合物共混物和二嵌段共聚物的相分离后期相区增长过程进行了研究。 最后,通过模型的进一步扩展,实现了对具有复杂结构的嵌段共聚物和复杂共混物的模拟。

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本论文主要借助原子力显微镜(AFM)、X-射线光电子能谱(XPS)等实验手段,纳米尺度上在线原位地研究了高温临界组成PMMMA/SAN(50/50,w/w)共混薄膜体系,分析并探讨了此共混薄膜表面相分离及其超薄膜体系的润湿/去润湿和相分离行为。首先,从敲击式AFM中相位图的成像原理出发,建立了一个高温下用原位AFM定性鉴别不同聚合物的纳米尺寸微区的方法,即:先在基底(硅)上铺展一层非常平坦的单一组分(SAN)薄膜,再在此千膜上,通过旋涂由选择性溶剂(冰醋酸)配制的另一组分(PMMA)的极稀溶液,使之不能形成一层连续的完整膜,最后在高温(175℃)下用敲击模式的原子力显微镜(TM-AFM)检测相位图随退火时间的变化。得到在175℃的相位图中,PMMA富相比SAN的富相显得更暗,这为后续工作提供了定性鉴别相区的方法。其次,高温下用原位AFM研究了PMMA/SAN薄膜表面相分离过程,在线观察了相分离的归并过程,定量地得到了临界相分离温度,并给出了特征波矢对时间依赖关系的标度指数,划分了相分离动力学演变的不同阶段。对于膜厚约为130nm的体系,表面相分离的临界温度大约为165℃,其表面相分离的特征波矢与时间的标度关系q+(t)-t-n,在整个实验时间内,随时间的演变过程中,显示了两个不同的指数变化区,即前期很慢的n=0.13和后期的n=1/3。0.13的指数关系可能是由于表面聚合物链的几何受限及表面富集相把部分新生成的另一相覆盖所致,1/3的指数关系可以认为是由普遍的Brownian扩散所致。而对于膜厚为50曲的此组成共混薄膜,得到的标度关系与C汕n线性理论吻合得非常好的Spinodal Deposition(SD)表面相分离的初期,即n=0,这是由于降低膜厚 增加了共混物的相容性,提高了临界温度,从而减缓了相分离过程,使得在我 们观测的时间范围内更易观察到表面相分离的初期。再次,用阶梯式降温的好M和XPS,发现了PMMA/SAN体系原位和离位实验结果存在巨大差别的主要原因之一—润湿温度的存在。对PMMA/SAN(50/50,w/w,-130nm)共混薄膜体系,原位AFM的退火和准淬火实验表明, 虽然在高温和室温、真空和常态、原位和离位,相分离的聚合物共混薄膜表面 形貌变化不大,但是表面物理性质却有很大的区别。原位XPS实验表明,未经 任何处理的样品在185℃退火时,很快在离表面很薄的下面形成一层PMMA含 量远低于本体值的薄层,之后最表面的PMMA也往本体迁移,直至表面SAN 的含量远高于它的本体值。对已在175℃退火20hr的此样品,逐渐降温退火过 程的原位XPS表明,当退火温度降至145oC时,样品表面几乎完全被PMMA覆盖,很好地验证了Conlposto等提出的润湿温度的假设,即对此体系,润湿温 度是原位和离位存在巨大的差异的主要因素之一,这与原位AFM的实验结果也,存在很好的一致性。最后,高温下原位观察了硅基底上PMMA/SAN超薄膜(膜厚-Rg)的去润湿、相分离过程和PMMA在基底上的润湿过程,以及云母基底上的该体系高温下的稳定润湿行为。以硅为基底的PMM刀sAN共混超薄膜在155”c下发生了类 似sPinodal dewetting的去润湿,其原因可能是在垂直于基底的浓度梯度引起的表面组成的涨落,对这种去润湿的动力学还进行了探讨。以硅为基底的PMMA/SAN共混超薄膜在175℃下不仅发生了类似spinodal dewetting的去润 湿,而且还发生了去润湿液滴内部的相分离以及相分离析出的PMMA润湿硅基底的过程,提出了一个简单的模型描述了这种复杂的过程。此外,还研究了不同基底对此共混超薄膜体系的润湿行为进行了研究,以云母为基底的此共混体系在175℃下长时间内是稳定的,其原因可能是云母与PMMA和SAN均有很强的作用力,足于补偿聚合物链在构象嫡上的损失。

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Experimental study of a liquid fed direct methanol fuel cell has been conducted in different gravity environments. A small single cell with 5 cm x 5 cm active area has single serpentine channel on the graphite cathode polar plate and 11 parallel straight channels on the graphite anode flow bed. Cell voltage and current have been measured and two-phase flow in anode channels has been in situ visually observed. The experimental results indicate that the effect of gravity on power performance of the direct methanol fuel cell is large when the concentration polarization governs fuel cells operation. Gravitational effect becomes larger at higher current density. Increasing methanol feeding molarity is conducive to weaken the influence of gravity on performance of liquid fed direct methanol fuel cells. Increasing feeding flow rate of methanol solution from 6 to 15 ml/min could reduce the size of carbon dioxide bubbles, while the influence of gravity still exist. Transport phenomena inside direct methanol fuel cells in microgravity is also analyzed and discussed.

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Cellulose hollow fiber membranes (CHFM) were prepared using a spinning solution containing N-methylmorpholine-N-oxide as solvent and water as a nonsolvent additive. Water was also used as both the internal and external coagulant. It was demonstrated that the phase separation mechanism of this system was delayed demixing. The CHFM was revealed to be homogeneously dense structure after desiccation. The gas permeation properties of CO2, N-2, CH4, and H-2 through CHFM were investigated as a function of membrane water content and operation pressure. The water content of CHFM had crucial influence on gas permeation performance, and the permeation rates of all gases increased sharply with the increase of membrane water content. The permeation rate of CO2 increased with the increase of operation pressure, which has no significant effect on N-2, H-2, and CH4. At the end of this article a detailed comparison of gas permeation performance and mechanism between the CHFM and cellulose acetate flat membrane was given. (C) 2003 Wiley Periodicals, Inc.

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The domain-structure of samples containing a series of starch/poly(sodium acrylate)-grafted superabsorbents, pure starch, pure poly(sodium acrylate), and blend of starch/poly(sodium acrylate) has been studied by high-resolution solid-state C-13 NMR spectroscopy at room temperature. The result shows that the crystallinity of starch decreases greatly in the grafted and blended samples.

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To clarify the mechanism of organic-inorganic hybrid membrane formation by phase-inversion method, the thermodynamical and theological properties of PSF/TiO2 casting solution were investigated by the viscosity measurement and the triangle phase diagram, respectively. TiO2 introduction decreased the non-solvent tolerance of casting solution with non-solvent 20% ethanol aqueous solution, which caused thermodynamic enhancement of phase separation, and also resulted in the change of theological properties from Newtonian fluid to non-Newtonian fluid and the viscosity increase of casting solution, which induced rheological hindrance in demixing process

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By incorporating self-consistent field theory with lattice Boltzmann method, a model for polymer melts is proposed. Compared with models based on Ginzburg-Landau free energy, our model does not employ phenomenological free energies to describe systems and can consider the chain topological details of polymers. We use this model to study the effects of hydrodynamic interactions on the dynamics of microphase separation for block copolymers. In the early stage of phase separation, an exponential growth predicted by Cahn-Hilliard treatment is found. Simulation results also show that the effect of hydrodynamic interactions can be neglected in the early stage.

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Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 degrees C, above the critical temperature, the amounts of PMMA and SAN phases were comparable.

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An improved free energy approach Lattice Boltzmann model(LBM) is proposed by introducing a forcing term instead of the pressure tensor. This model can reach the proper thermodynamic equilibrium after enough simulation time. On the basis of this model, the phase separation in binary polymer mixtures is studied by applying a Flory-Huggins-type free energy. The numerical results show good agreement with the analytic coexistence curve. This model can also be used to study the coarsening of microdomains in binary polymer mixtures at the early and intermediate stages.

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In this Letter, we report the morphological transition of dry block copolymer vesicles into onion-like multilamellar micelles induced through heating. When the temperature is higher than the glass transition temperature of block copolymer, the vesicles can collapse, and finally form onion-like multilamellarmicelles via micro phase separation. This phenomenon is observed in both A-B and A-B-A block copolymer vesicles, indicating that the technique used in this study can be an alternative method to synthesize multilamellar micelles.

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Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.