Effects of casting solvents on the formation of inverted phase in block copolymer thin films

Previously, an inverted phase (the minority blocks comprising the continuum phase) was found in solution-cast block copolymer thin films. In this study, the effect of casting solvents on the formation of inverted phase has been studied. Two block copolymers, poly(styrene-b-butadiene) (SB) (M-w = 73 930 Da) and poly(styrene-b-butadiene-b-styrene) (SBS) (M-w = 140 000 Da), with comparable block lengths and equal polystyrene (PS) weight fraction (similar to30 wt %) were used. The copolymer thin films were cast from different solvents, toluene, benzene, cyclohexane, and binary mixtures of benzene and cyclohexane. Toluene and benzene are good solvents for both PS and PB, but have a preferential affinity for PS, while cyclohexane is a good solvent for PB but a Theta solvent for PS (T-Theta = 34.5 degreesC). The differential solvent affinity for PS and PB was estimated in terms of a difference between the polymer-solvent interaction parameter, chi, for each block. Under an extremely slow solvent evaporation rate, the time-dependent phase behavior during such a solution-to-film process was examined by freeze-drying the samples at different stages, corresponding to different copolymer concentrations, rho.

Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We have investigated the inverted phase formation and the transition from inverted to normal phase for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer in solution-cast films with thickness about 300 nm during the process of the solution concentrating by slow solvent evaporation. The cast solvent is 1, 1,2,2-tetrachloroethane (Tetra-CE), a good solvent for both blocks but having preferential affinity for the minority PMMA block. During such solution concentrating process, the phase behavior was examined by freeze-drying the samples at different evaporation time, corresponding to at different block copolymer concentrations, phi. As phi increases from similar to 0.1 % (nu/nu), the phase structure evolved from the disordered sphere phase (DS), consisting of random arranged spheres with the majority PS block as I core and the minority PMMA block as a corona, to ordered inverted phases including inverted spheres (IS), inverted cylinders (IC), and inverted hexagonally perforated lamellae (IHPL) with the minority PMMA block comprising the continuum phase, and then to the lamellar (LAM) phase with alternate layers of the two blocks, and finally to the normal cylinder (NC) phase with the majority PS block comprising the continuum phase. The solvent nature and the copolymer solution concentration are shown to be mainly responsible for the inverted phase formation and the phase transition process.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

AlⅠ及UⅠ原子光电离截面相对论及非相对论理论计算

本文给出了在自洽场近似下,入射光子能量在x射线范围内(132.3～1500eV),使用相对论及非相对论计算AlI及UI原子壳层光电离截面及总截面。讨论了相对论效应及辐射场的多极展开对光电离截面数值的影响。

U原子光电离截面的理论计算

本文给出了U原子的HFS和Cooper势外壳层光电离截面的计算方法和计算结果。因为我们所编的Cooper模型势程序给出了从特定组态的某一个光谱项光电离的截面值,所以能将壳层相同、而所处的能级位置和光谱项不同的原子光电离截面值区别开。

GENERAL ALPHA-N INDEX AND ITS APPLICATION .1. GENERAL ALPHA-N INDEX AND ITS APPLICATION IN THE EXTRACTION OF Y, CE, U, AND TH BY NEUTRAL PHOSPHORUS EXTRACTANCTS

The general a(N) index is established for molecules containing heteroatoms, rings, and multiple bonds. The general a(N) index is able to describe molecules with minute differences in structure and can also reveal the properties of molecules. This theory is successfully applied to the case of neutral phosphorus extractants. Both the molecular polarity and steric effect are characterized by the general a(N) index. The relationships between these properties and the distribution ratios for extracting Y, Ce, U, and Th are also shown by the general a(N) index.

Sm和U原子光电离截面的模型势计算

本文给出了使用四种不同形式的势对Sm基态光学电子所属壳层光电离截面计算的结果,同时给出了U原子三个激发态参量形式的极化修正模型势光电离截面的计算结果.我们的结果与其他作者使用相同形式的势计算的结果较好地符合.使用参数形式的极化模型势计算光电离截面是一种有效的方法.

I~N电子组态谱项结构的U群方法

多电子原子或离子的光谱理论中,一个很重要的问题就是确定由于电子间相互作用所形成的光谱项。通常采用轨道角动量耦合,自旋角动量耦合以及泡里原理来确定.当电子数N和轨道角动量量子数l大时,要经过冗长而仔细的运算才能确定下来,相当麻烦。本文利用U群方法,给出确定l~N电子组态光谱项的一般方法,大大简化了程序和工作量。首先把U_(2l+1)群的不可约表示的基直接和l~N电子组态的光谱结构联系起来,并引入了不可约表示的分解规则,及给出单列表示相应光谱项的计算方法。使计算程序标准化。

广义α_N指数及其应用——Ⅰ.广义α_N指数及其在中性磷萃取剂萃取Y、Ce、U和Th性能方面的应用

首先引进一般有机化合物的广义a_N指数,该指数能分辨有微小结构差别的有机化合物分子。在此基础上,计算了某些中性磷萃取剂的广义a_N指数。并将其与萃取性能进行相关分析,得到了满意的结果。

Element enrichment and U-series isotopic characteristics of the hydrothermal sulfides at Jade site in the Okinawa Trough

The geochemical and U-series isotopic characteristics of hydrothermal sulfide samples from the Jade site (127A degrees 04.5'E, 27A degrees 15'N, water depth 1300-1450 m) at Jade site in the Okinawa Trough were analyzed. In the hydrothermal sulfide samples bearing sulfate (samples HOK1 and HOK2), the LREEs are relatively enriched. All the hydrothermal sulfide samples except HOK1 belong to Zn-rich hydrothermal sulfide. In comparison with Zn-rich hydrothermal sulfides from other fields, the contents of Zn, Pb, Ag, Cd, Au and Hg are higher, the contents of Fe, Al, Cr, Co, Ni, Sr, Te, Cs, Ti and U lower, and the Pb-210 radioactivity ratios and Pb-210/Pb ratios very low. In the hydrothermal sulfide mainly composed of sphalerite, the correlations between rare elements Hf and U, and Hf and Mn as well as that between dispersive elements Ga and Zn, are strongly positive; also the contents of Au and Ag are related to Fe-sulfide, because the low temperature promotes enrichment of Au and Ag. Meanwhile, the positive correlations between Fe and Bi and between Zn and Cd are not affected by the change of mineral assemblage. Based on the Pb-210/Pb ratios of hydrothermal sulfide samples (3.99x10(-5)-5.42x10(-5)), their U isotopic composition (U-238 content 1.15-2.53 ppm, U-238 activity 1.07-1.87 dpm/g, U-234 activity 1.15-2.09 dpm/g and U-234/U-238 ratio 1.07-1.14) and their Th-232 and Th-230 contents are at base level, and the chronological age of hydrothermal sulfide at Jade site in the Okinawa Trough is between 200 and 2000 yr.

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

Generation and evolution of magma beneath the East Pacific Rise: Constraints from U-series disequilibrium and plagioclase-hosted melt inclusions

Mid-ocean ridge basalt (MORB) samples from the East Pacific Rise (EPR 12 degrees 50'N) were analyzed for U-series isotopes and compositions of plagioclase-hosted melt inclusions. The Ra-226 and Th-230 excesses are negatively correlated; the Ra-226 excess is positively correlated with Mg# and Sm/Nd, and is negatively correlated with La/Sm and Fe-8; the Th-230 excess is positively correlated with Fe-8 and La/Sm and is negatively correlated with Mg# and Sm/Nd. Interpretation of these correlations is critical for understanding the magmatic process. There are two models (the dynamic model and the "two-porosity" model) for interpreting these correlations, however, some crucial parameters used in these models are not ascertained. We propose instead a model to explain the U-series isotopic compositions based on the control of melt density variation. For melting either peridotite or the "marble-cake" mantle, the FeOt content, Th-230 excess and La/Sm ratio increases and Sm/Nd decreases with increasing pressure. A deep melt will evolve to a higher density and lower Mg# than a shallow melt, the former corresponds to a long residence time, which lowers the Ra-226 excess significantly. This model is supported by the existence of low Ra-226 excesses and high Th-230 excesses in MORBs having a high Fe-8 content and high density. The positive correlation of Ra-226 excess and magma liquidus temperature implies that the shallow melt is cooled less than the deep melt due to its low density and short residence time. The correlations among Fe-8, Ti-8 and Ca-8/Al-8 in plagioclase-hosted melt inclusions further prove that MORBs are formed from melts having a negative correlation in melting depths and degrees. The negative correlation of Ra-226 excess vs. chemical diversity index (standard deviation of Fe-8, Ti-8 and Ca-8/Al-8) of the melt inclusions is in accordance with the influence of a density-controlled magma residence time. We conclude that the magma density variation exerts significant control on residence time and U-series isotopic compositions. (c) 2010 Elsevier B.V. All rights reserved.

中国北方风成堆积的风化作用与环境变迁—U-Th、~(10)Be及元素地球化学的研究

The surface of the Earth is continuously undergoing changes as a result of weathering-erosion, plate tectonics and volcanic processes. Continental weathering-erosion with its complex rock-water interactions is the central process of global biochemical cycling of elements, and affects the long-term ocean atmosphere budget of carbon dioxide both through the consumption of carbonic acid during silicate weathering and through changes in the weathering and burial rates of organic carbon. Rates of the weathering-erosion depend on a variety of factors, in particular rock properties and chemical composition, climate (especially rainfall), structure, and elevation. They are quite variable on a regional scale. Thus, environmental changes in a region could be indicated by the history of weathering-erosion in the region. Recent attention has focused on increased silicate weathering of tectonically uplifted areas in the India-Asia collision zone as a possible cause for falling atmospheric CO_2 levels in the Cenozoic era. The wind blown dust deposits in the Loess Plateau is derived from the arid and semiarid regions in northwestern China, in turn, where the deposits have been derived from the Qinghai-Xizang Plateau and the high mountains around. Therefore, geochemistry of the wind blown loess-paleosol and red clay sequences may provide insight both to paleoenvironmental changes on the Loess Plateau, and to the uplift and weathering-erosion histories of the Qinghai-Xizang Plateau. In this paper, uranium-thorium series nuclides and cosmogenic ~(10)Be have been employed as tracers of weathering intensities and histories of the dust sediments in the Loess Plateau. Major elements, such as Na, Al, Fe etc., are also used to estimate degree of chemical alteration of the dust sediments and to rebuild the history of weathering on the Loess Plateau. First of all, using a low-level HPGe γ-ray detector, we measured U and Th series nuclides in 170 loess and paleosol samples from five sites in the Loess Plateau, going back 2.6 Ma. The results show that ~(238)U activities are disequilibrium with its daughter nuclide ~(230)Th in young loess-paleosol sequence, indicating that weathering was happened both in dust deposition site and in dust source regions. Using concentrations of ~(238)U and ~(232)Th in the samples, we estimated the amounts of ~(238)U leached out of from paleosols due to weathering. Further, based on analyses of ~(230)Th in paleosols deposited in the past ca. 140 ka, we determined when the paleosols weathered in the source regions. We conclude that most of the weathering in the dust-source regions may have occurred during the interglacials before dust deposition.