Fractal Dimensions of κ-Carrageenan Gels during Gelation and Swelling

A photon scattering technique for research on the sol-gel and gel-sol transitions in κ-carrageenan-water systems with various carrageenan contents (CC) was utilized for characterizing the fractal dimensions during gelation and swelling. It was observed that the scattered photon intensity, I_sc, increased at all temperatures with an increase in the CC when I_sc was monitored against temperature. Additionally, the sol-gel transition temperatures were found to be much lower than the gel-sol transition temperatures, causing hysteresis of the phase transition loops. I_sc increased with an increase in CC at all test temperatures, which is attributed to the formation of a fractal-like carrageenan gel. After drying, the gels were used in swelling experiments where the gels were immersed in water at room temperature, reswelling to the original structure. It was observed that I_sc from the carrageenan gels increased as the CC was increased. The fractal dimension, d, during gelation was found to increase as the gelation temperature was increased. On the other hand, the d values during swelling decreased as the swelling time was increased.     

Magnetic resonance elastography and diffusion-weighted imaging of the sol/gel phase transition in agarose

The dynamics of the sol/gel phase transition in agarose was analyzed with magnetic resonance elastography (MRE) and diffusion-weighted imaging, providing complementary information on a microstructural as well as on a macroscopic spatial scale. In thermal equilibrium, the diffusion coefficient of agarose is linearly correlated with temperature, independent of the sol/gel phase transition. In larger agarose samples, the transition from the sol to the gel state was characterized by a complex position and temperature dependency of both MRE shear wave patterns and apparent diffusion coefficients (ADC). The position dependency of the temperature was experimentally found to be qualitatively similar to the behavior of the ADC maps. The dynamics of the temperature could be described with a simplified model that described the heat exchange between sol and gel compartments. The experiments supported the approach to derive temperature maps from the ADC maps by a linear relationship. The spatially resolved dynamics of the temperature maps were therefore employed to determine the elasticities. For this reason, experimental MRE data were simulated using a model of coupled harmonic oscillators. The calculated images agreed well with the experimentally observed MRE wave patterns.     

A two-compartment gel phantom for optimization and quality assurance in clinical BOLD fMRI

Clinical applications of blood oxygen level-dependent (BOLD) functional magnetic resonance imaging (fMRI) depend heavily on robust paradigms, imaging methods and analysis procedures. In this work, as a means to optimize and perform quality assurance of the entire imaging and analysis chain, a phantom that provides a well known and reproducible signal change similar to a block type fMRI experiment is presented. It consists of two gel compartments with slightly different T2 that dynamically enter and leave the imaged volume. The homogeneous gel in combination with a cylindrical geometry results in a well-defined T*2 difference causing a signal difference between the two compartments in T*2-weighted MR images. From time series data obtained with the phantom, maps of percent signal change (PSC) and t-values are calculated. As an example of image parameter optimisation, the phantom is demonstrated to be useful for accurate determination of the influence of echo time (TE) on BOLD fMRI results, taking the t-value as a measure of sensitivity. In addition, the phantom is proposed as a tool for quality assurance (QA) since reproducible time series and t-maps are obtained in a series of independent repeat experiments. The phantom is relatively simple to build and can therefore be used by any clinical fMRI center.     

Patchy胶体粒子的结晶、玻璃化和凝胶化问题

本文探讨了中性多缔合位点Patchy胶体粒子系统的相图及其相关问题. 在研究中,计入了分子间的硬芯Lennard-Jones势和缔合作用,进而阐明了系统的流体相(F),无规密积相(RCP)和面心立方相(FCC)之间转变的相态结构. 在体系丰富的相结构中,F-F,F-RCP及F-FCC相转变以及描述粒子间联结性的溶胶-凝胶转变相互影响,致使一些相态在不同相互作用强度时可以呈现亚稳态和稳态. 同时,本文重点阐述了缔合能量以及patch数目对体系的临界温度、临界密度、临界三相点以及溶胶-凝胶转变等的调控机制.     

Study on the propagation of coupling shock waves with phase transition under combined tension-torsion impact loading

Phase transition can strongly change the stress wave propagation features. In this paper, the characteristic wave propagation under combined tension and torsion impact loading was studied with a simplified constitutive model of phase transition considering both pressure and shear stress. The results showed that for loading from the austenitic phase to the mixed phase, the wave propagation was similar to that in the elasto-plastic materials. However, for an instantaneous loading from the austenitic phase or mixed phase directly to the martensitic phase, a coupling shock wave (CSHW) with phase transition was predicted due to the second phase strengthening effect, which has barely been studied before. Through analysis of the constitutive equations with phase transition and the discontinuity conditions of shock waves, the control equations of the generalized Hugoniot curve was obtained and the CSHW problem with phase transition was solved analytically. An independent numerical simulation of step loading along a NiTi thin walled tube suffering a combined tension-torsion impact loading was given to prove the existence of CSHW. The simulation discloses the formation mechanism of CSHW and the adjusting process of the stress state ahead of CSHW, which reflects the intrinsic characteristic of materials with strong nonlinear constitutive behavior.     

Probing the Sol-Gel Transition in SiO2 Hydrogels—A New Application of Near-Infrared Fluorescence

Picosecond time-resolved fluorescence spectroscopy has enabled us to use a near-infrared fluorescent dye to probe the sol-gel transition in SiO₂ hydrogels, polymerized from sulfuric acid and sodium silicate solution, for the first time. We compare the microviscosity surrounding the probe during the sol-to-gel transition as predicted by two alternative models which both describe the decay of fluorescence anisotropy well. The results for one rotational time and a residual anisotropy imply that macrogelation of the sol leads to relatively small changes in the mobility of the fluorophore caused by small changes in microviscosity, but after much longer times, e.g., 1500 min, the mobility of the fluorophore decreases, reflecting a rapid increase in microviscosity of over several orders in magnitude. In sharp contrast, analysis of the anisotropy in terms of two rotational times predicts little change in microviscosity over the whole polymerization process.     

琼脂糖凝胶/纳米金复合结构的制备及其表面增强拉曼性质

以琼脂糖凝胶为模板,将预先制备好的胶体金颗粒负载在琼脂糖凝胶的网状结构中,制备了琼脂糖凝胶/纳米金复合膜结构,采用透射电子显微镜、扫描电子显微镜、紫外-可见-近红外光谱仪对复合膜的结构和光学性质进行了表征,实验数据表明纳米金颗粒均匀的分散在琼脂糖凝胶膜上,并且呈现出优异的光学吸收特性。基于琼脂糖凝胶的溶胀收缩特性和纳米金颗粒可调的表面等离子体共振吸收特性,将琼脂糖凝胶/纳米金复合膜作为表面增强拉曼(SERS)基底材料,研究了其对拉曼信号分子尼罗蓝A(NBA)的SERS检测效果。结果表明,琼脂糖凝胶的多孔网状结构为纳米金颗粒的富集提供了良好的载体,随着琼脂糖凝胶在空气中失水收缩,纳米金颗粒间距离逐渐缩短,产生动态的热点效应,对拉曼信号分子具有良好的增强效应。     

Dynamic Mechanical Behavior of Ordered Off-Stoichiometric Polyurethane Systems at the Gel Point Threshold

Dynamic mechanical and thermal behavior of ordered off-stoichiometric polyurethane (PU) systems, before and after the gel point, based on the mesogenic diol 6,6′;-[ethylenebis(1,4-phenyleneoxy)]dihexan-1-ol (D),2(4)-methyl-1,3-phenylene diisocyanate (DI), and poly(oxypropylene)triol (T) were studied. Polymer samples were prepared at various initial molar ratios of the reactive groups, r = [OH]_T/[NCO]_DI/[OH]_D, ranging from 1/10/9 to 5/10/9 (the ratio [NCO]_DI/[OH]_D = 10/9 was constant); the total mole ratio of hydroxy (OH) and isocyanate (NCO) groups, rOH = [OH]/[NCO] = ([OH]_D)/[NCO]_DI,changed from 1 to 1.4. Dynamic mechanical measurements during the curing reaction showed that the power law parameters that characterize the critical gel state (gel strength S and relaxation exponent n) are dependent on the initial composition (the ratio r _OH). The gel-point critical ratio of reactive groups r^c _OH, found during curing in the ordered state of the diol (at low curing temperature), has revealed that the critical gel (CG) structure is determined by a contribution of strong physical interactions as well as chemical junctions and does not correspond to pure chemical gelation (CG structure formed at low temperature exhibits flow at elevated temperatures in the isotropic state). This fact suggests that formation of the mesophase enhances the connectivity of the molecular structure at the gel point. Dynamic mechanical behavior of fully cured chemical networks (r _OH < r _OH ^c ) and un-cross-linked (r _OH > r _OH ^c ) samples (and a CG sample) has also been investigated. Decreasing the r_OH ratio (increasing concentration of chemical cross-links in the systems) inhibits conformational rearrangements required for ordering; at the same time, the intensity of the slow relaxation process in the rubbery region decreases.     

Gelation and dynamic mechanical behavior of liquid crystalline networks

The dynamic mechanical behavior of polyurethane networks based on liquid crystalline (LC) diol, 6,6′-[ethylenebis(1,4-phenyleneoxy)]dihexanol (D), 2(4)-methyl-1,3-phenylene diisocyanate (DI), and poly(oxypropylene)triol (T) at the stoichiometric molar ratio of isocyanate (NCO) and hydroxy (OH) groups was studied. Samples were prepared at various initial molar ratios of the reactive groups [OH]_T/[NCO]_DI/[OH]_D from 1/1/0 to 1/40/39. The gelation studies during the curing reaction in the LC and isotropic states showed that the critical gel structure at the sougel transition exhibits a power-law mechanical behavior; the relaxation exponent in the LC state is always higher than that in the isotropic state. From viscoelastic results, it follows that formation of the LC mesophase enhances the connectivity of the molecular structure at the gel point. Introduction of chemical cross-links in fully cured networks reduces the flexibility of the elastically active network chains (EANCs) and inhibits conformational arrangements required for LC ordering. Increasing the content of LC diol in networks, which leads to an increase of the length of EANCs, increases the concentration of permanent physical interactions (trapped entanglements) in the systems; the intensity of the slow relaxation process in the rubbery region also increases.     

在NaCl和HTAB共存条件下甲基纤维素溶液凝胶化行为

利用流变仪研究了甲基纤维素(MC)溶液在NaCl、十六烷基三甲基溴化铵(HTAB)以及两者共存下MC溶液的凝胶化行为,发现其凝胶化温度随着NaCl浓度的增加而下降,随着HTAB浓度的增加而上升;但是MC/NaCl的凝胶化温度保持不变,与HTAB浓度无关,而MC/HTAB溶液的凝胶化温度则随着NaCl浓度的增加而下降．以上的实验结果表明,在NaCl存在下,HTAB将被诱导形成胶束,因此MC/NaCl的凝胶化温度保持不变;反之,当NaCl不存在时,HTAB将优先吸附到MC上而不会在溶液中形成胶束,尽管其浓度     

Low temperature channeling measurements of ion implantation lattice disorder in single crystal silicon

Lattice disorder for 200-keV Sb implantations into silicon has been studied by channeling effect analysis using 400 keV proton backscattering. Implantation and analysis were performed at low temperatures in the same system without warmup. In the temperature region between 85°K and room temperature the disorder production per incident ion at low doses is implantation temperature dependent. Approximately 18,000 silicon scattering centers per incident 200-keV Sb ion are observed for 90°K implantations, and this value is nearly a factor of three greater than at room temperature. Isochronal anneal curves of low fluence, low temperature implantations show, significant annealing below room temperature. The observed disorder production per incident ion decreases with increasing implantation temperature at temperatures 50 to 100°K lower than annealing occurs following 85 or 90°K implants. Strong similarities of the implantation temperature dependence and anneal behavior of the disorder exist for Sb and B implantations into silicon and suggest that much of the lattice disorder produced by ion implantation can be understood in terms of the basic properties of the silicon target material.     

钙钛矿锰氧化物La0.7Sr0.3MxMn1-xO3(M=Cr,Fe)的巨磁电阻效应与磁性

研究了溶胶 -凝胶法制备氧化物巨磁电阻材料的工艺 ,制备了La0 .7Sr0 .3 CrxMn1-xO3 (x =0 ,0 .10 ,0 .15 )和La0 .7Sr0 .3 FexMn1-xO3 (x =0 .0 5 ,0 .10 ,0 .16 )两系列的单相钙钛矿锰氧化物多晶样品 ,并研究了Cr ,Fe替代La0 .7Sr0 .3 MnO3 中部分Mn后对其结构、磁性和巨磁电阻性质的影响 .观察到La0 .7Sr0 .3 Cr0 .15Mn0 .85O3 和La0 .7Sr0 .3 Fe0 .0 5Mn0 .95O3 两个样品的电阻 温度曲线都出现了双峰 .定性讨论了可能产生双峰的机制 .随Cr(或Fe)替代量的增加 ,材料的居里温度很快下降 ,铁磁性减弱 ,导电性降低 ,巨磁电阻效应增强 .但与Fe掺杂相比 ,相同数量的Cr掺杂对材料的影响要小 .     

一步法紫外曝光制备TiO2光敏凝胶光栅的初步研究

 以钛酸丁酯和苯甲酰丙酮为原料,经sol-gel工艺,获得具有负性光刻胶性质的TiO₂光敏凝胶薄膜。它的敏感波长在360nm附近,与反应生成的螯合环有关。结合掩模曝光和显影工艺,将条状或网格状的光栅图形引入光敏凝胶表面,获得光敏凝胶光栅。     

Transitions in a Logistic Growth Model Induced by Noise Coupling and Noise Color

With unified colored noise approximation, the logistic growth model is used to analyze cancer cell population when colored noise is included. It is found that both the coupling between noise terms and the noise color can induce continuous first-order-like and re-entrance-like phase transitions in the system. The coupling and the noise color can also increase tumor cell growth for small number of cell mass and repress tumor cell growth for large number of cell mass. It is shown that the approximate analytic expressions are consistent with the numerical simulations.     

Transitions in a Logistic Growth Model Induced by Noise Coupling and Noise Color

With unified colored noise approximation, the logistic growth model is used to analyze cancer cell population when colored noise is included. It is found that both the coupling between noise terms and the noise color can induce continuous first-order-like and re-entrance-like phase transitions in the system. The coupling and the noise color can also increase tumor cell growth for small number of cell mass and repress tumor cell growth for large number of cell mass. It is shown that the approximate analytic expressions are consistent with the numerical simulations.     

钛酸钡铅纳米晶的结构和Raman光谱研究

以醋酸钡、醋酸铅和钛酸丁酯为原料,醋酸和甲醇为溶剂,采用溶胶-凝胶工艺制备了不同晶粒大小的掺铅(5mol%)钛酸钡(BPT)纳米晶。用XRD、TEM和Raman研究了BPT样品的晶粒大小、结构及其相变特性。结果表明BPT纳米晶最低晶化温度为550℃,高于650℃热处理的纳米晶BPT在常温下为四方相。随着晶粒尺寸的减小,BPT纳米晶由四方相向立方相过渡。     

虚功原理与义坐标

指出所选广义坐标使平衡点成为虚位移,进而成为广义力的奇点是导致“广义力”在平衡点上不为零的原因,而不是虚功原理本身的问题。     

模型化研究高分子凝胶体积相变中的共非溶性作用

基于Flory-Huggins理论,我们建立理论模型,研究在共非溶剂(CNS)中,高分子凝胶(PG)体积相变中的共非溶性作用.理论模型考虑PG中CNS的桥接作用、各种分子的混溶效应.研究发现,当CNS与高分子单体间的吸引强度较小时,CNS与高分子单体间桥接作用的减弱,会导致PG体积相变.当CNS与高分子单体间的吸引作用强度较大时,随着CNS与高分子单体间桥接作用的减弱,PG的体积分数呈现两次台阶式的转变,表明PG体系出现两次体积相变.这是由于桥接作用的减弱,虽然会有部分CNS分子被排挤出PG,但是并未完全消除CNS与高分子单体间的桥接吸引作用.所得理论结果符合实验观测,由此表明了共非溶性作用会在很大程度上调控PG的相变行为.     

First-principles calculations of structure and high pressure phase transition in gallium nitride

The phase transitions of semiconductor GaN from the Wurtzite (WZ) structure and the zinc-blende (ZB) structure to the rocksalt (RS) structure are investigated by using the first-principles plane-wave pseudopotential density functional method combined with the ultrasoft pseudopotential scheme in the generalized gradient approximation (GGA) correction. It is found that the phase transitions from the WZ structure and the ZB structure to the RS structure occur at pressures of 46.1 GPa and 45.2 GPa, respectively. The lattice parameters, bulk moduli and their pressure derivatives of these structures of GaN are also calculated. Our results are consistent with available experimental and other theoretical results. The dependence of the normalized formula-unit volume $V/V_{0 }$ on pressure $P$ is also successfully obtained.