小角x射线散射法研究甲基改性氧化硅凝胶的双分形结构

以正硅酸乙酯［Si(OC2H5)4,TEOS］和甲基三乙氧基硅烷［CH3Si(OC2H5)3,MTES］为前驱体，通过共水解法和两步法制备出两种不同的甲基改性氧化硅凝胶，在北京同步辐射光源(BSRF)小角x射线散射(SAXS)站测量了凝胶的散射强度，计算了凝胶的平均粒径、两相间比表面积等参数，在此基础上分析了凝胶的分形特征，发现存在两个尺度上的分形结构，分别对应于从SiO2原生颗粒到一次团聚体和从一次团聚体到簇团两种尺度.辅以透射电子显微镜(TEM)观测，证实由两种方法获得的凝胶具有非常不同的微观结构.实验证明，利用SAXS技术研究甲基改性凝胶的分形特征是获得凝胶微观结构的有力工具. 关键词： 甲基改性凝胶 氧化硅 小角x射线散射(SAXS) 分形结构     

两亲性嵌段聚合物的同步辐射小角x射线散射研究

应用同步辐射小角x射线散射(SAXS)方法研究了不同聚合条件下苯乙烯对乙烯基苯甲酸两亲性嵌段聚合物的聚集行为,结果发现该聚合物在选择性溶液中自组装形成胶束.胶束的形态和结构取决于嵌段聚合物的组成、浓度以及溶剂的性质等因素 关键词： 小角x射线散射 两亲性嵌段聚合物 分形维数 粒径     

用SAXS和XRD方法研究Ti02纳米颗粒微观结构

用溶胶一凝胶方法制备了TiO2纳米样品.并对该样品在300℃到800℃温度区域进行了退火处理.应用同步辐射x射线粉未衍射(XRD)方法研究了经不同热处理温度的TiO2纳米颗粒的结构相变.应用同步辐射小角x射线散射(SAXS)方法研究了TiO2纳米颗粒的表面分形与界面特性.得到纳米颗粒粒度与退火温度的变化规律,讨论r表面界面特征与相变的关系.     

水分子凝胶中有机凝胶因子聚集体的分形结构研究

水分子凝胶是一种新型软凝聚体系.是凝胶因子在很低的浓度下在水中聚集、自组装，使水凝胶化形成的凝聚体系.透射电镜(TEM)表明凝胶因子在水中聚集、自组装成细纤维状结构.通过对TEM照片进行数字化处理，采用Sandbox法和密度-密度相关函数法计算的结果表明凝胶因子在聚集组装过程中具有典型的分形特征.根据C++程序计算出分形维数D＝1.814—1.977.以分形理论对凝胶因子的聚集过程以及由此形成的水分子凝聚体系的分形特征进行了讨论.利用小角x射线散射(SAXS)研究进一步表明，凝聚体系的分形结构存在于尺度α 关键词： 分形 凝胶因子 水分子凝聚体系 透射电镜(TEM) 小角x射线散射(SAXS)     

用SAXS和XRD方法研究TiO2纳米颗粒微观结构

用溶胶-凝胶方法制备了TiO₂纳米样品,并对该样品在300℃到800℃温度区域进行了退火处理.应用同步辐射X射线粉末衍射(XRD)方法研究了经不同热处理温度的TiO₂纳米颗粒的结构相变.应用同步辐射小角X射线散射(SAXS)方法研究了TiO₂纳米颗粒的表面分形与界面特性.得到纳米颗粒粒度与退火温度的变化规律,讨论了表面界面特征与相变的关系. 关键词： X射线小角散射 X射线衍射 2纳米颗粒')" href="#">TiO₂纳米颗粒     

同步辐射SAXS技术在TATB含能材料微孔结构研究中的初步应用

TATB含能材料的微结构对该材料的感度等有明显的影响,因而对于材料的安全性有着特别重要的意义.小角X射线散射(SAXS)技术是一种分析物质微观结构的重要手段,应用SAXS分析技术可以获取材料中几纳米到几百纳米尺度范围的亚微结构信息.利用同步辐射作为X射线源对TATB钝感炸药进行了小角散射实验测量,获得了SAXS测量谱.对实验谱数据进行处理,可得到样品材料的颗粒分布及内部微孔大小等微结构参数.     

利用x射线小角散射技术研究微晶硅薄膜的微结构

采用x射线小角散射（SAXS）技术研究了由射频等离子体增强化学气相沉积（rf-PECVD）、 热丝化学气相沉积(HWCVD)和等离子体助热丝化学气相沉积(PE-HWCVD)技术制备的微晶硅（ μc-Si:H）薄膜的微结构.实验发现，在相同晶态比的情况下，PECVD沉积的μc-Si:H薄膜微 空洞体积比小，结构较致密，HWCVD沉积的μ-Si:H薄膜微空洞体积比大，结构较为疏松，PE -HWCVD沉积的μc-Si:H薄膜，由于等离子体的敲打作用，与HWCVD样品相比，微结构得到明 显改善.采用HWCVD二步法和PE-HWCVD加适量Ar离子分别沉积μc-Si:H薄膜，实验表明，微结 构参数得到了进一步改善.45°倾角的SAXS测量显示，不同方法制备的μc-Si:H薄膜中微空 洞分布都呈各向异性.红外光谱测量也证实了SAXS的结果. 关键词： 微晶硅薄膜 微结构 微空洞 x射线小角散射     

用小角X射线散射法研究溶胶结构

采用溶胶凝胶方法在碱性条件下制备了SiO2和ZrO2溶胶,应用同步辐射小角X射线散射(SAXS)法研究了溶胶的结构.结果表明,溶胶粒子是多分散的,其生长、聚集受RLCA和Eden模型的共同控制,是一种非线性的动力学过程,所形成的聚集体呈随机、分岔、稠密不同的结构,具有质量分形的特征.同时还发现所研究溶胶的散射曲线均不遵守Porod定理,形成负偏离或正偏离,这说明在溶胶粒子与分散介质间有过渡相存在.对上述偏离进行了定性和定量的分析,提出了正偏离时的定量解析方法,从而得到了胶体系统中有关过渡层(界面层)结构的 关键词：     

利用小角X射线散射技术研究组分对聚酰亚胺/Al2O3杂化薄膜界面特性与分形特征的影响

采用溶胶-凝胶方法制备无机纳米杂化聚酰亚胺(PI),应用同步辐射小角X射线散射(SAXS)方法研究不同组分杂化PI薄膜的界面特性与分形特征.研究结果表明:散射曲线不遵守Porod定理,形成负偏离,说明薄膜中有机相与Al₂O₃纳米颗粒间存在界面层,界面层厚度在0.54 nm到1.48 nm范围内;随无机纳米组分增加,界面层厚度增加,有机相与无机相作用变强;无机纳米颗粒同时具有质量分形和表面分形特征,其分布、集结是一种非线性动力学过程;随组分增加,其质量分形维数降低 关键词： 小角X射线散射 纳米杂化 聚酰亚胺 界面     

纳米团聚生长的多重分形谱

采用小角x射线散射（SAXS）方法，对两类具有代表性的纳米团聚的生长分形进行了表征.一 类为用化学方法 (水合肼溶液还原法) 制备的纳米金属Ni粉；另一类通过物理方法(纳米晶 化处理)，由非晶基体相中生长纳米晶相、形成非晶/纳米晶双相结构的Finemet (Fe_{73 .5} Cu₁Nb₃Si_13.5B₉) 合金.上述两 类材料的纳米团聚在生长过程中都存在 明显元素扩散迁移，形成在1—100 nm范围内的元素分布非均匀区域.这些元素分布的非均匀 区域具有多重质量生长分形特征，其尺度大小和分布方式对最终的材料的物理性能至关重要 .SAXS方法是表征这类具有分形生长特征的纳米团聚微观结构信息的强有力手段.从方法论的 角度详述了从SAXS测量到获得多重分形谱的处理过程，这一实验研究分析手段对于定量考察 纳米微结构形貌的生长机理和性能的其他研究课题有一定的帮助作用. 关键词： 纳米材料 分形生长 小角x射线散射 磁性材料     

催化剂对SiO2凝胶结构及复合体系发光性能的影响

用溶胶—凝胶的方法制备了染料掺杂的SiO2凝胶复合体系。无机基质制备过程中的各种条件对无机基质的微结构有很大影响,从而对复合材料的性能有很大影响。大量的研究表明,凝胶制备过程的诸多因素如催化剂、水的加入量及凝胶的后处理等因素影响最大,这些因素对凝胶结构的影响已有系统的研究,但其对有机—无机复合体系发光影响的研究还未多见。详细研究了在其他条件不变的情况下酸碱催化条件对复合体系结构及染料发光性能的影响。香豆素102(C102)在不同状态下的荧光分析表明,无论是碱还是酸催化所得薄膜复合材料,C102分子在其中基本都以单体的形式存在,与在溶液中相比发光移向短波。碱催化的样品其结构更有利于染料以单体的形式存在,但碱催化的膜表面粗糙,结构疏松,而酸催化的膜表面平整,结构致密。所以以HCl为催化条件的样品适合更进一步的应用。     

Repeated sorption of water in SBA-15 investigated by means of in?situ small-angle x-ray scattering

The effect of repeated cycles of water adsorption/desorption on the structural stability of ordered mesoporous silica SBA-15 is studied by small-angle x-ray scattering (SAXS). In?situ sorption measurements are conducted using a custom-built sorption apparatus in connection with a laboratory SAXS setup. Two striking irreversible changes are observed in the sorption isotherms as derived from the integrated SAXS intensity. First, the capillary condensation pressure shifts progressively to lower relative pressure values with increasing number of sorption cycles. This effect is attributed to chemisorption of water at the silica walls, resulting in a change of the fluid-wall interaction. Second, the sorption cycles do not close completely at vanishing vapour pressure, suggesting that progressively more water remains trapped within the porous material after each cycle. This effect is interpreted to be the result of an irreversible collapse of parts of mesopores, originating from pore wall deformation due to the large Laplace pressure of water acting on the pore walls at capillary condensation and capillary evaporation.     

Loading channels of SiO 2 mesoporous matrices with Fe oxides

After embedding hematite nanowires (15 wt.% Fe) into a MCM-41 hard template, we have explored alternative routes to induce the structural transformations that lead from hematite to maghemite and magnetite embedded nanowires. The impregnation media (ethanol or water) and the calcination atmosphere (air and NO/He) on the hematite nanowires production play a significant role at the time of reducing and re-oxidizing the embedded hematite nanoparticles. The solids were characterized by X-ray diffraction, nitrogen adsorption, and Mössbauer spectroscopy. The results indicate that the effect of the solvent on the structural properties of the iron species is more important than the calcination atmosphere. The best conditions for iron magnetic nanowires not to get outside of the MCM-41 channels over the treatments are reached using water as the solvent and air as the calcination atmosphere. When ethanol is the solvent used over the preparation step, the end iron oxides are in the form of nanotubes spread out on the amorphous silica walls of the matrix.     

Iron oxide nanoparticles hosted in silica aerogels

The investigated hybrid materials consist of non-agglomerated iron oxide particles hosted in silica aerogels. The composite material can be produced as a monolith, in any shape, and with different dilutions of the iron oxide phase. Two sol–gel chemistry routes have been followed: a solution of Fe(NO₃)₃·9H₂O has been added either to the silica gel or to the initial sol; in the latter, the iron salt provided the water required for the gel polymerisation. To obtain monolithic aerogels, the gels were dried by hypercritical solvent evacuation. On the other hand, some gels were dried by slow and controlled evaporation of the solvent, resulting in xerogels. Several heat treatments have been performed and the iron oxide particle phase, growth mechanism and crystallinity have been analysed. The composite materials were characterised by means of X-ray diffraction, M?ssbauer spectrometry and superconducting quantum interference device magnetometry. It was observed that the particle sizes (in the nanometre range) and the thermal stability of the iron oxide phases strongly depend on the preparation method that determines the microstructure of the host material. Consequently, the magnetic properties of the nanoparticles can be controlled via synthesis conditions, matrix properties and thermal treatments. Received: 5 March 2001 / Accepted: 16 June 2001 / Published online: 30 August 2001     

Preparation of almost dispersant-free colloidal silica with superb dispersiblility in organic solvents and monomers

Surface modification of silica nanoparticles synthesized by the sol–gel process was performed using coupling agents, 3-(trimethoxysilyl) propyl methacrylate (MSMA) and/or trimethyethoxylsilane (TMES). The chemical structures of the formed particles were analyzed by means of Fourier Transform Infrared Spectroscopy (FTIR) and solid-state Si-Nuclear Magnetic Resonance (Si-NMR), and the particle sizes were determined by Transmission Electron Microscopy (TEM) imaging. The latter results indicate that such surface modifications can effectively lessen the serious aggregation being common to pure silica nanoparticles. In some cases, separate particles of ca. 5–10 nm dia. could be obtained, when both MSMA and TMES were employed during the modification process. Dynamic light scattering method was adopted to examine the stability of the prepared silica sols during a long-term storage. It was found that the aggregation phenomenon can essentially be eliminated in case that the surface of silica contained sufficient amount of TMES moiety. Vacuum distillation was used to remove the volatile components such as methanol, ethanol, and water from the silica sol. The condensed product, containing 2 wt% residual solvent, appeared as a uniform transparent paste-like material, which can be dispersed in common organic solvents and monomers within a few seconds.     

沉降介质对单分散SiO2微球重力组装欧泊模板的影响

 以氨水作催化剂、正硅酸乙酯为硅源、乙醇为溶剂,采用改进溶胶-凝胶法制备了系列单分散SiO₂微球,研究了平均粒径为250,280,320 nm单分散SiO₂微球在水、无水乙醇、丙酮等介质中的沉降与自组装过程。还对单分散体系重力沉降组装欧泊模板的形成机理进行了讨论。SEM表明,微球在无水乙醇和丙酮沉降介质中均能组装形成3维有序密堆积结构的欧泊,但在无水乙醇中要优于在丙酮中。沉降速度实验表明,相同粒径的单分散SiO₂微球在水、乙醇、丙酮作为沉降介质中的沉降速度相差并不大,沉降介质对重力水平沉降组装模板的影响主要是由于其表面张力与粘度不同造成的。     

Self—assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small—angle x—ray scattering

The aggregation behaviour of styrene-vinyl benzoic acid (PS_m-b-PVBA_n) amphiphilic diblock copolymers in selective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We have carried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymers of narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found that the aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms flat disc objects with the ratio of radius ω=0.4. The average radius gyration R_g of the copolymer decreases as solvents change from isopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with the addition of CoCl_2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h)∝h^{-α} in different selective solutions, suggesting that the PS_m-b-PVBA_n coils have self-similar structure behaviour or a fractal structure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changes dramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (D_m) from 2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course of changing solvents, decreasing surface fractal dimension (D_s) from 2.98 to 2.58 indicates that the copolymer micelle change from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasing D_m and D_s from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rather compact and rough disc form by adding CoCl_2 in ethanol solvents.     

Effect of polyvinylpyrrolidone on the structure and laser damage resistance of sol–gel silica anti-reflective films

The effect of polyvinylpyrrolidone (PVP) on the structure and laser-induced damage threshold (LIDT) of sol–gel silica anti-reflective films is investigated. The results of dynamic light scattering, transmission electron microscopy, and small angle X-ray scattering, show that the PVP molecules surrounded the silica sol particles through the strong hydrogen bonds between Si-OH groups and the PVP. As a result, the growth of silica particles was restricted and thus the interface layer between the silica particles and the solvent become thickened with PVP content. Furthermore, the PVP reduced the porosity of the film, so the anti-reflection properties of the film were weakened. A multi-fractal analysis showed that the appropriate addition of PVP, 1 weight percent (wt%), could improve the surface fractal structure of the film, but that higher PVP content resulted in reduced surface uniformity. The addition of PVP lead to improved LIDT.     

明胶水溶液分形性质的光散射研究

本文通过动态光散射技术并结合静态光散射及粘滞系数实验研究了明胶水溶液在不同温度、不同浓度下的分形性质。当Ｔ＞Ｔｇｅｌ时（Ｔｇｅｌ为胶凝临界温度），水为明胶的良好溶剂。明胶分子在水溶液中符合自避无规行走模型，分维ｄｆ＝５／３。当Ｔ＜Ｔｇｅｌ时，明胶水溶液需经历从溶液到凝胶的胶凝过程。在胶凝过程中，动态光散射弛豫谱分段具有指数衰减和随后的伸展指数两种模式，且伸展指数衰减的宽度参数β逐渐从０．８减少到胶凝点的０．６７，与此相对应，分维由５／３逐渐增加到２．０。在胶凝点，通过静态光散射及粘滞系数实验测得分维为２．０。     

PVA–APTEOS/TEOS Hybrid Sol–Gel Pervaporation Membrane for Dehydration of Ethanol

Novel organic–inorganic hybrid membranes were prepared by co-hydrolysis and co-condensation reactions of aminopropyltriethoxysilane (APTEOS) and tetraethylorthosilicate (TEOS) in poly(vinyl alcohol) (PVA) aqueous solution. These sol–gel reactions make a silica nanoparticles network which cross-links the structure of membranes. As a result, swelling properties of the membranes change due to these cross-linking reactions. The relative molar content of APTEOS to (APTEOS + TEOS) was changed from 0.0 to 0.75. The effect of APTEOS to (APTEOS + TEOS) on morphology as well as pervaporation performance of the membranes for dehydration of ethanol was investigated. It was found out that the hybrid membranes with a certain mass ratio of 1:1 (APTEOS + TEOS to PVA) exhibit higher permselectivity and more permeation flux for dehydration of ethanol aqueous mixtures compared with the PVA–TEOS membranes. Because hydrolysis and condensation reactions of mixed silanes make smaller silica nanoparticles, the permeability properties of the membranes improve in comparison with those of the membranes prepared using a single silane.