单分散核-壳结构介孔二氧化硅微球的合成

在酸性条件下, 采用非离子表面活性剂嵌段共聚物为模板剂, 季铵盐阳离子表面活性剂为共导向剂, 在预先合成的尺寸均一的单分散实心氧化硅微球表面包裹了有序介孔氧化硅层, 进一步通过高温水热处理, 获得了具有良好分散性和均匀尺寸的介孔壳层(孔径7 nm)氧化硅微球(~500 nm). 氧化硅微球外部包裹的介孔壳层具有较大的比表面积(188 m2/g)和孔容(0.23 cm3/g).     

可用于色谱固定相的介孔氧化硅球材料的合成

采用非离子型嵌段高分子表面活性剂EO₂₀PO₃₀EO₂₀ (P65)为结构导向剂, 正硅酸乙酯为硅源, 在酸性介质中, 静置法制备了微米级介孔氧化硅球. 通过改变合成温度、反应时间或者无机盐KCl的加入量, 可以调节介孔氧化硅球的直径(9.0～17.6 μm); 加入1,3,5-三甲苯(TMB)或者调节水热温度, 可以调节介孔氧化硅球的孔径(2.3～4.8 nm). 采用X射线衍射(XRD)、N₂吸附-脱附、扫描电镜(SEM)、激光散射粒度分布和对溶菌酶的吸附等方法, 对介孔氧化硅球的结构、孔性质、形貌、吸附性质等进行了表征. 实验发现, 孔径较小的介孔氧化硅球(≤4.3 nm)对溶菌酶的吸附不明显(≤42 mg/g), 而孔径(4.8 nm)大于溶菌酶直径的材料对溶菌酶有较大的吸附量(192 mg/g), 说明孔径均匀可调的介孔氧化硅球材料可以很好地用作体积排阻色谱柱的固定相.     

十二烷基苯磺酸钠改性的尿素和甲醛聚合杂化法合成氧化硅微球

本文在存在十二烷基苯磺酸钠时利用正硅酸乙酯水解液中尿素和甲醛的结晶性聚合反应合成得到了氧化硅微球。首次考察了尿素和甲醛的物质的量比、尿素和甲醛的总用量、正硅酸乙酯(TEOS)用量、酸用量、以及十二烷基苯磺酸钠用量对所得氧化硅微球结构和形貌特征的影响。适当选择这些用量范围可以得到结构稳定、分散均匀的氧化硅微球。在微球生长中尿素和甲醛的量不足时,其突出的结晶性聚合与氧化硅杂化反应进程相互影响,导致了氧化硅微球核壳结构的形成。酸用量增加使氧化硅微球的孔径分布从复杂的双峰转变成均匀的单峰。表面活性剂的使用使氧化硅微球的孔分布从0～80 nm范围内的连续分布转化成单一分布。这些结果对正硅酸乙酯水解液直接合成氧化硅微球方法的推广和应用具有重要指导意义。     

功能性硅烷在纳米氧化硅表面的自组装

在分散体系中,两种功能性硅烷,甲基丙烯酰氧丙基三甲基硅烷(MPTES)和氨丙基三甲基硅烷(APTES)在纳米氧化硅表面形成自组装单分子层,用XPS 和FTIR对所得自组装单分子层进行了表征.元素分析结果表明,所得功能性纳米氧化硅中的功能基含量分别为1.03 mmol/g甲基丙烯酰氧基/丙烯酰氧丙基纳米氧化硅(MPSN)和3.34 mmol/g氨基/氨丙基纳米氧化硅(APSN).LSS 分析结果表明,未修饰纳米氧化硅、 MPSN和APSN在甲苯分散体系中的平均流体力学直径大约分别为240、 45和560 nm.     

二元阴阳离子表面活性剂法合成介孔氧化硅囊泡

以十二烷基磺酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)为表面活性剂, 在SDS与CTAB的摩尔比为1.0~2.3时, 以正硅酸乙酯(TEOS)为硅源, 在氨水-水体系中于68℃下合成介孔氧化硅囊泡. 通过透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 热重分析仪(TGA)和氮气吸附-脱附实验仪对合成的产物进行表征. 结果表明, 合成的产物为介孔氧化硅囊泡聚集体, 孔径约为4 nm, 样品的Brunauer-Emmett-Teller(BET)比表面积为826 m²/g. 对介孔氧化硅囊泡的形成机理做了初步探讨.     

预置粒子对均匀胶体粒子形成的影响

研究预置粒子对于均匀胶体粒子形成的影响,对深入了解均匀粒子的形成机理以及开拓覆盖技术的应用具有重要意义.所谓预置粒子就是在经升温陈化能够生成均匀胶体粒子的溶液中,于陈化前加入的具有一定形态(组成、形状和大小),一定浓度的胶体粒子,新形成的沉淀物因预置粒子的表面性质、形态和浓度的不同而变化.据文献报导,新沉淀的形成过程有:①新粒子的形成与预置粒子的存在无关,新沉淀物独立成核并成长为独立的稳定     

微米级SiO合成多孔氧化硅/硅/碳储锂复合材料

以微米级SiO为原料,通过简单的高温煅烧、碳包覆和酸刻蚀制备多孔氧化硅/硅/碳复合材料,复合材料比表面积和平均孔径分别为32.9 m~2/g和3 nm。纳米硅分散在缓冲介质氧化硅多孔体系中,表面包覆一层薄而均匀的碳层。所得的复合材料具有较好的循环稳定性,在0.3 m A/g下,50次循环后可逆容量保持在645.1 m A·h/g。多孔结构、氧化硅缓解了硅在脱嵌锂过程的体积膨胀,碳层提高了复合材料的导电性和结构稳定性。     

乙二醛存在时脲醛树脂的控制性聚合现象

考察了乙二醛存在时脲醛树脂的控制性聚合现象.聚合微球的粒径分散在1.0～14μm之间,但当乙二醛存在时粒径集中在6.5～9.0μm;控制乙二醛的用量和比例可以调整所得微球的大小、改善微球的形貌和均匀性.添加乙二醛或增加乙二醛的比例能大幅延长沉淀反应的诱导期(延长25%以上);红外分析以及XRD分析结果证明醛基总量或甲醛比例的增加都可减小聚合产物的结晶性特征;乙二醛的存在调整了脲醛树脂的成核过程或初级粒子的生长速度,推测乙二醛覆盖了聚合物的表面或表面活性位,限制了尿素甲醛的扩散反应过程.乙二醛存在时杂化过程所得氧化硅微球的粒径仅为杂化微球的20%,分析结果推测杂化微球中存在氧化硅的径向含量梯度,这种梯度是氧化硅纳米粒子的杂化和脲醛树脂的聚合速度差异造成的.     

嵌段共聚物与阳离子表面活性剂混合模板合成介孔SiO_2

利用三嵌段共聚物EO_(20)PO_(70)EO_(20)与阳离子表面活性剂CTAB作为混合 模板合成了内部孔结构与外观形貌同时受到调控的介孔氧化硅。与使用单一共聚物 模板制备的介孔氧化硅相比，在混合模板作用下得到的介孔氧化硅的孔结构有序度 降低，而孔径则随混合模板中共聚物的质量分数的降低而减小。在EO_(20)PO_(70) EO_(20)与CTAB质量比为1:1时可得到形貌完好、表面光滑的介孔氧化硅微米球，其 平均孔径为3.2nm，比表面积为972m~2/g。     

有机/无机复合介孔膜的合成及其生物酶吸附行为研究

以正硅酸四乙酯(TEOS)为硅源、三嵌段共聚物(F127)为表面活性剂, 聚碳酸酯膜为硬模板, 并采用抽滤法在聚碳酸酯膜内的亚微米级孔道中组装介孔氧化硅从而制备出有机(聚碳酸酯)/无机(介孔氧化硅)复合介孔膜. 通过扫描电镜、能量分散光谱以及透射电镜等实验表征了该有机/无机复合介孔膜的组成、结构及形貌. 研究结果表明: 通过该方法可以在聚碳酸酯膜内孔道中形成长度为9 μm、直径为200 nm的一维氧化硅棒状材料, 且该棒状材料具有无序蠕虫状和有序体心立方的混合介孔结构, 有序体心立方介孔的平均孔径约为8.5 nm. 另外, 初步考察了该复合介孔膜对生物酶的物理吸附行为, 结果表明其对肌红蛋白酶的单位吸附负载量为5.85 mg/g.     

Mechanisms of hydroxyapatite formation on porous gel-silica substrates

The variables affecting the nucleation and crystallization of biological hydroxy carbonate apatite (HCA) on porous gel-silica substrates are examined. Texture is the critical variable with the rate of HCA formation increasing as pore size and pore volume increase, with pore sizes >2 nm required to achieve rapid kinetics (4–6 days) of fully crystallized HCA. The concentration of silanol groups on the silica surface does not control the rate of HCA formation although metastable surface defects, such as trisiloxane rings, may be involved in HCA nucleation.     

Universal Asymptotics of the Thermodynamic Characteristics of the Nucleation on Small Macroscopic Nuclei of Soluble Surfactants

Asymptotic behavior of thermodynamic characteristics of nucleation on small macroscopic nuclei of soluble surfactants at their complete dissolution in a nucleating droplet is studied. It is taken into account that, in the region of small sizes of nuclei and corresponding small sizes of critical nuclei of liquid phase, the chemical potential of condensate and the work of droplet formation are affected by the presence of dense surfactant adsorption monolayer on the droplet surface. It is shown that, as the limiting surface area per surfactant molecule in adsorption monolayer increases, the behavior of thermodynamic characteristics of nucleation in the region of small nucleus sizes is characterized by the transition from asymptotics at the adsorption of almost all substance comprising nucleus in a monolayer to the asymptotics at constant adsorption. The study performed is not limited by the selection of specific adsorption isotherms; therefore, the obtained asymptotic dependences of thermodynamic characteristics on the nucleus size can be considered as universal for the heterogeneous nucleation on the nuclei of soluble surfactants.     

Heterogeneous critical nucleation on a completely wettable substrate

Heterogeneous nucleation of a new bulk phase on a flat substrate can be associated with the surface phase transition called wetting transition. When this bulk heterogeneous nucleation occurs on a completely wettable flat substrate with a zero contact angle, the classical nucleation theory predicts that the free-energy barrier of nucleation vanishes. In fact, there always exists a critical nucleus and a free-energy barrier as the first-order prewetting transition will occur even when the contact angle is zero. Furthermore, the critical nucleus changes its character from the critical nucleus of surface phase transition below bulk coexistence (undersaturation) to the critical nucleus of bulk heterogeneous nucleation above the coexistence (oversaturation) when it crosses the coexistence. Recently, Sear [J. Chem. Phys. 129, 164510 (2008)] has shown, by a direct numerical calculation of nucleation rate, that the nucleus does not notice this change when it crosses the coexistence. In our work, the morphology and the work of formation of critical nucleus on a completely wettable substrate are re-examined across the coexistence using the interface-displacement model. Indeed, the morphology and the work of formation changes continuously at the coexistence. Our results support the prediction of Sear and will rekindle the interest on heterogeneous nucleation on a completely wettable substrate.     

Hit and miss of classical nucleation theory as revealed by a molecular simulation study of crystal nucleation in supercooled sulfur hexafluoride

Classical nucleation theory pictures the homogeneous nucleation of a crystal as the formation of a spherical crystalline embryo, possessing the properties of the macroscopic crystal, inside a parent supercooled liquid. In this work we study crystal nucleation in moderately supercooled sulfur hexafluoride by umbrella sampling simulations. The nucleation free energy evolves from 5.2kBT at T=170 K to 39.1kBT at T=195 K. The corresponding critical nucleus size ranges from 40 molecules at T=170 K to 266 molecules at T=195 K. Both nucleation free energy and critical nucleus size are shown to evolve with temperature according to the equations derived from the classical nucleation theory. Inspecting the obtained nuclei we show, however, that they present quite anisotropic shapes in opposition to the spherical assumption of the theory. Moreover, even though the critical nuclei possess the structure of the stable bcc plastic phase, the only mechanically stable crystal phase for SF6 in the temperature range investigated, they are shown to be less ordered than the corresponding macroscopic crystal. Their crystalline order is nevertheless shown to increase regularly with their size. This is confirmed by a study of a nucleus growth from a critical size to a size of the order of 10(4) molecules. Similarly to the fact that it does not affect the temperature dependence of the nucleation free energy and of the critical nucleus size, the ordering of the nucleus with size does not affect the growth rate of the nucleus.     

Forms and applications of the nucleation theorem

The nucleation theorem is a general relation between the nucleation work, the nucleus size, and the supersaturation or other thermodynamic parameters of the old phase. The theorem appears in different forms, depending not only on the chosen set of independent variables describing the nucleation work but also on which of these variables is changed while the others are held fixed. This paper gives a rigorous, systematic, and comprehensive presentation of various forms of the nucleation theorem and shows how some of them can be applied to concrete cases of nucleation. Both theoretical and experimental applications of the theorem to nucleation in unary, binary, or ternary phases are considered.     

Kinetic model of electrochemical nucleation

The process of electrochemical nucleation is analyzed in terms of stochastic formation of clusters of different size over the electrode surface. It is shown that the ground equation of the atomistic theory of nucleation can be derived without resort to the thermodynamic approach, in particular, the concept of the nucleus energy and its dependence on the nucleus size.     

Effect of the surface-stimulated mode on the kinetics of homogeneous crystal nucleation in droplets

The thermodynamics of surface-stimulated crystal nucleation demonstrates that if at least one of the facets of the crystal is only partially wettable by its melt, then it is thermodynamically more favorable for the nucleus to form with that facet at the droplet surface rather than within the droplet. So far, however, the kinetic aspects of this phenomenon had not been studied at all. In the present paper, a kinetic theory of homogenous crystal nucleation in unary droplets is proposed by taking into account that a crystal nucleus can form not only in the volume-based mode (with all its facets within the droplet) but also in the surface-stimulated one (with one of its facets at the droplet surface). The theory advocates that even in the surface-stimulated mode crystal nuclei initially emerge (as subcritical clusters) homogeneously in the subsurface layer, not "pseudo-heterogeneously" at the surface. A homogeneously emerged subcritical crystal can become a surface-stimulated nucleus due to density and structure fluctuations. This effect contributes to the total rate of crystal nucleation (as the volume-based mode does). An explicit expression for the total per-particle rate of crystal nucleation is derived. Numerical evaluations for water droplets suggest that the surface-stimulated mode can significantly enhance the per-particle rate of crystal nucleation in droplets as large as 10 microm in radius. Possible experimental verification of the proposed theory is discussed.     

Accounting for fluctuations in cluster parameters upon the description of nucleation in supersaturated vapor

A theory is proposed for stationary homogeneous nucleation in supersaturated vapor in which a modified expression for the rate of cluster evaporation was used to calculate the equilibrium distribution over the nucleus sizes and the rates of their formation. This rate was determined by the extrapolation to the region of small sizes of the corresponding expression for the macroscopic droplet derived according to thermodynamic notions that take fluctuations into account. Modified dependences of the size of critical nucleus and the rate of nucleation on the supersaturation and the temperature are determined and compared with the data of the classical theory of nucleation and experimental results.     

Nucleation in the presence of slow microscopic dynamics

Nucleation of a new thermodynamic phase is often a slow process due to the need to overcome a high free-energy barrier. However, there are other sources of slow dynamics; for example, at high densities/low temperatures, the movement of individual molecules or spins may be slow. Here, we study nucleation in a simple phenomenological model that has this type of slow microscopic dynamics. We do this to better understand how the two sources of slow dynamics interact. We find that as nucleation is intrinsically slow, only very slow microscopic dynamics strongly affect how nucleation occurs. The composition of the nucleus at the top of the nucleation barrier is much less sensitive to slow microscopic dynamics than is the composition of the nucleus once it is postcritical. However, slow dynamics affects not only the rate but also the pathway, which no longer goes over the saddle point in the free energy. We also find that the slow microscopic dynamics can cause sampling problems in an algorithm developed to calculate nucleation rates, and so cause it to predict the rate incorrectly.     

Kinetic theory of heterogeneous nucleation; effect of nonuniform density in the nuclei

The heterogeneous nucleation of a liquid from a vapor in contact with a planar solid surface or a solid surface with cavities is examined on the basis of the kinetic theory of nucleation developed by Nowakowski and Ruckenstein [J. Phys. Chem. 96 (1992) 2313] which is extended to nonuniform fluid density distribution (FDD) in the nucleus. The latter is determined under the assumption that at each moment the FDD in the nucleus is provided by the density functional theory (DFT) for a nanodrop. As a result of this assumption, the theory does not require to consider that the contact angle which the nucleus makes with the solid surface and the density of the nucleus are independent parameters since they are provided by the DFT. For all considered cases, the nucleation rate is higher in the cavities than on a planar surface and increases with increasing strength of the fluid-solid interactions and decreasing cavity radius. The difference is small at high supersaturations (small critical nuclei), but becomes larger at low supersaturations when the critical nucleus has a size comparable with the size of the cavity. The nonuniformity of the FDD in the nucleus decreases the nucleation rate when compared to the uniform FDD.