蒙脱土/二氧化钛复合颗粒电流变液材料的制备及其性能

利用溶胶-凝胶法制备了一种新型的蒙脱土/二氧化钛(MMT/TiO_2)复合电流变 颗粒材料，FT-IR，XRD，SEM分析表明TiO_2以纳米晶的形态包覆于蒙脱土表面。电 流变性能测试表明，MMT/TiO_2复合颗粒的电流变效应比纯蒙脱土电流变液有显著 提高，当颗粒体积分数为25%，直流电场强度为3kV/mm时，TiO_2质量分数为22.7% 的MMT/TiO_2复合颗粒电流变液的静态屈服应力达8.3kPa，此值约为纯蒙脱土电流 变液的4倍。同时发现TiO_2包覆量对电流变效应有重要影响。     

Enhanced electrorheological activity of mesoporous Cr-doped TiO2 from activated pore wall and high surface area

To enhance electrorheological (ER) activity by improving interfacial polarization, we prepared a new mesoporous Cr-doped TiO2 ER material by a copolymer-templated sol-gel method. The material was characterized by differential scanning calorimeter and thermogravimetric (DSC-TG) analysis, Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, and X-ray photoelectron spectroscopy (XPS) techniques. The ER activity was studied by the rheological curve and yield stress under an electric field. The results showed that the mesoporous Cr-doped TiO2 ER material possessed a high surface area over 200 m2/g and a crystalline anatase pore wall doped by different valent Cr ions. The ER activity of mesoporous Cr-doped TiO2 was higher than that of nonporous Cr-doped TiO2. The yield stress and ER efficiency of the mesoporous Cr-doped TiO2 ER suspension was 3 times as high as that of the nonporous Cr-doped TiO2 ER suspension, 7 times as high as that of the mesoporous undoped TiO2 ER suspension, and 20 times as high as that of the nonporous pure TiO2 ER suspension. Furthermore, the ER activity of mesoporous Cr-doped TiO2 showed a dependence on surface area, and the high porosity or surface area samples showed higher ER activity. The dielectric spectra analysis showed that the mesoporous Cr-doped TiO2 ER suspension possessed a significantly larger interfacial polarizability compared with the nonporous Cr-doped TiO2 ER suspension, and the regular change of polarizability with surface area or porosity was in accordance with the change of ER activity with surface area or porosity. The improvement of dielectric properties or polarization could well explain the enhancement of the ER activity of mesoporous Cr-doped TiO2.     

Preparation and electrorheological property of rare earth modified amorphous BaxSr1-xTiO3 gel electrorheological fluid

In this paper, we present a newly developed rare earth modified amorphous barium strontium titanate (Ba(x)Sr(1-x)TiO3) gel/silicone oil electrorheological (ER) fluid. The ER behaviors of suspensions of pure and rare earth modified amorphous Ba(x)Sr(1-x)TiO3 particles in silicone oil have been investigated under a dc electric field. The shear yield stress of the rare earth modified amorphous BaTiO3 gel/silicone oil ER fluid could reach 14.9 kPa at E=3.5 kV/mm while the leaking current density was very low, about 7.64 microA/cm2. The ER fluids with a higher volume fraction had a higher current density and a higher shear yield stress under the same electric field. The ER fluid has a long-term stability against sedimentation. The problem of caking was not serious and the agglomerated particles could be easily broken up by strongly stirring.     

Preparation of montmorillonite/titania nanocomposite and enhanced electrorheological activity

We prepared a new type of electrorheological particle composed of TiO2 nanocrystallites-coated montmorillonite (MMT/TiO2) nanocomposite by the sol-gel technique. The characterizations including TGA, XRD, TEM, SEM, EDS, and FTIR showed that TiO2 was deposited on the surface of the MMT flakes with anatase nanocrystallite. An obviously enhanced ER effect was found in the MMT/TiO2 nanocomposites based ER fluids compared with pure MMT and TiO2. Furthermore, the temperature and sedimentation stabilities of the MMT/TiO2 ER fluids had also been improved greatly. Interestingly, the content of TiO2 was demonstrated to have an important influence on the ER effect. When the content of TiO2 was about 20 wt%, the ER effect of MMT/TiO2 ER fluid reached its maximum, which was about 5 times that of pure MMT ER fluid and 27 times that of pure TiO2 ER fluid. Based on dielectric analysis, the significant ER enhancement by formation nanocrystallites-coated montmorillonite was attributed to the enhanced interfacial polarization in this nanocomposite particle due to the effective limitation of the long-range drift of active ions in montmorillonite particles.     

Application of liquid phase deposited titania nanoparticles on silica spheres to phosphopeptide enrichment and high performance liquid chromatography packings

A novel core-shell composite (SiO(2)-nLPD), consisting of micrometer-sized silica spheres as a core and nanometer titania particles as a surface coating, was prepared by liquid phase deposition (LPD). Here, we show the resulting core-shell composite to have better efficient and selective enrichment for mono- and multi-phosphopeptides than commercially available TiO(2) spheres without any enhancer. The material exhibited favorable characteristics for HPLC, which include narrow pore size distribution, high surface area and pore volume. We also show that the core-shell composite can efficiently separate adenosine phosphate compounds due to the Lewis acid-base interaction between titania and phosphate group when used as HPLC packings. After coating the silica sphere with titania by LPD, the silanol of silica spheres will be shielded and that the stationary phase, C(18) bonded SiO(2)-3LPD, could be used under extreme pH condition.     

Facile preparation method of SiO2/PS/TiO2 multilayer core-shell hybrid microspheres

Organic-inorganic hybrid particles have many potential applications, but almost all of this research was focused on the hybrid particles containing one kind of inorganic nanoparticles. This paper presented a facile preparation method for SiO2/PS/TiO2 multilayer core-shell hybrid microspheres. In this approach, positively charged SiO2/PS core-shell hybrid particles were first synthesized by miniemulsion polymerization using cationic initiator and emulsifier. These positively charged SiO2/PS hybrid particles were mixed with tetra-n-butyl titanate for sol-gel reaction to directly form SiO2/PS/TiO2 multilayer core-shell hybrid microspheres. Some influencing parameters such as surfactant concentration, tetra-n-butyl titanate amount, and glacial acetic acid amount were investigated. TEM, TGA, and EDX analyses indicated that titania layers were successfully coated onto the surfaces of hybrid microspheres.     

稀土掺杂TiO2颗粒的制备及其悬浮液的电流变特性

通过掺杂稀土元素,使TiO2电流变液的屈服强度提高到近5 kPa (3 kV/mm).用DSC-TG、 IR和XRD等手段对材料的Sol-gel制备过程和产物的晶体结构进行了分析.结果表明纯TiO2和掺杂稀土TiO2凝胶的分解分三阶段完成,并形成锐钛矿结构.掺杂浓度小于一定值时,稀土离子以置换Ti位固溶于TiO2晶格中并引起晶格膨胀.认为适当掺杂所导致的晶格常数变化改善了材料的介电性能,从而使TiO2的电流变性能优化.     

Encapsulation of titanium(IV) oxide particles in hollow silica for size-selective photocatalytic reactions

A core-shell composite of TiO2 particles encapsulated in a hollow silica was fabricated, and the core-shell composite showed size-selective photocatalytic activity for decomposition of organics without reducing the intrinsic activity of the naked TiO2 core.     

层层组装法制备核壳SiO_2/Pt粒子及其CO电氧化和原位电化学FTIR光谱

采用层层组装法合成了核壳SiO2/Pt粒子,用电化学循环伏安法(CV)和原位电化学傅里叶变换红外(FTIR)光谱研究了SiO2/Pt粒子对CO分子的氧化和吸附行为.透射电子显微研究表明:包覆SiO2的Pt壳是由团聚的Pt纳米微粒构成,其平均厚度大约为26nm.CO在SiO2/Pt粒子修饰的玻碳(GC)电极上的主氧化峰为0.49V(vsSCE),表现出比本体Pt金属好的催化性能.电化学FTIR光谱研究发现:线性CO在SiO2/Pt粒子上的IR吸收带的方向发生倒反,而且在不同的研究电位下,每个吸收带劈裂为两个间隔约为14cm-1的吸收带,这种劈裂现象在饱和吸附CO的Pt金属表面上是很难观察到的.这些异常的红外吸收现象可能是由SiO2/Pt粒子的结构效应导致的.     

Supramolecular core-shell nanosilica@liposome nanocapsules for drug delivery

The fabrication of core-shell structural nanosilica@liposome nanocapsules as a drug delivery vehicle is reported. SiO(2) nanoparticles are encapsulated within liposomes by a W/O/W emulsion approach to form supramolecular assemblies with a core of colloidal particles enveloped by a lipid bilayer shell. A nanosilica core provides charge compensation and architectural support for the lipid bilayer, which significantly improves their physical stability. A preliminary application of these core-shell nanocapsules for hemoglobin (Hb) delivery is described. Through the H-bonding interaction between the hydroxyl groups on nanosilicas and the amino nitrogens of Hb, Hb-SiO(2) nanocomplexes in which the saturated adsorption amount of Hb on SiO(2) is 0.47 g g(-1) are coated with lipids to generate core-shell Hb-SiO(2)@liposome nanocapsules with mean diameters of 60-500 nm and Hb encapsulation efficiency of 48.4-87.9%. Hb-SiO(2)@liposome supramolecular nanovehicles create a mode of delivery that stabilizes the encapsulated Hb and achieves long-lasting release, thereby improving the efficacy of the drug. Compared with liposome-encapsulated Hb and Hb-loaded SiO(2) particles, such core-shell nanovehicles show substantially enhanced release performance of Hb in vitro. This finding opens up a new window of liposome-based formulations as drug delivery nanovehicles for widespread pharmaceutical applications.     

Electrorheological characterization of polyaniline-coated poly(methyl methacrylate) suspensions

Surface-conductive particles consisting of a poly(methyl methacrylate) (PMMA) core and a polyaniline (PA)-coated shell were synthesized and adopted as suspended particles for electrorheological (ER) fluids. The PA-PMMA composite particles synthesized were monodisperse and spherical in shape. The PA-PMMA suspensions in silicone oil showed typical ER characteristics under an applied electric field. The PA-PMMA composite particles possess a higher dielectric constant and conductivity than the pure PA particle, within an acceptable conductivity range for ER fluids, but the PA-based ER fluid showed larger shear-stress enhancement than the PA-PMMA-based systems. This phenomena can be explained by the interfacial polarizability of PA-based ER fluids, which is the difference between the ER fluid's dielectric constant and loss factor - this polarizability was higher than that of PA-PMMA-based ER fluids, as shown by the dielectric spectrum of each fluid. The insulating PMMA core suppressed the interfacial polarization in ER fluids, resulting in reduced interaction among particles under an imposed electric field.     

微乳法制备纳米TiO2 /SiO2的结构及光催化研究

Nanosized TiO₂ and TiO₂/SiO₂ particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM，N₂ adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO₂/SiO₂ nanoparticles are with a monodispersed spherical phase and a uniform size distribution，and TiO₂ particles are dispersed on the surface of SiO₂. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO₂, suppressed the phase transformation of titania from anatase to rutile. And due to the addition of SiO₂, the average size of titania decreased from 38 nm in pure TiO₂ to 5 nm in TiO₂/SiO₂. It was found, under UV light irradiation, TiO₂/SiO₂ particles showed higher activity than pure TiO₂, and TiO₂/SiO₂(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.     

In situ sol-gel preparation of polysaccharide/titanium oxide hybrid colloids and their electrorheological effect

A new type of organic/inorganic hybrid colloid, made of modified carboxylmethyl starch (CMS) and titanium oxide (TiO(2)), was synthesized by an in situ sol-gel technique. IR spectra analysis shows strong a interaction of functional groups between two components, whose dispersion is almost at the molecular level. Due to the highly active surfaces hybrid particles and their characteristic dielectric behavior in accordance with the previous theoretic calculation, the suspensions of hybrids in silicone oil display a remarkable ER effect. The static yield stress can be above 20 kPa (shear rate 5 S(-1)) under a direct current field of 4 kV/mm at room temperature, much higher than that of simple blends of starch and titanium dioxide. In the meanwhile, the temperature dependence and sedimentation stability were optimized. Based on existing experimental results, we propose that dielectric properties and surface (interface) activity are two necessary conditions fulfilling the requirement of high ER activity. The combination of both factors may effectively reduce the activation energy needed for ERF restructuring.     

Electrorheological fluids based on glycerol-activated titania gel particles and silicone oil with high yield strength

This article describes an electrorheological (ER) fluid based on glycerol-activated titania organic-inorganic hybrid gel particles and silicone oil with high yield strength. Based on a physical picture of a water-activated ER system, glycerol that has a high dielectric constant and boiling point is in situ prepared in the amorphous titania gel during the sol-gel processing. A small amount of ionic surfactant hexadecyltrimethylammonium bromide (CTAB) is employed to enhance charge carriers in particles. FTIR and XRD techniques are used to determine the nature and structure of the hybrid gel. Rheology test results show that a large static yield stress greater than 12.6 kPa is obtained when 3 kV/mm dc electric field is applied. This value is close to the value predicted by H. Conrad (MRS Bull. 8 (1998) 35) in theory. Furthermore, dynamic shear stress as a function of shear rate and temperature is also investigated. This ER fluid exhibits strong temperature dependence and a wide working temperature range from 0 to 120 degrees C, while its leaking current density is still low. More interesting is that the glycerol content is demonstrated to have an influence on ER effect and temperature dependence. Measurement of the dielectric properties of ER fluids shows enhancement of the dielectric constant and dielectric loss due to addition of glycerol and a regular dependence of them on temperature, which well explains the strong ER effect.     

块状TiO2/SiO2气凝胶的非超临界干燥法制备及其表征

分别通过TiO2和SiO2的单独溶胶和TiO2/SiO2复合凝胶,并添加干燥控制化学添加剂甲酰胺,形成比较完善的凝胶网络结构,同时通过正硅酸乙酯的乙醇溶液浸泡,低表面张力溶剂替换和分级陈化以及干燥等步骤,实现了块状TiO2/SiO2复合气凝胶的非超临界干燥制备.所得TiO2/SiO2气凝胶为无色或乳白色轻质块状多孔固体,表观密度约0.4～0.9g/cm3,孔隙率约80%～95%.它由直径约10nm的TiO2和SiO2微粒相互分散复合而成,孔洞直径约几十纳米.其相态SiO2为无定形,TiO2为锐钛矿晶型.随着焙烧温度的升高,直到800℃不发生相变化.     

Guest-controlling effects on ER behaviors of beta-cyclodextrin polymer

An effective and novel approach to obtaining electrorheological particles with high performance through the formation of host-guest complexes has been achieved. The significant preponderance of the host-guest complex formation is that the host structure can be controlled easily by adding different guests. Based on this point, six supramolecular complexes of beta-cyclodextrin cross-linking polymer with salicylic acid (beta-CDP-1), 5-chlorosalicylic acid (beta-CDP-2), 3,5-dichlorosalicylic acid (beta-CDP-3), 5-nitrosalicylic acid (beta-CDP-4), 3,5-dinitrosalicylic acid (beta-CDP-5), or 3-hydroxy-2-naphthoic acid (beta-CDP-6) particles were synthesized. The electrorheological yield stresses of the suspensions of these particles in silicone oil have been investigated under DC electric fields. It was found that the yield stress of the typical beta-CDP-1 ER fluid was 5.6 kPa in 4 kV/mm, which is much higher than that of pure beta-cyclodextrin polymer (beta-CDP), that of pure salicylic acid as well as that of the mixture of the host with the guest. It is clearly indicated that the formation of supramolecular complexes between beta-CDP and salicylic acid can enhance the ER properties of the host. The similar results for other supramolecular complexes with different guests have also been obtained under the same DC electric fields. The yield stress of supramolecular complexes is strongly affected by the structure of guests. Among the six investigated guests, 3-hydroxy-2-naphthoic acid gave the highest ER property having a yield stress of 9.8 kPa under 4 kV/mm DC while cross-linked with beta-CDP to form beta-CDP-6. The yield stress of beta-CDP-6 was significantly increased by 72% in comparison with that of the pure beta-CDP. However, the yield stress of beta-CDP-1-5 slightly increased by 34-41% as compared with that of the pure beta-CDP. The achieved results indicate that the ER effect of host-guest complexes can be greatly affected by the changes of the tremendous guest structure, whereas the slight guest structural transposition, such as altering different groups of a guest, can only obtain the adjacent electrorheological behavior. The dielectric properties of these host-guest complexes also proved that the ER effect can be affected by the properties of guest.     

钛酸四丁酯水解制备聚苯乙烯/二氧化钛核壳粒子及空心二氧化钛微球

通过无皂乳液聚合方法制备了阳离子型及阴离子型聚苯乙烯(PSt)乳胶粒,并对后者用γ-氨丙基三乙氧基硅烷(KH550)进行了表面改性制得了乳胶粒表面载正电荷的乳液.在乙醇与水的混合溶剂中,分别使用以上3种PSt乳胶粒为核加入钛酸四丁酯制备了核壳型PSt/TiO2复合粒子.结果显示,仅在使用经KH550改性的阴离子PSt乳...     

新型SiO2/SiO2核壳型固定相的制备与评价

采用层层自组装的方法,以微米多孔硅胶小球为核,将硅胶纳米粒子多层包覆,制备了核壳型SiO2/SiO2硅胶小球.透射电子显微镜表明这种硅胶小球具有明显的核壳结构,氮气吸附实验证明该硅胶小球是典型的介孔材料,具有良好的介孔结构和窄的孔径分布.将其作为基质制备碳十八键合核壳型SiO2/SiO2色谱固定相,该固定相的碳含量与未...     

Synthesis and electrorheological properties of oxalate group-modified amorphous titanium oxide nanoparticles

A kind of titanium oxide nanoparticles modified with varying amounts of oxalate group was prepared using a modified hydrolysis method. The microstructure, dielectric properties, and electrorheological (ER) performance were investigated. The results indicate that the oxalate group can effectively improve the dielectric properties and surface polarizability of the particles, and the ER performance of modified titanium oxide-based ER fluid is much higher than that of pure titanium oxide-based ER fluid. The shear stress of suitable oxalate group-modified amorphous titanium oxide-based ER fluid with a volume fraction of 30% reaches 47.5 kPa at E = 5 kV/mm, and the current density is less than 18 μAcm⁻². The yield stress can be up to 114 kPa at E = 5 kV/mm with a volume fraction of 40%.     

Photophoretic assembly and migration of dielectric particles and Escherichia coli in liquids using a subwavelength diameter optical fiber

We demonstrate a photophoretic assembly and migration of dielectric (SiO(2) and TiO(2)) particles and bacteria (Escherichia coli) in liquids by using a subwavelength diameter fiber. With a lightwave at 1.55 μm launched into the fiber, the objects are radiated by the leaking light of the fiber to yield negative photophoretic forces which drive the objects to move toward the fiber, with an average assembling/migrating speed of 5-15 individuals per second (ind/s). The influences of laser-on duration, optical power, and size of particles on the photophoretic velocities are also investigated.