介孔SiO2负载和包覆的纳米金属颗粒的制备与研究

制备了以SiO2为核、介孔SiO2为壳的核-壳颗粒负载纳米金属颗粒以及介孔SiO2壳层包覆SiO2负载的纳米金属颗粒。结果表明,十六烷基三甲基溴化胺(CTAB)作为模板剂,有助于介孔SiO2壳层包覆SiO2核的结构形成,介孔SiO2壳层的孔径方向垂直于SiO2核的表面;在聚乙烯吡咯烷酮(PVP)的稳定作用下,Pt纳米颗粒能均匀地分布在介孔SiO2壳层的表面。单分散SiO2颗粒经过3-氨丙基三乙氧基硅烷(APS)功能化后,可负载纳米金属颗粒。进一步研究表明,以SiO2负载纳米金属颗粒为核,NH3.H2O,乙醇和水为分散剂,CTAB为模板剂,正硅酸乙酯(TEOS)为硅源,还能制备介孔SiO2壳包覆SiO2负载的纳米金属颗粒,而且介孔SiO2壳层的厚度可通过TEOS的含量调节。     

SiO2／Ag核壳复合粒子的制备与表征

首次引入活性SiO2微球作为核基，采用自组装液相还原技术，定向的在核基上沉积纳米银颗粒得到SiO2／Ag核壳复合粒子；并用红外、x射线衍射、场发射扫描电镜、能谱等分析表征该核壳复合粒子的形貌与结构。结果表明：利用活性SiO2作为核基，pH值为12．4，有表面活性剂参与的条件下，通过改变银前驱体浓度，可实现表面包覆致密、银壳厚度可控的核壳复合粒子化学制备技术。     

SiO_2@Ag核壳粒子表面形貌及壳层厚度影响因素的研究

用溶胶-凝胶法制备单分散的亚微米二氧化硅,经表面巯基化改性后,采用自组装化学镀法在其表面包Ag,得到SiO2@Ag核壳复合粒子,研究还原剂的种类、浓度和反应温度对核壳结构SiO2@Ag亚微米颗粒形貌及表面Ag壳层厚度的影响规律。结果表明:还原剂的种类对SiO2@Ag核壳复合粒子表面形貌影响较大,还原性太弱很难在二氧化硅表面形成致密均匀的银层,还原性太强则容易形成散银;还原剂浓度增加使二氧化硅表面银颗粒的粒径增大,银壳层厚度增大,但是当还原剂浓度到达一定的值后,浓度对银粒径大小和银壳厚度的影响变弱;反应温度对SiO2@Ag核壳复合粒子表面形貌也有较大影响,0~30℃时,银粒子随温度升高尺寸变大,银壳厚度也相应增大,若温度继续增加到50℃后则开始出现散银,包覆效果变差。     

Ag@SiO_2/Eu(Ⅲ)配合物纳米复合颗粒的制备及荧光性能研究

通过三步反应成功将铕配合物(EuTP)包覆在纳米核壳结构Ag@SiO2复合颗粒的表面。采用化学还原法制备了粒径25~30nm且分散性良好的纳米银溶胶;然后采用改进的Stber法制备了壳层厚度在20nm左右的Ag@SiO2复合颗粒;以氧化铕、α-噻吩甲酰三氟丙酮、邻菲罗啉为原料制备EuTP,并成功包覆在核壳结构的表面。分别采用TEM、FTIR、XRD等对样品的结构进行了表征,并通过对比相同浓度的三价铕的配合物EuTP与复合粒子Ag@SiO2@EuTP的荧光发射光谱发现,SiO2壳层厚度在20nm左右时Eu配合物的荧光强度明显增强,而且随着核壳结构表面配合物浓度的增大,包覆层的厚度增大,荧光强度也呈现增强趋势,对于稀土的研究具有重要的意义。     

核壳结构Co/SiO_2非晶态纳米颗粒的制备和性能

主要研究了核壳结构Co/SiO2非晶态纳米颗粒的制备及性能。正硅酸乙酯水解生成二氧化硅,水溶液中硼氢化钠还原氯化钴生成钴单质,存在硅烷偶联剂APS时,将二者进行结合生成二氧化硅包覆在钴颗粒表面。采用XRD、TEM、FT-IR、VSM等手段对样品进行表征。     

核壳结构NaYF_4:Yb~(3+)、Er~(3+)/SiO_2颗粒的制备及其光谱性能

以正硅酸乙酯为原料,采用水解法,对100 nm亲水及20 nm亲油的NaYF4:Yb3+、Er3+上转换发光纳米颗粒进行了表面修饰,制备出了NaYF4:Yb3+、Er3+/SiO2核壳结构.研究了反应时间、反应前驱体浓度等工艺条件对包覆效果的影响.结果表明,经过二氧化硅包覆后的亲水及亲油大、小颗粒都可以均匀地分散在亲水溶剂中.在室温下,分别对SiO2壳层包覆前后的NaYF4:Yb3+、Er3+纳米颗粒的上转换发光光谱进行对比研究,发现两种粒子都能在980 nm激光激发下,产生550 nm的绿光及670 nm的红光,且包覆后纳米颗粒的发光位置及整体发光强度与包覆前相比没有受到影响.     

SiO2包覆Fe2O3纳米粒子的制备和性能

在近球形α-Fe2O3颗粒的悬浮液中,以正硅酸乙酯(TEOS)为硅源,氨水和尿素为催化剂,合成了Fe2O3-SiO2核-壳粒子.应用TEM.XRD对Fe2O3-SiO2核-壳粒子结构进行了测定.研究了TEOS.氨水的浓度对核-壳粒子结构的影响.UV-Vis吸收光谱表明,SiO2壳层消除了Fe2O3纳米粒子的表面悬挂键,产生增强的激子发射,使得核-壳粒子的吸收峰发生蓝移.根据带边吸收峰的波长计算出核-壳粒子中Fe2O3的禁带宽度为2.25 eV.     

SiO_2空心纳米微球的合成

为了改善聚合物粒子与SiO2粒子之间的亲和力及SiO2粒子在聚合物粒子表面的吸附,首先使用共单体4-乙烯基吡啶(4VP)功能化苯乙烯(PS)粒子,合成了聚(苯乙烯-共-4-乙烯基吡啶)(P(St-4VP))粒子。然后在NH4OH/乙醇介质中,将溶胶-凝胶法生成的SiO2粒子包覆在P(St-4VP)粒子表面,聚合物核被溶解得到SiO2空心纳米微球。随着P(St-4VP)粒子中共单体4VP含量以及正硅酸乙酯(TEOS)用量增加,SiO2空心纳米微球的壳层厚度增加,且壳层表面变得粗糙。随着PVP用量增加,SiO2空心纳米微球的平均尺寸下降,其壳层从松散粗糙变得致密光滑。NH4OH用量增加对SiO2空心纳米微球尺寸和形态的影响不大。     

分散聚合法制备SiO2/PAM核壳复合微球

采用分散聚合法制备出以SiO2为核、PAM为壳的核壳复合微球。根据Stber法制备了单分散SiO2微球,粒径随着TEOS、氨水浓度的增加而增大。采用硅烷偶联剂对SiO2微球进行表面处理,TEM显示处理后的微球继续保持单分散性,粒径有所增加。以SiO2微球或处理后的SiO2微球为核,采用分散聚合法在其上包覆AM,借助TEM、IR对其进行表征;研究发现,以处理后的Si O2微球为核能得到核壳结构,这种SiO2/PAM核壳微球的粒径大约为163 nm,包覆层30 nm左右。     

α-N（OH）2/SiO2核壳以及α-Ni（OH）2空心微球的制备及表征

采用以正硅酸乙酯（TEOS）水解为基础的硅溶胶种子生长法制备了粒径约为270nm的近单分散二氧化硅球型颗粒.采用一种新的溶液生长法,以氢氟酸作为溶液中镍离子配位剂,加入氨水调节溶液pH值的同时作为镍离子补充配位剂,60℃水浴条件下在已制得SiO2微球表面均匀包覆α-Ni（OH）2得到Ni（OH）2/SiO2核壳结构,Ni（OH）2壳层厚度约为35nm.结合多步包覆法提高Ni（OH）2壳层厚度,三次包覆后壳层厚度达到约100nm,四次包覆后约为140nm.采用20wt%的强碱NaOH溶液对三次包覆后的Ni（OH）2/SiO2核壳结构进行处理,得到了壳层厚度约为95nm的α-Ni（OH）2空心微球.空心微球具有较大的比表面积为141.06m2/g.     

Synthesis of ultra-small hollow silica nanoparticles using the prepared amorphous calcium carbonate in one-pot process

The ultra-small hollow silica nanoparticles were synthesized using the prepared amorphous calcium carbonate (ACC) particles as a template. The ACC particles were firstly prepared by carbonation method, which procedure was conducted in the methanol solvent to form the Ca(OCH₃)₂ layers on the ACC particles. An effect of methanol concentration on the morphology of ACC particles was also investigated. The prepared ACC particles were directly coated by silica through adding tetraethoxysilane (TEOS) into the methanol solvent. Hence, the ACC-silica core-shell particles were obtained since the ACC particles have a positive charge and interact with hydrolyzed TEOS. The ACC particles could be stabilized through the reaction between methanol and calcium ions when the methanol concentration was increased over than 40?vol%.     

单分散SiO_2/TiO_2/SiO_2多层复合微球的制备

采用一种以醇盐水解法为基础的生长硅溶胶的方法,制备了粒径为２００ｎｍ的单分散二氧化硅球形颗粒,并将其作为核心,利用常温连续进料的钛酸丁酯水解的多步法,在二氧化硅核心外经多次包覆形成厚层二氧化钛;在正硅酸乙酯的水解和陈化环境下,将上述ＴｉＯ２／ＳｉＯ２复合颗粒外再包覆一薄层二氧化硅,形成一种高折射率,可用于组装光子晶体的ＳｉＯ２／ＴｉＯ２／ＳｉＯ２多层复合微球．对该复合微球用重力沉降法、透射电镜法（ＴＥＭ）、Ｘ射线能谱分析法（ＥＤＳ）进行了表征．其中,重力沉降法是一种将Ｓｔｏｋｅｓ公式为基础推导的复合颗粒的粒径与沉降速度关系式所得的一系列数据进行拟合外延,来测定复合颗粒的粒径及包覆厚度的方法．     

SiO_2/SiCN核壳陶瓷微球的制备及表征

采用乳液技术和先驱体转化法相结合,利用改性后SiO_2颗粒表面的双键引发聚硅氮烷(PSN)原位聚合,得到SiO_2/PSN核壳结构微球,经高温裂解过程成功制备SiO_2/SiCN核壳陶瓷微球。研究SiO_2与PSN原料的质量比、固化时间和热解温度对核壳微球形成过程和形貌的影响,并采用SEM,EDS,TEM,FT-IR,XRD对微球的微观形貌、化学成分及物相进行表征。结果表明:SiO_2与PSN质量比为1∶4时,200℃固化4h得到表面颗粒分布均一、包覆完全的SiO_2/PSN核壳微球;经800~1200℃热处理后,得到能保持原来形貌的非晶态SiO_2/SiCN核壳陶瓷微球;1400℃热解产物发生结晶,生成了SiO_2,SiC和Si_3N_4晶相。     

核-壳结构粒子SiO_2@Bi_2O_3的制备及红外发射率研究

为了研究制备复合隐身粒子的方法,采用溶胶-凝胶法制备了核-壳结构SiO2@Bi2O3粒子.通过XRD、TEM及发射率测试仪对制备的材料的结构、形貌和性能进行了表征.XRD表明在700℃可以得到Bi2O3纯相;红外发射率测试表明,Bi2O3具有较低的红外发射率,在SiO2表面包覆Bi2O3后,在3～5μm和8～14μm两个测试波段都能降低SiO2的红外发射率.通过核-壳结构的形式,在较高发射率的样品表面涂覆红外发射率较低的样品,可以提高红外隐身效果.     

UV-curable SiO2-TiO2 films for the realization of diffractive optical elements

Hybrid SiO2-TiO2 films are prepared starting from tetraisopropoxy titanate and 3-glycidoxipropyltrimethoxysilane, using the sol-gel process. During the sol synthesis titania clusters grow, conferring to the samples a photocatalytic activity. In this paper we exploit this property for the fabrication of surface-relief gratings. The realized structures are characterized by SEM, AFM and profilometric measurements, while the presence of titania clusters is confirmed by TEM analyses.     

SiO2含量对新型PA6/EP/SiO2纳米材料体系聚合反应的影响

采用廉价的环氧树脂(EP)与正硅酸乙酯(TEOS)反应生成改性前驱体,然后水解,再将水解液与熔融己内酰胺混匀,通过原位生成法制备出新型PA6/EP/SiO2纳米复合材料。研究了SiO2无机粒子的加入对PA6聚合反应的影响。端基分析和高效液相色谱仪(HPLC)测试结果表明:随SiO2加入量的增加,PA6分子量及低聚物含量有下降趋势。     

氢氧焰燃烧合成核壳结构纳米 TiO2/SiO2复合颗粒及机理分析

利用多重射流氢氧焰燃烧反应器，通过控制进料方式，以TiCl4和SiCl4为原料合成了具有典型核壳结构的纳米TiO2／SiO2复合颗粒，并分析了氢氧焰燃烧合成过程中核壳结构的形成机理．在纳米TiO2／SiO2复合颗粒中，无定形的SiO2均匀地包覆在晶态TiO2颗粒表面形成核壳结构，引入SiO2不但有效抑制TiO2晶粒的生长，而且抑制了锐钛相向金红石相的转变．在TiCl4和SiCl4次序进料时，TiCl4优先反应并通过成核生长生成TiO2纳米颗粒，SiCl4反应生成的SiO2通过在TiO2颗粒表面非均相成核生长，形成核壳结构的纳米复合颗粒．     

Epoxidised natural rubber/silica hybrid nanocomposites by sol-gel technique: Effect of reactants on the structure and the properties

This paper reports the effects of various reaction parameters such as solvent, mole ratio of water to tetraethoxysilane and temperature on the structure and the properties of epoxidised natural rubber/silica organic-inorganic hybrid nanocomposites, prepared by sol-gel technique. The sol-gel reaction was conducted at a constant concentration of tetraethoxysilane (45 wt% with respect to the rubber), used as the precursor for silica under a constant pH of 1.5. Infrared spectroscopic studies and the ash content data indicated the maximum silica generation in tetrahydrofuran compared to chloroform and carbon tetrachloride, which are less polar and had low affinity towards water than the former. The silica particles prepared from tetrahydrofuran were scattered within the rubber matrix with an average dimension of 100 nm, as evident from the transmission electron microscopic study. Dispersion of nanosilica within the composites was obtained when the tetraethoxysilane to water mole ratio was maintained up to 1:2, beyond which the resultant composites showed phase separation due to the agglomeration of the silica particles. High gelling temperature of the hybrids also resulted in phase separated morphology, probably due to the accelerated condensation reaction in the composites. All the phase separated composites showed higher infrared optical density and transmission loss compared to the nanocomposites. Poor mechanical reinforcement was observed from the dynamic mechanical analysis of the uncured composites having larger silica particles. On the contrary, better mechanical properties were achieved with the nanocomposites containing 90–100 nm silica. The nanocomposite prepared with 1:2 tetraethoxysilane to water mole ratio in tetrahydrofuran under room temperature showed the highest tensile strength and 100% tensile modulus, probably due to better polymer-filler interaction, in the uncrosslinked state and after crosslinking.     

Synthesis of high concentration colloid solution of silica-coated AgI nanoparticles

Methods for high concentration silica-coated silver iodide (AgI/SiO2) particles, which could be practically used as X-ray contrast agent, were examined. The first was a single-step method, which was to prepare AgI nanoparticles at an AgI concentration of 5 x 10(-3) M and coat the AgI nanoparticles with silica shell by a St?ber method. The second was a multiple-step method, which was to repeat a step for preparing a AgI/SiO2 particle colloid solution with 10(-3) M AgI 5 times for adjusting a final AgI concentration to 5 x 10(-3) M. In the two methods, dominant particle aggregation took place, though core-shell particles were also produced. The third was a salting-out method, which was to salt out AgI/SiO2 particles in their colloid solution prepared at an AgI concentration of 10(-3) M, remove supernatant by decantation, and redisperse the particles in a fresh solvent. Consequently, AgI/SiO2 particles with an AgI concentration as high as 0.05 M were successfully prepared with the salting-out method, and their core-shell structure was not damaged during the salting-out.     

Fabrication of antibacterial monodispersed Ag-SiO2 core-shell nanoparticles with high concentration

Monodispersed Ag-SiO₂ core-shell nanoparticles with a high concentration of 400 mg/L were successfully fabricated by using tetraethoxysilane as silica precursor and reducing silver nitrate with ascorbic acid in the presence of cetyltrimethylammonium bromide as stabilizing agent. The nanoparticles had a spherical silver core in a size range from 14-26 nm in diameter and an amorphous silica shell of 15-28 nm thickness, respectively. The antibacterial effects of Ag-SiO₂ core-shell particles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were tested by the usual twofold serial dilution method for minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC). The results indicated that the core-shell nanoparticles owned excellent antibacterial effects.