块体溶胶-凝胶生物活性玻璃的制备与表征

由于溶胶-凝胶工艺和玻璃组分的限制,从凝胶制备块体生物玻璃有一定难度.获得块体凝胶的关键步骤是干燥工艺,其中毛细管压力起决定作用.用一种简便可靠的方法,制备了均匀、透明、无裂纹的块体溶胶-凝胶生物玻璃585.选用合适的干燥添加剂(DCCA),结合准平衡干燥可以有效防止干燥过程中的凝胶开裂.体外浸泡试验表明,该样品具有优良的生物活性,但是机械强度不高.在玻璃组分中引入TiO₂后,选择合适的DCCA制得的块体材料保持一定的生物活性,同时抗压强度明显提高.讨论了不同的DCCA对干燥过程的不同作用机理和对材料的介孔结构特征的影响,以及TiO₂对提高凝胶骨架和材料整体强度的贡献,还有对体外生物活性的影响.     

SiO2多孔凝胶的制备及对铈的吸附性能研究

以正硅酸乙酯(TEOS)为硅源,利用溶胶-凝胶法通过分相途径制备了SiO2多孔凝胶,并对合成的SiO2多孔凝胶进行了热处理,借助扫描电子显微镜(SEM )、红外光谱(IR )、差热-失重综合分析仪(TG-DTA)等分析手段,研究了SiO2多孔凝胶内部结构、热稳定性等性质,并且采用间歇法研究了其对溶液中铈的吸附性能,从而...     

溶胶-凝胶法制备纳米二氧化硅微球

在不同醇介质中,以氨水作为催化剂,正硅酸乙酯为硅源,利用溶胶-凝胶法制备了单分散纳米SiO2微球,利用激光粒度仪得到了微球粒径,利用扫描电镜得到了SiO2形貌,用能谱仪进行了元素成分分析。研究表明,随着氨水用量提高,溶液中OH-浓度增大,SiO2微球粒径增大;随着水用量增加,SiO2粒径有所增大,当水量太多时,粒径反而有下降趋势;在不同介质中,随着烃基中碳数和粘度改变,SiO2粒径会呈现不同变化。     

阶层多孔二氧化硅块体材料的制备与表征

以正硅酸甲酯(TMOS)为前驱体、0.01 mol·L^-1盐酸为催化剂、聚环氧乙烷(PEO, 分子量为10 000)为相分离剂、环氧丙烷(PO)为凝胶促进剂、十二烷基硫酸钠(SDS)为造孔剂, 采用溶胶-凝胶伴随相分离制备阶层多孔二氧化硅块体材料, 利用差热分析(DTA)、热重分析(TG)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、N2吸附/脱附装置等测试技术对所制得的阶层多孔块体进行了表征, 探究造孔剂SDS对大孔和介孔结构的影响机理。研究表明:SDS在凝胶过程中以胶束的形式进入到骨架中形成介孔孔道;当SDS为0.21 g时, 块体材料的阶层多孔结构最优, 大孔孔径为1~3 μm, 介孔孔径为4~5 nm, 比表面积为650 m²·g^-1;800 ℃热处理后, 大孔结构和骨架上的介孔基本保持, 比表面积仍能达到421 m²·g^-1, 体现出良好的热稳定性。     

阶层多孔二氧化硅块体材料的制备与表征

以正硅酸甲酯(TMOS)为前驱体、0.01 mol·L-1盐酸为催化剂、聚环氧乙烷(PEO,分子量为10 000)为相分离剂、环氧丙烷(PO)为凝胶促进剂、十二烷基硫酸钠(SDS)为造孔剂,采用溶胶-凝胶伴随相分离制备阶层多孔二氧化硅块体材料,利用差热分析(DTA)、热重分析(TG)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、N2吸附/脱附装置等测试技术对所制得的阶层多孔块体进行了表征,探究造孔剂SDS对大孔和介孔结构的影响机理。研究表明:SDS在凝胶过程中以胶束的形式进入到骨架中形成介孔孔道;当SDS为0.21 g时,块体材料的阶层多孔结构最优,大孔孔径为1~3μm,介孔孔径为4~5 nm,比表面积为650 m2·g-1;800℃热处理后,大孔结构和骨架上的介孔基本保持,比表面积仍能达到421 m2·g-1,体现出良好的热稳定性。     

溶胶-凝胶法制备壳聚糖/SiO2杂化材料

以正丁酐（Butyric anhydride)、壳聚糖(Chitosan）、甲基丙烯酰氧基丙基三甲氧基硅烷（MPTMS）、正硅酸乙酯（TEOS）为原料,采用迈克尔加成反应合成了丁酰壳聚糖-MPTMS,配合酸催化sol-gel过程,制备了透明的壳聚糖/SiO2杂化材料,FTIR表征了杂化材料的结构。TGA,SEM以及力学性能测试结果表明,杂化材料的成型工艺对材料的表面形貌、热分解温度以及力学性能的影响显著。     

PbF2·SiO2基玻璃陶瓷的溶胶-凝胶制备及结构转变研究

采用溶胶-凝胶法制备了PbF2·SiO2纳米晶玻璃陶瓷块体;利用TG-DSC和IR技术分析了干凝胶在热处理过程中有机基团的分解及内部原子键合方式的演变;结合XRD和TEM研究了凝胶玻璃中PbF2纳米晶粒的长大过程,并分析了Er3+掺杂的影响.结果表明,采用此方法制备的PbF2.SiO2纳米晶粒玻璃陶瓷具有较好的成形性,晶化温度在320℃左右;经480℃热处理,镶嵌在玻璃基体中的PbF2晶粒尺度约为10-25nm,材料透明性良好.在PbF2·SiO2系统中掺入少量的Er3+,将提高PbF2的晶化温度,降低玻璃陶瓷的显微硬度;掺杂可能对PbF2晶粒表面原子的活性起抑制作用,阻碍晶粒的表面迁移,使晶粒的生长速度明显降低.     

SiO2阶层多孔结构搭建及块体材料制备机理

借助溶胶-凝胶结合相分离和模板法进行了阶层多孔结构的搭建及二氧化硅多孔块体材料的制备,表征了阶层多孔块体的显微结构及孔结构特性,分析了阶层多孔结构的搭建机理。研究结果表明,三嵌段共聚物聚环氧乙烷-聚环氧丙烷-聚环氧乙烷（P123）的加入不仅诱导共混体系发生相分离,调控大孔结构的形成,同时形成球形胶束并作为模板剂进入骨架,而1,3,5-三甲基苯（TMB）的加入使P123形成的胶束膨胀且更加稳定,在骨架上成功引入了球形介孔,骨架中凝胶粒子相互聚集形成微孔,从而搭建贯通大孔-球形介孔-微孔同时分布的阶层多孔结构,并获得相应的多孔块体材料;当正硅酸甲酯（TMOS）：P123：TMB摩尔比为1：0.015：0.353时,多孔块体材料的阶层多孔结构最优,大孔孔径为0.5-1.5 μm,介孔孔径为3-4 nm,显气孔率66.1%,比表面积为616 m²·g^-1。     

溶胶-凝胶法制备掺Sm3+的SiO2玻璃的结构及发光性能

利用溶胶-凝胶技术制备了掺不同量Sm3+和不同退火温度下的SiO2凝胶和玻璃,通过三维荧光光谱、激发光谱、发射光谱的测试,确定了Sm3+在SiO2凝胶玻璃中的最佳激发波长为360 nm,最强发射波长为610 nm,激发光谱的峰位置在360、393、464 nm处,发射光谱的峰位置在578、591、595、610、732nm处,分别归属于4G5/2-6H5/2、4G5/2-6H7/2、4G5/2-6H11/2跃迁,并证明当掺杂量达到1.15%时,Sm3+的发光最强,当Sm3+的掺杂量超过1.15%时,发生浓度猝灭效应.     

溶胶-凝胶法原位生成SiO2改性硅基耐烧蚀材料

建立了在硅基耐烧蚀材料中用溶胶-凝胶法原位生成SiO2的方法.首先将硅橡胶、气相白炭黑、纤维等原料混炼硫化制备出硫化胶.然后将硫化胶依次浸入四氢呋喃、原硅酸乙酯和正丁基胺水溶液中进行预溶胀处理、物理扩散和化学反应,得到原位生成SiO2.SEM照片显示,在硅基耐烧蚀材料中原位生成的SiO2颗粒呈球形,粒径在40~60 nm,但分布不均匀,在硫化胶表层存在富集现象.实验结果表明,原位生成SiO2平均含量增加,硅基耐烧蚀材料的抗拉强度增加,线烧蚀率下降;含13.7%原位生成SiO2硅基耐烧蚀材料抗拉强度为5.82 MPa,线烧蚀率为0.071 mm/s.     

Antireflective and Self-cleaning Properties of SiO2/TiO2 Double-Layer Films Prepared by Cost-E ective Sol-Gel Process

SiO₂/TiO₂ double-layer films with antireflective and self-cleaning properties were prepared by dip-coating glass substrate into cost-effective SiO₂ and TiO₂ sol successively and subse-quently being calcined at 500 oC. The optical and structural properties of films have been in-vestigated by UV-visible spectrophotometer and field emission scanning electron microscope, respectively. At the same time, self-cleaning property generated from superhydrophilicity and photocatalysis was obtained. The results indicated that the as-prepared SiO₂/TiO₂ double-layer films show maximum transmittance of 95% and self-cleaning property.     

Ionic transport studies on (PEO)6:NaPO3 polymer electrolyte plasticized with PEG400

Conduction characteristics of the poly(ethylene oxide) based new polymer electrolyte (PEO)₆:NaPO₃, plasticized with poly(ethylene glycol) are investigated. Free standing flexible electrolyte films of composition (PEO)₆:NaPO₃ + x wt.% PEG₄₀₀ (30 ? x ? 70) are prepared by solution casting method. A combination of X-ray diffraction (XRD), optical microscopy and differential scanning calorimetry (DSC) studies have indicated enhancement in the amorphous phase of polymer due to the addition of plasticizer. Further, a reduction in the glass transition temperature observed from the DSC result has inferred increase in the flexibility of the polymer chains. The cationic transport number (t_Na⁺) of 0.42 determined through combined ac-dc technique has confirmed ionic nature of conducting species. Ionic conductivity studies are carried out as a function of composition and temperature using complex impedance spectroscopy. The electrolyte with maximum PEG₄₀₀ content has exhibited an enhancement in the conductivity of about two orders of magnitude compared to the host polymer electrolyte. The complex impedance data is analyzed in conductivity, permittivity and electric modulus formalism in order to throw light on transport mechanism. A solid state electrochemical cell based on the above polymer electrolyte with a configuration Na|SPE|(I₂ + acetylene black + PEO) has exhibited an open circuit voltage of 2.94 V. The discharge characteristics are found to be satisfactory as a laboratory cell.     

Phase Separation Process of Polymer—Incorporated Silica-Zirconia Sol-Gel System

Gels with interconnected domain morphologies in the micrometer-range have been prepared in the silica-zirconia system. The domain formation kinetics in the gelling solution have been examined. Growth of an ordered structure on the length scale of micrometers, for which the kinetics are interpreted as spinodal decomposition, was observed by time-resolved light scattering measurements. The remarkable feature of the silica-zirconia system was that a time-dependent decrease of the wavelength of compositional fluctuations was observed. This occurred in the early stage, probably because the fast condensation reaction which was induced by the addition of zirconia, lead to a substantial change in quench depth on a timescale similar to that of the growth of concentration fluctuations. In the following stage, the coarsened domain structure was frozen-in by the sol-gel transition as the permanent morphology.     

Compatibilisation effect of PP-g-MA copolymer on iPP/SiO2 nanocomposites prepared by melt mixing

In the present study, a series of iPP/SiO₂ nanocomposites, containing 1, 2.5, 5, 7.5, 10 and 15 wt% SiO₂ nanoparticles, were prepared by melt mixing in a twin screw co-rotating extruder. Poly(propylene-g-maleic anhydride) copolymer (PP-g-MA) containing 0.6 wt% maleic anhydride content was added to all nanocomposites at three different concentrations, 1, 2.5 and 5 wt%, based on silica content. Mechanical properties such as tensile strength at break and Young’s modulus were found to increase and to be mainly affected by the content of silica nanoparticles as well as by the copolymer content. For the tensile strength at break as well as for yield point, a maximum was observed, corresponding to the samples containing 2.5-5 wt% SiO₂. At higher concentrations, large nanosilica agglomerates are formed that have as a result a decrease in tensile strength. Young’s modulus increases almost linearly on the addition of SiO₂, and takes values up to 60% higher than that of neat iPP. Higher concentrations of PP-g-MA resulted in a further enhancement of mechanical properties due to silica agglomerate reduction. This finding was verified from SEM and TEM micrographs. Evidently the surface silica hydroxyl groups of SiO₂ nanoparticles react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual SiO₂ nanoparticles in the iPP matrix. The enhanced adhesion in the interface of the two materials, as a result of the mentioned reaction, has been studied and proved by using several equations. The increased Vicat point of all nanocomposites, by increasing the PP-g-MA content, can also be mentioned as a positive effect.     

溶胶-凝胶法制备改性TiO2纳米薄膜及其防腐蚀性能

应用溶胶-凝胶法和浸渍提拉技术在316L不锈钢表面分别制备TiO2纳米膜和 B-Fe-Ce改性的TiO2纳米膜. 采用场发射扫描电子显微镜(FE-SEM)、原子力显微镜(AFM)、拉曼光谱法和能量分散谱(EDS)对薄膜进行表征,通过电化学阻抗谱(EIS)和动电位阳极极化曲线的测试考察薄膜的耐蚀性及对不锈钢的保护性能. 结果表明:两种纳米薄膜均含锐钛矿型的TiO2纳米颗粒,纯TiO2纳米膜与改性后的纳米膜中颗粒直径分别约为15和10 nm. TiO2/316L不锈钢和 B-Fe-Ce-TiO2/316L不锈钢膜电极浸泡在0.5 mo.lL-1 NaCl溶液后,后者的电化学反应电阻较大,动电位阳极极化曲线的稳定钝化区较宽,击穿电位更高,说明改性的纳米膜的耐蚀性及其保护性能更好.     

快速制备高掺杂CuO/SiO2复合气凝胶

通过环氧丙烷预反应法, 以乙腈为溶剂快速制备了高掺杂的氧化铜/二氧化硅复合气凝胶. 在典型的合成过程中, 将正硅酸甲酯(TMOS)、乙腈、去离子水和环氧丙烷混合进行预反应, 然后将该溶液与氯化铜的乙腈-水溶液混合并添加环氧丙烷, 在35℃烘箱中静置0.5 h 后转化为湿凝胶, 再经过CO₂超临界流体干燥和热处理即可获得黑色块状CuO/SiO₂复合气凝胶. 最终气凝胶样品密度约为180 mg·cm^-3, 比表面积高达625 m2·g^-1, 平均掺杂比为19.91%±2.42% (Cu:Si 摩尔比), 压缩模量为1.639 MPa, 具有成型性好、分散均匀等优点,是良好的背光源靶材料. 本论文还通过对比实验对凝胶化过程的机理进行分析, 结果表明, 通过改变溶剂和采用环氧丙烷预催化均衡了两种不同前驱体的反应速率, 实现了共凝胶的目的. 此外, 该方法还有望为其它金属氧化物/二氧化硅复合气凝胶的制备提供新思路.     

In situ preparation of poly(ethylene terephthalate)-SiO2 nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were synthesized by using the in situ polymerization approach. Sol-gel transformation based on the hydrolysis and condensation of tetraethoxysilane (TEOS) is used to prepare the inorganic phase, concurrent with condensation polymerization of terephthalic acid and ethylene glycol to produce the PET matrix. Due to the simultaneous formation of the polymer matrix and the inorganic networks, a macrophase separation is avoided, and the resulting materials have a high degree of homogeneity. The morphology and the crystallization behavior of the composites were examined by scanning electron microcopy (SEM) and differential scanning calorimetry (DSC), respectively.     

Synthesis and characterization of poly(EMA-co-HEA)/SiO2 nanohybrids

A series of silica-based organic-inorganic nanocomposites, which attempt to mimic the properties of mineralized matrix tissues from natural bone or dentin, have been prepared and characterized as potential candidates for the synthetic matrix of scaffolds for bone or dentin regeneration. The synthesis procedure consisted in the copolymerization of ethyl methacrylate (EMA) and hydroxyethyl acrylate (HEA) during the simultaneous acid-catalyzed sol-gel polymerization of tetraethoxysilane (TEOS) as a silica precursor, giving rise to poly(EMA-co-HEA)/SiO₂ nanohybrids with silica contents in the range of 0-30 wt%. Different structures of silica within the organic polymeric matrix were inferred from infrared spectroscopy, energy dispersive X-ray spectroscopy, thermogravimetry, pyrolysis, density assessments, solvent uptake and transmission electron microscopy. TEOS was efficiently hydrolyzed and condensed to silica during the sol-gel process in all cases, and presented a homogeneous distribution in the polymeric matrix, in the form of nanodomains either interdispersed or continuously interpenetrated with the organic network, depending on the silica content. Silica contents above 10% produced co-continuous interpenetrated structures where the silica network reinforces mechanically the organic matrix and at the same time confers bioactivity to the surfaces.     

Controlled synthesis of AB2 amphiphilic triarm star-shaped block copolymers by ring-opening polymerization

This paper describes the synthesis of a novel amphiphilic AB₂ triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(ε-caprolactone) (PCL). A series of AB₂ triarm star-shaped copolymers with different molecular-weights for the PCL block were successfully synthesized by a three-step procedure. α-Methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of α-methoxy-ω-hydroxy-poly(ethylene oxide) (MPEO) on epichlorohydrin. In a second step, the α-methoxy-ω,ω′-dihydroxy-poly(ethylene oxide) (PEO(OH)₂) macroinitiator was prepared by the selective hydrolysis of the ω-epoxy end-group of the PEO-epoxide chain. Finally, PEO(OH)₂ was used as a macroinitiator for the ring-opening polymerization (ROP) of ε-caprolactone (εCL) catalyzed by tin octoaote (Sn(Oct)₂). PEO-epoxide, PEO(OH)₂ and the AB₂ triarm star-shaped copolymers were assessed by ¹H NMR spectroscopy, size exclusion chromatography (SEC) and MALDI-TOF. The behavior of the AB₂ triarm star-shaped copolymer in aqueous solution was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM).     

通过RAFT聚合制备SiO2/接枝共聚物纳米杂化粒子

以二氧化硅(SiO2)纳米粒子表面键接的二硫代苯甲酸酯作为可逆加成-断裂-链转移(RAFT)聚合反应的链转移剂, 在室温下引发苯乙烯和马来酸酐进行表面RAFT交替共聚反应, 制得了SiO2/苯乙烯-alt-马来酸酐杂化材料. 通过聚氧化乙烯(PEO)的羟基与马来酸酐的酯化反应, 将PEO接枝到SiO2纳米粒子的表面, 增加了硅粒子的生物相容性. 用FTIR, TGA和TEM对杂化材料的结构、组成和形貌进行了表征.