Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water–isopropanol mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis and cocondensation reaction for the pervaporation separation of water‐isopropanol mixtures. The resulting membranes were characterized by Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The glass transition temperature of these membranes varied from 100 to 120°C with increasing TEOS content. Effects of crosslinking density and feed compositions on the pervaporation performances of the membranes were studied. The membrane containing 1.5:1 mass ratio of TEOS to PVA gave the highest separation selectivity of 900 at 30°C for 10 mass % of water in the feed mixture. It was found that the separation selectivity and permeation flux data are strongly dependent on the water composition of the feed and operating temperature. However, the membrane with the highest crosslinking density showed unusual pervaporation properties. The overall activation energy values were calculated using the Arrhenius‐type equation. The activation energy values for the permeation and diffusion varied from 49.18 to 64.96 and 55.13 to 67.31 kJ/mol, respectively. Pervaporation data have also been explained on the basis of thermodynamic quantities. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1304–1315, 2004     

纳米二氧化硅溶胶粒子的制备研究

以TEOS为前驱体,氨水作为催化剂,制备了单分散纳米二氧化硅溶胶,并且探讨了反应条件对二氧化硅溶胶粒径的影响。结果表明:在保持其它条件不变的情况下,随着NH4OH/TEOS摩尔比的增大,二氧化硅溶胶的粒径也增大;随着H2O/TEOS摩尔比的逐渐增大,二氧化硅溶胶的粒径先增大后基本不变;随着EtOH/TEOS摩尔比的增大,二氧化硅溶胶的粒径减小;随着反应温度的升高,二氧化硅溶胶的粒径显著减小。     

球形二氧化硅的制备与改性

正硅酸乙酯（TEOS）为硅原,在无水乙醇中通过氨水催化得到球形二氧化硅粒子。通过改变无水乙醇用量得到不同粒径的球形二氧化硅（SiO2）,粒子粒径分布在180～300nm之间。反应过程中加入硅烷偶联剂KH-570对球形二氧化硅粒子改性,随着偶联剂用量的增加,在红外光谱图中1400cm^-1处出现峰值,说明亚甲基的C—H键特征峰强度增加了,二氧化硅粒子表面KH-570的有机官能团增加了,且KH-570对二氧化硅粒子起到了改性作用。将制备好的球形二氧化硅在氮气保护下用丙烯酸甲酯（MA）进行包覆,在红外谱图中1400cm^-1出现C—H键的特征峰,1800cm^-1,处也有了酯基的特征峰,说明球形二氧化硅粒子表面存在了丙烯酸甲酯的官能团,丙烯酸甲酯接枝到了二氧化硅表面。     

Case study: Root cause of fluorine detection during TiN ARC layer corrosion of AlSiCu metal lines

The present study examines the cause of fluorine detection during the corrosion of the TiN antireflection coat (ARC) layer of AlSiCu metal lines. When a crack is generated in the tetraethyl orthosilicate (TEOS) oxide or spin-on-glass (SOG) film of an LSI device, the corrosion of the TiN ARC layer (TiO_xN_y-oxidation) may occur due to residual moisture inside the device. In this case, concentrated fluorine is detected around the corroded TiN ARC layer by energy-dispersive X-ray spectroscopy (EDX) analysis. Fluorine concentration was correlated with the degree of corrosion on the TiN ARC layer, suggesting the contribution of fluorine to the corrosion of this layer. When a wider distribution of fluorine concentrations was evaluated, however, the concentration of fluorine and the degree of corrosion on the TiN ARC layer did not match; instead, a higher concentration of fluorine was observed near the crack of the TEOS oxide film. The corroded TiN ARC layer of the sample was then removed, and the Al line of the underlying layer was observed. Etching was observed on the Al line surface where a high concentration of fluorine was detected. More specifically, EDX analysis detected that fluorine reacted with the Al line in the underlying layer after diffusion through the TiO_xN_y film, causing decreased film density due to the corrosion of the TiN ARC layer.     

SiO_2杂化环保型酚醛树脂的研究与制备

以正硅酸乙酯(TEOS)为前驱体,成功制备了玻璃纤维增强型改性PF(酚醛树脂)基复合材料的基体树脂——环保型纳米SiO2/PF。研究结果表明:当w(TEOS)=10%时,PF/SiO2复合材料的综合性能相对最好,其拉伸强度(758 MPa)、弯曲强度(945 MPa)和冲击强度(261 kJ/m2)分别比未改性体系提高了144%、53%和30%;改性PF体系的最大失重速率温度比纯PF体系提高了40～50℃,其热分解第二阶段的活化能由134.41 kJ/mol升至240.72 kJ/mol;玻璃纤维增强型PF/SiO2复合材料的线烧蚀率和质量烧蚀率分别比纯PF体系降低了22.5%和8.4%。     

正硅酸乙酯对水泥基材料性能的影响

对水泥基材料表面处理是提高其耐久性和服役寿命的有效方法之一,但是目前的表面处理方法存在各种弊端。采用正硅酸乙酯(TEOS)和常用的表面处理剂硅酸钠对水泥基材料进行表面防护,研究其对水泥基材料强度、吸水量、抗氯离子渗透性能和抗碳化性能的影响。结果表明,TEOS对水泥基材料的性能提升具有较好的作用;采用TEOS处理后,水泥净浆、砂浆和混凝土的强度提高率分别为20.8%、10.2%、12.5%;TEOS相对于硅酸钠能够更好地减小碳化深度、氯离子渗透性能和吸水量;采用TEOS处理后,碳化深度减少51.4%,氯离子渗透深度减少50.0%,吸水量减少55.5%。     

季铵化聚乙烯醇/聚二甲基二烯丙基氯化铵/正硅酸乙酯杂化阴离子交换膜的制备与性能表征

通过在季铵化聚乙烯醇(QPVA)和聚二甲基二烯丙基氯化铵(PDADMAC)混合聚合物水溶液中添加正硅酸乙酯(TEOS)进行溶胶-凝胶反应,制备得到了不同配比的溶胶-凝胶铸膜液,并将各铸膜液在模具中干燥得到杂化膜,随后将杂化膜在戊二醛/丙酮溶液中交联得到尺寸稳定的杂化阴离子交换膜。考察了季铵化聚乙烯醇和聚二甲基二烯丙基氯化铵铸膜液的质量比对杂化膜稳定性的影响。主要分析了4种尺寸稳定阴离子交换膜的外观形貌、红外光谱、微观形貌、热稳定性、含水/甲醇率和膜的离子交换容量。结果表明,QPVA/0.25PDADMAC/0.1TEOS碱性杂化膜在甲醇中尺寸稳定,微观结构致密,在65～140℃时热稳定性优良,离子交换容量可达到1.091 41 mmol/g。具有在中低温型碱性直接甲醇燃料电池中使用的潜力。     

改性甲基丙烯酸酯/SiO2-TiO2纳米复合材料的制备与表征

用原住复舍、溶胶-凝胶法制备了有机聚合物链段与无机相间有共价键存在的改性甲基丙烯酸酯类共聚物／SiO2-TiO2杂化纳米复合材料。通过红外光谱，透射电镜，扫描电镜对材料的结构和形态进行了表征，并对纳米分散相的形态、分布和界面状况对杂化材料的物理化学性能及氧阻透性能进行了测试．对结构与性能的关系进行了探讨．