无机纤维增强SiO2气凝胶隔热复合材料的研究进展

SiO_2气凝胶因其独特的纳米孔结构而具有低密度、低热导率等特点,具备成为高效隔热材料的潜力,然而SiO_2气凝胶的力学性能较差,极大地限制了其在隔热领域的应用。采用无机纤维作为增强体,制备的SiO_2气凝胶复合材料同时具有较好的力学和隔热性能,是目前国内外高性能隔热材料的研究热点之一。综述了无机纤维增强SiO_2气凝胶隔热复合材料的制备方法及其研究进展,并展望了其未来发展方向。     

热处理温度对复合SiO2隔热多孔陶瓷材料性能的影响

以SiO_2微粉、SiO_2气凝胶、石英纤维为主要原料,通过改变原料配比,采用半干法成型制备了SiO_2复合隔热多孔材料,通过X射线衍射分析(XRD)、扫描电子显微镜(SEM)等测试方法,研究了不同烧结温度(400~1000℃)对复合SiO_2隔热多孔陶瓷的物相组织、显微结构及物理性能的影响。结果表明当烧结温度升高至800℃时,试样保持着最佳的综合性能:其显气孔率为43.33%、体积密度为1.22g/cm3、抗折强度为2.05MPa、耐压强度为17.30 MPa,试样中均匀分布着大量呈球型、孤立的亚微米级气孔。     

SiO2溶胶-凝胶转变过程的动力学研究及应用

以硅酸乙酯为前驱体,通过水解法制备SiO₂溶胶,系统研究了SiO₂胶体的溶胶-凝胶转变过程。讨论了不同参数(如pH值、温度、硅酸乙酯的浓度等)对溶胶体系胶凝时间的影响,并对该过程的活化能进行了计算。结果表明:在酸性条件下,溶胶分子的生长模式为线性;随pH值增加,体系胶凝时间先增加后减少,拐点在pH等于2处;活化能与体系的pH有关。同时对上述结果从化学键、电荷密度、反应机理等方面进行了合理的解释。     

纳米纤维素增强SiO2气凝胶力学性能与微观结构

为克服SiO₂气凝胶强度低、易破碎等缺点,通过原位溶胶-凝胶法制备纳米纤维素（CNF）增强SiO₂气凝胶,并对SiO₂气凝胶的化学结构、微观形貌和力学、物理性能进行表征分析,探讨了CNF对SiO₂气凝胶力学性能的增强机制。结果表明：CNF独特的纳米级网络结构可增强SiO₂颗粒之间的联结强度;Si-OH（960 cm^-1）和Si-O-Si（1 225 cm^-1、1 056 cm^-1和800 cm^-1）等特征吸收峰的出现表明,CNF与SiO₂之间形成稳定的化学键联结;采用不同含量CNF气凝胶作为SiO₂增强相均可达到增强力学性能的效果,同时仍能保持SiO₂气凝胶本身质轻、高孔隙率、高比表面积等特性;当以CNF质量分数为6wt%的溶液制备气凝胶时,CNF增强SiO₂气凝胶具有最优的力学性能,压缩模量和压缩强度分别为12.43 MPa和2.59 MPa。     

SiO2对铝合金熔体直接氧化的影响

本文研究了在高温空气氛中涂覆在Al-Mg-Si合金表面的SiO₂对铝合金直接氧化的影响规律。实验揭示了SiO₂对Al-Mg-Si合金熔体直接氧化生长表面的形态的影响规律,发现SiO₂有助于Al₂O₃/Al复合材料以光滑的方式进行氧化生长,提高了材料的致密度。实验还发现,SiO₂可消减Al-Mg-Si合金熔体直接氧化所需的孕育期,缩短Al₂O₃/Al复合材料的生长时间。     

纳米SiO2/尼龙66复合材料的力学性能和热性能

采用熔融共混的方法在双螺杆挤出机上制备出纳米SiO₂/尼龙66复合材料,并对其力学性能和热性能进行了研究。结果表明：复合材料的拉伸强度和弹性模量随纳米SiO₂含量的增加而提高。当SiO₂质量分数为3％时,复合材料的拉伸强度达到最大,增幅为11.2％;当SiO₂质量分数为5％时,弹性模量达到最大, 增幅为30.1％。复合材料的储能模量和玻璃化转变温度较纯尼龙66也有明显提高。差示扫描量热法（DSC）分析显示,纳米SiO₂的加入一方面阻碍了尼龙66的结晶过程,降低了材料的结晶温度;另一方面它又能作为形核剂,增加尼龙66的形核位置,提高形核率。     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

热处理温度对TiO2/SiO2复合气凝胶光催化性能的影响

采用溶胶–凝胶法在常压下经不同温度热处理制备了TiO2/SiO2复合气凝胶光催化剂,利用XRD、TGA和BET等手段对其微观结构进行表征,以甲基橙溶液光催化降解实验评价其光催化性能,研究了热处理温度对TiO2/SiO2复合气凝胶的微观结构及光催化性能影响规律.结果表明:随着热处理温度升高,TiO2/SiO2复合气凝胶中锐钛矿结晶度升高,晶粒尺寸增大,比表面积减小,使TiO2/SiO2复合气凝胶对甲基橙溶液的光催化降解活性呈现先升后降的变化趋势.当热处理温度为700℃左右,紫外光照20 min TiO2/SiO2复合气凝胶对甲基橙溶液的降解率达到95.4%.     

酸碱条件对水玻璃为源制备SiO2气凝胶的影响

以廉价的工业水玻璃为凝胶前躯体,柠檬酸为凝胶促进剂,使用溶胶-凝胶与CO2超临界干燥工艺制备了块状的SiO2气凝胶,并探讨了酸性和碱性条件对所制备SiO2气凝胶结构与性能的影响.实验结果表明:水玻璃在酸性条件(pH≈4)和碱性条件(pH≈10)下均可以制备出完整、无开裂的二氧化硅气凝胶块体样品,酸性和碱性环境对水凝胶和最终SiO2气凝胶结构和性能的影响较大.酸性条件下获得的水凝胶呈透明块体,而碱性条件下所得水凝胶为白色不透明体.与碱性条件下制备的SiO2气凝胶相比,酸性条件下所得气凝胶具有更高的比表面积、较大的密度以及尺寸较小的胶体粒子.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

常压干燥制备SiO2气凝胶复合材料研究进展

SiO_2气凝胶复合材料具有低密度、低热导、高强度等优异性能,已在航空航天、石油化工、建筑保温等领域获得较好应用。然而现有成熟的超临界干燥制备SiO_2气凝胶复合材料工艺需要维持高温、高压条件,能耗高、危险性大且设备复杂,常压干燥制备工艺由于所需条件温和、设备简单,有望实现连续性规模化生产。本文结合国内外关于常压干燥制备SiO_2气凝胶复合材料的研究进展,按照颗粒、纤维等增强相的不同,对常压干燥制备SiO_2气凝胶复合材料进行综述并对其未来发展方向进行了展望。     

Influence of plasma heating of wafer substrates on SiO2 deposition rate in a TEOS/O2 high-density plasma CVD system

The influence of plasma heating of the Si and glass wafer substrates on silicon dioxide (SiO₂) deposition rates by a tetraethylorthosilicate/O₂ supermagnetron (high-density) plasma CVD were investigated. With a fixed RF power of 100 W supplied to both upper and lower electrodes, the SiO₂ deposition rate on the Si wafer substrate decreased with increasing wafer-stage temperature, showing a negative activation energy for the deposition rate. When Si and glass wafers were attached to the electrode using adherent thermal conductors, the film thickness increased almost linearly with regard to the deposition time, and both deposition rates became almost the same (about 310 Å/min). When both wafers were simply laid on the electrode without an adhesive bond and hence with poor thermal contact, the film thickness increased nonlinearly with deposition time, showing a gradual decrease in deposition rate with time, being as low as 80 and 150 Å/min, respectively for Si and glass wafers, for a deposition time of 15 min. The difference between the two deposition rates on Si and glass wafers in the case of poor thermal contact to the lower electrode is thought to be caused by plasma heating and related mainly to differences in optical absorption characteristics of the two wafer substrates. Variations in measured thickness distributions across the substrate surface were attributed to an antisymmetric plasma density distribution in the direction perpendicular to the magnetic field lines caused by E×B electron drift.     

SiO2 layer thickness effects on the (001) texture of FePtCu:SiO2 nanocomposite films

The influence of SiO₂ layer thickness of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ multilayer nanocomposite films on their structural and magnetic properties were investigated. The films were deposited on (001) textured FePt films, and then annealed at 873 K. The crystalline texture of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ films changes drastically with respect to the thickness of the SiO₂ layers. In the film with 50-Å thick SiO₂ layers, the (111) peak was strong although the (001) orientation is dominant, and self-organized spherical FePtCu particles were formed in the SiO₂ matrix. However, in the film with 19-Å thick SiO₂ layers, flat FePt grains with perfect (001) orientation were obtained. In addition, twins with different crystalline orientations were seen in the above films with different thicknesses of the SiO₂ layers. Accordingly, different perpendicular hysteresis loops were obtained.     

Simulation of Si and SiO2 etching in CF4 plasma

The reactive ion etching (RIE) of Si and SiO₂ in CF₄ plasma is considered. The dependences of RIE rates of Si and SiO₂ on pressure have maxima due to the presence of single-atom vacancies. The RIE rates approach the maximum values at different pressures but at the same concentration of SiF and SiOF molecules in the adsorbed layer. Using the obtained results Si/SiO₂ etching selectivity is investigated.     

Y2O3添加量对Al2O3/ZrO2共晶陶瓷显微组织及力学性能的影响

为探索第三组元Y₂O₃添加对Al₂O₃/ZrO₂共晶陶瓷显微组织与机械性能的影响,本文利用低温度梯度的高温熔凝法制备了直径为20 mm的Al₂O₃/ZrO₂(Y₂O₃)共晶陶瓷块体,采用SEM、EDS及XRD技术对共晶陶瓷进行微结构分析,并利用维氏压痕法对其硬度和断裂韧性进行测试。SEM结果表明,凝固组织由群集的共晶团结构组成,随着Y₂O₃添加量的增加,共晶团形态由胞状转变为枝晶状,内部相间距在1~2 μm范围内变化。力学测试表明,Y₂O₃摩尔分数小于1.1%时,由于组织内部存在低硬度m-ZrO₂及微裂纹缺陷,故陶瓷硬度较低,约为(9.53±0.22 )GPa;当Y₂O₃摩尔分数为1.1%时,陶瓷硬度最大,约为(18.05±0.27)GPa;当Y₂O₃的摩尔分数大于1.1%时,由于共晶团边界区内气孔缺陷及粗大组织增多,引起陶瓷硬度值略有下降。低Y₂O₃摩尔分数添加时,陶瓷断裂韧性相对较高,约为(6.30±0.16)MPa·m^1/2,这与其内部存在大量微裂纹缺陷有关;随着Y₂O₃添加量的增加,陶瓷的微裂纹数量减少、边界区内缺陷增多,断裂韧性降低。     

N2 adsorption curve of mesoporous SiO2: A neglected characterization technique

Mesoporous SiO₂ sieve and SiO₂ nanoparticles were synthesized by a traditional method in the presence and absence of tri-block copolymer surfactant P123 as structure directed agent respectively. The characterization results show that the mesoporous SiO₂ sieve has larger specific area (789 m²/g) than SiO₂ nanoparticles (373 m²/g), and there exists a substantial difference in the N₂ adsorption curves between the two samples. A speculative scheme shows that the formation of bottleneck during the N₂ adsorption process of mesoporous SiO₂ sieve should be responsible for the phenomenon.