紫外光固化二氧化硅/丙烯酸酯亲水杂化薄膜

紫外光照射下制备了用于改善玻璃表面亲水性的二氧化硅/丙烯酸酯透明杂化薄膜,其水接触角小于5°,具有优异的亲水性。讨论了反应时间、反应温度、丙烯酸羟丙酯用量和正丙醇用量与薄膜亲水性的关系。通过SEM对薄膜表面形貌进行了研究,发现薄膜具有多孔结构,SiO₂溶胶粒子均匀分布在膜层中。研究表明,以硅溶胶（ml）与丙烯酸羟丙酯（mol）配比为50∶0.15在40℃时反应1 h制备杂化溶胶,且涂膜液用20%（质量）正丙醇稀释时所制备的杂化薄膜亲水性最好。     

溶胶-凝胶法制备PEW/SiO2杂化材料及表征

通过熔融接枝反应将乙烯基三甲氧基硅烷（VTMS）接枝到聚乙烯蜡（PEW）分子链上,接枝物红外光谱（FTIR）的1090、1030、960 cm^-1等处出现了—Si—O—CH3的特征吸收峰。以正硅酸乙酯（TEOS）为前驱体,混入接枝PEW中,通过溶胶-凝胶法（sol-gel）制备了PEW/SiO₂杂化材料。使用透射电镜（TEM）和热重分析（TG）研究了杂化材料的形态及性能,结果表明,通过sol-gel可以制备SiO₂含量为0. 98%～4. 12%的杂化材料,SiO₂颗粒与PEW接枝物分子间具有良好的相容性,纳米SiO2的存在提高了PEW的耐热性能,当SiO₂含量为3. 75%时,PEW的分解温度提高了21. 34℃。     

Mn2+-SiO2-TiO2纳米薄膜光催化性能的研究

在溶胶-凝胶法制备Mn²⁺掺杂TiO₂催化剂的基础上，掺入SiO₂纳米粉体，制备了一种新的Mn²⁺SiO₂TiO₂纳米薄膜。以甲醛为降解对象，探讨该种新薄膜的光催化性能，并与单纯TiO₂薄膜、Mn²⁺-TiO₂薄膜和SiO₂-TiO₂薄膜进行比较。结果表明，500 ℃焙烧，掺杂m(Mn²⁺)∶m(SiO₂)∶m(TiO₂)＝1.0∶12∶100 时，Mn²⁺-SiO₂-TiO₂纳米薄膜的光催化活性最高，150 min后甲醛降解率达88%，是单纯 TiO₂薄膜的1.8倍。该薄膜稳定性较好，经重复7次使用,最大降解率只下降7%，表明其稳定性较好。     

SO42－/SiO2-ZrO2固体超强酸催化乳酸乙酯的合成研究

采用溶胶-凝胶法制得SiO₂-ZrO₂基质材料，然后通过浸渍法制备SO₄^2－/SiO₂-ZrO₂固体超强酸。对SO₄^2－/SiO₂-ZrO₂固体超强酸催化乳酸乙酯的合成反应进行了研究。适宜的反应条件为：稀硫酸浸泡16 h，反应温度80 ℃，反应时间4 h，催化剂用量为每摩尔乳酸1.5 g。反应酯化率达92.7％。     

硅烷偶联剂对聚甲基丙烯酸甲酯/二氧化硅纳米复合材料结构与性能的影响

采用乙烯基三乙氧基硅烷(WD-20)作为偶联剂,通过溶胶-凝胶法合成了聚甲基丙烯酸甲酯(PMMA)/二氧化硅(SiO₂)纳米复合材料,采用紫外-可见光谱、红外光谱、扫描电子显微镜和热机械分析等研究了材料的结构和性能.结果表明,WD-20的加入对纳米复合材料透明性、耐热性能和微观形态结构有较大影响,随着WD-20用量的增加,纳米复合材料透明性增加,SiO₂分散相尺寸变小,玻璃化转变温度增加.当WD-20与四乙基原硅酸盐（TEOS）之比为0.2时,所制备的纳米复合材料的溶胶分数为6%、玻璃化转变温度为250 ℃以上、可见光透过率在80％以上、SiO₂分散相尺寸小于100 nm.     

载体和制备方法对铜系一步法合成

以甲醇与乙醇一步反应合成异丁醛反应为基础，研究了不同载体对铜基催化剂反应性能的影 响。分别以SiO₂、SiO_2-ZrO₂、SiO_2-Al₂O₃、Al₂O₃和SiO₂-TiO₂为载体，采用溶胶-凝胶和 浸渍法制备催化剂。采用TPR、XRD和BET等技术对催化剂进行表征。结果表明，复合氧 化物特别是SiO₂-ZrO₂和SiO₂-TiO₂作载体能提高催化剂的比表面积，活性组分分散 好，催化剂的催化性能较好。     

PVA作纺丝助剂制备莫来石-氧化铝长纤维

用氯化铝和铝粉为原料制备了铝溶胶,再向铝溶胶加入硅溶胶、封端剂和聚乙烯醇（PVA）纺丝助剂,制得莫来石-氧化铝溶胶,研究了纺丝助剂加入量对溶胶纺丝性能的影响。研究发现,溶胶在浓缩时,胶粒间发生缩合反应,形成线性或非线性的分子链,生成可纺的黏性溶胶;在溶胶中加入纺丝助剂,铝/硅离子或胶粒与纺丝助剂的活性基团发生缩聚反应,生成有机-无机的杂化分子链,提高了溶胶的纺丝性能;在加入封端剂的同时,加入质量分数为1%的PVA,凝胶纤维的最大长度可达100 cm。凝胶纤维在1 200 ℃下烧结1 h后,得到的陶瓷纤维的物相为γ-Al₂O₃和莫来石相,纤维表面光滑、直径均匀。     

聚二甲基硅氧烷杂化材料的合成及性能研究

溶胶凝胶方法一般是金属醇盐在酸或碱的催化条件下水解缩合制备高纯度材料的一种方法。电纺法是聚合物溶液或熔体借助高压静电作用进行喷射拉伸而获得超细或纳米级纤维的一种纺丝方法。本文综合两种方法,制备PDMS/SiO_2-TiO_2抽丝纤维和PDMS/SiO_2电纺纤维。制备PDMS/SiO_2杂化纤维,以正硅酸乙酯为原料,采用溶胶凝胶法制备了硅溶胶,再加入PDMS溶液,通过静电纺丝制备PDMS/SiO_2杂化纤维膜。通过加入不同量的正硅酸乙酯,来比较PDMS/SiO_2杂化纤维膜的可电纺性能的改变及PDMS/SiO_2杂化纤维膜杂化纤维的平均直径的大小变化趋势。制备PDMS/SiO_2-TiO_2抽丝纤维,以正硅酸乙酯和钛酸四丁酯为原料,通过溶胶-凝胶法制备Si-Ti溶胶,随后再加入聚二甲基硅氧烷(PDMS)溶液,通过提拉法制备PDMS/SiO_2-TiO_2抽丝纤维。在制备PDMS/SiO_2-TiO_2杂化纤维时,加入不同量的正硅酸乙酯和钛酸四丁酯,比较PDMS/SiO_2-TiO_2杂化纤维的平均直径的变化趋势。     

改性硅溶胶憎水薄膜的制备

从接触角变化的角度研究了甲基三甲氧基硅烷(MTMS)、乙烯基三乙氧基硅烷(ETES)、γ- (甲基丙烯酰氧基)丙基三甲氧基硅烷(MPMS)等不同端官能团硅烷偶联剂改性硅溶胶制备的杂化溶胶;采用MPMS改性TiO₂制备了TiO₂-SiO₂/丙烯酸羟丙酯杂化溶胶,采用紫外固化工艺在玻璃表面制备了憎水薄膜。采用傅里叶红外光谱（FTIR）、扫描电子显微镜（SEM）、接触角测试仪等手段对薄膜的结构与性能进行了分析与表征。研究表明：MPMS改性纳米TiO₂与MTMS改性硅溶胶相容性良好,通过在MTMS改性硅溶胶中添加改性纳米TiO₂含量为0.1%时,薄膜水接触角最大可达140°左右。在玻璃表面涂膜前后光学性能无明显变化,具有广泛的应用前景。     

纳米γ-Fe2O3复合氧化物的制备与气敏性质

用溶胶-凝胶法制备了纳米γ-Fe₂O₃及γ-Fe₂O₃/SiO₂复合氧化物,用热重-差热分析 (TG-DTA)、X射线衍射 (XRD)、透射电镜 (TEM)和二次粒度分布对纳米粒子进行表征,并考察了γ-Fe₂O₃、γ-Fe₂O₃/SiO₂敏感材料对CO、H₂、C₂H₄、C₆H₆等气体的敏感系数及其焙烧温度对敏感系数的影响,并选择了敏感材料对气体检测的最佳工作温度.结果表明,γ-Fe₂O₃/SiO₂纳米复合氧化物中SiO₂对提高γ-Fe₂O₃的相变温度、加强热稳定性及提高催化和气体敏感系数起很大作用.     

聚乙烯醇/二氧化硅杂化膜的制备及渗透蒸发分离环己醇（酮）/环己烷

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,经溶胶-凝胶（sol-gel）法制备了不同二氧化硅（SiO2）含量的 PVA/SiO2杂化膜。傅里叶变换红外光谱（FT-IR）表明,随着SiO2含量增大,1060cm?1和970cm?1处Si—O—Si特征吸收峰的相对强度逐渐加强,说明TEOS与PVA发生了交联反应;同时膜的分解温度从248℃升高到342℃。杂化膜的SiO2含量从10 %增大到40 %,其玻璃态温度从115℃升高到124℃。以水为溶剂,测定了杂化膜的耐溶剂性能,与PVA膜相比,杂化膜的耐溶剂性能显著提高。以质量比为0.950/0.025/0.025的环己烷/环己醇/环己酮为原料,测定杂化膜的分离性能,结果表明SiO2含量从10 %增大到40 %,通量从15.94 g/(m2?h)升高到75.69 g/(m2?h),环己醇的分离因子从1.8升高到2.65。     

Characterization of poly(vinyl alcohol)/poly(ethylene glycol) hydrogels and PVA-derived hybrids by small-angle X-ray scattering and FTIR spectroscopy

The purpose of this study is to develop novel poly(vinyl alcohol) (PVA)/poly(ethylene glycol) (PEG) hydrogel blends and PVA-derived organic-inorganic hybrid materials and perform nanostructural characterizations. PVA and PEG hydrogels were prepared by dissolving the polymer in aqueous solution, followed by addition of glutaraldehyde (GA) chemical crosslinker. Hybrids were synthesized by reacting PVA in aqueous solution with tetraethoxysilane (TEOS). PVA/TEOS were also modified in the nanometer-scale by crosslinking with GA during the synthesis reaction. Hydrogels and hybrids were characterized by using small-angle X-ray scattering synchrotron radiation (SAXS) and Fourier transform infrared spectroscopy (FTIR). Thin film samples were prepared for SAXS experiments. SAXS results have indicated different nano-ordered disperse phases for hydrogels made of PVA, PEG, PVA/GA, PVA/PEG. Also, PVA/TEOS and PVA/TEOS/GA hybrids have indicated different X-ray scattering patterns. FTIR spectra have showed major vibration bands associated with organic-inorganic chemical groups present in the hybrid nanocomposites PVA/TEOS and PVA/TEOS/GA. PVA/PEG hydrogels and PVA-derived hybrid materials were successfully produced with GA crosslinking in nanometer-scale network.     

聚乙烯醇/二氧化硅互穿网络膜的研究

采用溶胶凝胶法制备了聚乙烯醇/二氧化硅有机/无机互穿网络结构。扫描电子显微镜(SEM)观察到样品表面光滑,均匀;原子力显微镜(AFM)观察到样品中无机相与有机相呈互穿网络结构,且随无机物的增多两相分布更均匀;元素分析结果为纯PVA中w(O)为38%,随着无机物的增多w(O)逐渐降低为24.9%,是硅羟基与醇羟基之间脱去水,两相之间进行交联的结果;29SiNMR表明随无机物的增多,化学位移Q3的强度有所降低而化学位移Q4值却略有上升,说明硅羟基含量逐渐减少,两相交联程度逐渐增大,与元素分析结果相印证;热重曲线(TG)表明,无机物的加入使PVA的热降解温度由400℃提高到420℃,进一步证明两相之间已形成网状结构。     

PVA/PEG/TEOS杂化膜制备及性能研究

以聚乙烯醇(PVA)与聚乙二醇(PEG)共混,并与正硅酸乙酯(TEOS)进行交联反应制备杂化膜。FTIR证实杂化溶胶液发生交联反应形成共价键Si—O—C,WXRD观察表明加入TEOS改变了膜结晶度,加入PEG提高了PVA膜对乙醇/水溶液的渗透通量,但分离因子下降,随着TEOS的加入,膜的分离因子提高。在TEOS质量分数为10%时,杂化膜的分离因子达到最大。提高退火温度可以提高膜的分离因子,但通量下降。在100℃下退火12 h的杂化膜对乙醇质量分数为85%的乙醇/水溶液的分离性能最佳。     

Pervaporation dehydration of ethyl acetate aqueous solution using the doubly modified polyvinyl alcohol (PVA) composite membrane

Polyvinyl alcohol–tetraethoxysilane–perfluorosulfonic acid (PVA–TEOS–PFSA) hybrid membrane was prepared by sol–gel method through PVA being modified doubly by PFSA and TEOS. With polyacrylonitrile (PAN) ultrafiltration membrane as a substrate membrane, PVA–TEOS–PFSA/PAN composite membrane was fabricated by dip-coating method for pervaporation (PV) dehydration of ethyl acetate (EAc) aqueous solution. The hybrid membrane was characterized by swelling degree, static contact angle, Fourier transform infrared spectra and scanning electron microscope. Effects of PFSA and TEOS contents in coating solution on PV performance of composite membrane were investigated, respectively. With increasing PFSA content, the permeation flux of composite membrane increased, while the separation factor decreased. Just the opposite, the increase of TEOS content resulted in the decrease in permeation flux and the increase in separation factor. In addition, the PV performances of composite membranes were also investigated at different feed temperatures and water concentrations in feed, respectively. The PVA–TEOS–PFSA/PAN composite membrane, which was prepared from coating with PVA/PFSA mass ratio of 80/20 and TEOS content of 20 wt%, exhibited the permeation flux of 347.9 g m^?2 h^?1 and the separation factor of 2218 for PV dehydration of 2 wt% water of EAc solution at 40 °C.     

Pervaporation characteristics and structure of poly(vinyl alcohol)/poly(ethylene glycol)/tetraethoxysilane hybrid membranes

Poly(vinyl alcohol) (PVA) blended with poly(ethylene glycol) (PEG) was crosslinked with tetraethoxysilane (TEOS) to prepare organic–inorganic PVA/PEG/TEOS hybrid membranes. The membranes were then used for the dehydration of ethanol by pervaporation (PV). The physicochemical structure of the hybrid membranes was studied with Fourier transform infrared spectra (FT‐IR), wide‐angle X‐ray diffraction WXRD, and scanning electron microscopy (SEM). PVA and PEG were crosslinked with TEOS, and the crosslinking density increased with increases in the TEOS content, annealing temperature, and time. The water permselectivity of the hybrid membranes increased with increasing annealing temperature or time; however, the permeation fluxes decreased at the same time. SEM pictures showed that phase separation took place in the hybrid membranes when the TEOS content was greater than 15 wt %. The water permselectivity increased with the addition of TEOS and reached the maximum at 10 wt % TEOS. The water permselectivity decreased, whereas the permeation flux increased, with an increase in the feed water content or feed temperature. The hybrid membrane that was annealed at 130°C for 12 h exhibited high permselectivity with a separation factor of 300 and a permeation flux of 0.046 kg m^?2 h^?1 in PV of 15 wt % water in ethanol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of poly(vinyl alcohol)/tetraethyl orthosilicate hybrid membranes modified with TMPTMS by sol-gel method for removal of lead from aqueous solutions

Poly(vinyl alcohol)/tetraethyl orthosilicate (PVA/TEOS) ion exchange hybrid membranes modified with 3-mercaptopropyltrimethoxysilane (TMPTMS) were prepared by the sol-gel method, and their applications for the removal of lead ions from aqueous solutions in a batch sorption process were studied. The functional groups of the hybrid membranes were characterized by FTIR. Batch adsorption studies such as TMPTMS content, pH, adsorbent dose, contact time, initial concentration and temperature were evaluated. The maximum adsorption capacity of lead ions was found to be 61.62mg g^?1, respectively. The kinetic data were analyzed by pseudo-first-order and pseudo-second-order kinetic models. The Freundlich and Langmuir isotherm models were applied to describe the equilibrium data. Thermodynamic parameters indicated that the lead adsorption onto the membrane is an endothermic and spontaneous process. The PVA/TEOS/TMPTMS hybrid membrane is regenerated by 0.5M HNO₃/0.1 M HCl in equal ratio solution and the adsorption capacity did not change remarkably after five sorption-desorption cycles.     

溶胶-凝胶法制备PVA/SiO2杂化材料及性能表征

以正硅酸乙酯（TEOS）和聚乙烯醇（PVA）为原料，采用溶胶-凝胶法制备PVA／SiO2杂化材料，研究丁其制尊T艺和作为玻璃板防雾涂层的应用；通过FT—IR分析证明SO-O-Si的生成及-OH键的保留，使用分光光度计研究其透光率，并对不同质量分数（SiO2）下的雾度、硬度和耐水性进行了讨论。     

Preparation of chitosan bicomponent nanofibers filled with hydroxyapatite nanoparticles via electrospinning

Chitosan (CS) bicomponent nanofibers with an average diameter controlled from 100 to 50 nm were successfully prepared by electrospinning of CS and poly(vinyl alcohol) (PVA) blend solution. Finer fibers and more efficient fiber formations were observed with increased PVA contents. On this contribution, a uniform and ultrafine nanofibrous CS bicomponent mats filled with hydroxyapatite (HA) nanoparticles were successfully electrospun in a well devised condition. An increase in the contents of HA nanoparticles caused the conductivity of the blend solution to increase from 1.06 mS/cm (0 wt % HA) to 2.27 mS/cm (0.5 wt % HA), 2.35 mS/cm (1.0 wt % HA), respectively, and the average diameter of the composite fibers to decrease from 59 ± 10 nm(0 wt % HA) to 49 ± 10 nm (0.5 wt % HA), 46 ± 10 nm (1.0 wt % HA), respectively. SEM images showed that some particles had filled in the nanofibers whereas the others had dispersed on the surface of fibers, and EDXA results indicated that both the nanoparticles filled in the nanofibers and those adhered to the fibers were HA particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(vinyl alcohol) nanocomposites made from cellulose nanofibers

A method using a combination of ball milling, acid hydrolysis, and ultrasound was developed to obtain a high yield of cellulose nanofibers from flax fibers and microcrystalline cellulose (MCC). Poly(vinyl alcohol) (PVA) nanocomposites were prepared with these additives by a solution‐casting technique. The cellulose nanofibers and nanocomposite films that were produced were characterized with Fourier transform infrared spectrometry, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. Nanofibers derived from MCC were on average approximately 8 nm in diameter and 111 nm in length. The diameter of the cellulose nanofibers produced from flax fibers was approximately 9 nm, and the length was 141 nm. A significant enhancement of the thermal and mechanical properties was achieved with a small addition of cellulose nanofibers to the polymer matrix. Interestingly, the flax nanofibers had the same reinforcing effects as MCC nanofibers in the matrix. Dynamic mechanical analysis results indicated that the use of cellulose nanofibers (acid hydrolysis) induced a mechanical percolation phenomenon leading to outstanding and unusual mechanical properties through the formation of a rigid filler network in the PVA matrix. X‐ray diffraction showed that there was no significant change in the crystallinity of the PVA matrix with the incorporation of cellulose nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009