Structural evolution up to 1100 °C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 °C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (∼4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 °C and 800 °C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 °C and pore elimination is the predominant process above 900 °C. At 1000 °C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 °C. This temperature is even higher than that found for foaming of non-exchanged xerogels.     

Synthesis and characterizations of nano sized MgO and its nano composite with poly(vinyl alcohol)

Magnesium oxide (MgO) nano particle was synthesized by ultrasound assisted one pot method and thus synthesized nano MgO was mixed with poly(vinyl alcohol) (PVA) to prepare the polymer nano composite. The influence of the nano sized MgO on the structural modification of PVA was evaluated. The particle size and morphology of MgO was confirmed by High Resolution Transmission Electron Microscopy (HRTEM). The properties of PVA/MgO nano composite materials were characterized by Fourier Transform Infrared analysis (FTIR), Thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC) like analytical tools.     

Polyvinyl alcohol cross-linked macroporous polymeric hydrogels: Structure formation and regularity investigation

A series of novel polyvinyl alcohol (PVA) hydrogels were synthesized by cross-linking of acrylate-modified PVA in aqueous solutions. Hydrogels were prepared at a temperature range −7.5 to −25 °С, macromer concentration 4-12 wt.%, and initiator concentration 0.4 to 1.6 mg/ml. The swelling behavior of polymeric hydrogels in aqueous media with different pH and ionic strength values was investigated. It was shown that they possess a high level of water absorption. The influence of different factors (porosity, pore size, and pore size distribution) and reaction conditions on the hydrogel structure was studied. The interior morphology of the hydrogel networks exhibits a complicated structure filled by fibrillar, lamellar and dendritic formations consisting of cross-linked polymer. The dispersed pores which are randomly distributed can be observed inside these formations and between them.     

High porosity silica xerogels prepared by a particulate sol–gel route: pore structure and proton conductivity

The lower cost and higher hydrophilicity of silica xerogels could make them potential substitutes for perfluorosulfonic polymeric membranes in proton exchange membrane fuel cells (PEMFCs). For that purpose, we need to obtain micro or micro and mesoporous silica xerogels with a high porosity. The preparation of micro (<2 nm) and micro and mesoporous silica xerogels (2<d_poresize10 nm) from particulate as oppossed to polymeric suspensions of silica using tetraethyl orthosilicate (TEOS) as precursor is used. Two techniques of varying packing density have been performed in this work: (1) Control of the aggregation degree in the sol by adjusting its pH before gelation (pH 5, 6 and 8) and (2) Mixture of sols with a different average particle size (particles formed under acid and base catalyzed reactions). Proton conductivity of the obtained xerogels was studied as a function of temperature and relative humidity (RH). High pore volume, high porosity and small pore size SiO₂ xerogels have been achieved in the calcination temperature range from 250 to 550 °C. The calcined xerogels showed microporosity or micro and mesoporosity in the whole range of calcination temperatures. By mixing sols (molar ratio: acid/base=4.8) porosities up to 54.7±0.1% are achieved, at 250 °C of firing temperature. According to EMF measurements, electrical transport is due to protons in this kind of materials. The proton conductivity of the studied xerogels increased linear with measured temperature. A S-shaped dependence of the conductivity with the RH was observed with the greatest increase noted between 58% and 81% RH. Xerogels with a low porosity (40.8±0.1%) and an average pore size less than 2.0 nm showed lower values of proton conductivity than that of xerogels with a higher porosity and a higher average pore size in the whole range of temperature and RH. When silica xerogels, with the highest conductivity, are treated at pH 1.5, that property increased from 2.84×10⁻³±5.11×10⁻⁵ S/cm to 4.0×10⁻³±7.2×10⁻⁵ S/cm, at 81% RH and 80 °C. It indicates that the surface site density of these materials has a strong effect on conductivity. Proton conductivity values achieved are less than one order of magnitude lower than that of Nafion, under the same conditions of temperature and RH.     

Morphological and mechanical properties of hybrid matrices of polysiloxane–polyvinyl alcohol prepared by sol–gel technique and their potential for immobilizing enzyme

Hybrid matrices of polysiloxane–polyvinyl alcohol (POS–PVA) were prepared by sol–gel technique using different concentrations of the organic component (polyvinyl alcohol, PVA) in the synthesis medium. The goal was to prepare carriers for immobilizing enzyme by taking into consideration properties as hardness, mean pore diameter, specific surface area and pore size distribution. The matrices were activated with sodium metaperiodate to render functional groups for binding the lipase from Candida rugosa, used here as a study model. Results showed that low proportion of PVA gave POS–PVA with low surface area and pore volume, although with higher hardness. The chemical activation decreased the pore volume and increased the pore size with a decrease on the surface area of about 60–75%. The matrices for enzyme immobilization were chosen considering the best combination of high surface area and hardness. Thus, the POS–PVA prepared with 5.56 × 10^?5 M of PVA with a surface area of 123 m²/g and hardness of 71 HV (50 gf 30 s) was shown to be suitable to immobilize the lipase, with an immobilization yield of about 40%.     

Effect of the counter-ion of the basification agent on the pore texture of organic and carbon xerogels

Organic and carbon xerogels were prepared by polycondensation of resorcinol with formaldehyde in water, followed by evaporative drying and, eventually, pyrolysis. The pH of the precursor’s solution was fixed at 6.0 in all cases by adding various hydroxides as basification agent. Three alkali metal hydroxides (LiOH, NaOH and KOH) and three alkaline earth metals hydroxides (Ca(OH)₂, Ba(OH)₂, Sr(OH)₂) were used. It was found that the pore texture of the organic and carbon xerogels is totally independent on the cation size, but depends on the charge and concentration of the counter-cation. Indeed, the pore size of the alkaline earth metal loaded samples is larger than that of the alkali metal-doped xerogels. As a matter of fact, to reach the same initial pH, the concentration in alkali metal hydroxide must be twice that of the alkaline earth metal base. The effect of ions on the pore texture was thus attributed to electrostatic effects on the microphase separation process that occurs prior to gelation.     

Free-standing crystalline CaCO3 films composed of three-dimensional microstructures with different morphologies

Crystalline vaterite CaCO₃ self-standing films composed of three-dimensional microstructures were synthesized by a simple gas diffuse method with the assistance of poly(vinyl alcohol) (PVA). The microstructures with different morphology (sphere-like, rose-like, and pumpkin-like) were self-assembled by three-dimensional oriented attachment of faceted micro-platelets, and the films were all stable in air for more than one year. The concentrations of Ca²⁺ ions and PVA all played important roles in the formation of vaterite crystal phase. In addition, the introduction of salt (NaCl, NaNO₃) would reduce the size of the micro-platelets significantly. A possible mechanism for the formation of the self-standing films is put forward.     

Size‐dependent spectroscopic,optical, and electrical properties of PbSe nanoparticles

Stable crystalline Lead Selenide nanoparticles (PbSe NPs) were prepared with a cubic (sphalerite) phase in polyvinyl alcohol (PVA) matrix. Moreover, XRD was used to characterize the PbSe NPs in PVA. The size were controlled by Pb:Se ions ratio in which the particle size was found to be inversely proportional to this ratio up to 16:1. FT‐Raman and FT‐IR measurements indicated the decrease of crystallization of PVA due to doping with PbSe NPs as indicated by the appearance of a peak at 1124 cm^‐1 that increases by size reduction of PbSe NPs. The Photoluminescence and electrical measurements monitored the interaction of PbSe NPs with PVA which increased by decreasing the particle size. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase separation in the solution of water glass and poly(vinyl alcohol)

Silica gel samples with macropores were prepared from solutions of silicate and poly(vinyl alcohol) (PVA), where macropores were formed by fixing a transitional structure of phase separation. Among the silica sources tested, tetraethoxysilane (TEOS), colloidal silica and water glass, only the system with water glass shows phase separation and forms macroporous silica gel. In the system with TEOS, ethanol formed during hydrolysis of TEOS becomes good solution and stabilizes the system not to induce phase separation. In the system with colloidal silica, dense structure of silica is probably not suitable for controlling phase separation and gelation. In the system with water glass, driving force of phase separation is considered to be a repulsive interaction between solvent molecules and PVA interacting with silica surface and the solution separates into a phase rich in solvent and that rich in silica and PVA. One of the features in the water glass-PVA system is insensitivity of macropore size against compositional change in the solution, i.e. macroporous morphology in the resultant silica gel hardly changes by changing the composition ratio in the solution. This would be an advantage in the preparation of well-defined macroporous silica from water glass, whose composition varies among the product lot number, because reproducibility in macroporous morphology is ensured regardless of the lot number of the water glass.     

Positron annihilation study of pore size in ordered SBA-15

Ordered mesoporous materials such as SBA-15 possess a network of channels and pores with a well-defined size in the nanoscale range (2–50 nm). This particular pore architecture makes them suitable candidates for a variety of applications. Different techniques have been used to measure pore diameters. PALS (positron annihilation lifetime spectroscopy) nanoprobe has been used to investigate free volume in several materials, including mesoporous silica. PALS can be used to find out if the micropore and mesopore structures of samples prepared under different experimental conditions are different. Indeed, considering that the pores present a cylindrical shape, an equation was developed that uses specific pore volumes, theoretical density, and specific surface measurements to evaluate structural connectivity. Our goal is to determine the influence of aging temperature on the porous structure of SBA-15 samples. The structural evolution was studied by PALS, small-angle X-ray (SAXS), N₂ adsorption desorption isotherms and computational modeling to evaluate connectivity. The variation of aging temperature changes the pore structure, indicating the presence of micropores and connections between mesopores. Materials aged at high temperatures present the lowest microporosity.     

Nanoscopic replication of cross-linked hydrogel in high-porosity nanoporous silica

Nanoscopic network structure of N-isopropylacrylamide (NIPAM) gel cross-linked with N,N′-methelenbisacrylamide (BIS) was replicated in sol–gel derived silica matrix. As a result of that, the silica became a nanoporous solid with a high-porosity, which reaches 60–80%. The porosity was totally due to mesopores whose size was within 10 nm. Electron microscope observation revealed that the nanoscale network structure were replicated in the silica matrix as considered to be constituted from the main polymer chains and their interconnecting cross-linkers. The mesh size observed in the TEM micrograph matches the span length estimated from the molar ratio (∼80) of the main chain moiety (NIPAM) to that of cross-linker (BIS). When the weight ratio of NIPAM to silica matrix is smaller than unity, the pore size distribution measured by nitrogen adsorption/desorption has a sharp peak at 2 nm indicating that the worm-like nanopore is formed as a replica of an individual NIPAM chain. The peak position in the pore size distribution shifts to a larger value as the weight ratio of NIPAM was increased, suggesting the nanoscale segregation of NIPAM chains in the silica matrix. Therefore, the resultant size of the nanopores are considered to be determined at the moment of the structural freezing caused by the completion of the cross-linking in NIPAM gel. The completion of cross-linking (gellation) eliminates the mobility both of silica and NIPAM/BIS moiety. The TEM micrograph of a sample prepared at a large weight ratio also shows that larger nanopores tend to be generated when the template NIPAM moiety is more abundant.     

水系流延技术制备95氧化铝陶瓷基片的研究

本论文采用水系流延技术制备了95氧化铝陶瓷基片,主要对浆料中各种添加剂的作用作了系统研究.分散剂通过与无机粉料的吸附,提供双重稳定效应使浆料具有较好的分散性,实验中分散剂PAA(聚丙烯酸)最佳的用量为0.5wt;.粘结剂PVA(聚乙烯醇)最佳用量为4.5wt;.塑化剂PEG(聚乙二醇)的加入可以降低粘结剂的玻化温度,提高坯片柔韧性.塑化剂与粘结剂的用量比值(R)在1～1.2之间为宜.最终获得了具有一定强度、韧性、表面光滑的坯片,烧结出密度为3.785g/cm395氧化铝陶瓷基片.     

Sol‐gel synthesis of electrospun BaO/MnO nanocomposite fibers and their magnetic characterization

A new approach, combining in‐situ sol‐gel process with electrospinning, was used to prepare magnetic barium acetate/manganese acetate/poly (vinyl alcohol) (PVA) composite nanofibers. The composite gel was synthesized by sol‐gel method in the presence of 10 wt.% PVA aqueous solution. PVA was used as stabilizer and polymeric matrix. The resultant barium acetate/manganese acetate/PVA composite nanofibers were calcined at 1023 K for 5 h. This formed BaO/MnO nanocomposite crystalline fibers with average diameter less than 100 nm and were characterized with Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Energy Dispersive X‐ray Analysis (EDAX), powder X‐ray diffractometer (XRD), UV‐Vis‐Spectroscopy (UV) and Vibrating Sample Magnetometer (VSM) respectively. These composite fibers exhibited a uniform cylindrical morphology, with the BaO/MnO nanoparticles implanted in the fibers. M‐H curves were obtained at 300 K and 20 K. From the M‐H curves, room temperature ferromagnetism was observed at 300 K. At low temperatures, the ferromagnetic behavior was masked by the paramagnetic behavior. The saturation magnetization at 300 K was found to be 0.004 emu /g and the saturation magnetization at 20 K was found to be 0.658 emu /g. The magnetization at 20 K was found to be very large and it was several times larger than at 300 K. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth characteristics of ultra long double-ended acicular ZnO synthesized by a hydrothermal process

Double-ended acicular ZnO structure can be synthesized via a hydrothermal process with tetramethylammonium hydroxide and zinc acetate as precursors and polyvinyl alcohol (PVA) as a structure-directing agent. The as-prepared ZnO products show the well crystalline wurtzite structure with growth direction along [0 0 0 1]. For the first time, PVA is found to be employed as a reservoir of Zn²⁺ ions in the present study, and can control the concentration of Zn²⁺ in reaction solution, and the acicular morphology can be formed at the two ends of the 1-D ZnO structure, due to the effect of secondary growth that occurs as the sufficient concentration of Zn²⁺ ions chelated by PVA releasing to the reaction solution. Furthermore, the size of the 1-D ZnO structure can be tuned by different amounts of PVA addition.     

Silica xerogels and aerogels synthesized with ionic liquids

The synthesis of silica gels with ionic liquids (IL) as either additives or co-solvents is described. The wet gels were either dried by supercritical CO₂ or by evaporation to obtain aerogels or xerogels, respectively. The effects of two ionic liquids: 1-butyl-3-methyl imidazolium tetrafluororate (IL1) and 1-butyl-4-methyl pyridinium tetrafluoroborate (IL2), on the structural and textural characteristics of gels were investigated. IL2 showed a more important influence than IL1, on the gelation time and gel structure, according to solid state NMR investigations. With both types of ionic liquids, the average pore radius of xerogels increased from ≈2 nm at an IL to Si molar ratio n_IL/n_Si = 0.07, to ≈4 nm at n_IL/n_Si ≈ 1.5 and the size distributions were rather well centered about each mean radius. Hence, ionic liquids appeared as interesting additives to target gels with a given pore size.     

莫来石陶瓷超滤膜的制备与表征

以正硅酸乙脂(TEOS)和Al(NO_3)_3·9H_2O为主要原料,聚乙烯醇(PVA)和甘油为添加剂,通过溶胶-凝胶法和浸渍涂覆法在管状α-Al_2O_3支撑体上制备莫来石陶瓷超滤膜.采用XRD、SEM、N2吸附法、渗透通量和截留分子量测定等方法对制备的超滤膜进行了结构和性能表征.结果表明,莫来石单相溶胶浓度为0.28 mol/L、pH=2.0、PVA和甘油加入量分别为1.5 wt;和6 wt;时,经三次涂覆和1200 ℃保温2 h烧成后,可获得表面结构均匀平整、不开裂的莫来石超滤膜;制备的莫来石超滤膜平均孔径为8.4 nm,厚度约1.8 nm,其平均纯净水渗透通量和聚乙二醇(PEG)截留分子量分别为46.8 L·m~(-2)·h~(-1)·(10~5 Pa)~(-1) 和9 kDa.     

Preparation of electroactive silica mesopores by encapsulating polyaniline chains into silica framework via nonsurfactant templating sol-gel route

Electroactive silica mesopores have been synthesized by encapsulating different loadings of polyaniline chains into a silica network through sol-gel reactions of TEOS in the presence of polyaniline latex with D-glucose. It should be noted that the electroactive silica mesopores at higher polyaniline loading was found to reveal higher surface areas, larger pore volume, and slightly larger pore diameters as compared to that of neat non-electroactive silica mesopores.     

聚乙烯醇改性磷酸银的光催化活性研究

在制备的磷酸银表面吸附少量的聚乙烯醇(PVA),并通过热处理制备了DPVA/Ag3 PO4复合材料.使用傅立叶红外光谱法(FT-IR)和荧光光谱法(PL)对DPVA/Ag3 PO4复合材料进行表征.分析得知,经聚乙烯醇复合改性的DPVA/Ag3 PO4复合微粒中存在共轭结构,光生电子-空穴对复合率降低,光催化活性得到显著提高.研究了不同条件(复合比例、热处理温度、热处理时间)下制备的复合光催化剂在可见光下催化降解甲基橙的光催化性能.当PVA与Ag3 PO4质量比为1:4000,热处理温度为190℃,热处理1 h时光催化效果最好.     

Preparation of cresol–formaldehyde carbon aerogels via drying aquagel at ambient pressure

Carbon aerogels were prepared from mixed cresol (Cm) and formaldehyde (F) via the sol–gel process followed by drying at ambient pressure and carbonization. The inexpensive feedstock of mixed cresol and the simple drying process could be as an alternative economical route to the classical resorcinol–formaldehyde synthesis process. In our process, organic precursor gels were synthesized via polycondensation of cresol with formaldehyde in an aqueous alkaline (NaOH) solution. After gelation the solvent was removed via drying at ambient pressure to obtain organic aerogels that exhibit a drying shrinkage below 5% (linear). Upon carbonization of the organic aerogels at 1173 K, monolithic carbon aerogels (denoted as CmF carbon aerogels) can be produced. Nitrogen adsorption results showed that the CmF carbon aerogels have abundant mesopores and micropores with a dominant pore diameter of 25–40 nm. An increase of the BET surface area and a modification of the pore size distribution of CmF can be realized by a CO₂ activation. The images of scanning electron microscopy (SEM) indicated that the microstructure of carbon aerogels can be effectively controlled and tailored by varying the synthetic conditions during the initial sol–gel process.     

Preparation and physical properties of (PVA)0.75(NH4Br)0.25(H2SO4)xM solid acid membrane

In this work, solid acid membrane consisting of poly(vinyl alcohol) (PVA), ammonium bromide (NH₄Br) and sulfuric acid (SA) has been prepared by a solution casting technique method. X-ray diffraction of the (PVA)_0.75(NH₄Br)_0.25(H₂SO₄)_xM polymer matrix and pure (PVA)_0.75(NH₄Br)_0.25 revealed the difference in crystallinity between them. The effect of different amounts of SA on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared electrolytes can reach 3.1 × 10⁻² S cm⁻¹ at room temperature. The conductivity measurements carried out at different temperatures indicate that all the films follow Arrhenius behavior and that the activation energy decreases with the increase in SA concentration. The a.c. conductivity seems to follow the universal power law.