Droplet Micro‐Reactor for Internal Gelation to Fabricate ZrO2 Ceramic Microspheres

A droplet micro‐reactor was developed to realize the internal sol–gel reaction of ZrO₂ inside the droplet. The reactants are only allowed to combine when the droplet forms, meanwhile, they are able to mix well and react to form gel particles with a proper designed structure of the micro‐reactor. In this condition, the mixing efficiency was determined by the structure of the micro‐reactor and the flow rate ratio of the two components. After sintering, ZrO₂ ceramic microspheres are acquired with high sphericity and narrow size distribution. This droplet micro‐reactor overcomes the gelation of the premixed sol and reactant in the channel, and it has been demonstrated to be more stable with a longer running time.     

Polymerization of lactides and lactones. III. Ring-opening polymerization of DL-lactide by the (η3-C3H5)2Sm(μ2-Cl)2(μ3-Cl)2Mg(tmed)(μ2-Cl)Mg(tmed) complex

Ring-opening polymerization of DL -lactide (LA) has been initiated with the (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(η₂-Cl)Mg(tmed) complex both in bulk and solution. The effects of reaction conditions, such as reaction time, reaction temperature, and monomer/initiator molar ratio on the polymerization has been discussed. The results showed that (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(μ₂-Cl)Mg(tmed) was more effective for the polymerization of LA, and high molecular weight of polylactide was obtained by this initiator. The solvent affected the polymerization significantly. The polymerization mechanism was in agreement with the coordination mechanism. The polymer was characterized by FTIR, ¹H-NMR, and DSC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2857–2862, 1999     

μ‐Gels as support materials for dinuclear olefin polymerization catalysts

μ‐Gels which consist of poly(organosilicon) networks can be employed as efficient support materials for ethylene polymerization catalyst precursors. Alkylaluminum cocatalysts can be fixed on the μ‐gel surfaces using the PHT (“partially hydrolyzed trimethylaluminum”) method. The influence of different aluminum/water ratios on the ethylene polymerization properties of these heterogeneous systems is investigated. Dinuclear silicon bridged zirconium complexes are used as catalyst precursors yielding polyethylenes with broad or bimodal molecular weight distributions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Seed‐Free Synthesis and Characterization of Zeolite Faujasite Aluminosilicate Coating on α‐Alumina Supports

NaY zeolite was synthesized by a simple sol–gel technique. NaY zeolite membrane was formed on the alumina substrate using optimized solution composition and synthesis conditions. The formation of the NaY zeolite was ascertained by X‐ray powder diffraction, which showed that the crystallinity improved with annealing. The high‐resolution transmission electron microscopy images of samples annealed at 300°C showed the formation of cubic structure corresponding to NaY zeolite. Brunauer–Emmett–Teller analysis revealed that the synthesized zeolite is a well crystallized NaY zeolite. The SEM images revealed the formation of fine structure NaY zeolite membrane on α‐alumina substrate.     

New anion exchanger organic–inorganic hybrid materials and membranes from a copolymerof glycidylmethacrylate and γ‐methacryloxypropyl trimethoxy silane

Organic–inorganic hybrid materials and mem branes were prepared through coating on Teflon plate or dip‐coating on microporous alumina substrates with the solution of glycidylmethacrylate (GMA) and γ‐methacryloxypropyl trimethoxy silane (γ‐MPS) copolymer, followed by ring‐opening of the GMA moiety with trimethylamine hydrochloric and sol–gel reaction of the γ‐MPS moiety. Composition of the GMA and γ‐MPS copolymer was varied by changing the feed ratio of GMA to γ‐MPS during the copolymerization. So the thermal stability, hydrophilicity, electrical properties, etc. of the hybrid materials and membranes were varied. Results showed that as the γ‐MPS amount increased in the copolymer, T_d (the temperature on thermogram at 5% weight loss) value of the hybrid materials and water contact angle of the hybrid membrane generally increased, while the anion exchange capacity, water uptake (W_R) and pure water flux decreased. The charge transition point of the hybrid membranes deduced from their streaming potential behavior decreased from pH > 12 to pH = 7–8 as the γ‐MPS amount increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3580–3589, 2006     

一锅法从卟啉配体合成μ-氧代四苯基双核铁卟啉

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.     

Ruthenium(II)‐Catalyzed Protocol for Preparation of Diverse α,β‐ and β,β‐Dihaloenones from Diazodicarbonyls

Efficient one‐step syntheses of α,β‐ and β,β‐dihaloenones were achieved by ruthenium(II)‐catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers several significant advantages, which include ease of handling, mild reaction conditions, one‐step reaction, and the use of an effective and non‐toxic catalyst. The synthesized compounds were further transformed into highly functionalized novel molecules bearing aromatic rings on the enone moiety using the Suzuki reaction.

     

Performance Tests and Pressure Drop Measurements in the Anode Flowfield of a μDMFC

Cell performance tests and measurements of the pressure drops in the anode flow channels of a custom‐made microdirect methanol fuel cell (μDMFC) are conducted and studied for different methanol concentrations (0.5–2 M), flow rates (10–20 sccm) and operating temperatures (40–80 °C). The anode flowfields consist of three channel/four pass flow channels with widths of 500–2000 μm and a total length of 300–400 mm. Moreover, flow characteristics of the CO₂ gas bubbles and methanol solution in the anode flow channels are identified and analysed for CO₂ fraction through visualisation. Finally, an optimal channel size for the present μDMFC is obtained.     

A statistical study of poly(ε‐caprolactone) crystallinity in poly(ε‐caprolactone)–silica sol–gel materials and their in vitro calcium phosphate‐forming ability

Composite poly(ε‐caprolactone) (PCL)–silica materials for potential use in orthopaedic applications have been prepared by a sol–gel method using an experimental design approach to investigate the effect of synthesis variables, separately and together, on the physical form of the organic polymer. A combination of differential scanning calorimetry, X‐ray diffraction and Fourier‐transform infrared methods were used to obtain information on the arrangement of the organic polymer in the hybrid material. As our studies investigated the effect of synthesis variables simultaneously, it was possible to establish that the increase of tetraethyl orthosilicate (TEOS)/PCL and HCl/TEOS molar ratios decreased the poly(ε‐caprolactone) crystallinity and provided for a better mixing of the two phases. At a mechanistic level it was possible to show that increase in catalyst content affected the condensation of silicon containing species. In vitro calcium phosphate‐forming ability tests using the static biomimetic method have been carried out on selected PCL–silica sol–gels. In vitro bioactivity was only observed for PCL–silica sol–gel composites with high silica content (30% weight). Changes in catalyst levels had a smaller but still significant effect. Calcium phosphate formation on largely non‐porous surfaces is proposed to occur via the formation of a silica sol–gel layer, and is influenced by the topography and the chemistry of the materials surface. Copyright © 2003 Society of Chemical Industry     

Preparation and characterization of chitosan/α‐zirconium phosphate nanocomposite films

Nano‐fillers play an important role in the final structure and properties of nanocomposites. The objective of the work presented here was to prepare nanocomposite films of chitosan/α‐zirconium phosphate using a casting process, with α‐zirconium phosphate (α‐ZrP) as nano‐filler and chitosan as matrix. The effects of α‐ZrP on the structure and properties of the nanocomposites were investigated. X‐ray diffraction patterns showed that α‐ZrP crystals were intercalated by n‐butylamine. The results from scanning electron microscopy and transmission electron microscopy indicated that α‐ZrP could be uniformly dispersed in the chitosan matrix when α‐ZrP loading in the composites was less than 2 wt%. A strong interaction between α‐ZrP and chitosan formed during the film‐forming process. Tensile testing showed that the tensile strength and elongation at break of nanocomposite films achieved maximum values of 61.6 MPa and 58.1%, respectively, when α‐ZrP loading was 2 wt%. The parameter B calculated from tensile yield stress according to the Pukanszky model was used to estimate the interfacial interaction between the chitosan matrix and α‐ZrP. Films with a loading of 2 wt% α‐ZrP had the highest B value (3.2), indicating the strongest interfacial interaction. The moisture uptake of the nanocomposites was reduced with addition of α‐ZrP. It can be concluded that α‐ZrP as nano‐filler in a chitosan matrix can enhance the mechanical properties of nanocomposites due to the strong interactions between α‐ZrP and chitosan. Copyright © 2010 Society of Chemical Industry     

Preparation and characterization of polyimide/Al2O3 hybrid films by sol–gel process

A sol–gel process has been developed to prepare polyimide (PI)/Al₂O₃ hybrid films with different contents of Al₂O₃ based on pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA) as monomers. FESEM and TEM images indicated that Al₂O₃ particles are relatively well dispersed in the polyimide matrix after ultrasonic treatment of the sol from aluminum isopropoxide and thermal imidization of the gel film. The dimensional stability, thermal stability, mechanical properties of hybrid PI films were improved obviously by an addition of adequate Al₂O₃ content, whereas, dielectric property and the elongation at break decreased with the increase of Al₂O₃ content. Surprisingly, the corona‐resistance property of hybrid film was improved greatly with increasing Al₂O₃ content within certain range as compared with pure PI film. Especially, the hybrid film with 15 wt % of Al₂O₃ content exhibited obviously enhanced corona‐resistance property, which was explained by the formation of compact Al₂O₃ network in hybrid film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Binuclear Iron(III) Phthalocyanine(μ‐Oxodimer)‐Catalyzed Oxygenation of Aromatic Hydrocarbons with Iodosylbenzene Sulfate and Iodosylbenzene as the Oxidants

Two binuclear iron(III) phthalocyanine‐(μ‐oxodimer) complexes were tested in catalytic oxygenation reactions of several aromatic hydrocarbons using iodosylbenzene (PhIO)_n or oligomeric iodosylbenzene sulfate [(PhIO)₃SO₃]_n as the oxidants. Results of this study demonstrate that [(PhIO)₃SO₃]_n is the most reactive oxygenating reagent that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene. The pyridine‐containing binuclear μ‐oxobis{iron(III)‐pyridino[3,4]‐9(10),16(17),23(24)‐tri‐tert‐butyltribenzoporphyrazine} is significantly more active as compared to the traditional μ‐oxobis[iron(III)‐2,9(10),16(17),23(24)‐tetra‐tert‐butylphthalocyanine].     

Preparation and degradability of poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid)/SiO2 hybrid material

Poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid) (PLA‐PEG‐PLA)/SiO₂ hybrid material is prepared by sol–gel method using tetraethoxysilane (TEOS) and PLA‐PEG‐PLA as raw material. From Fourier transform infrared spectroscopy (FTIR) and X‐ray photoelectron spectroscopy (XPS) spectra, the hydroxyl groups of the silica sol derived from partially hydrolysis of TEOS and the unhydrolyzed ethoxy groups of TEOS can react with PLA‐PEG‐PLA. Differential scanning calorimetry (DSC) curves imply that the glass transition temperature (T_g) of PLA‐PEG‐PLA/SiO₂ hybrid material is higher than that of PLA‐PEG‐PLA and increases with the increase of silica content. X‐ray diffraction (XRD) analysis results show that PLA‐PEG‐PLA and PLA‐PEG‐PLA/SiO₂ hybrid material are both amorphous. Field scanning electron microscope (FSEM) photographs show that when PLA‐PEG‐PLA/SiO₂ hybrid material has been degraded for 12 weeks in normal saline at 37°C, a three‐dimensional porous scaffold is obtained, which is available for cell growth and metabolism. Moreover, the hydroxyl (? OH) groups on SiO₂ of PLA‐PEG‐PLA/SiO₂ hybrid material could buffer the acidity resulted from the degradation of PLA, which is beneficial to proliferation of cell in tissue repairing. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of substituents in the manganese μ-oxo porphyrins catalyzed oxidation of cyclooctane with molecular oxygen

Electron-donating or electron-withdrawing substituents at the porphyrin rings considerably increase the catalytic activity of the manganese monomeric and μ-oxo porphyrins in the oxidation of cyclooctane with molecular oxygen without the use of sacrificial co-reductant. The change in the catalytic activity is due to the nature and number of the substituents in the porphyrin ring.     

Highly Enantioselective Michael Addition of Cyclic 1,3‐Dicarbonyl Compounds to β,γ‐Unsaturated α‐Keto Esters

A highly enantioselective Michael addition of cyclic 1,3‐dicarbonyl compounds to β,γ‐unsaturated α‐keto esters catalyzed by amino acid‐derived thiourea‐tertiary‐amine catalysts is presented. Using 5 mol% of a novel tyrosine‐derived thiourea catalyst, a series of chiral coumarin derivatives were obtained in excellent yields (up to 99%) and with up to 96% ee under very mild conditions within a short reaction time.     

Stabilized dispersions of titania nanoparticles via a sol–gel process and applications in UV‐curable hybrid systems

Organic–inorganic hybrid UV‐curable coatings were synthesized through blending UV‐curable components and stabilized titania sol prepared via a sol–gel process of tetrabutyl titanate (TBT) with three different stabilizers, acetylacetone (Acac), isopropyl tri(dioctyl)pyrophosphato titanate coupling agent (TTPO) and a polymerizable organic phosphoric acid (MAP). The size and the dispersion of titania particle in the UV‐cured organic matrix were dominated by the properties of these stabilizers. A cured hybrid film with titania particle size around 20 nm was obtained when TTPO was utilized as protection agent for the sol. It is interesting that the hardness and flexibility of the photocured hybrid films were improved simultaneously, in contrast to results with neat organic UV‐curable formulations. Copyright © 2006 Society of Chemical Industry     

Preparation and properties of castor oil‐based polyurethane/α‐zirconium phosphate composite films

Novel castor oil‐based polyurethane/α‐zirconium phosphate (PU/α‐ZrP) composite films with different α‐ZrP loading (0–1.6 wt %) and different NCO/OH molar ratios were synthesized by a solution casting method. The characteristic properties of the PU/α‐ZrP composite films were examined by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and tensile testing. The results from Fourier transform infrared spectroscopy indicated that strong intermolecular hydrogen bonding formed between α‐ZrP and PU, XRD and SEM results revealed that the α‐ZrP particles were uniformly distributed in the PU matrix at low loading, and obvious aggregation existed at high loading. Because of hydrogen bonding interactions, the maximum values of tensile strength were obtained with 0.6 wt % α‐ZrP loading and 1.5 of NCO/OH molar ratio in the matrix. Evidence proved that the induced α‐ZrP used as a new filler material can affect considerably the mechanical and thermal properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of rigid‐rod polyimide/silica hybrid materials by sol–gel process

Polyimide (PI) materials with a low coefficient of thermal expansion (CTE) while still retaining high strength and toughness are desirable in various applications. In this study a sol–gel process was used to incorporate silica into homopolyimides and copolyimides with highly rigid structures in an attempt to pursue this aim. A number of highly rigid monomers were used, including pyromellitic dianhydride (PMDA), p‐phenylene diamine (PPA), m‐phenylene diamine (MPA), benzidine, 2,4‐diaminotoluene, and o‐toluidine. No homopolyimide flexible films were obtained. However, it was possible to obtain flexible films from the copolyimides. Therefore, a copolyimide based on PPA, MPA, and PMDA (PPA/MPA = 2/1 mol) was then chosen as the matrix to prepare the PI/silica hybrids. Flexible films were obtained when the silica content was below 40 wt %. The hybrid films possessed low in‐plane CTEs ranging from 14.9 to 31.1 ppm with the decrease of the silica content. The copolyimide film was strengthened and toughened with the introduction of an appropriate amount of silica. The thermal stability and the Young's modulus of the hybrid films increased with the increase of the silica content. The silica particle size was assessed by scanning electron microscopy and was about 100 nm for the hybrids containing 10 and 20 wt % silica and 200–500 nm for the hybrids containing 30 and 40 wt % silica. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 794–800, 2001     

Comparative Study of Silver Nanoparticles Coated and Uncoated NiO–Fe2O3–CaO–SiO2–P2O5 Ferromagnetic Bioactive Ceramics

Bioactive ferromagnetic ceramics of system xNiO–(3?x)Fe₂O₃–52CaO–30SiO₂–15P₂O₅, (x = 0, 3 mol%) have been prepared in the laboratory using sol–gel technique. Silver nanoparticles coating has been undertaken on the surface of synthesized samples. Comparative study of silver nanoparticles coated and uncoated samples has been undertaken with the help of transmission electron microscopy, X‐ray diffraction (XRD), degradation, drug delivery, hemolysis, antimicrobial, and cell culture studies. XRD patterns indicate the growth of hydroxyl apatite layer on the surface of coated as well as uncoated samples. Ferromagnetic properties of samples have been investigated with the help of vibrating sample magnetometer technique. Samples have shown good response as drug carriers under normal conditions as well as under the influence of magnetic field. Drug release mechanism and mesoporus nature of samples have been investigated with the help of Brunauer–Emmett–Teller technique. Nonreactivity of samples (coated and uncoated) with red blood cells and white blood cells show nontoxic nature of the samples. Coated samples have shown better antimicrobial properties against six different microorganisms, including some resistive strain like methicillin‐resistant Staphylococcus aureus with minimum inhibitory concentration of 0.05 mg/ml as compared to uncoated samples. It has been observed that samples also provide a healthy environment for the growth of MG 63 cell lines. It has been noticed that presence of silver nanoparticles on the surface of samples improve degradation and antimicrobial properties.     

Synthesis and Magnetic Characterization of SolGel‐Derived Submicrometer NaGd(WO4)2

NaGd(WO₄)₂ (NGW) submicrometer powder was derived by solgel method, and its magnetic properties were investigated for magnetic texturing application. The analysis of X‐ray diffraction indicates the formation of tetragonal phase. Organic liberation with respect to temperature in the samples and carbon content in the prefired powder was analyzed using FTIR results. Raman spectra confirm the tetrahedral tungstate formation and corresponding vibrations. UV‐Vis Reflectance study revealed the corresponding absorption of NGW host and gadolinium ions. The morphology and approximate size of the synthesis powder was observed with SEM micrographs. The paramagnetic nature of NGW was confirmed with EPR, and VSM analysis at room temperature and paramagnetic to antiferromagnetic phase transition was observed around 5 K. Results indicate that NGW powders can be used for magnetic texturing to grow transparent ceramic.