Biocompatible hybrid particles of poly(l-lactic acid)@silica

Silica and poly(l-lactic acid) (PLLA) are each a biocompatible polymer with many proven bio-applications. We describe a new hybrid made of these components in the form of submicron particles. The particles are prepared by entrapping PLLA in a forming sol–gel particle in an emulsion, the droplets of which are the micro-reactors in which the particles form. The dispersed phase is a hydrophobic solution of PLLA in tetraethoxysilane (TEOS) and chloroform and the dispersing phase is a water–ethanol solution of Triton X-100 at a basic pH, which acts also as the catalyst for the on-setting the sol–gel processes. The polyester@silica particles were fully characterized by scanning electron microscopies, by thermal gravimetric analysis and differential scanning calorimetry (DSC) by X-ray diffraction (XRD), and by ζ potential measurements. Another aspect of this report relates to the ability to dope these hybrid particles with a functional dopant, which is then used to follow up their degradation in acidic solution.     

Detailed investigation of gel–sol transition temperature of κ-carrageenan studied by DSC, TMA and FBM

A broad temperature range of the gel–sol transition of κ-carrageenan was precisely examined by differential scanning calorimetry (DSC), thermomechanical analysis (TMA) and the falling ball method (FBM). κ-Carrageenan the transition temperature of which ranged from 290 to 350 K was used as a representative sample of a thermo-reversible hydrogel. The starting of transition attributed to dissociation of the weak cross-linking zone of aggregated double helices was detected as a change of expansion coefficient by TMA and as an endothermic deviation by DSC. Peak temperature of endotherm by DSC agreed well with the temperature where expansion changed from positive to negative value and this temperature was attributed to gel–sol transition caused by dissociation of double helices’ assembly. Transition temperature measured by FBM was observed at a temperature higher than those obtained by DSC and TMA, which was attributed to decomposition of double helices.     

Structure,hydrophilicity and corrosion resistance of sol–gel derived Ag-containing TiO2 film on plasma nitrided 316L stainless steel

Pure and Ag-containing TiO₂ films (Ag/Ti = 3.3 at.%) are coated on plasma nitrided 316L stainless steel by sol–gel method for biomedical applications. The addition of Ag does not cause obvious change in TG–DSC curves of the dried gels. The rough surface generated by plasma nitriding and the addition of Ag improve structural integrity of the TiO₂ films. X-ray diffraction reveals N loss and oxidation of the nitride layer during calcination treatment, and peaks of Ag or its oxides are not detected. X-ray photoelectron spectroscopy analysis indicates that Ag presents as metallic state in the film. Water contact angles of the coating samples decrease with UV irradiation treatment. The potentiodynamic polarization tests in a Ca-free Hank’s balanced salt solution show that the TiO₂ coated samples have decreased corrosion resistance due to N loss and oxidation of the nitride layer. The methods for crystallization of TiO₂ gel layers with minimized or avoided structural changes of the nitride layer will be tried in order to improve corrosion resistance of the duplex treated 316L stainless steel.     

Photocatalytic degradation of methyl red by porous zinc hydroxide under visible light irradiation

In the present study, porous zinc hydroxide was successfully prepared via a simple sol–gel route. The synthesized porous zinc hydroxide was characterized using scanning electron microscopy (SEM), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) techniques. In addition, the prepared porous zinc hydroxide was studied as a photocatalyst for the degradation of methyl red. The degradation behavior of porous zinc hydroxide was investigated systematically. The experimental results showed that the obtained porous zinc hydroxide displayed excellent degradation efficiency (89%) under visible light irradiation. Thus, porous zinc hydroxide can be used as an effective photocatalyst for the degradation of methyl red, which can be used for industrial wastewater treatment.     

Mesoporous titania photocatalyst: effect of relative humidity and aging on the preparation of mesoporous titania and on its photocatalytic activity performance

Mesoporous TiO₂ has been synthesized by the sol–gel method, using a nonionic triblock copolymer P123 as surfactant template under acidic conditions. The as-prepared samples were characterized by thermogravimetry–differential thermal analysis (TG–DTA), nitrogen absorption–desorption (BET), field emission scanning electron microscopy, and transmission electron microscopy. The photocatalytic activity of the mesoporous TiO₂ was evaluated by degradation of methylene blue under high-intensity UV light irradiation; the amount of methylene blue was measured by UV–visible spectroscopy. TG–DTA analysis revealed that the surfactant had been removed partly in as-synthesized samples. BET analysis proved that all the samples retained mesoporosity with a narrow pore-size distribution (4.5–6.3 nm) and high surface area (103–200 m²/g). All calcined mesoporous TiO₂ had high photocatalytic activity in the photodegradation of methylene blue.     

Effect of gamma irradiation on ethylene–octene copolymers

Two ethylene–octene copolymers (POE) were irradiated with ⁶⁰Co gamma radiation and influence of irradiation atmosphere, absorbed dose and heat treatment of samples on the crosslinking were studied. Thermal properties and crystalline morphology of non-irradiated and irradiated POE were determined by using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXS), respectively. The Charlesby–Pinner equation was used to describe the relationship between absorbed dose and sol fraction. The gel fraction of irradiated POE was lower and decreased with the increase of octene content when irradiated in oxygen, compared to irradiation in nitrogen atmosphere. The gel fraction increased significantly with the increasing of absorbed dose for the two copolymers. Heat treatment of samples prohibited the crosslinking of irradiated POE. The DSC results indicated that a subtle change of thermal properties of POE was observed before and after gamma irradiation at low dose. No change was found from the WAXS spectra of non-irradiated and irradiated POE. For heat-treating samples, the Charlesby–Pinner equation can not fit perfectly with the relationship between the sol fraction and absorbed dose, but it fits well with the crosslinking reaction of POE pellets.     

NiO/SiO_2Al_2O_3催化剂上CO氧化的原位DSC研究

通过对溶胶凝胶超临界干燥法制备的ＮｉＯ／ＳｉＯ２Ａｌ２Ｏ３催化剂上ＣＯ氧化反应的原位ＤＳＣ测试，实现了对催化剂的活性以及催化剂制备参数影响反应性能的规律考察，同时与实际微反结果进行了比较。结果表明：微反的结果与ＤＳＣ测试结果取得较好的一致性，催化剂的ＣＯ氧化活性与ＤＳＣ半峰温值呈现相应的变化规律；在四个制备参数中以载体对活性的影响最大。对各ＤＳＣ曲线的活化能计算表明，活化能值的大小可以较好地反映催化剂的反应行为。     

Copper Oxide Nanoparticle Modified Sol–Gel‐Derived Carbon Ceramic by Microwave Irradiation,and Its Application for Determination of Adenine at Very Low Potential

In this work the copper oxide nanoparticles simultaneous with sol–gel‐derived carbon ceramic production were synthesized and doped in ceramic by microwave irradiation in a few minutes without using any catalyst and organic solvent. The ceramic composition was characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and Fourier transforms infrared (FT‐IR), and its surface morphology was investigated by scanning electron microscopy (SEM). The proposed ceramic with detection limit of 0.1 µM, was used for electrocatalytic determination of adenine at potential about 700 mV lower than its usual oxidation potential.     

Synthesis,Characterization, and Photocatalytic Activity of N‐Doped TiO2 Nanotubes

N‐doped TiO₂ nanotubes with high photocatalytic activity were prepared by the combination of sol‐gel process with hydrothermal treatment. The prepared materials are characterized with transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), x‐ray diffraction (XRD), x‐ray photoelectron spectra (XPS), and UV‐vis spectra. Photocatalytic performance of the N‐doped TiO₂ nanotubes is studied by testing the degradation rate of methyl orange under UV irradiation. Obtained results indicate that N‐doped TiO₂ nanotubes have high catalytic activity for photocatalytic oxidation.     

Preparation and characterization of MPEG–PCL diblock copolymers with thermo‐responsive sol–gel–sol phase transition

MPEG–PCL diblock copolymers consisting of methoxy polyethylene glycol (MPEG, 750 g/mol) and poly(?‐caprolactone) (PCL) were synthesized by ring‐opening polymerization. Aqueous solutions of the synthesized diblock copolymers were prepared by dissolving the MPEG–PCL diblock copolymers at concentrations in the range of 0–20 wt %. When the PCL molecular weight was 3000 or greater, the polymer was only partially soluble in water. As the temperature was increased from room temperature, the diblock copolymer solutions showed two phase transitions: a sol‐to‐gel transition and a gel‐to‐sol transition. The sol‐to‐gel phase transition temperature decreased substantially with increasing PCL length. The sol–gel–sol transition with the increase in temperature was confirmed by monitoring the viscosity as a function of temperature. The temperature ranges of the phase transitions measured by the tilting method were in full agreement with those determined from the viscosity measurements. The maximum viscosity of the copolymer solution increased with increasing hydrophobicity of the diblock copolymer and with increasing copolymer concentration. X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses revealed that the diblock copolymers exhibited crystalline domains that favored the formation of an aggregated gel because of the tight aggregation and strong packing interactions between PCL blocks. Scanning electron micrographs of the diblock copolymer solutions in the sol state showed interconnected polyhedral pore structures, whereas those of the gel state revealed a fibrillar‐like morphology. Atomic force microscope (AFM) studies of the sol and gel surfaces showed that the sol surface was covered with fine globular particles, whereas the gel surface was covered with particles in micron‐scale irregular islets. These findings are consistent with uniform mixing of the diblock copolymer and water in the sol state, and aggregation of PCL blocks in the gel state. In conclusion, we confirm that the MPEG–PCL diblock copolymer solution exhibited a sol–gel–sol transition as a function of temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5413–5423, 2006     

Photocatalytic degradation of Br-trihalomethanes by nanosized TiO<Subscript>2</Subscript>/diatomite hybrid photocatalyst

Nanosized TiO₂/diatomite catalyst was prepared by sol–gel method at ambient temperature. Diatomite was used as a carrier, tetrabutyl titanate served as a source of titanium. The photocatalytic degradation of Br-THMs was successfully achieved in the presence of TiO₂/diatomite under Xe-light irradiation. It was suggested that Br-THMs were debromized in a stepwise manner. The rate of degradation increases markedly with increasing extent of substitution of Br-THMs by bromine because the C–Br bond is less stable than the C–Cl bond. Furthermore, the degradation of Br-THMs was caused by the action of hydroxyl free radicals, the signals of which were registered by means of electron spin resonance (ESR) spectroscopy.     

Photo-assisted electrodeposition of sol–gel films on p-type semiconductors

A new approach for the deposition of sol–gel films on semiconducting substrate using photo-electrochemical technique is presented. The deposition is based on accelerating sol–gel condensation reaction by the catalyzing effect of electrochemically generated OH⁻ ions when applying both negative potentials and light irradiation onto p-type semiconductors. Results show that both the negative shift in potential and the increase in light intensity facilitate the deposition kinetics of silica sol–gel films. Surface patterning is further achieved with the assistance of a laser.     

Catalytic degradation of gaseous benzene by using TiO2/goethite immobilized on palygorskite: Preparation,characterization and mechanism

The nano-TiO₂/goethite/palygorskite catalysts were prepared by sol–gel method. The morphology and structure of the catalysts were analyzed by X-ray diffraction (XRD), UV–Vis reflection spectrometer, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and N₂ adsorption-desorption measurement. The results indicated that the self-made catalysts had excellent catalytic performance on gaseous benzene degradation. In the case of benzene concentration at 30 mg/m³, the degradation efficiency, over TiO₂/goethite/palygorskite composite with mass ratio of 10:5:5, reached 70.4% after 180 min 254 nm UV irradiation. The reaction mechanism and kinetics study showed that palygorskite/goethite/TiO₂ composites photocatalytic degradation benzene was mainly caused by oxidizing property of electron–holes and oxygen synergy effect.     

Multi-parameter evaluation of fast sol–gel process by terahertz measurements

We present a feasibility study to apply terahertz (THz) spectroscopy and THz imaging as non-destructive diagnostic tools for sol–gel analysis, manufacturing and quality control. By performing THz spectroscopy on liquid and solid samples we were able to follow several key parameters during the sol–gel formation process and of the final product. Sol–gel transformations were monitored by THz absorption, whereas density changes have been observed through changes in refractive indices. Time domain spectroscopy (TDS), both in transmission and reflection geometries, was used to monitor the properties of fast sol–gel resins. THz imaging of gold coated, thin-film sol–gel enables us to determine inhomogeneities and defects in their internal structure. We demonstrated that THz spectroscopy can be implemented as an online analytical tool for multi-parameter evaluation of the sol–gel process during fabrication, and of the final product.     

The influence of molecular orientation on the crosslinking/oxidative behaviour of iPP exposed to gamma radiation

This paper presents a study of the influence of structural peculiarities, uniaxial orientation and fibrillar structure on the radiation-induced changes in iPP. For the purposes of this study, iPP was oriented via solid-state stretching at elevated temperature to various draw ratios and, later on, gamma irradiated in air. In order to investigate orientation- and/or radiation-induced structural changes, optical microscopy (OM), scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), infrared spectroscopy (IR) and gel measurements were employed. To quantify the degree of molecular orientation, Herman’s orientation function (f_c), was used. IR spectroscopy and gel measurements were used to determine the changes in the oxidative degradation and degree of network formation, respectively. Sol-gel analysis was studied in detail using the Charlesby-Pinner (C-P) equation. The radiation-induced changes in the structure and evolution of oxygen-containing species were also studied through dielectric loss (tan δ) analysis in a wide frequency range; the polar groups that were introduced by irradiation in apolar iPP were considered as tracer groups. Conclusions derived according to different methods were compared. Presented results reveal two different radiation-induced dynamics; gamma irradiation of initial and fully developed fibrillar iPP structures leads to significantly different crosslinking and/or oxidation response.     

Effects of ultrasonic treatment on unfilled butadiene rubber

The ultrasonic treatment of unfilled butadiene rubber (BR) gum with a grooved‐barrel ultrasonic reactor was carried out, leading to changes in the structure and physical properties. The ultrasonic treatment of BR gum led to gel formation, with the amount dependent on the amplitude. The rheological and mechanical properties of the ultrasonically treated samples and their vulcanizates were measured and compared with those of the virgin samples. Gel permeation chromatography measurements of the sol part of the virgin and the treated samples were carried out. Rheological property and molecular weight measurements indicated the creation of a branched structure and the occurrence of degradation in ultrasonically treated BR gum. Because of degradation, the tensile strength and Young's modulus of treated BR were lower than those of untreated BR, whereas the elongation at break was practically intact. Differential scanning calorimetry (DSC) curves at a high‐temperature range showed exothermic peaks with enthalpy reduction in the treated BR, indicating a decrease in the number of double bonds due to gel formation. DSC curves at a low‐temperature range indicated increased crystallinity in the treated samples. Competing reactions of gel formation, branching, and degradation occurred during the ultrasonic treatment. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2959–2968, 2003     

Degradation of p-aminophenol wastewater using Ti-Si-Sn-Sb/GAC particle electrodes in a three-dimensional electrochemical oxidation reactor

In this study, Ti-Si-Sn-Sb/GAC particle electrodes were prepared by sol–gel method. The particle electrodes were characterized by SEM, XRD, EDX, and BET then used to carry out three-dimensional (3D) electrocatalytic oxidation degradation on simulated refractory p-aminophenol (PAP) wastewater. The effects of initial pH, cell voltage, aeration flow rate and initial PAP concentration on degradation experiments were investigated. Under the optimal conditions, the PAP and COD removal rates were 89.45% and 75.17% respectively. In addition, the possible degradation mechanism of PAP was further investigated by UV–Vis and HPLC. Finally, it was found that the Ti-Si-Sn-Sb/GAC particle electrodes with high catalytic activity and excellent stability could significantly improve the PAP wastewater removal efficiency.     

Effect of X-ray radiation on the structure of P (VDF/TrFE) copolymers

Structural changes in poly(vinylidene fluoride)-trifluoroethylene [P(VDF-TrFE)] copolymers caused by X-ray irradiation were investigated by molecular weight determination, EPR analysis, FTIR spectroscopy, gel content, DSC thermal analysis, X-ray diffraction, and piezoelectricity measurements. Samples exhibit radiation-induced conductivity (RIC) due to the formation of radical ions. These radicals are generated by bond cleavage, which could react, leading to structural changes such as oxidation, double bond formation, chain scission, and crosslinking. The increasing gel content with radiation dose indicated that crosslinkings of the polymer chains predominate. Irradiation on P(VDF-TrFE) caused the melting temperature, heat of fusion, and Curie temperature to decrease. These results are consistent with the partial destruction of crystalline domains. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1201–1205, 1997     

Surface properties,adherence, and photocatalytic activity of sol–gel dip-coated TiO2–ZnO films on glass plates

In this study, TiO₂–ZnO nanostructured films prepared from different Ti/water mole ratios were deposited on glass plates by a sol–gel dip-coating method. The structural and surface properties, adherence, and photoactivity of synthesized TiO₂–ZnO coatings in methylene blue degradation were investigated. Among the as-prepared TiO₂–ZnO coatings from sols with different Ti/water mole ratios (1, 0.66, 0.5, and 0.4), the highest sol concentration (Ti/water mole ratio of 1) showed the highest methylene blue photodegradation of almost 80% after 400 min of UV irradiation. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray (EDX), and UV-vis diffuse reflectance spectra (DRS) confirmed that at high sol concentrations (Ti/water mole ratios of 1 and 0.66), a mixed phase of anatase and rutile is formed, whereas at a Ti/water mole ratio of 0.5, just pure rutile is formed. In detail, decreasing the sol concentration increases the cracks, degree of agglomeration, and the thickness of coatings. UV-vis DRS studies also confirm that decreasing the sol concentration in synthesized TiO₂–ZnO films leads to a shift in the absorption region of the coating to the UV region. Moreover, decreasing the sol concentration declines the coating adherence onto glass plates. TEM images of the TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 revealed the formation of ZnO nanorods around a spherical TiO₂, which indicates the presence of strong interaction between TiO₂ and ZnO nanoparticles. The TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 was then evaluated at different methylene blue concentrations, pH values, and number of coatings. After five consecutive runs, no significant decrease in the photodegradation efficiency was observed. Scanning electron microscopy (SEM) picture of used coating showed a smooth and stable layer without any detachment. Thermogravimetric analysis (TG) and sonication test confirmed thermal and mechanical stabilities of this coating as well.