A novel silica aerogel microspheres loaded with ammonium persulfate gel breaker for mid-deep reservoirs

Sol–gel based transparent functional coatings such as easy-to-clean coatings, anti-glare coatings, anti-reflective coatings, and anti-fingerprint coatings have been developed and commercialized for display applications. These coatings can be applied by a spray process on the glass substrates followed by a low temperature curing at 100° to 150?°C. Hydrophobic easy-to-clean coatings exhibit high water contact angles at ≥115°, with an excellent wear durability by passing 10,000 cycles using #0000 steel wool under 1?kg load. In addition, easy-to-clean coatings show a silky touch feel with a coefficient of friction of less than 0.03. Anti-glare coatings without particles have a gloss value between 50 to 100 gloss units, an adhesion of 5B, a pencil hardness ≥8?H, and no sparkling issues on touch screen displays. A combination of easy-to-clean coatings on top of anti-glare coatings significantly increases the stylus pen durability. Single-layer anti-reflective coatings show a transmittance increase of 1.5% to 2.0% by spray coating on a single side of the glass substrate, or a transmittance increase of more than 4.0% by dip-coating on a polycarbonate substrate. Anti-fingerprint coatings show less obvious fingerprints on the coated glass surface compared to those on uncoated glass surface. These coating solutions have been scaled up to 1000?kg batch in PPG’s Tianjin plant, China.

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Anti-glare coatings with irregular surface microstructures formed during a spray process have a gloss value between 50 to 100 gloss units, a pencil hardness ≥8H, and no sparkling issues on touch screen displays. Optical profiler image (with ×50.3 magnification) of the anti-glare coating surface (70 gloss units) shows irregular microstructure patterns which are random locally but uniform in large area. The light scattering on the anti-glare coating surface is caused by these irregular surface microstructures. Thus the specular reflection is significantly reduced, causing glare reduction, gloss decrease, and haze increase.

     

A diffusion method for determining sizes of nanoparticles suspended in a gas

The diffusion deposition of particles suspended in a gas in diffusion batteries composed of cylindrical fibers is considered. It is assumed that the particle-size spectrum is described by a lognormal distribution. It is shown in the asymptotic approximation that the dependences of the penetration coefficients on the diffusion battery parameters and flow velocity plotted for particles with the same geometrical mean sizes, but different degrees of polydispersity, in fact intersect at the same point. It is also shown that, at small nanoparticle size r (on the order of several nanometers), when the diffusion coefficient is D ～ r ^?2, the intersection point corresponds to a penetration coefficient of about 0.37. The results obtained agree with the numerical data.     

Comparing the photocatalytic activity of N-doped and S-doped titanium dioxide nanoparticles for water splitting under sunlight radiation

The objective of this research is to compare the photocatalytic activity of nanoparticles of N-doped and S-doped titanium dioxide in water splitting by using sunlight radiation for hydrogen production. The sol–gel method was used for the preparation of nanoparticles of doped TiO₂ and the weight percent of doping element was 2, 4, 6 and 8. The prepared nanoparticles were identified by absorbance spectra of UV–Vis and FT-IR, TGA, XRD patterns, FE-SEM images and EDX spectra. The nanoparticles of S–\({\text{TiO}}_{2}\) indicated the lower band gap and lesser particle size versus N–\({\text{TiO}}_{2}\) nanoparticles. Nevertheless, the nanoparticles of N–\({\text{TiO}}_{2}\) showed the higher photocatalytic activity in hydrogen production process. The activity of doped samples with sulfur (S–\({\text{TiO}}_{2}\)) was reduced by the presence of sulfate anions, and the absorption of radiation in the samples surface was due to a decrease in the number of electron–hole pair in photocatalyst. The photocatalytic activity of N–\({\text{TiO}}_{2}\) was also increased with the increasing in weight fraction of N atoms, and the highest hydrogen production was obtained in 6 wt% of nitrogen.     

Method development and inter-laboratory comparison about the determination of titanium from titanium dioxide nanoparticles in tissues by inductively coupled plasma mass spectrometry

Nanosized titanium dioxide (TiO₂) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO₂. Total Ti levels were chosen to evaluate the presence and distribution of TiO₂ nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO₃) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO₂ nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO₂ dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 μg Ti/g tissue agreed well.

A rapid and simple microwave-assisted digestion procedure for spectrophotometric determination of titanium dioxide photocatalyst on activated carbon

Deposition of titanium dioxide (TiO₂) on activated carbon (AC) surface has been widely utilized for the production of TiO₂/AC photocatalyst, which can be used in photo-degradation of pollutants. In this work, a fast and simple digestion procedure has been developed for the spectrophotometric quantitative analysis of TiO₂ in TiO₂/AC photocatalyst. Microwave-assisted digestion was used in the procedure. The microwave-digestion procedure was optimized using the single-variable method. Variables optimized included time of ashing, effective digestion time, volume and concentration of sulfuric acid, effect of adding a digestion catalyst, effect of sample pulverizing and on–off time cycle of the microwave. The analysis was completed spectrophotometrically after addition of hydrogen peroxide to the digested solution. Procedure precision and accuracy was tested by application to photocatalyst samples containing known amounts of TiO₂, and compared with previously published spectrophotometric procedures. The proposed microwave procedure was capable of recovering 98.4–101.1% of TiO₂ in the catalyst in less than 10 min, without the need for sample ashing. Analytical precision is 1.42–2.39% relative standard deviation (R.S.D.). In terms of accuracy and precision, the proposed microwave procedure was comparable with other procedures, but the proposed microwave procedure was superior in terms of shorter procedure duration.     

A novel process for making alkaline iron oxide nanoparticles by a solvo thermal approach

In the present work alkaline iron oxide nanoparticles are synthesized by a novel solvo thermal approach and characterized exhaustively by various complementary techniques. Field emission scanning electron microscopy (FESEM) studies reveal that the size of nanoparticles is in the range of 31.5 nm to 96.9 nm. Energy-dispersive X-ray spectroscopy spectral analysis reveals the presence of oxygen, carbon, iron, and sodium. The X-ray diffraction studies confirm the formation of tetragonal NaFeO₂ as the major phase along with orthorhombic NaFeO₂·H₂O and rhombohedral FeCO₃ (siderite) as the minor phases. Fourier transform infrared spectroscopy exhibits peaks due to the stretching and bending vibrations of O-H, C=O, CH₃-N, CH₃, C-H, C-N, and Fe-O groups. Differential scanning calorimetry (DSC) results display an endothermic peak at 100.85°C and a very small endothermic peak at 791.56°C with 819.73 mJ and 349.28 mJ energies respectively. These DSC peaks can be correlated with thermal gravimetric analysis (TGA) peaks representing 31.04% weight loss and 7.70% weight loss respectively in the sample at around 160°C and 980°C respectively.     

A novel capillary electrophoretic method for determining methylglyoxal and glyoxal in urine and water samples

Two non-electroactive biomarkers methylglyoxal (MGo) and glyoxal (Go) in urine and environmental water samples were determined for the first time by capillary electrophoresis with amperometric detection (CE-AD) after derivatizing with an electroactive compound 2-thiobarbituric acid. Experimental conditions of derivatization and CE-AD detection were optimized. Highly linear response was obtained for these two biomarkers over three orders of magnitude with good correlation (r² > 0.999). The limits of detection (LODs) and limits of quantitation (LOQs) of MGo and Go were 0.2 μg L⁻¹ and 1.0 μg L⁻¹, 0.5 μg L⁻¹ and 2.0 μg L⁻¹, respectively. The average recovery and relative standard deviation (RSD) were within the range of 90.9–101.3% and 0.7–2.2%, respectively. The proposed CE-AD method provides a reliable and sensitive quantitative evaluation of MGo and Go in real sample matrices by employing relatively simple and inexpensive instrument.     

Enhanced photocatalytic activity for titanium dioxide by co-modification with copper and iron

A copper(II) and iron(III) co-modified titanium dioxide nano material was prepared by a simple sol–gel process using titanium(IV) isopropoxide plus copper(II) and iron(III) nitrates as raw materials. The as-prepared nanocomposites were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy and photoluminescence spectra. The XRD results showed that the undoped TiO₂ nanoparticles mainly include anatase phase while the Cu, Fe-codoped TiO₂ nanoparticles showed a mixture of anatase phase with a small fraction of rutile phase displaying higher activity than the pure anatase phase. Optical characterization showed that the codoping with copper(II) and iron(III) resulted in a red shift of adsorption and lower recombination probability between electrons and holes, which were associated with high photocatalytic activity of the Cu, Fe-codoped TiO₂ nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of the samples was tested by aqueous methyl orange degradation. The capability of the codoped catalyst was much higher than that of the pure TiO₂ catalyst under visible irradiation. A mechanism is proposed in order to account for the enhanced catalytic activity.     

A novel approach for Apocynum venetum/cotton blended fabrics modification by cationic polymer nanoparticles

Apocynum venetum/cotton blended fabrics have been subjected to treat with cationic polymer nanoparticles followed by dyeing with Acid Red B,and then studied for their dyeing performance and morphology.The investigation on the effect of modification factors on the blended fabrics indicated that the 0.5 g/L nanoparticles concentration,60 min treating time,60 °C treating temperature and pH 6-8 are the optimum modification process to improve the dyeability of acid dye.In addition,the SEM images show that nanoparticles can be adsorbed on the surface of modified A.venetum or cotton fibers,and the two different fibers could have the same adsorption ability to Acid Red B.     

Determination of trace molybdenum in biological and water samples by graphite furnace atomic absorption spectrometry after separation and preconcentration on immobilized titanium dioxide nanoparticles

A new method has been developed for the determination of trace molybdenum based on separation and preconcentration with TiO₂ nanoparticles immobilized on silica gel (immobilized TiO₂ nanoparticles) prior to its determination by graphite furnace atomic absorption spectrometry (GFAAS). The optimum experimental parameters for preconcentration of molybdenum, such as pH of the sample, sample flow rate and volume, eluent and interfering ions, have been investigated. Molybdenum can be quantitatively retained by immobilized TiO₂ nanoparticles at pH 1.0 and separated from the metal cations in the solution, then eluted completely with 0.5 mol L^?1 NaOH. The detection limit of this method for Mo was 0.6 ng L^?1 with an enrichment factor of 100, and the relative standard deviation (RSD) was 3.4% at the 10 ng mL^?1 Mo level. The method has been applied to the determination of trace amounts of Mo in biological and water samples with satisfactory results.     

Equilibrium and kinetic study of novel methyltrimethoxysilane magnetic titanium dioxide nanocomposite for methylene blue adsorption from aqueous media

Novel magnetic titanium dioxide nanoparticles decorated with methyltrimethoxysilane (Fe₃O₄@TiO₂‐MTMOS) were successfully fabricated via a sol–gel method at room temperature. The synthesized material was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis and vibrating sample magnetometry. The removal efficiency of the adsorbent was evaluated through the adsorption of methylene blue (MB) dye from water samples. The adsorption isotherm and kinetics were evaluated using various models. The Langmuir model indicated a high adsorption capacity (11.5 mg g^?1) of Fe₃O₄@TiO₂‐MTMOS. The nanocomposite exhibited high removal efficiency (96%) and good regeneration (10 times) compared to Fe₃O₄ and Fe₃O₄@TiO₂ at pH = 9.0. Based on the adsorption mechanism, electrostatic interaction plays a main role in adsorption since MB dye is cationic in nature at pH = 9, whereas the adsorbent acquired an anionic nature. The newly synthesized Fe₃O₄@TiO₂‐MTMOS can be used as a promising material for efficient removal of MB dye from aqueous media.     

A novel approach for the preparation of AgBr nanoparticles from their bulk solid precursor using CTAB microemulsions

Microemulsions are suitable reaction media to prepare a wide variety of nanoparticles and provide control over their sizes. However, as typically used, microemulsions limit rates of rapid reactions and suffer from low reactant solubilization capacity. This work presents a new application of a novel approach aimed at minimizing these limitations. This approach, which was previously applied for AgCl nanoparticle preparation, involves solubilization of a bulk silver halide in the form of higher halides, by means of reaction with the surfactant counterion of a microemulsion, and the reprecipitation of silver halide nanoparticles in the water pools of individual reverse micelles. CTAB microemulsions were employed because they possess a reactive counterion and are known to have a high solubilization capacity for ionic reactants. Despite their high solubilization capacity, CTAB microemulsions achieved lower nanoparticles uptake (molar concentration of the colloidal nanoparticles) for the same surfactant concentration when compared to our previous study. The effect of the following variables on the nanoparticle uptake and the particle size was investigated: (1) operation variables, including rate of mixing and temperature; and (2) microemulsion variables, including CTAB and n-butanol concentrations, and water-to-surfactant mole ratio, R. These variables provide a comprehensive test to the proposed mechanism and expose the role of the surfactant layer rigidity. The nanoparticle uptake increased as the rate of mixing, temperature, and CTAB concentration increased, and decreased as n-butanol concentration and R increased. High n-butanol concentration and R values reduced the effective surfactant concentration and contributed to less surfactant layer rigidity and to particle aggregation.     

Spectrophotometric determination of tungsten(VI) enriched by nanometer-size titanium dioxide in water and sediment

The adsorption of W (VI) on different metal oxides (TiO₂, ZrO₂), different crystal form of TiO₂ (rutile, anatase) with high surface areas was studied and compared under different pH. A novel method for preconcentration of W (VI) with nanometer size titanium dioxide (rutile) and determination by spectrophotometry has been developed. W (VI) was selective adsorbed on 100 mg TiO₂ from 250 ml solution at pH 3.0, then eluted by 2 ml 9 mol l⁻¹ sodium hydroxide solution. The eluent was adjusted to 5 ml pH 0 solution, added 0.5 ml 12 mol l⁻¹ HCl, 0.3 ml 3% TiCl₃, 0.3 ml 50% NH₄SCN, stirred for 20 min, used for the analysis of W (VI) by measuring the absorbance at 402 nm with spectrophotometry, based on the chromogenic reaction between the W (VI) and the mixture of TiCl₃ and NH₄SCN. This method gave a concentration enhancement of 50 for 250 ml sample, eliminated the sizable interferences on direct determination with spectrophotometry. Detection limits (3σ, n=11) of 1.2 ng ml⁻¹, relative standard deviation of 2.3% at 10 ng ml⁻¹ level were obtained. The method was applied to determine the W (VI) in hot spring water, river water, tap water and stream sediment. Analytical recoveries of W (VI) added to samples were 98–101%.     

A simple method for determining the total amount of physically and chemically bound water of different cements

A novel environmentally friendly flame-retardant compound, diethyl 3-(triethoxysilanepropyl) phosphoramidate (DTP) was synthesized via a simple one-step procedure with good yield and characterized by FT-IR and ¹H-NMR, ³¹P-NMR and ²⁹Si-NMR. The synthesized compound was coated onto cotton fabrics with different levels of add-ons (5–17 mass%) using the traditional pad-dry-cure method. SEM and XPS were conducted to characterize the surfaces of the coated cotton fabrics. The XPS results showed that DTP was attached to cotton through covalent bond. Cone calorimeter test showed that the cotton fabric treated with DTP became less flammable due to the lower HRR, THR and CO₂/CO ratio. The modified cotton fabrics exhibited efficient flame retardancy, which was evidenced by limiting oxygen index (LOI) and vertical flammability test. Cotton fabrics treated with DTP in 5–17 mass% add-ons had high LOI values of 23–32%. Thermogravimetric analysis results show that the usage of DTP promotes degradation of the cotton fabrics and catalyzes its char formation.     

A novel approach for designing simple point charge models for liquid water with three interaction sites

A simultaneous improvement of the diffusion and dielectric properties of the simple point charge (SPC) model for liquid water appears to be very difficult with conventional reparametrization of the commonly used Lennard-Jones and Coulomb interaction functions and without including a self-energy correction in the effective pair-potential as is done in the SPC/E model. Here, a different approach to circumvent this problem is presented. A short-range interaction term, which corrects the oxygen-oxygen energy at small distances by small amounts of energy, was introduced in the nonbonded interaction function. This additional force-field term allows to derive new parameter sets for SPC-like water models that yield better agreement with experimental data on liquid water. Based on previous investigations of the force-field parameter dependence of the water properties of SPC-like models, the necessary parameter changes to obtain a lower diffusion coefficient and a larger dielectric permittivity were specified and accordingly six new models were developed. They all represent an improvement over SPC in terms of structural and diffusional properties, four of them show better dielectric properties also. One model, SPC/S, has been characterized in more detail, and represents most properties of liquid water better than SPC while avoiding the larger discrepancies with experimental values regarding density, thermal compressibility, energy, and free energy of the SPC/E model. We conclude that the use of a simple, short-ranged additional oxygen-oxygen interaction term makes a simultaneous improvement of the diffusion coefficient and the dielectric properties of water feasible.     

Magnetic titanium oxide nanoparticles for hemimicelle extraction and HPLC determination of organophosphorus pesticides in environmental water

We report on a method for the extraction of organophosphorus pesticides (OPPs) from water samples using mixed hemimicelles and magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) modified by cetyltrimethylammonium. Fe₃O₄@TiO₂ nanoparticles were synthesized by a hydrothermal process and then characterized by scanning electron microscopy and Fourier transform IR spectrometry. The effects of the quantity of surfactant, extraction time, desorption solvent, pH value, extraction volume and reuse of the sorbent were optimized with respect to the extraction of OPPs including chlorpyrifos, dimethoate, and trichlorfon. The extraction method was applied to analyze OPPs in environmental water using HPLC along with UV detection. The method has a wide linear range (100–15,000 ng L^?1), good linearity (r?>?0.999), and low detection limits (26–30 ng L^?1). The enrichment factor is ~1,000. The recoveries (at spiked levels of 100, 1,000 and 10,000 ng L^?1) are in the range of 88.5–96.7 %, and the relative standard deviations range from 2.4 % to 8.7 %.