Colloidal crystal layers of hexagonal nanoplates by convective assembly

Particles of the zeolite ZSM-2 prepared as nearly hexagonal nanoplatelets were coated onto flat substrates by a convective assembly technique. On the submillimeter scale, coatings ranged in patterns from striped to continuous. Particles were preferentially oriented out-of-plane, as supported by X-ray diffractometry. The novel observation is that where the particle coating was only a monolayer thick, particles were locally close-packed and uniformly oriented both in and out of plane in a hexagonal colloidal crystalline arrangement that may be described as being tiled (observations by scanning electron microscopy). This is the first documented demonstration of convective assembly applied to anisometric nanoparticles that resulted in particulate coatings with locally ordered microstructure, i.e., colloidal crystallinity.     

Colloidal aggregation phenomena: Spatial structuring of TEOS-derived silica aerogels

In this contribution, the homogeneity of silica aerogels made from tetraethyl orthosilicate (TEOS) was studied by means of Fourier transform infrared (FTIR) and 29Si nuclear magnetic resonance (NMR) spectroscopies. FTIR spectra show a slight difference in the asymmetric Si-O-Si stretching vibration frequency in the outer and inner part of the aerogels. According to the 29Si NMR data, a higher relation Q4/Q3 was obtained in the inner parts of the gels compared with their outer parts, proving the difference in the cross linkage of the silica network. The obtained results are interpreted in terms of the specific spatial structuring of the colloidal suspensions due to the presence of gravity.     

Effective moisture diffusivity and activation energy during convective drying of bread containing clove oil/orange oil

The aim of present study was to investigate the characteristic drying behaviour of bread with the convective drying method for increasing bread shelf life. Effective moisture diffusivity and activation energy were compared in detail. According to the results, bread samples were dried between 0 and 450 min for 40 °C, 0–180 min for 50 °C and 60 °C, respectively. The experimental data with high coefficient of determination (R²) changed between 0.889 and 0.998. The values of D_eff were obtained between 1.21 × 10^?9-1.22 × 10^?8 m²/s. Also, E_a values were found to be in range of 82.47–100.49 kJ/mol for bread samples which had additive-free and additive. When the bread samples without additives and the breads with essential oils were compared, it was found that the activation energy increased with the use of additives. Moisture content values decreased with the increase in time. Drying rate and moisture content relation showed the expected behaviour, thermally and morphologically.     

Active control of nanolitre droplet contents with convective concentration gradients across permeable walls

Nanolitre droplets in microfluidic devices can be used to perform thousands of independent chemical and biological experiments while minimizing reagents, cost and time. However, the absence of simple and versatile methods capable of controlling the contents of these nanolitre chemical systems limits their scientific potential. To address this, we have developed a method that is simple to fabricate and can continuously control nanolitre chemical systems by integrating a time-resolved convective flow signal across a permeable membrane wall. With this method, we can independently control the volume and concentration of nanolitre-sized drops without ever directly contacting the fluid. Transport occurring in these systems was also analyzed and thoroughly characterized. We achieved volumetric fluid introduction and removal rates ranging from 0.23 to 4.0 pL s(-1). Furthermore, we expanded this method to perform chemical processes. We precipitated silver chloride using a flow signal of sodium chloride and silver nitrate droplets. From there, we were able to separate sodium chloride reactants with a water flow signal, and dissolve silver chloride solids with an ammonia hydroxide flow signal. Finally, we demonstrate the potential to deliver large molecules and perform physical processes like crystallization and particle packing.     

Wetting phenomena on micro-grooved aluminum surfaces and modeling of the critical droplet size

The behavior of water droplets on aluminum surfaces with parallel grooves tens of microns in width and depth is considered, and a mechanistic model is developed for predicting the critical droplet size-droplets at incipient sliding due to gravity. The critical droplet size is nearly 50% smaller on micro-grooved surfaces than on the same surface without micro-grooves. The application of existing models fails to predict this behavior, and a new model based on empiricism is developed. The new model provides reasonable predictions of the critical droplet size for a given inclination angle, advancing contact angle, and maximum contact angle. When the grooves are aligned parallel to gravity, the maximum apparent contact angle does not occur at the advancing front but rather along the side of the droplet because of contact-line pinning. Droplets on these surfaces are elongated and possess a parallel-sided base contour shape. Novel data are provided for droplets in a Wenzel state, a Cassie-Baxter state, and combined state on micro-grooved surfaces, and the ability of the empirical model to handle these variations is explored. These findings may be important to a broad range of engineering applications.     

Significance of minor components of milk fat

In order to establish criteria for the evaluation of the genuineness of milk fat and its derivatives, research has been carried out on some minor components (mono- and diglycerides and cholestrol esters). Most determinations of milk fat diglycerides showed significant qualitative and quantitative differences compared with other fat sources, and especially with tallow. In particular, the milk fat diglycerides C30–C32–C34–C36 showed characteristic fingerprints. Moreover, the sterol fractions (free and esterified) have also been evaluated. The cholesterol ester profile in milk lipids includs fatty acides from 10 to 18 carbon atoms, while tallow basically showed only C14–C16–C18. In comparison, phytosteral esters with C16 and C18 fatty acids have been found in vegetable fats. These results lead to the hypothesis of possible use of these methods in addition to those most commonly applied (TG-FAME). Furthermore, the natural variability of milk fat components makes a final evaluation of these methodologies difficult unless experimental work is extended to more samples and performed by several research groups.     

The impact of drying phenomena and heat treatment on the structure of porous silicon

Porous silicon (PS) has received a great deal of attention due to its light emitting properties. This characteristic has led to a wide range of applications (optoelectronic devices, physical and chemical sensors, solar cells??). Indeed, this material is a good candidate for improving the ratio quality/price of solar cells. Its fabrication needs anodisation of single crystalline silicon in a mixture of HF/methanol solution. In order to simulate the different steps needed to ??develop?? the solar cells, PS layers (single or two layers) were subjected to different annealing. In this article, we discuss the influence of drying and annealing on the morphology of PS. SEM observations and gravimetric measurements are reported.     

Lack of Syneresis during Gelation of Dense Colloidal Suspensions

This study reports experimental results about the shrinkage of particle networks produced by pH-induced destabilization of dense colloidal suspensions. The resulting solid networks exhibit no syneresis effects, at least prior to aging of the gel. From this lack of syneresis it is concluded that the solidification in wet particle systems either is not purely determined by energy (but is also influenced by entropic effects) or cannot be explained within the framework of (static) equilibrium thermodynamics at all. Copyright 2000 Academic Press.     

Fingering phenomena during spreading of surfactant solutions

Fingering instabilities are observed at the contact line of drops of surfactant solutions spreading spontaneously on solid surfaces coated by a film of solvent. The occurrences of instabilities, and the characteristics of the instability pattern, are controlled by the surfactant concentration and the thickness of the film adsorbed or deposited on the substrate. This work provides experimental data as a basis for forthcoming theoretical analyses.     

Isomerization of alkenes during drying over zeolites

We observed that zeolite 5A, a zeolite commonly used for drying, isomerized 1-butene and 1-hexene at room temperature. The activity for 1-butene isomerization on 3A, 4A, 5A and 13X zeolites at temperatures of 300 to 565 K is reported.     

The relative importance of transport phenomena in recycling isoelectric focusing.

The various transport phenomena involved in recycling isoelectric focusing are analyzed for their contributions to band spreading so as to find ways of improving the resolution of this liquid-phase protein purification method. A numerical model is proposed that takes into account diffusion, electroosmosis and electrophoretic migration as a function of pH. The electrohydrodynamic effects have so far been neglected in these calculations. The results of these calculations are compared with experimental measurements performed in different chamber geometries, with a variety of proteins and under different operating conditions, always chosen to avoid flow instabilities. This comparison shows that the resolution of this process is greatly impaired if the electroosmotic slip velocity at the wall is not suppressed.     

In-line determination of metabolites and milk components with electrochemical biosensors

Electrochemical biosensors for lactate, pyruvate and β-hydroxybutyrate based on oxygen, hydrogen peroxide, and NADH sensors coupled with oxidase and dehydrogenase enzymes were developed and used in conjunction with an artificial pancreas in experiments with extracorporeal circulation. Such procedures allow the fate of these species involved in glucose metabolism to be clarified during insulin treatment of diabetic patients. Studies with a glucose oxidase electrode for in-line determination of glucose produced by hydrolysis of cellobiose in a bioreactor are reported; for the determination of glucose in the presence of high concentrations of cellobiose, the purity of glucose oxidase is important in obtaining linear calibration plots. Impurities like amylase, maltase, invertase, and galactose oxidase, which are usually present in commercial preparations of glucose oxidase, must be absent. Another application is the amperometric determination of lactose, lactate and glucose in milk samples by using a hydrogen peroxide sensor coupled with β-galactosidase, lactate oxidase and glucose oxidase. The procedures outlined are simple and the short response times enable milk to be monitored during processing.     

Contribution of thermal analysis to the description of transport phenomena of pesticides

The vaporization enthalpies of two acetanilide pesticides, alachlor (2’,6’-diethyl-N-(methoxymethyl)-2-chloroacetanilide) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl] acetamide), were determined by processing non-isothermal thermogravimetry data according to the Clausius-Clapeyron equation. The reliability of the procedure proposed was tested carrying out some experiments at different heating rates using acetanilide as a reference compound. A good agreement is found among the vaporization enthalpies derived from all the multi-heating rate experiments as well as with the one predicted from the vapor pressure data taken from literature. The vaporization temperatures (T _vap=470±2 K and T _vap=479±2 K) and enthalpies (Δ_vap H°(436 K)=85±1 kJ mol^–1 and Δ_vap H°(436 K)=70±1 kJ mol^–1) for alachlor and metolachlor, were selected, respectively.     

Assembly of nanoparticles at the contact line of a drying droplet under the influence of a dipped tip

The manipulation of colloidal nanoparticles (NPs) in a drying droplet has critical importance not only for several industrial applications but also their assembly into patterns on surfaces. The influence of a tip with hydrophilic or hydrophobic surfaces dipped into a drying droplet on hydrophilic or hydrophobic surfaces on the behavior of 98 nm latex NPs was investigated. The formation of concentric rings on hydrophilic glass surfaces regardless of the surface chemistry of the dipped tip was observed. On the other hand, no pattern formation on hydrophobic surfaces was observed with the insertion of the tip. With a hydrophilic tip, the concentric rings were formed due to stick-slip motion of the solvent contact line resulting from competition between pinning and capillary forces while the capillary effect was not effective until the surface of the tip was changed by adherent NPs making the tip surface available for water adherence with a hydrophobic tip, which results in the pulling of droplet towards the tip. It is also found that the tip thickness and suspension concentration significantly influences the formation of concentric rings on surfaces. This simple procedure can be used to influence the distribution or assembly of NPs in the droplet area.     

Viscoelastic phenomena during electrochemical deposition of polyaniline films

Electrochemical quartz crystal microbalance (EQCM) and crystal admittance measurements were used to study the potentiodynamic electrodeposition of polyaniline films. Variations in peak admittance provided the distinction between acoustically thin and acoustically thick films. In the former instance, the Sauerbrey equation was used to interpret the EQCM frequency shift in gravimetric terms. In the latter case, admittance spectra were interpreted viscoelastically to yield shear storage and loss moduli. Variations in storage modulus with potential (within a given deposition cycle) and with number of deposition cycles (at a given potential) were small, covering the range 1.1–1.6 × 10⁷ dyn cm⁻². Variations in loss modulus were much more dramatic, increasing from very low levels typical of a simple fluid to values similar to the storage modulus. More subtle variations of both components within a single potential cycle were highlighted using a novel differential format. This revealed two peaks, correlating with the first film redox process and with further film oxidation/polymerization. Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June 2006.     

Simple model for transport phenomena: microscopic construction of Maxwell demonlike engine

We present a microscopic Hamiltonian framework to develop Maxwell demonlike engine. Our model consists of an equilibrium thermal bath and a nonequilibrium bath, latter generated by driving with an external stationary, Gaussian noise. The engine we develop can be considered as a device to extract work by modifying internal fluctuations. Our theoretical analysis focuses on finding the essential ingredients necessary for generating fluctuation induced transport under nonequilibrium condition. An important outcome of our model is that the net motion occurs when the nonlinear bath is modulated by the external noise, creating the nonzero effective temperature even when the temperature of both the baths are the same.     

Shape changes during the drying of droplets of suspensions

During drying of droplets of suspensions, several flow regimes contribute to the radial flow of powder to the periphery to leave a pile-up of powder at the rim. It is shown that the shape of the droplet residues can be controlled both by restricting evaporation and by combining high and low boiling point solvents which modify particle flows and produce a range of droplet residues varying from a concave "doughnut" shape, sometimes with a central hole, to a convex dome shape. Addition of formamide to aqueous suspensions is shown to affect powder deposition by setting up a Marangoni flow rather than by reducing evaporation at the periphery. The results find direct application in thick-film combinatorial printing of ceramics to form small disks by droplet drying.     

Study of cool-Dame phenomena during self-ignition of methane-oxygen mixtures

Experimental studies and kinetic simulation have shown that the formation of cool flames is as typical of oxidation of methane as of oxidation of its homologs. Phenomena peculiar to the cool-flame processes in closed systems are observed, namely, the region of a negative temperature coefficient of the reaction, single and double cool-flame flashes, two stage ignition, and light radiation in the range of luminescence of formaldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2445–2449, October, 1996.