THE ELECTROHYDRODYNAMICS OF THE CHARGED LIQUID JET ISSUING FROM AN ELECTRIFIED TAYLOR CONE. UNIVERSAL SCALING LAWS

A hybrid experimental–numerical approach to study the dynamics of capillary electrified jets, which uses a quasi-one-dimensional model and the experimentally measured shape of an actual liquid thread (Gañán-Calvo (1997) J. Fluid Mech. 335, 165–188) has been employed in this work to analyze the electrohydrodynamics of the liquid micro-jets issuing from Taylor cones. Different liquids have been used in this study, with electrical permittivities from 6.5 to 38 times the vacuum permittivity, and electrical conductivities ranging from 8.5 to 4.5e-4 S m^-1. Up to 25 different jet shapes corresponding to steady and absolutely stable conditions have been digitized, and the corresponding surface charge distribution, normal external and internal electric fields at the surface, the axial electric field (the slender approach allows to consider the axial electric field constant in the transversal direction), the liquid velocity distribution, the electric current convected by the surface and the one driven through the bulk by Ohmic conduction at each axial point have been calculated. In particular, one of the liquid jets analyzed corresponded to the onset of stability of the steady cone-jet mode, where we supply just the (minimum) liquid flow rate that the electrostatic suction effect at the cone-jet neck is able to withdraw at the minimum needle–electrode potential difference for a given stable cone elongation. This has revealed a surprising result: even in this critical situation, the inner normal electric displacement is at most a mere 15% of the outer one, and this happens only at one point of the whole cone-jet, located close to the point at which the convected electric current equals the current driven by bulk conduction (i.e. a little downstream of the cone-jet neck), being the inner displacement at other points of the jet and the cone hundreds of times smaller than the outer displacement. As one increases the liquid flow rate, the ratio of the maximum inner displacement to the outer displacement becomes proportionally smaller. This result clarifies for the first time the controversy about charge relaxation phenomena in cone-jet electrosprays, since it can be used to show from a physicochemical argument that the charge layer at the whole cone-jet surface is almost relaxed even at the onset of stability, at least for liquid permittivities of the order of the ones used in this study. This result also guarantees a homogeneous bulk conductivity along the hole cone-jet. Secondly, and similarly interesting, the kinetic energy per unit volume acquired by the liquid in the jet results independent of the flow rate for a given liquid and a cone elongation, explained by the fact that the normal electric field (or surface charge distribution) which provokes the main acceleration force (the electrostatic suction effect, at the cone-jet neck and the beginning of the jet) results independent of the flow rate as well. A universal scaling of the electro-hydrodynamic variables, jet size and total emitted electric current is proposed, and the experimental results are collapsed into a universal collection of distributions of non-dimensional variables along the axis. The resulting droplet size, also measured in the same experiments, scales as the jet radius, and the droplet charge results proportional to its surface, a result shown by many investigators but never explained. Other previously used electrohydro-dynamic hypotheses and scaling laws are discussed under these new results.     

TAYLOR CONE ELECTROHYDRODYNAMICS. THE MINIMUM AND MAXIMUM FLOW RATES IN ELECTROSPRAYING

The surface charge at the liquid–gas interface in cone-jet electrospraying, almost relaxed from an electrochemical point of view, is driven by the radial electric field created to supply the current to the cone tip that the microjet withdraws. The electric stress applied on the liquid surface provokes a low or high Reynolds number motions in the electrified meniscus depending on a dimensionless parameter which relates the liquid viscosity and its electrical conductivity. The analysis of the surface motion is essential to quantify the surface current convected to the cone’s tip, which is shown to be negligible compared to the one driven by bulk conduction. In the case of high Reynolds number motions, we show mathematically, and also experimentally, the emergence of an interesting self-rotation phenomenon.In addition, an analysis of the equations governing the electrohydrodynamics of the charged liquid ligament issuing from the tip of an electrified meniscus in a steady cone-jet suggests the mechanisms which set the stability limits of this steady regime. It is shown that for low and moderate liquid polarities (less than 40 times the vacuum permittivity), the minimum liquid flow rate that can be electrosprayed in a steady cone-jet is reached when the surface tension stress at the cusp from which the jet issues, which provokes a resulting pressure gradient against the flow, overcomes the electrostatic “suction” effect. To show the role of the different forces involved, we have carried the calculation of the intervening ones in the momentum equation using the digitized shape of a cone-jet close to the minimum flow rate in the case of a permittivity 6.5 times larger than the vacuum one. For larger polarities, which impose large electrical conductivities as well, the role of viscous forces, polarization forces, and charge relaxation effects is discussed. In addition, we have carried out experimental measurements of the minimum flow rate using several different liquids. These results are discussed and compared with the experimental data from different authors, as well as with other previously given scaling laws and estimations of the minimum flow rate in cone-jet electrospraying.     

Crystallization and relaxation dynamics of glass-forming liquids at the Kauzmann temperature

If the entropy extrapolation of supercooled liquids (SCL) suggested by Kauzmann was correct, then they would have the same entropy as their stable crystalline phase at a certain low temperature, below the laboratory glass transition (T_g), known as the Kauzmann temperature (T_K). Extrapolating even further, the liquid entropy would be null at a temperature above absolute zero, violating the Third Law of Thermodynamics and constituting a paradox. Several possibilities have been proposed over the past 70 years to solve this paradox with different degrees of success. Our objective here is to access liquid dynamics at deep supercoolings to test the so-called crystallization solution to the paradox. By comparing the relaxation and crystallization kinetics determined above T_g and extrapolated down to T_K, a possible solution would be that the crystallization time is shorter than the relaxation time, which would mean that a SCL cannot reach the T_K. In this case, the liquid stability limit or kinetic spinodal temperature (T_ks) should be higher than T_K. We tested two fragile glass-forming liquids (diopside and wollastonite) and two strong liquids (silica and germania). For the fragile substances, T_ks ? T_K, hence such a supercooled liquid cannot exist at T_K, and the entropy crisis is averted. On the other hand, the results for the strong liquids were inconclusive. We hope the findings of this work encourage researchers to further investigate the liquid dynamics of different strong glass-forming systems at deep supercoolings.     

Chemometric solid-state C NMR analysis of morphology and dynamics in irradiated crosslinked polyolefin cable insulation

The relative concentrations and carbon spin-lattice relaxation constants (T_1,C) of the amorphous, intermediate, and crystalline phases of unaged crosslinked polyolefin cable insulation (ultimate elongation, e=310%), ⁶⁰Co γ-irradiated (e=22%), and irradiated+annealed (e=220%) samples were determined by chemometric analyses of directly polarized solid-state ¹³C NMR spectra. The T_1,C relaxation curves of the intermediate and amorphous components were found to be mono-exponential. The intermediate component contains 23±5% of the CH₂ segments in the unaged sample and has an T_1,C relaxation constant of 1.4±0.3 s. γ-Irradiation caused a slight decrease in the amount of intermediate component to 19±5% and an increase of the relaxation constant to 1.8±0.3 s. The subsequent annealing of the irradiated sample resulted in an additional increase of the relaxation constant to 2.1 s and a slight loss of crystallinity. The amorphous T_1,C relaxation constants were found to be identical in all three samples and have a value of 0.38±0.03 s. At ambient temperature, the crystalline phase was found to relax via chain diffusion from the intermediate component. The rate of helical jumps was twice as fast in the irradiated and irradiated+annealed samples compared with the unaged material.     

Control of the confined and unconfined crystallization in glassy-crystalline poly(vinylcyclohexane)-b-poly(ethylene)-b-poly-(vinylcyclohexane) triblock copolymer in solution

The influence of the solvent evaporation rate on the crystallization of the poly(vinylcyclohexane)-b-poly(ethylene)-b-poly(vinylcyclohexane) (PVCH-PE-PVCH) triblock copolymer with the high T_g of PVCH segment in chloroform was investigated. The competition between the crystallization of PE block and the vitrification of PVCH in the triblock copolymer was controlled through changing the solvent evaporation rate in the solution system at different temperatures (T_e). It was found that the melting temperature (T_m) of PVCH-PE-PVCH samples increased with increasing the T_e when the T_e was lower than the solvent boiling point (bp), depending on the crystalline temperatures. However, when T_e was just a little above the solvent bp, two melting peaks, which corresponding to the fusion of the confined and unconfined crystals, respectively, were observed on the DSC curves of the samples. As T_e increased to be higher temperature, only one lower melting peak, which corresponding to the fusion of the confined crystals, existed for each samples. It was also found that the crystallinity (X_c) of the samples decreased gradually when T_e was lower than the solvent bp, and then decreased suddenly when T_e was just a little above the solvent bp, finally reached a plateau (about 13.5%) at higher T_e. The changes in X_c of the samples depend on the evaporating time in the solution. The results should be related to the competition between the crystallization of PE block in solvent and the vitrification of PVCH block with the solvent evaporation. Furthermore, the competition was controlled through changing the solvent evaporation rate. The confined and unconfined crystallization of the samples could be freely adjusted.     

THE SURFACE CHARGE IN ELECTROSPRAYING: ITS NATURE AND ITS UNIVERSAL SCALING LAWS

The electrospraying of liquids in steady cone-jet mode follows a well-defined EHD mechanism described and quantified in this work using a hybrid experimental–numerical technique: a collection of emitted microjet shapes corresponding to several liquids and different flow rates have been digitized and introduced in a quasi-one-dimensional analytical model. A universal value of the surface charge on the liquid microjet and the resulting charged droplets, independent of their size and of the liquid permittivity, has been found. The surface charge is shown to be always in equilibrium, being the liquid bulk quasi-neutral. From these findings, we finally present a consistent general scaling of all EHD variables involved which is experimentally verified. In this scaling, the electric current I and the characteristic microjet radius R_o are both proportional to the square root of the emitted flow rate, Q^1/2, and independent of the liquid permittivity ε_i.     

Synthesis and properties of cyclopentadithiophene-based poly(silarylenesiloxane) derivatives

Poly(silarylenesiloxane) derivatives with 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety, bearing dimethyl- (P1), methylphenyl- (P2) and diphenyl- (P3) substituents on silyl moieties, were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M1), 2,6-bis(methylphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M2), and 2,6-bis(diphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M3), respectively. P1-P3 exhibited the good solubility in common organic solvents, such as benzene, toluene, chloroform, dichloromethane, THF, and so on. The glass transition temperatures (T_gs) of P1, P2 and P3 were determined by differential scanning calorimetry to be 56, 97 and 137 °C, respectively, depending on the substituent on the silyl moieties. No melting temperatures (T_ms) of P1, P2 and P3 were observed, suggesting the obtained P1-P3 are amorphous polymers. The temperatures at 5% weight loss (T_d5s) of P1, P2 and P3 were 460, 459 and 479 °C, respectively, indicating that the larger number of phenyl group on the silyl moieties resulted in the better thermostability. Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra by introducing silyl substituents onto 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety. In addition, the bathochromic shift of the maximum absorption (λ_abs) and the increase in the fluorescence quantum yield (Φ_F) were observed by the introduction of phenyl group onto the silyl moieties.     

On the estimation of the Kauzmann temperature from relaxation data

The well known WLF equation describing the relaxation behaviour of glass-forming liquids near the glass transition temperature has been rederived on the basis of Adam and Gibbs' excess entropy model, making use of a novel expression for the entropy of undercooled liquids. It has been shown that C₂ in the WLF equation is a nearly constant fraction of (T_s - T₂), where T_s and T₂ are the reference and the Kauzmann temperatures, respectively. It is demonstrated that the values of T₂ obtained from the relaxation data agree well with those calculated from thermodynamic data. The arguments used provide an explanation for the universality of the WLF constant, C₂.     

ELECTROSTATIC SOL–SPRAY DEPOSITION OF NANOSTRUCTURED CERAMIC THIN FILMS

Electrospraying has been developed into an electrostatic spray deposition technique for the deposition of ceramic thin films. The cone-jet spraying mode appears to be the most preferable for this purpose, and the domain where the cone-jet mode exists was found to depend strongly on the nozzle design. A nozzle with a large diameter and a tilted outlet widens the windows for both the applied high DC voltage and the flow rates of a precursor liquid keeping the cone-jet mode intact. The results of three nozzle designs are compared, one of which has been selected for feeding two different precursor liquids simultaneously. With three relevant sols as precursor liquids, nanostructured thin films of ZnO, ZrO₂, and Al₂O₃ have been deposited. Their morphologies are dependent on the preparation of the precursor sols and the deposition temperature. Highly porous films were obtained by using a high deposition temperature and a sol prepared from a metal alkoxide or a metal acetate.     

Nanodroplet formation and exclusive homogenously nucleated crystallization in confined electrospun immiscible polymer blend fibers of polystyrene and poly(ethylene oxide)

By utilizing electrospun blend fibers of polystyrene (PS) and poly(ethylene oxide) (PEO) with diameters in sub-microns, nanodroplets of the minor component (PEO) were obtained by annealing the blend fibers above the glass transition temperature (T_g) of the matrix polymer (PS), as a result of the Rayleigh-Plateau instability in the melt. However, direct thermal annealing of the PS/PEO blend fibers led to poor Rayleigh breakup of the PEO fibers in the PS matrix, and fractionated crystallization with both homogeneous and heterogeneous nucleation was observed, probably due to a broad size distribution of PEO particles. On the contrary, after confining the PS/PEO blend fibers with a high T_g polymer, poly(4-tert-butyl styrene) (P4tBS, T_g ∼ 143 °C), well-defined Rayleigh breakup of the PEO fiber was achieved by annealing the P4tBS-coated PS/PEO blend fibers at 150 °C. Consequently, exclusive homogeneously nucleated PEO crystallization was observed at −20 °C. This report could provide a universal method to achieve nano-sized droplets for the study of nanoconfinement effect by utilizing electrospun immiscible polymer blend fibers without addition of any compabitilizers.     

Pulsed n.m.r. studies of molecular motion in wet nylon-6,6 fibres

The influence of water molecules on molecular motion in commercial nylon-6,6 fibres has been investigated by pulsed n.m.r. techniques. Transient n.m.r. signals, T₂ and T₁ relaxation times for the fibre protons were measured as a function of temperature and moisture (D₂O) content. Above the glass transition temperature, T_g, of the fibre, separation of the signal into two components, a ‘rigid’ and ‘non-rigid’ fraction, was possible. For wet fibres, the temperature at which the ‘non-rigid’ or ‘mobile’ component appeared was reduced as the water content was increased and the ‘mobile fraction’ increased with temperature. This behaviour is explained in terms of the mobilization of amorphous chain segments above the T_g and their ability to be ‘plasticized’ by water molecules. The effect of D₂O molecules and paramagnetic Mn²⁺ ions on T₁ relaxation of rigid and mobile segments provided further information on the properties of accessible chain segments between and on the crystallite surfaces. A chain folded model of semi-crystalline morphology has been adopted throughout the discussion.     

Behaviour of the spin-spin relaxation time for natural rubber vulcanizates under large deformation

The spin-spin relaxation time, T₂, for DCP-cured natural rubber with various crosslink densities, v_e, has been measured under various deformation. T₂ is separated into two components: one is the long T₂ component, T_2L, for the mobility of amorphous network chains, the other is the short one, T_2S, for that of the strain-induced crystalline chains. T_2L decreased exponentially with increasing extension ratio,α, and the decreasing rate was more remarkable with increasing v_e. The α and v_e dependence of T_2L has been quantitatively explained by the equation experimentally derived by Nishi et al.T_2L under various extension increased and became almost constant with increasing temperature, while the corrected fraction of T_2S, T_2S (%), gradually decreased. The apparent melting point, T_m, at which the corrected T_2S (%) was zero under various deformation was determined. The α dependence of T_m, has been discussed by using Flory's equation.     

Retarded relaxation and breakup of deformed PA6 droplets filled with nanosilica in PS matrix during annealing

The effect of hydrophilic silica nanoparticles (SiO₂) on the relaxation and breakup dynamics of selectively filled polyamide (PA6) droplets with different degrees of deformation in polystyrene (PS) matrix during quiescent annealing were in situ investigated. It was found that, with the increase of silica content, the relaxation process of PA6 droplets was slowed down gradually and the relaxation mode was changed correspondingly. The critical break aspect ratios (AR_cr) of PA6 droplets were also improved with the increase in SiO₂ nanoparticle contents. Comparisons of the experimental values of AR_cr, characteristic relaxation time (τ_d) and breakup time (t_b) of the SiO₂-filled PA6 droplets with corresponding theoretical values were made. The results of comparison were discussed in terms of viscoelasticity and interfacial tension. It was proposed that the alternation of the viscoelastic properties of PA6 droplets in stead of the interfacial tension change of the blends was responsible for the phenomena observed.     

Structures and rheological properties of reactive solutions of block copolymers. Part I. Diblock copolymers in a liquid epoxy monomer

P(S-b-MMA) and P(B-b-MMA) diblock copolymers (BCP) have been solubilized in a liquid epoxy. The obtained solutions have been characterized by rheology and small angle X-ray scattering (SAXS). As in the solid state, BCP can self-organize in solution to form well-ordered micellar structures. The two blocks respective roles have been clearly identified: at room temperature the PS or the PB block microsegregates while the PMMA block for which epoxy constitutes a good solvent, acts as a stabilizer of the microphase separation. The geometries and thermal stabilities of the ordered structures depend strongly on the molar masses and the chemical nature of the BCP blocks. For instance, the total molar mass of the BCP has to be high enough to obtain a periodic structure. On the contrary, if this molar mass is too high, too long relaxation times prevent the system from reaching its equilibrium. For the P(S-b-MMA) copolymer solution, a transition temperature from an order to a disorder state (T_ODT) is observed. The origin of this transition has been attributed to a solubilization of the PS domains around T_ODT. Macroscopically, this transition can be defined as a solid-like to a liquid-like transition. In the case of the P(B-b-MMA) copolymer solution, no order-disorder transition has been observed: it can be explained by the fact that the PB blocks are not soluble in epoxy at any temperature, up to T=200 °C.     

Structural and dynamic heterogeneity in a telechelic polymer solution

We utilize molecular dynamics simulations to investigate the implications of micelle formation on structural relaxation and polymer bead displacement dynamics in a model telechelic polymer solution. The transient structural heterogeneity associated with incipient micelle formation is found to lead to a ‘caging’ of the telechelic chain end-groups within dynamic clusters on times shorter than the structural relaxation time governing the cluster (micelle) lifetime. This dynamical regime is followed by ordinary diffusion on spatial scales larger than the inter-micelle separation at long times. As with associating polymers, glass-forming liquids and other complex heterogeneous fluids, the structural τ_s relaxation time increases sharply upon a lowering temperature T, but the usual measures of dynamic heterogeneity in glass-forming liquids (non-Gaussian parameter α₂(t), product of diffusion coefficient D and shear viscosity η, non-Arrhenius T-dependence of τ_s) all indicate a return to homogeneity at low T that is not normally observed in simulations of these other complex fluids. The greatest increase in dynamic heterogeneity is found on a length scale that lies intermediate to the micellar radius of gyration and intermicellar spacing. We suggest that the limited size of the clusters that form in our (low concentration) system limit the relaxation time growth and thus allows the fluid to remain in equilibrium at low T.     

Synthesis and gas permeability of nitrated and aminated Poly(diphenylacetylene)s

Poly(diphenylacetylene) [PDPA] derivatives were nitrated using a mixture of nitric acid and sulfuric acid. Nitration of poly[1-(p-trimethylsilyl)phenyl-2-phenylacetylene] (1a) proceeded, and the nitro groups were substituted to trimethylsilyl groups on benzene rings. The degree of nitration (DN) increased with reaction time, and it reached 0.41 for 3.0 h. Fluorine-containing PDPA (1b and 1c) showed less reactivity for nitration, and the DNs were only 0.18 and 0.06, respectively, under the same conditions. Nitration of PDPAs having n-butyl and t-butyl groups (1d and 1e) afforded the nitrated PDPAs, whose DN were 0.20 and 0.14, respectively. Reduction of nitro groups on PDPAs proceeded quantitatively to produce the corresponding PDPAs possessing amino groups (3a-e). Aminated PDPAs exhibited high CO₂ permselectivity compared to the corresponding non-aminated PDPAs. The CO₂ permeability coefficients of aminated PDPAs (3a-d) were lower than those of the corresponding polymers (1a-d) because the polymer chain packing was strengthened by the intermolecular interaction between polar amino groups, but t-butyl group-containing aminated PDPA (3e) showed high CO₂ permeability than 1e because the chain packing was weakened by the steric repulsion of bulky t-butyl groups.     

Interactions of binary liquid mixtures with polysaccharides studied using multi-dimensional NMR relaxation time measurements

Nuclear magnetic resonance transverse T₂ relaxation time has proven to be a valuable parameter for characterizing liquid/polymer interactions. This measurement is applicable to many food, personal care, and cosmetic products that contain multi-component liquid mixtures. Here, we investigate the interactions of corn starch with water/glycerol mixtures of different weight compositions and explore liquid exchange dynamics; such a system is relevant to the personal care industry. We use a combination of chemical shift resolved ¹H T₂ relaxation measurements and corresponding two-dimensional T₂ relaxation exchange experiments using both a conventional experimental protocol and a modified method with the addition of NMR chemical shift selectivity. Two relaxation regimes were evident for the hydroxyl ¹H (found in both water and glycerol) whilst three relaxation regimes are evident for the aliphatic glycerol ¹H associated here with strongly bound, weakly bound, and free (bulk) liquid, respectively. At higher water contents preferential absorption of glycerol was evident. T₂-T₂ exchange maps with a range of storage times reveal molecular exchange rates between all three regimes due to self-diffusion. Rapid exchange of water between the bulk and bound locations was evident in the case of pure water. Exchange rates for hydroxyl ¹H was considerably reduced by the inclusion of glycerol.     

Synthesis and characterization of poly(tetramethylsilarylenesiloxane) derivatives bearing benzodithiophene moieties

Poly(tetramethylsilarylenesiloxane) derivatives bearing benzo[1,2-b;4,5-b′]dithiophene (P1) and benzo[2,1-b;3,4-b′]dithiophene (P2) moieties were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)benzo[1,2-b;4,5-b′]dithiophene (M1) and 2,7-bis(dimethylhydroxysilyl)benzo[2,1-b;3,4-b′]dithiophene (M2), respectively. It was deduced that P1 is a crystalline polymer while P2 is an amorphous one from the results of differential scanning calorimetry (DSC). Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra when dimethylsilyl substituents were introduced on the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons. The fluorescence quantum yields (Φ_Fs) were not improved by the introduction of dimethylsilyl groups onto the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons, whereas the improvement in the Φ_Fs was remarkable in the case of poly(tetramethylsilarylenesiloxane) derivatives that possessed the corresponding fused benzene ring systems, i.e., poly(tetramethyl-2,6-silanthrylenesiloxane) and poly(tetramethyl-1,8-silphenanthrylenesiloxane).     

EXPERIMENTAL STUDY OF THE JET BREAK UP FOR EHDA OF LIQUIDS IN THE CONE-JET MODE

The scaling laws developed by Fernández de la Mora (1994, J. Fluid Mech. 260, 155–184) and by Gañán-Calvo (1994, J. Aerosol Sci. 25S, S309–S310) have been verified since then through various experiments. Chen and Pui (1997, Aerosol Sci. Technol. 27, 367–380) investigated the dependence of the current and droplet diameter with the permittivity of the liquid. Hartman et al. (1997) developed a physical model to describe the spraying of liquids in the cone-jet mode. These two approaches compare remarkably concerning the current produced by the cones. Nonetheless some differences have appeared concerning the jet break up. Namely, the scaling of the jet diameter with the flow rate and the conductivity is different in both approaches.Thus, we present here an original experimental study to investigate these differences. It was conducted using a High-Speed Spray Imaging System (HSSIS) purchased from Oxford Laser. This system consists of a digital camera (KODAK) connected to a computer which is equipped with a frame grabber. A long-distance microscopic lens is fixed to a camera. The illumination of the subject is done by an infrared laser. A control box synchronizes the camera and the laser. Pictures can be made with an illumination time down to 0.5 ms and the separation between two following pictures can be down to 15 ms. The optical system allows us to see objects down to a few micrometers but only objects bigger than 10 mm can be accurately measured. The experiments were done using five different liquids namely, ethanol, butanol, isobutanol, 2-butanone and ethylene glycol. For each liquid the conductivity and the flow rate were varied. For each situation photos were taken to determine the jet size, the break up of the jet, the droplet size and the droplet velocity. Moreover, for every situation the spray current was measured.Our results show that the jet diameter for the different liquids studied exhibits a dependence on the flow rate at a power ∼0.6. This indicates firstly, that the model developed by Hartman is correct in its calculation of the jet diameter and secondly, that the break up of the jet cannot be assimilated to the one of an unchanged jet. Nevertheless our results must be put in perspective with the fact that the jet diameter is measured at a fixed distance from the cone, while the jet length varies with the flow rate. Further, our study brought some other interesting results.First, concerning the jet break-up mechanism. It is a known fact that within the range where IμQ^1/2 the jet can break up due to varicose or kink instabilities. The results showed that for a given liquid the break up was going from varicose to kink with the flow rate going up. Second, they also showed that the number of satellites produced between two main droplets increases with the flow rate.Moreover, we have tried to define, as a function of liquid properties, a limit which separates the two types of jet break up mechanism (varicose or kink). This is of primary importance because it is known that the size distribution of the main droplets is much narrower when the jet breaks up due to varicose instability.     

Migration of 1,3-diazacyclohexane sub-rings in ring-contracted macrocyclic silver(I) complexes

Mononuclear and dinuclear silver(I) complexes with contracted macrocyclic ligands were synthesized ([AgL^d]BPh₄, 1, and [Ag₂L^b](BPh₄)₂ · 2(DMF), 2). X-ray structural analysis revealed that in 1 the coordinated ligand L^d adopted a ring-contracted cis-form, with two 1,3-diazacyclohexane sub-rings positioned in a cis-configuration with respect to the macrocyclic ring center, while in 2 the ligand L^b adopted a ring-contracted trans-form. ¹H NMR and X-ray structural analysis revealed that the cis- and trans-forms are interconvertible depending on whether the complex is mononuclear or dinuclear and whether it is in crystalline form or in solution; i.e., the 1,3-diazacyclohexane sub-ring is capable of migration in ring-contracted macrocyclic silver(I) complexes.