Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

Purification of phosphoric acid by solvent extraction

This work follows a feasibility study (187) which suggested that a process for purifying wet-process phosphoric acid by solvent extraction should be economically viable. The work was divided into two main areas, (i) chemical and physical measurements on the three-phase system, with or without impurities; (ii) process simulation and optimization. The object was to test the process technically and economically and to optimise the type of solvent. The chemical equilibria and distribution curves for the system water - phosphoric acid - solvent for the solvents n-amyl alcohol, tri-n-butyl phosphate, di-isopropyl ether and methyl isobutyl ketone have been determined. Both pure phosphoric acid and acid containing known amounts of naturally occurring impurities (Fe P0 4 , A1P0 4 , Ca3(P04)Z and Mg 3(P0 4 )Z) were examined. The hydrodynamic characteristics of the systems were also studied. The experimental results obtained for drop size distribution were compared with those obtainable from Hinze's equation (32) and it was found that they deviated by an amount related to the turbulence. A comprehensive literature survey on the purification of wet-process phosphoric acid by organic solvents has been made. The literature regarding solvent extraction fundamentals and equipment and optimization methods for the envisaged process was also reviewed. A modified form of the Kremser-Brown and Souders equation to calculate the number of contact stages was derived. The modification takes into account the special nature of phosphoric acid distribution curves in the studied systems. The process flow-sheet was developed and simulated. Powell's direct search optimization method was selected in conjunction with the linear search algorithm of Davies, Swann and Campey. The objective function was defined as the total annual manufacturing cost and the program was employed to find the optimum operating conditions for anyone of the chosen solvents. The final results demonstrated the following order of feasibility to purify wet-process acid: di-isopropyl ether, methylisobutyl ketone, n-amyl alcohol and tri-n-butyl phosphate.

Solvent extraction of phosphoric acid

This work investigated the purification of phosphoric acid using a suitable organic solvent, followed by re-extraction of the acid from the solvent using water. The work consisted of practical batch and continuous studies and the economics and design of a full scale plant, based on the experimental data. A comprehensive literature survey on the purification of wet process phosphoric acid by organic solvents is presented and the literature describing the design and operation of mixer-settlers has also been reviewed. In batch studies, the equilibrium and distribution curves for the systems water-phosphoric acid-solvent for Benzaldehyde, Cyclohexanol and Methylisobutylketone (MIBK) were determined together with hydrodynamic characteristics for both pure and impure systems. The settling time increased with acid concentration, but power input had no effect. Drop size was found to reduce with acid concentration and power input. For the continuous studies a novel horizontal mixer~settler cascade was designed, constructed and operated using pure and impure acid with MIBK as the solvent. The cascade incorporates three air turbine agitated, cylindrical 900 ml mixers, and three cylindrical 200 ml settlers with air-lift solvent interstage transfer. Mean drop size in the fully baffled mixer was correlated. Drop size distributions were log-normal and size decreased with acid concentration and power input and increased with dispersed phase hold-up. Phase inversion studies showed that the width of the ambivalent region depended upon rotor speed, hold-up and acid concentration. Settler characteristics were investigated by measuring wedge length. Distribution coefficients of impurities and acid were also investigated. The following optimum extraction conditions were found: initial acid concentration 63%, phase ratio of solvent to acid 1:1 (v/v), impeller speed recommended 900 r.p.m. In the washing step the maximum phase ratio of solvent to water was 8:1 (v/v). Work on phosphoric acid concentration involved constructing distillation equipment consisting of a 10& spherical still. A 100 T/d scale detailed process design including capital cost, operating cost and profitability was also completed. A profit model for phosphoric acid extraction was developed and maximised. Recommendations are made for both the application of the results to a practical design and for extensions of the study.

[Bmim]Br-3 as a new reagent for regioselective mono-bromination of activated aromatics under solvent-free conditions

Reaction of activated aromatics containing phenols, naphthol, methoxynaphthalenes, anisole etc. with 1-butyl-3-methylimidazolium tribromide ([Bmim]Br-3) under solvent-free conditions, selectively gave the corresponding monobromination products with excellent yields.

[bmim]Br3 as a new reagent for regioselective monobromination of arylamines under solvent-free conditions

Reaction of arylamines with 1-butyl-3-methylimidazolium tribromide ([bmim]Br3) under solvent-free conditions, gave selectively the corresponding monobromination products with excellent, yields.

A convenient synthesis of 5-benzylidenethiazolidine-2, 4-diones under microwave irradiation without solvent

A series of 5-benzylidenethiazolidine-2,4-diones was synthesised by the Knoevenagel condensation of aromatic aldehydes with thiazolidine-2,4-dione in the presence of catalytic amounts of piperidine and acetic acid under microwave irradiation without solvent in good yields.

A solvent-free matrix application method for matrix-assisted laser desorption/ionization imaging of small molecules

Matrix application continues to be a critical step in sample preparation for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI). Imaging of small molecules such as drugs and metabolites is particularly problematic because the commonly used washing steps to remove salts are usually omitted as they may also remove the analyte, and analyte spreading is more likely with conventional wet matrix application methods. We have developed a method which uses the application of matrix as a dry, finely divided powder, here referred to as dry matrix application, for the imaging of drug compounds. This appears to offer a complementary method to wet matrix application for the MALDI-MSI of small molecules, with the alternative matrix application techniques producing different ion profiles, and allows the visualization of compounds not observed using wet matrix application methods. We demonstrate its value in imaging clozapine from rat kidney and 4-bromophenyl-1,4-diazabicyclo(3.2.2)nonane-4-carboxylic acid from rat brain. In addition, exposure of the dry matrix coated sample to a saturated moist atmosphere appears to enhance the visualization of a different set of molecules.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Use of a solvent-free dry matrix coating for quantitative matrix-assisted laser desorption ionization imaging of 4-bromophenyl-1,4-diazabicyclo(3.2.2)nonane-4-carboxylate in rat brain and quantitative analysis of the drug from laser microdissected tissue regions

A dry matrix application for matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) was used to profile the distribution of 4-bromophenyl-1,4-diazabicyclo(3.2.2)nonane-4-carboxylate, monohydrochloride (BDNC, SSR180711) in rat brain tissue sections. Matrix application involved applying layers of finely ground dry alpha-cyano-4-hydroxycinnamic acid (CHCA) to the surface of tissue sections thaw mounted onto MALDI targets. It was not possible to detect the drug when applying matrix in a standard aqueous-organic solvent solution. The drug was detected at higher concentrations in specific regions of the brain, particularly the white matter of the cerebellum. Pseudomultiple reaction monitoring imaging was used to validate that the observed distribution was the target compound. The semiquantitative data obtained from signal intensities in the imaging was confirmed by laser microdissection of specific regions of the brain directed by the imaging, followed by hydrophilic interaction chromatography in combination with a quantitative high-resolution mass spectrometry method. This study illustrates that a dry matrix coating is a valuable and complementary matrix application method for analysis of small polar drugs and metabolites that can be used for semiquantitative analysis.

Solvent induced NMR chemical shifts that arise from molecular encounters

Recently Homer and Percival have postulated that intermolecular van der Waals dispersion forces can be characterized by three mechanisms. The first arises via the mean square reaction field < R1; 2> due to the transient dipole of a particular solute molecule that is considered situated in a cavity surrounded by solvent molecules; this was characterized by an extended Onsager approach. The second stems from the extra cavity mean square reaction field < R2; 2> of the near neighbour solvent molecules. The third originates from square field electric fields E2BI due to a newly characterized effect in which solute atoms are `buffeted' by the peripheral atoms of adjacent solvent molecules. The present work concerns more detailed studies of the buffeting screening, which is governed by sterically controlled parameter (2T - T)2, where and are geometric structural parameters. The original approach is used to characterise the buffeting shifts induced by large solvent molecules and the approach is found to be inadequate. Consequently, improved methods of calculating and are reported. Using the improved approach it is shown that buffeting is dependent on the nature of the solvent as well as the nature of the solute molecule. Detailed investigation of the buffeting component of the van der Waals chemical shifts of selected solutes in a range of solvents containing either H or Cl as peripheral atoms have enabled the determination of a theoretical acceptable value for the classical screening coefficient B for protons. 1H and 13C resonance studies of tetraethylmethane and 1H, 13C and 29Si resonance studies of TMS have been used to support the original contention that three (< R1; 2> , < R2; 2> and E2BI) components of intermolecular van der Waals dispersion fields are required to characterise vdW chemical shifts.

A study of the dynamic behaviour of a pulsed column solvent extraction plant

A study has been made of the dynamic behaviour of a nuclear fuel reprocessing plant utilising pulsed solvent extraction columns. A flowsheet is presented and the choice of an extraction device is discussed. The plant is described by a series of modules each module representing an item of equipment. Each module consists of a series of differential equations describing the dynamic behaviour of the equipment. The model is written in PMSP, a language developed for dynamic simulation models. The differential equations are solved to predict plant behaviour with time. The dynamic response of the plant to a range of disturbances has been assessed. The interactions between pulsed columns have been demonstrated and illustrated. The importance of auxillary items of equipment to plant performance is demonstrated. Control of the reprocessing plant is considered and the effect of control parameters on performance assessed.

A novel process for the production of castor oil by direct solvent extraction

This research was undertaken to: develop a process for the direct solvent extraction of castor oil seeds. A literature survey confirmed the desirability of establishing such a process with emphasis on the decortication, size, reduction, detoxification-deallergenization, and solvent·extraction operations. A novel process was developed for the dehulling of castor seeds which consists of pressurizing the beans and then suddenly releasing the pressure to vaccum. The degree of dehulling varied according to the pressure applied and the size of the beans. Some of the batches were difficult-to-hull, and this phenomenon was investigated using the scanning electron microscope and by thickness and compressive strength measurements. The other variables studied to lesser degrees included residence time, moisture, content, and temperature.The method was successfully extended to cocoa beans, and (with modifications) to peanuts. The possibility of continuous operation was looked into, and a mechanism was suggested to explain the method works. The work on toxins and allergens included an extensive literature survey on the properties of these substances and the methods developed for their deactivation Part of the work involved setting up an assay method for measuring their concentration in the beans and cake, but technical difficulties prevented the completion of this aspect of the project. An appraisal of the existing deactivation methods was made in the course of searching for new ones. A new method of reducing the size of oilseeds was introduced in this research; it involved freezing the beans in cardice and milling them in a coffee grinder, the method was found to be a quick, efficient, and reliable. An application of the freezing technique was successful in dehulling soybeans and de-skinning peanut kernels. The literature on the solvent extraction, of oilseeds, especially castor, was reviewed: The survey covered processes, equipment, solvents, and mechanism of leaching. three solvents were experimentally investigated: cyclohexane, ethanol, and acetone. Extraction with liquid ammonia and liquid butane was not effective under the conditions studied. Based on the results of the research a process has been suggested for the direct solvent extraction of castor seeds, the various sections of the process have analysed, and the factors affecting the economics of the process were discussed.

The molecular design of a new solvent for the absorption of carbon dioxide

Gas absorption, the removal of one or more constitutents from a gas mixture, is widely used in chemical processes. In many gas absorption processes, the gas mixture is already at high pressure and in recent years organic solvents have been developed for the process of physical absorption at high pressure followed by low pressure regeneration of the solvent and recovery of the absorbed gases. Until now the discovery of new solvents has usually been by expensive and time consuming trial and error laboratory tests. This work describes a new approach, whereby a solvent is selected from considerations of its molecular structure by applying recently published methods of predicting gas solubility from the molecular groups which make up the solvent molecule. The removal of the acid gases of carbon dioxide and hydrogen sulfide from methane or hydrogen was used as a commercially important example. After a preliminary assessment to identify promising moecular groups, more than eighty new solvent molecules were designed and evaluated by predicting gas solubility. The other important physical properties were also predicted by appropriate theoretical procedures, and a commercially promising new solvent was chosen to have a high solubility for acid gases, a low solubility for methane and hydrogen, a low vapour pressure, and a low viscosity. The solvent chosen, of molecular structure Ch3-COCH2-CH2-CO-CH3, was tested in the laboratory and shown to have physical properties, except for vapour pressures, close to those predicted. That is gas solubilities were within 10% but lower than predicted. Viscosity within 10% but higher than predicted and a vapour pressure significantly lower than predicted. A computer program was written to predict gas solubility in the new solvent at the high pressures (25 bar) used in practice. This is based on the group contribution method of Skold Jorgensen (1984). Before using this with the new solvent, Acetonyl acetone, the method was show to be sufficiently accurate by comparing predicted values of gas solubility with experimental solubilities from the literature for 14 systems up to 50 bar. A test of the commercial potential of the new solvent was made by means of two design studies which compared the size of plant and approximate relative costs of absorbing acid gases by means of the new solvent with other commonly used solvents. These were refrigerated methanol(Rectisol process) and Dimethyl Ether or Polyethylene Glycol(Selexol process). Both studies showed in terms of capital and operating cost some significant advantage for plant designed for the new solvent process.

Molecular dynamics study of solvent transport in nanoscale osmosis

An ideal of osmotic equilibrium between an ideal solution and pure solvent separated by a semi-permeable membrane is studied numerically using the method of molecular dynamics. The osmotic flow is observed as the inflow of the solvent across the membrane from the dilute to the concentrated side. The validity of van't Hoff's law for osmotic pressure is confirmed over a wide range of concentrations. It is found that the law is established by a balance between non-uniform partial pressures of solute and solvent. Furthermore, the present model permits an understanding of the mechanism of the osmotic flow in the relaxation process as the liquids evolve from the initial state to the equilibrium state. We focus in particular on the interaction between solute and solvent. ©2008 The Physical Society of Japan.