Graphene oxide dispersions in organic solvents

The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.     

Cocklebur-shaped colloidal dispersions

Unique cocklebur-shaped colloidal dispersions were prepared using a combination of a nanoextruder applied to the aqueous solution containing methyl methacrylate (MMA) and n-butyl acrylate (n-BA) with azo-bis-isobutyronitrile (AIBN) or potassium persulfate (KPS) initiators and stabilized by a mixture of sodium dioctyl sulfosuccinate (SDOSS) and 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DCPC) phospholipid. Upon extrusion and heating to 75 degrees C, methyl methacrylate/n-butyl acrylate (MMA/nBA) colloidal particles containing tubules pointing outward were obtained as a result of DCPC phospholipids present at the particle surfaces. The same cocklebur-shaped particles were obtained when classical polymerization was used without a nanoextruder under similar compositional and thermal conditions, giving a particle size of 159 nm. However, when Ca(2+) ions are present during polymerization, cocklebur morphologies are disrupted. Because DCPC tubules undergo a transition at 38 degrees C, such cocklebur morphologies may offer numerous opportunities for devices with stimuli-responsive characteristics.     

Aqueous polyurethane dispersions

This review describes basic chemistry, preparation process, and physical properties of aqueous polyurethane disperisons and the derived films, along with the methods of post treatment to modify the properties. Basic way to render a polyurethane water dispersible without external emulsifier has been described. Regarding the methods of preparation, four major processes are described and compared. Methods to improve the relatively poor water and solvent resistance of aqueous polyurethane dispersions which is introduced by the hydrophilicity and linear structure of polyurethane have been discussed with an emphasis on acrylate incorporations.     

Polymer modified colloidal dispersions

The effect of added polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) on a dispersion of polystyrene particles stabilised with grafted methoxy PEG chains is discussed. PVA adsorbed more strongly on the particles compared to PVP. Polymer addition led to stable mixtures in the case of PVA compared to depletion phase separation observed in the case of PVP. Rheological measurements showed thickening of the dispersion and absence of any structure in the case of PVA, in contrast to structure formation in the case of PVP due to depletion phase separation. A weak gel state was reached for ca. 7% w/w PVP. The observed behaviour is in accord with the relative propensity of PVA and PVP to interact with the particle surface, the grafted chains and their solubility in water. The solvency of the free polymer chains dominated the overall behaviour while the contribution from the incompatibility between free and grafted chains was conterbalanced by differences in the free polymer adsorption on the particles.     

Stability of non-aqueous dispersions

Summary Theoretical values of the magnitude and location of potential energy maxima, of stability ratio and of half-life for colloidal dispersions in hydrocarbon media have been computed from the DLVO theory of colloid stability for spherical particles of radii 200–10,000 Å, and for a range of surface potential (5–80 mV) andHamaker constant (5×10^–13–1×10^–11 erg). The stability relationships show a marked dependence on particle size but are relatively insensitive to the value of theHamaker constant. The results may with some confidence be used to predict the stability of a dispersion in a hydrocarbon medium.

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Zusammenfassung Die Maxima der potentiellen Energie, die Stabilitätsverhältnisse und die Halbwertszeiten von kolloiden Dispersionen in Kohlenwasserstoffen wurden nach der Theorie vonDerjaguin, Landau, Verwey undOverbeek für kugelige Teilchen mit Radien von 200 bis 10000 Å und für Oberflächenpotentiale von 5 bis 80 mV berechnet. Für dieHamaker-Konstante wurden Werte von 5×10^–13 bis 1×10^–11 eingesetzt. Die Stabilität zeigt eine deutliche Abhängigkeit von der Partikelgröße, wird aber von der Größe derHamaker-Konstanten nur wenig beeinflußt.Die Resultate können zu Voraussagen über die Stabilität von Dispersionen in Kohlenwasserstoffen herangezogen werden.

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With 5 figures     

Colloidal dispersions of polyindole

Polyindole dispersions consisting of 20–30-nm-sized nanoparticles are prepared by chemical oxidation with ferric chloride using sodium dodecyl sulphate, poly(vinyl alcohol) and poly(vinyl acetate) as steric stabilizers. Pure acetonitrile and acetonitrile–water mixtures are used as solvents. The particle size depended on the concentrations of monomer and the steric stabilizer. The dispersions are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, thermal analysis and cyclic voltammetry techniques.     

pH-Responsive chitosan-mediated graphene dispersions

Homogeneous aqueous suspensions of graphene have been prepared by chemical reduction of graphene oxide in the presence of chitosan. The graphene sheets in thus prepared suspensions can be switched reversibly between a well dispersed and a more aggregated state with pH as a stimulus.     

Industrial applications of dispersions

In this review some industrial applications of dispersions have been discussed. After a general introduction, some specific topics have been covered. The preparation of dispersions using condensation and dispersion methods was discussed in terms of the various interfacial processes involved such as nucleation and growth, wetting, breaking of aggregates and agglomerates as well as comminution. The process of emulsification (for production of liquid/liquid dispersions) was also analyzed in terms of the interfacial processes such as reduction in interfacial tension, interfacial elasticity and viscosity. The control of the properties of dispersions was described in terms of the interaction forces between the particles or droplets in the system. These interaction forces are governed by the structure and properties of the interfacial region such as double layers, presence of adsorbed surfactant or polymer layers. Four main types of interaction forces may be distinguished : hard-sphere, electrostatic, steric and van der Waals. Combination of these forces lead to three general energy-distance curves that can be used to describe the state of the dispersion (stable, flocculated or coagulated). The various physical states of suspensions and emulsions produced on standing were schematically presented and they could be explained in terms of the energy-distance curves. The flow characteristics (rheology) of dispersions could also be accounted for in terms of the various interaction forces between the particles.Solubilization and microemulsions, which produce thermodynamically stable dispersions, could be described in terms of the balance between the interfacial energy and entropy of dispersion of the system. The driving force for producing such thermodynamically stable systems was the ultra low interfacial tension which could be achieved by using a combination of surfactants. The application of microemulsions in various fields such as solubilization, enhanced oil recovery and energy production was briefly described.The application of dispersions in microncapsulation and slow release was described in terms of interfacial polymerization, coacervation and multiple emulsion formation. These systems find application in medicine, agrochemicals and cosmetics. The application of dispersions in pharmacy and medicine was also described by quoting specific examples such as liposomes (vesicles), nanoparticles and magnetic microspheres. These systems have potential use in targeting delivery of drugs.     

Stability of non-aqueous dispersions

Ohne Zusammenfassung     

Stability of non-aqueous dispersions. Paper 7. Electrostatic stabilization of concentrated colloidal dispersions

The stability of colloidal dispersions in apolar media is reviewed beginning with dilute dispersions. A criterion for the definition between dilute and concentrated dispersions is presented followed by a new interpretation of Levine's theory for concentrated colloidal dispersions in apolar media [J. Colloid Interface Sci., 54 (1976) 34]. We conclude that concentrated dispersions containing submicron particles are generally unstable leading to coagulation. Successive coagulations lead to the formation of larger secondary particles, “coagulates”, which are ultimately stable to further coagulation and exist in energetic minima.     

Photoresponsive surfactants in microgel dispersions

Microgel particles are cross-linked polymer particles. When dispersed in a good solvent for the polymer concerned, they are able to respond to a range of external stimuli by changing volume. Hence, microgel particles are suited to numerous applications (for example, controlled uptake and release) in the pharmaceutical, coatings, and water treatment industries. In this work, pH-sensitive, 0.5 wt % cross-linked poly(2-vinylpyridine) (PVP) microgel particles have been prepared and characterized. When the dispersion pH is decreased below 4.5, the pyridine groups become protonated and the microgel network becomes positively charged, causing the particles to expand. To investigate the possibility of using light as a trigger for effecting volume changes, the interaction of these microgel particles with a photodegradable anionic surfactant, 4-hexylphenylazosulfonate (C(6)PAS), has been investigated using dynamic light scattering and electrophoretic mobility measurements. The electrostatic attraction between the positively charged microgel network (at solution pH 3) and the negatively charged headgroups on the surfactant molecules caused a dramatic decrease in particle volume, and charge-reversal of the particles occurred with increasing surfactant concentration. The UV irradiation of phenylazosulfonate surfactants destroys the anionic headgroup of the molecules, and the microgel particles re-swell. The irradiation of PVP dispersions in the presence of C(6)PAS, along with mixed surfactant systems of sodium dodecyl sulfate plus C(6)PAS, has been investigated.     

Computer simulation of colloidal dispersions

This paper discusses recent applications of statistical mechanics to dispersions with particular emphasis on the computer simulation of the dynamic properties.Fundamental to any computation on a colloidal dispersion is the knowledge of the potential of mean force for at least a pair of suspended particles. At low-to-moderate particle concentrations for stable dispersions, statistical mechanical calculations based on the normal DLVO pair potential produce reasonable agreement with experiment for a number of equilibrium properties of simple latex dispersions. This phenomenon indicates that under these conditions the DLVO pair potential is a reasonable effective pair potential. However, recent Monte Carlo simulations and experimental measurements with liquids of spherical molecules suggest that the force between a pair of dispersed particles at very small separation may differ significantly from that predicted by DLVO theory.The computation of dynamic properties of dispersions involves problems not encountered in the above equilibrium calculations. In particular, one must include the effects of indirect hydrodynamic as well as direct interactions among the particles. This computation may be easily accomplished at moderately low particle concentrations and the results of such calculations are able to give a very detailed analysis of the results of Photon Correlation Spectroscopy measurements on ion exchanged polystyrene latex suspensions at low concentration. These computations also, once again, emphasize the usefulness of DLVO pair potentials as effective pair potentials for systems of strongly interacting particles.     

Dielectric spectroscopy of thixotropic dispersions

The full characterization of a dispersion requires measurement of the degree of dispersion and knowledge of the type of structuring assumed by the dispersed particles. Dielectric spectroscopy in the low frequency range is a promising experimental approach to this problem.     

Quercetin-PVP K25 solid dispersions

Quercetin is a flavonoid very well studied and has already entered clinical trials emerging as prospective anticancer drug candidate. In addition, quercetin has being reported to its free-radical scavenging activity and suggests potential uses for the prevention and treatment of pathologies as atherosclerosis, chronic inflammation, and others. However, quercetin is sparingly soluble in water, which may be responsible for its limited absorption upon oral administration. The solid dispersion of quercetin with polyvinylpyrrolidone Kollidon^® 25 (PVP K25) suggests an interesting way to increase quercetin solubility, antioxidant activity, and consequently bioavailability. Then, the purpose of this study was to prepare solid dispersions of quercetin with PVP K25 and evaluate their thermal characterization, antioxidant activity and quercetin improvement solubility. For this purpose, quercetin-PVP K25 solutions were dried and quercetin-PVP K25 solids were obtained. The formation of quercetin-PVP K25 solid dispersion was evaluated by solubility studies, powder X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetry (TG), and antioxidant activity. It was observed that PVP K25 was able to provide quercetin clear aqueous solutions and that quercetin solubility was increased in a PVP K25 concentration dependent manner, improving solubility even 436-fold the pure quercetin. The results obtained with XRD, FT-IR, DSC, and TG demonstrated possible quercetin-PVP K25 solid dispersion formation. Besides, the antioxidant activity of the quercetin-PVP K25 solid dispersions dissolved in aqueous solution and pure quercetin dissolved in methanol showed IC₅₀ value of 0.61 ± 0.03 and 1.00 ± 0.02 μg/mL, respectively, demonstrating that the solid dispersions presented a significant increase in antioxidant activity (P < 0.05). Putting results together, it was possible to conclude there was the formation of quercetin-PVP K25 solid dispersion.     

Sodium dispersions in elementary analysis

Summary Gently warming the compound with a dispersion of sodium in a suitable organic solvent reduces nitrogen to ammonia and sulfur, to sulfide.

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Zusammenfassung Stickstoff wird zu Ammoniak und Schwefel zu Sulfid reduziert, wenn die organische Verbindung vorsichtig mit einer Dispersion von metallischem Natrium in einem geeigneten organischen Lösungsmittel erwärmt wird.

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Résumé En chauffant doucement le composé avec une dispersion de sodium dans un solvant organique convenable, l'azote est réduit en ammoniac et le soufre en sulfure.

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On the occasion of the hundredth return ofFriedrich Emich's birthday.     

Depletion flocculation in colloidal dispersions

The destabilisation of colloidal dispersions by free, non-adsorbing polymer molecules in solution is reviewed from both a theoretical and experimental perspective. Consideration is given to the behaviour of polymers in solution in relation to the theories proposed by Flory, de Gennes, and Scheutjens and Fleer. Similarly, the theories describing the behaviour of polymers at or near an interface are also examined together with an outline of their relevance to the depletion interaction. The depletion interaction itself is also comprehensively reviewed, taking into account the different segment density profile theories currently in the scientific literature. Experimental reports of the depletion phenomena are described, covering both hard sphere and soft sphere systems, with both the direct and indirect evidence of the depletion interaction being considered.     

The microrheology of colloidal dispersions

Summary A theory of doublet formation, the first step in coagulation of dilute monodisperse spherical sols subjected to shearing motion, in which Brownian motion dominates the effects of shear is presented. Contrary to Smoluchowski's predictions, it is found that the increase in the rate of coagulation due to shear is not proportional to the shear rateG, but toG _1/2 with the proportionality constant depending on the perikinetic capture efficiency, the translational diffusion constant and sphere radius. With non-spherical particles the increase rate due to shear also varies with G_1/2 and depends, in addition, on particle size and shape.

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Zusammenfassung Eine Theoriefür Doppelkugelformationen als der erste Schritt in der Koagulation von verdünnten, monodispersen, kugelförmigen Solen wird präsentiert. Die Sole sind -einer Scherströmung ausgesetzt, in der die Brownsche Molekularbewegung über die Effekte der Scherbeanspruchung dominiert. Im Gegensatz zu Smoluchowskis Voraussagen wurde gefunden, daß die Steigung im Ausmaß der Koagulation, hervorgerufen durch die Scherung, nicht einfach dem GeschwindigkeitsgradientenG, sondernG _1/2 proportional ist. Die Proportionalitätskonstante hängt vom perikinetischen Einfangwirkungsgrad, der translatorischen Diffusionskonstanten und dem Kugelradius ab. Mit nicht-kugeligen Teilchen variiert das Koagulationsausmaß auch mitG _l/2, hängt aber zusätzlich von Teilchengröße und Gestalt ab.

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List of Symbols ai constant of integration - d distance at whichf _t changes sign - diffusion tensor - D ,D functions describing radial and tangential components of diffusion - function defined in [39] - f(r ^*),f (r ^*) function representing radial part ofn, belonging to eigen value - g(, ) function representing tangential part ofn - i –1 - J, J _B,J _S flux, due to Brownian motion, due to shear - k Boltzmann constant - k _i constant of integration - K(r ^*) function defined in [28] - l, m integers - n, normalized number concentration, value in outer expansion - N; N ₀ number concentration of single particles; at infinity - O (r ^*) of orderr ^* - P operator defined in [14] - P ^|m|(cos) associated Legendre polynomials - Q constant defined in [34] - Pe _t ^1/2 r^* - R radius of imaginary sphere around reference sphere - operator defined in [13] - T absolute temperature - U velocity vector - Pe _{t 1/2}x _i - z _l function defined in [22] - ; ^* defined in [20 a] ; + - _p; _{p p} ^* perikinetic capture efficiency(/2); _p ^*/2 - _l, ₂ collision efficiencies - ₃ 2₂/3x03C0; - ; ^* constant defined in [39b]; 2 - constant defined in [27] - gamma function - percentage increase in capture frequency due to shear - arbitrarily small distance - eigen value - differential operatorM With 3 figuresThis work was supported by Grant MA-4012 of the Medical Research Council of Canada