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1.
Two ternary phase diagrams of the cationic perfluorosurfactant diethanolheptadecafluoro-2-undecanolmethylammonium chloride (DEFUMAC) with an anionic perfluorosurfactant lithium perfluorooctanesulfonate (LiFOS) and an anionic hydrocarbon surfactant lithium dodecyl sulfate (LiDS) have been established at 25°C. The total surfactant concentration was less than 20wt%. In a wide mixing region of the LiFOS/DEFUMAC system, a lamellar-type phase,P , was identified by its texture under a polarization microscope and by its x-ray diffraction pattern. Dispersed fragments ofP -phase are present in the dilute solutions in which one surfactant was in excess. The anisotropy of electrical conductivity, flow birefringence, dynamic light scattering, and electric briefringence demonstrate that theP fragments are disk-like with a radius of 0.7 m. The disk-likeP particles are transformed by shear into a spherical aggregate ofL above a critical shear gradient. LiDS/DEFUMAC mixed solution forms dispersed and precipitatedL in the dominant region. Radius and micropolarity of the dispersedL aggregates are decreased as the ratio of LiDS:DEFUMAC approaches 1:1. On the basis of x-ray diffraction measurement the structure of precipitatedL -phase seems to consist of monolayers.  相似文献   

2.
The effect of representing dielectric properties in terms of the complex polarizability c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.  相似文献   

3.
The influence of the addition of liquid paraffin (LP) on the structure of the lamellar (L ) and hexagonal (H1) mesophases formed in mixtures of water (W) and BRIJ 96 (B) was studied. Mesophases were identified using polarization microscopy and small angle x-ray diffraction (SAXD). Repeat spacings were also determined with SAXD. Depending on theW/B ratio, addtion ofLP toL gives a large, almost linear one-dimensional swelling or an initial swelling followed by a gradual transition to H1.L with a highLP-content gives a diffraction pattern showing only the first order diffraction maximum, possibly a result of undulations of the layers. The lamellar structure, however, was confirmed using freeze fracture electron microscopy (FFEM). Addition ofLP to H1 gives an initial swelling followed by a transition to a transparent, highly viscous, isotropic phase, called the gel-phase (G). The diffraction pattern obtained fromG yields little information on its structure. A large swelling ofG withLP was observed. From the degree of swelling as a function of hydrocarbon content it was inferred that this phase consists of spherical aggregates forming a close-packed structure. Using FFEM, textures were visualized resembling those obtained from the isotropic mesophase (I1) in water-surfactant mixtures. Finally, geometrical factors are discussed that may play a role in the formation of the gel-phase.  相似文献   

4.
CPS GL 799     
The effect of illumination on transport of sulfonated bisazo direct dyes, CI Direct Yellow 12, and CI Direct Yellow 4, into a cellulose membrane has been studied at various temperatures. Transport of CI Direct Yellow 12, which exhibits photoinduced reversible trans-cis isomerism in aqueous solution into a cellulose membrane, was influenced by illumination. It is likely that the transport was influenced by transisomerization of the photoisomeric dye and the diffusivity was controlled by surface diffusion rather than by pore diffusion under both light and dark conditions.Notations C Concentration of dye in the pores (mol/dm3) - C E Concentration of electrolyte in the bulk solution (mol/dm3) - C o Concentration of dye in the bulk solution (mol/dm3) - D p Pore diffusivity (m2/s) - D s Surface diffusivity (m2/s) - [M] Mean concentration of dye in membrane (mol/dm3) - [M] L Local concentration of dye in membrane (=q+ p C) (mol/dm3) - [M] Mean concentration of dye in membrane (mol/kg) - [M] L Local concentration of dye in membrane (=q/V+ p C) (mol/dm3) - F Fractional attainment of equilibrium - l Thickness of membrane (m) - q Concentration of dye adsorbed on pore wall (mol/dm3) - q o Adsorbed concentration of dye in equilibrium withC o (mol/dm3) - q Concentration of dye adsorbed on pore wall (mol/kg) - q o Adsorbed concentration of dye in equilibrium withC o (mol/kg) - t Time (s) - V Volume of membrane swollen with water per unit dry cellulose (dm3/kg) - x C/C o - y q/q o - z Distance that the dye diffused in the membrane (m) - q o / o C o - D s /D p - Coefficient of the Freundlich isotherm - p Pore void fraction - z/l - p D p t/l 2 - s D s t/l 2  相似文献   

5.
We investigate experimentally and theoretically the isothermic growth of two spherulites of different modification into a supercooled isotactic polypropylene film. The faster growing-spherulite grows around the-spherulite, and finally the-spherulite is symmetrically and completely included in. In contrast to literature but in agreement with experimental evidence we find that the grain boundary between the teardropshaped-spherulite and the surrounding-spherulite consists of two parts, where one is always an arc of a logarithmic spiral. This-spherulite ends always in a vertex. Its angle depends on the ratio of the two growth rates only. Behind the vertex an intrinsic--grain boundary exists, degenerating to a channel in bulk material. The growth fron of the-spherulite, which ends on the logarithmic spiral or on the intrinsic grain boundary during growth, consists of an arc of a circle continued by an arc of a logarithmic spirial, too.  相似文献   

6.
Three series of segmented polyurethanes based on MDI, variable chain extender, and polypropylene oxide of MW=1000, 2000, and 3000 were synthesized and their dielectric behavior examined.Dielectric relaxations in the segmented polyurethanes were investigated between –150°C and +150°C in the 100 Hz to 10 kHz range. In general, three transitions, designated as, , and were observed, and ascribed in accordance with calorimetric relaxations to glass transitions of the hard and soft segments, and Shatzki-type motions, respectively. The effect of structure variables such as soft segment size, type of chain extender (ethylene glycol, butane diol, and hexane diol) and soft segment concentration, as well as the effect of interaction of the phases on dielectric properties was discussed. It was found that a certain degree of phase mixing exists in all series, detected by the variation of theT g of the soft segment with soft segment concentration, contrary to DSC results, which was ascribed to thermal treatment prior to the dielectric measurements. It appears that interfacial polarization becomes important only above the transition temperature.  相似文献   

7.
Molecular motions in poly(diethyl siloxane) were studied by solid-state29Si-NMR in the temperature range 180–350 K. In this temperature range two solid phases 1 and 2, a mesophase m, and an amorphous isotropic phase exist. The nature of the chain mobility in the different phases was deduced from the resulting changes in the NMR line-shape governed by anisotropic chemical shift. In the intermediate solid phase 2 its anisotropy is reduced by 25% compared with the low temperature phase 1 due to the onset of oscillations around the chain axis and conformational transitions. In the mesophase m the polymer chain rotates about its long axis yielding an axially symmetric chemical shift tensor opposite in sign to that in the 1, 2 phases. The broad transition of the mesophase into the isotropic phase is accompanied by an increase in a narrow Lorentzian line arising from the amorphous phase. The results are compared with previous1H NMR, Raman-spectroscopy and x-ray measurements.After completion of this work we learnt that PDES has recently also been studied through13C-MAS and29Si-NMR by Möller et al. [13].  相似文献   

8.
Secondary structural changes of chymotrypsinogen A,-chymotrypsin, and their isolated polypeptides Cys1-Leu13, Ile16-Tyr146, and Ala149-Asn245were examined in aqueous solutions of sodium dodecyl sulfate (SDS), urea, and guanidine hydrochloride (residue numbers from chymotrypsinogen). After the fragmentation by the cleavage of disulfide bridges in-chymotrypsin, the helical structure was formed in the isolated polypeptide 16–146 where the helical segments do not exist in the protein state. The polypeptide 149–245, where the helical segments of the parent protein are originally located, contained no helices. The polypeptide 1–13 was almost disordered. The three polypeptides, chymotrypsinogen,-chymotrypsin and the polypeptide 16–146, clearly showed differences in the stabilities of helical structures in solutions of urea and guanidine hydrochloride. The addition of SDS accelerated the formation of helical structures in each polypeptide except for 1–13.  相似文献   

9.
The binary phase behaviour of two potentially polymerisable quaternary ammonium surfactants in water has been investigated. Allyldodecyldimethylammonium bromide (ADAB) a single-chain surfactant displays a conventional phase progression upon increasing concentration. Whereas the doublechain analogue allyldidodecylmethylammonium bromide (ADDAB) forms two lamellar liquid crystalline phases built from surfactant bilayers, which transform via a first order phase transition. The formation of two distinct lamellar phases and their coexistence has been evidenced by optical microscopy, small-angle x-ray scattering and D2O deuterium quadrupolar nuclear magnetic resonance spectroscopy. The lamellar phase formed at higher surfactant compositions is a normal lamellar phase (typeL ) consisting of bilayers which are on average parallel and flat. The lower compositional lamellar phase (typeL ) in contrast may not be comprised of planar bilayers but rather aggregates having a high degree of curvature in comparison to those of theL phase. The presence of the allyl polymerisable moiety in the head group position of these surfactants has the effect of reducing the rigidity of the surfactant and increasing its solubility in comparison to nonpolymerisable analogues. Polymerisation of the surfactants was attempted by using thermal and photochemical initiation in isotropic and self-assembled systems. Polymerisation occurred to approximately 30% for DADB but did not occur for ADDAB. Where polymerisation did occur the polymer was incorporated into the monomer matrix by interweaving between the surfactant aggregates. The polymers had a molecular wieght not greater than 8000 Daltons, independent of the monomer concentration of the original solution and type of polymerisation.  相似文献   

10.
A liquid crystalline main-chain polymer was slightly crosslinked by a reaction with, -difunctionalized oligo-siloxanes. Crosslinking does not disturb the liquid crystalline phases, which are identified by x-ray measurements as smecticB and smecticA phases. Measurements of the elastic properties of the crosslinked sample show rubber-like elasticity, even in the liquid crystalline phases. A difference of 7 K was found between cooling and heating for the smecticA/isotropic transition from DSC and mechanical measurements.  相似文献   

11.
A theory of adsorption kinetics of solutes onto a solid surface from the solution phase is proposed in which a time delay is introduced into the solute concentration on the surface. Equations governing the adsorption kinetics are similar to those for membrane transport with time delay (Ohshima and Kondo, Biophys. Chem. (1989) 33: 303). It is found that introduction of time delay causes, under certain conditions, overshoot or oscillation in the solute concentrations, both in the solution phase and on the surface. The criterion for oscillation depends on the scaled delay time , the ratio of the possible maximum amount of solutes adsorbed on the surface to the total solute amountR, and the scaled binding constantK. When the number of the binding sites is small, the criterion for oscillation is expressed as >exp(–1), where =(/K) exp().  相似文献   

12.
PTFE shows in the whole temperature range investigated a triclinic crystal structure with cell parametersa=0.952 nm,b=0.559 nm,c=1.706 nm,=87.9°, = 90.0° and=91.8°. The temperature dependence ofa andb-axis is linear, thec-axis shows a change in thermal expansion at 150 K. The inherent strain is small. The crystallite sizes are measured, paracrystalline distortions are absent.The bipolymers show only an ordered arrangement in lateral direction under maintenance of the helical structure. The lateral arrangement is very distorted and the range of order is aboutD L 10 nm.  相似文献   

13.
The molecular conformations of poly(N5-dihydroxyethylaminopropyl-L-glutamine) and poly(N5-dihydroxyethyl-L-glutamine) were investigated in reversed micelles of AOT as well as in aqueous solutions. Both poly(-amino acid)s assume disordered structures in pure water. The conformation of poly(N5-dihydroxyethylaminopropyl-L-glutamine) transits into-helix in the reversed micelles as the molar ratio of water to AOT (w0=[H2O]/[AOT]) becomes smaller. A similar conformational transition was also observed in aqueous solutions when a certain amount of AOT was added. Under these conditions, however, poly(N5-dihydroxyethyl-L-glutamine) did not undergo a conformational transition into-helix.  相似文献   

14.
The solubilization behavior of oleyl alcohol by pure and mixtures of surfactants systems have been studied in terms of the maximum additive concentration (MAC), the solubilizing power, and the particle sizes of micelles with or without oleyl alcohol. The surfactants used are amphoteric (N,N-dimethyl-N-lauroyl lysine, DMLL; N,N,N-trimethyl-N-lauroyl lysine, TMLL; N,N-dimethyl-N-(carboxymethyl)-lauryl ammonium, DMCL), anionic (sodium dodecyl sulfate, SDS) and nonionic (alkyl polyoxyethylene ethers).The maximum additive concentration of oleyl alcohol by pure surfactants is larger by nonionic surfactants than by others.For a nonionic surfactant system mixed with DMLL, the mixing effect of surfactant on the increase in the MAC is not recognized. While, for DMLL mixed with SDS, the MAC becomes larger than that by pure surfactants. This may be attributed to the fact that the large micellar size will result in increasing the maximum additive concentration.  相似文献   

15.
The structure-property relationships derived here permit the prediction of both the zero-shear viscosity 0, as well as the shear rate dependent viscosity . Using this molecular modeling it is now possible to predict over the whole concentration range, independently of the molecular weight, polymer concentration and imposed shear rate. However, the widely accepted concept: dilute — concentrated, is insufficient. Moreover it is necessary to take five distinct states of solution into account if the viscous behavior of polymeric liquids is to be described satisfactorily. For non-homogeneous, semi-dilute (moderately concentrated) solutions the slope in the linear region of the flow curve (= must be standardized against the overlap parameterc · []. As with the 0-M-c-relationship, a-M -c- relationship can now be formulated for the complete range of concentration and molecular weight. Furthermore, it is possible to predict the onset of shear induced degradation of polymeric liquids subjected to a laminar velocity field on the basis of molecular modeling. These theoretically obtained results lead to the previously made ad hoc conclusion (Kulicke, Porter [32]) that, experimentally, it is not possible to detect the second Newtonian region.Roman and Italian symbols a exponent of the Mark-Houwink relationship - b exponent of the third term of the 0-M -c relationship - c concentration /g · cm–3 - E number of entanglements per molecule - F(r) connector tension - f function - G i A shear modulus; A indicates that it /Pa has been evaluated by a transient shear flow experiment; i is the shear rate to whichG A refers to - G storage modulus /Pa - G p plateau modulus /Pa - H() relaxation spectrum /Pa - h shift factor (0/r) - K H Huggins constant - K b third constant of the 0-M -c relationship - K constant of the Mark-Houwink relationship - M molecular weight /g · mol–1 - M e molecular weight between two /g · mol–1 entanglement couplings - N number of segments per molecule - n slope in the power-law region of the flow curve - p p-th mode of the relaxation time spectrum - R gas constant /8.314 J·K–1·mol–1 - r direction vector - T temperature /K Greek symbols ß reduced shear rate - shear rate /s–1 - shear viscosity /Pa·s - s solvent viscosity /Pa·s - sp specific viscosity - 0 zero-shear viscosity /Pa·s - apparent viscosity at shear rate - reduced viscosity - viscosity of polymeric liquid in /Pa·s the second Newtonian region - [] intrinsic viscosity/cm3·g–1 - screening length/m - /g·cm –3 density - relaxation time/s - 0 experimentally derived relaxation time/s - angular frequency of oscillation Indices conc concentrated - corr slope corrected - cr critical - deg degradation - e entanglement - exp experimental - mod moderately concentrated/semi-dilute - n number average - p polymer - R Rouse - rep reptation - s solvent - sp specific - theo theoretical - weight average - relaxation time - o experimental or steady state - * critical - ** transition moderately conc. — conc. - + transition dilute — moderately cone. Paper presented at the 2nd bilateral U.S.-West German Polymer Symposium, Yountville, the 7th–11th September 1987.  相似文献   

16.
The effects of particle size on polyacrylamide (PAAm,M w =59×104, 500×104) adsorption were investigated using a series of well-characterized hematite (-Fe2O3) dispersions. The -Fe2O3 particles with highly monodisperse and nearly spherical shape ranged in radius from 23 nm to 300 nm. the maximum amount of PAAm adsorption (M m ) in each system, showed a steady increase with decreasing particle radius and was influenced strongly by particle concentrations in the medium. Furthermore, it was realized that the diameter of -Fe2O3 particles after treatment with PAAm under different particle concentrations decreased with increasing particle concentration. The relation between particle concentration in the medium and particle size after treatment was also influenced by the medium pH, i.e., at the medium pH close to the isoelectric point of -Fe2O3 particles (pHo=9.2), the particle size after treatment increased with increasing particle concentration. All these results suggest that in the system of ultra-fine particles, the mixing process between particle-particle and polymerparticle will play an important role on the conformation of adsorbed polymer layer.  相似文献   

17.
Adsorption isotherms of NO, SO2, NH3, and CO2 on-FeOOH dispersed activated carbon fibers at 303 K were examined to determine the role of surface modification in micropore filling. The parameters on micropore structures were obtained from both nitrogen adsorption at 77 K and benzene adsorption at 303 K; both isotherms were of BDDTI type and gave the same micropore volume. The preoxidation conditions of ACF, prior to the deposition of-FeOOH against the NO adsorptivity were examined. The dispersion of-FeOOH on ACF was effective in enhancement of micropore filling, irrespective of the adsorbate molecule. We determined the degree of volume filling for each gas by the use of a DR plot. The modified DR plot for an NO gas, of which the critical temperature was much lower than 303 K, was proposed. The degree of volume filling for various gases was correlated with the deviation of each boiling point from 303 K and with the van der Waalsa constant.  相似文献   

18.
The special nature of the outer-most water-rich region of theL 2-phase in the ternary system sodium octanoate-octanoic acid-water is evidenced by its somewhat turbid appearance and by the character of its equilibria with adjacent phases. The phase contains aggregated acid sodium octanoate which is dispersed in a very dilute aqueous solution of sodium octanoate. The acid octanoate has the composition 1 NaC82 HC8x H2O and is composed of closely packed amphiphilic units, all with the polar groups in the same direction. This acid soap obviously forms double-layered aggregates with the lipophilic hydrocarbon chains pointing inwards and the polar groups pointing outwards towards the surrounding bulk-water. The phase is formed when octanoic acid is added to theL 1-phase of the system just above the l.a.c.; in this aqueous solution, the acid reacts with dissolved acid octanoate 1 NaC81 HC8x H2O and that results in the formation of the slightly soluble acid soap 1 NaC8 2 HC8x H2O that separates as a new phase, the turbidL 2 phase. On further addition of octanoic acid, the content of the mentioned acid soap increases until the solution phase is transformed into a liquid crystalline lamellarD-phase with the same acid soap composition. This formation of acid soap 1 NaA2 HA on addition of fatty acid to the dilute soap solution just above the l.a.c., has been known for a long time to occur in various systems containing a long-chain sodium soap. However, at suitably low temperatures, the reaction in these systems does not result in separation of the acid soap in the liquid crystalline, but in the solid crystalline state.  相似文献   

19.
The results of X-ray diffraction patterns of homologous thallium soaps TlC n (n-8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20 and 22) in dependence on the temperature showed that the structures of the phases below the temperature range of the liquid-crystalline neat phase (so called phase C1, phase C2, phase I, phase II) are crystalline-like, not liquid-crystalline.As function of the chain length of the fatty acid group, we found the following phase sequences to be a function of temperature: TlC8: phase Ineat phase: TlC9–Tl14: phase C2phase IIphase Ineat phase; TlC15, TlC16: phase C1phase IIphase Ineat phase; TlC17–TlC22: phase C1phase IIneat phase.From the X-ray patterns of the thallium soaps were calculated the lattice parameters and the unit cells of these homologues at various temperatures. The comparison between the lattice parameters of the homologues showed, surprisingly, that these parameters were independent of chain length and temperature. This X-ray data are the basis for the following development of structure models of the phase C1, phase C2, phase I, and phase II, including the neat phase (see Part 2).  相似文献   

20.
A basic requirement for that type ofL 2-phase which exists in the system sodium octanoate-octanoic acid-water is the formation of acid-soaps. In order for the phase to be formed at all, the temperature must lie above the melting point of the fatty acid so that a reaction in non-aqueous milieu between neutral soap and fatty acid is possible. In order to obtain the characteristic shape and complete extension of the phase in direction of high water content the temperature must be so high that also the hydrated acid-soaps occur in fluid state. On the other hand the temperature cannot be so high that the acid-soaps become unstable.At temperatures at which the phase has obtained its full extension those circumstances differs which in different regions regulate the location of the phase borders; they depend on the composition of the acid soaps and on their amounts. In that part of the phase where the molar ratio between octanoic acid and sodium octanoate lies between 2 and 3 and where one has a continuous transition from reversed to normal structure only the two acid octanoates 1 NaC8 2 HC8 x H2O and 1 NaC8 3 HC8 x H2O occur and both are at 20 °C in fluid state.At water contents from about 22 % to 40 % the hydrate-water molecules belonging to the first mentioned soap are capable of contributing actively to the formation of large aggregates of acid-soap, a process which however is counteracted by the inmixing of the latter acid-soap. This mixture of the two acid-soaps decides in this region where the border of the phase will lie in direction towards an increased content of sodium octanoate; the result is that in spite of the fact that the hydration is increased, the border is only slowly displaced towards a higher content of fatty acid. As soon as the hydration of the acid octanoates has been completed and the additional water occurs as unbound bulkwater, the location of the phase boundary will no longer be influenced by the water content — now it will be the amphiphilic composition of the acid-soaps that determines the location of the border and it remains at the molar ratio 2.5 between octanoic acid and sodium octanoate at water contents from about 40% and up to 82%.In the direction of decreasing content of neutral sodium octanoate and increased content of water theL 2-phase both at the highest content of fatty acid and the highest contents of water will be in equilibrium with the water-richL 1-phase; in the first mentioned region with theL 1-phase below the lac where at the border it is saturated with octanoic acid and in the latter region with theL 1-phase just above the lac, where the dilute sodium octanoate solution contains dissolved 1 NaC8 1HC8 x H2O. In the large central part of theL 2-phase, from about 20 % to about 86 % of water, the location of the border is dominated by the acid octanoate 1 NaC8 3 HC8 x H2O and that makes an equilibrium with theL 1-phase impossible; instead one has an equilibrium via a two-phase zone between the amphiphile-rich region of theL 2-phase and its water-rich region. In the first region the location of the border is regulated by the decreasing capability of the hydrated acid octanoate 1 NaC8 3 HC8 x H2O to dissolve octanoic acid; in the latter it is regulated by the fact that 1 NaC8 3 HC8 x H2O is the most fatty acid-rich acid-soap that is formed and that the octanoic acid is very little soluble in water and in the aqueous solution of this acidsoap.The middle part of theL 2-phase, especially the region between about 55 % and 82 % of water, constitutes a direct continuation of the liquid crystalline lamellarD-phase. The liquid crystalline character of theD-phase is lost at the transition, but the lamellar organization is retained. That the molecules at least up to a water content of about 40 % are of the original reversed type and have an elongated shape with a central part of hydrated polar groups, from which core the hydrocarbon chains extend in two opposite directions, is the reason to that they, at crowding, form transient layer-like agglomerates of tightly packed more or less parallel molecules; this facilitates the transformation to coherent double amphiphilic layers, in which all molecules lie with the hydrated polar groups outwards toward coherent domains of bulk-water, without another liquid phase occurs.  相似文献   

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