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1.
Formation and rheological behavior of viscoelastic wormlike micelles in aqueous solution of a mixed system of nonionic fluorinated surfactants, perfluoroalkyl sulfonamide ethoxylate, C8F17SO2N(C3H7)(CH2CH2O)nH (abbreviated as C8F17EOn) was studied. In the water-surfactant binary system C8F17EO20 forms an isotropic micellar solution over wide concentration range (>85 wt %) at 25 degrees C. With successive addition of C8F17EO1 to the aqueous C8F17EO20 solution, viscosity of the solution increases swiftly, and a viscoelastic solution is formed. The oscillatory rheological behavior of the viscoelastic solution can be described by Maxwell model at low-frequency region, which is typical of wormlike micelles. With further addition of C8F17EO1, the viscosity decreases after a maximum and phase separation occurs. Addition of a small amount of fluorinated oils to the wormlike micellar solution disrupts the network structure and decreases the viscosity sharply. It is found that polymeric oil, PFP (F-(C3F6O)nCF2CF2COOH), decreases the viscosity more effectively than the perfluorodecalin (PFD). The difference in the effect of oil on rheological properties is explained in terms of the solubilization site of the oils in the hydrophobic interior of the cylindrical aggregates, and their ability to induce rod-sphere transition.  相似文献   

2.
Upon the addition of a short EO chain nonionic surfactant, poly(oxyethylene) dodecyl ether (C12EOn), to dilute micellar solution of sodium dodecyl sulfate (SDS) above a particular concentration, a sharp increase in viscosity occurs and a highly viscoelastic micellar solution is formed. The oscillatory-shear rheological behavior of the viscoselastic solutions can be described by the Maxwell model at low shear frequency and combined Maxwell-Rouse model at high shear frequency. This property is typical of wormlike micelles entangled to form a transient network. It is found that when C12EO4 in the mixed system is replaced by C12EO3 the micellar growth occurs more effectively. However, with the further decrease in EO chain length, phase separation occurs before a viscoelastic solution is formed. As a result, the maximum zero-shear viscosity is observed at an appropriate mixing fraction of surfactant in the SDS-C12EO3 system. We also investigated the micellar growth in the mixed surfactant systems by means of small-angle X-ray scattering (SAXS). It was found from the SAXS data that the one-dimensional growth of micelles was obtained in all the SDS-C12EOn (n=0-4) aqueous solutions. In a short EO chain C12EOn system, the micelles grow faster at a low mixing fraction of nonionic surfactant.  相似文献   

3.
We have studied the structure and rheological behavior of viscoelastic wormlike micellar solutions in the mixed nonionic surfactants poly(oxyethylene) cholesteryl ether (ChEO15)-trioxyethylene monododecyl ether (C12EO3) and anionic sodium dodecyl sulfate (SDS)-C12EO3 using a series of glycerol/water and formamide/water mixed solvents. The obtained results are compared with those reported in pure water for the corresponding mixed surfactant systems. The zero-shear viscosity first sharply increases with C12EO3 addition and then decreases; i.e., there is a viscosity maximum. The intensity (viscosity) and position (C12EO3 fraction) of this maximum shift to lower values upon an increase in the ratio of glycerol in the glycerol/water mixed solvent, while the position of the maximum changes in an opposite way with increasing formamide. In the case of the SDS/C12EO3 system, zero-shear viscosity shows a decrease with an increase of temperature, but for the ChEO15/C12EO3 system, again, the zero-shear viscosity shows a maximum if plotted as a function of temperature, its position depending on the C12EO3 mixing fraction. In the studied nonionic systems, worm micelles seem to exist at low temperatures (down to 0 degrees C) and high glycerol concentrations (up to 50 wt %), which is interesting from the viewpoint of applications such as drag reduction fluids. Rheology results are supported by small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) measurements on nonionic systems, which indicate micellar elongation upon addition of glycerol or increasing temperature and shortening upon addition of formamide. The results can be interpreted in terms of changes in the surface curvature of aggregates and lyophobicity.  相似文献   

4.
We present the formation of viscoelastic wormlike micelles in mixed amino acid-based anionic and nonionic surfactants in aqueous systems in the absence of salt. N-Dodecylglutamic acid (designated as LAD) has a higher Krafft temperature; however, on neutralization with alkaline amino acid l-lysine, it forms micelles and the solution behaves like a Newtonian fluid at 25 degrees C. Addition of tri(oxyethylene) monododecyl ether (C(12)EO(3)) and tri(oxyethylene) monotetradecyl ether (C(14)EO(3)) to the dilute aqueous solution of the LAD-lysine induces one-dimensional micellar growth. With increasing C(12)EO(3) or C(14)EO(3) concentration, the solution viscosity increases gradually, but after a certain concentration, the elongated micelles entangle forming a rigid network of wormlike micelles and the solution viscosity increases tremendously. Thus formed wormlike micelles show a viscoelastic character and follow the Maxwell model. Tri(oxyethylene) monohexadecyl ether (C(16)EO(3)), on the other hand, could not form wormlike micelles, although the solution viscosity increases too. The micelles become elongated; however, they do not appear to form a rigid network of wormlike micelles in the case of C(16)EO(3). Rheological measurements have shown that zero shear viscosity (eta(0)) increases with the C(12)EO(3) concentration gradually at first and then sharply, and finally decreases before phase separation. However, no such maximum in the eta(0) plot is observed with the C(14)EO(3). The eta(0) increases monotonously with the C(14)EO(3) concentration till phase separation. In studies of the effect of temperature on the wormlike micellar behavior it has been found that the eta(0) decays exponentially with temperature, following an Arrehenius behavior and at sufficiently higher temperatures the solutions follow a Newtonian behavior. The flow activation energy calculated from the slope of log eta(0) versus 1/T plot is very close to the value reported for typical wormlike micelles. Finally, we also present the effect of neutralization degree of lysine on the rheology and phase behavior. The formation of wormlike micelles is confirmed by the Maxwell model fit to the experimental rheological data and by Cole-Cole plots.  相似文献   

5.
The formation and rheological behavior of a viscoelastic wormlike micellar solution in an aqueous solution of a nonionic fluorinated surfactant, perfluoroalkyl sulfonamide ethoxylate, of structure C8F17SO2N(C3H7)(CH2CH2O)10H was studied. Temperature-induced viscosity growth is observed even at low-surfactant concentration (approximately 1 wt %), and viscosity reaches the maximum at a temperature T(eta)-max. Upon successive increases in the temperature, the viscosity decreases, and ultimately a phase separation occurs. Small-angle X-ray scattering (SAXS) measurements confirm the presence of cylindrical aggregates at low temperature, which undergo continuous one-dimensional growth with increasing temperature, and ultimately, an indication of a slight lamellarlike structural pattern is observed, which probably comes from the formation of micellar joints or branching. Such changes in the microstructure result in a decrease in the viscosity and stress-relaxation time, while the network structure is retained; the trends in the evolution of shear modulus (Go) and relaxation time (tauR) with temperature are in agreement with this. With increased surfactant concentration, the temperature corresponding to the viscosity maximum (T eta-max) in the temperature-viscosity curve shifts to lower values, and the viscosity at temperatures below or around T eta-max increases sharply. A viscoelastic solution with Maxwellian-type dynamic rheological behavior at low-shear frequency is formed, which is typical of entangled wormlike micelles. Rheological parameters, eta(o) and Go, show scaling relationships with the surfactant concentrations with exponents slightly greater than the values predicted by the living-polymer model, but the exponent of tauR is in agreement with the theory. Dynamic light-scattering measurements indicate the presence of fast relaxation modes, associated with micelles, and medium and slow modes, associated with transient networks. The disappearance of the slow mode and the predominance of the medium mode as the temperature increases support the conclusions derived from SAXS and rheometry.  相似文献   

6.
Short haired wormlike micelles in mixed nonionic fluorocarbon surfactants   总被引:2,自引:0,他引:2  
We have studied the rheological behavior of viscoelastic wormlike micellar solution in a mixed system of nonionic fluorinated surfactants, perfluoroalkyl sulfonamide ethoxylate, C(8)F(17)SO(2)N(C(3)H(7))(CH(2)CH(2)O)(n)H abbreviated as C(8)F(17)EO(n) (n=10 and 20). Above critical micelle concentration, the surfactant, C(8)F(17)EO(20) forms small spherical micelles in water and the viscosity of the solution remains constant regardless of the shear rate, i.e., the solutions exhibit Newtonian behavior. However, upon successive addition of the C(8)F(17)EO(10) the viscosity of the solution increases and at certain C(8)F(17)EO(10) concentration, shear-thinning behavior is observed indicating the formation wormlike micelles. Contrary to what is expected, there is a viscosity increase with the addition of the hydrophilic C(8)F(17)EO(20) to C(8)F(17)EO(10) aqueous solutions at certain temperature and concentration, which could be attributed to an increase in rigidity of the surfactant layer and to the shifting of micellar branching to higher temperatures. The oscillatory-shear rheological behavior of the viscoelastic solution can be described by Maxwell model at low frequency. Small-angle X-ray scattering (SAXS) measurements confirmed the formation of small spherical micellar aggregates in the dilute aqueous C(8)F(17)EO(20) solution. The SAXS data shows the one-dimensional growth on the micellar size with increase in the C(8)F(17)EO(10) concentration. Thus, the present SAXS data supports the rheological data.  相似文献   

7.
The rheological behavior of micellar cubic phases in C12EO25 systems and related emulsions has been investigated. In the aqueous C12EO25 binary system, the transition from the cubic phase to the micellar solution is associated with a sudden drop in viscosity and with a small enthalpy of transition. The elastic modulus and viscosity of the cubic phases show a maximum with concentration but remain very high within the range of existence of the cubic phase. Several relaxation processes seem to be present in binary cubic phases, and some of them occur in a time scale that can be followed by both rheology and dynamic light scattering measurements. Upon addition of a small amount of oil (decane), the rheological behavior changes remarkably. As the oil fraction increases, the relaxation times also increase and, finally, highly concentrated, gel-like emulsions are obtained. Contrary to conventional concentrated emulsions, the viscosity of cubic-phase-based emulsions is decreased by increasing the fraction of the dispersed phase. The non-Maxwellian rheological behavior at low oil fractions is described according to the model of slipping crystalline planes, modified by using a distribution of bulk relaxation times, and good fitting to the experimental data is obtained.  相似文献   

8.
A study of the phase and rheological behavior of anionic surfactant sodium dodecyl trioxyethylene sulfate (SDES) and nonionic polyoxyethylene sorbitan monooleate (Tween-80) with alkanoyl-N-methylethanolamide (C(12), NMEA-12; and C(16), NMEA-16) in aqueous system is presented. Upon addition of NMEA to the semi-dilute solution of SDES or Tween-80, induces micellar growth leading to the formation of a gel-like highly viscoelastic solution in the maximum viscosity region. These solutions obey the Maxwell model of a viscoelastic fluid. It was observed from rheological measurements that NMEA-16 is more effective than NMEA-12 to induce the micellar growth of surfactants. The relationship between the marked changes in viscosity with surfactant-cosurfactant mixing ratio based on the experimental observations is discussed.  相似文献   

9.
A highly viscoelastic micellar solution of nonionic surfactants in a dilute region was recently reported. A transient network of wormlike micelles formed with the addition of short-EO-chain poly(oxyethylene) dodecyl ether surfactants (C12EO(j), j = 1-4) to poly(oxyethylene) cholesteryl ethers (ChEO(m), m = 10 and 15). A gradual increase in micellar length with an increasing C12EO(j) concentration was assumed from the results of model calculations and rheological measurements. We report in this study the results of structural investigations with small-angle neutron scattering (SANS) to confirm this assumption. Tuning from spherical to wormlike and to locally flat structures can be achieved by way of three methods. One can either increase the C12EO(j) concentration or decrease j (smaller headgroup size) at a fixed concentration of C12EO(j). The third possibility is to increase the temperature at a fixed composition. All three methods result in the same structural transition. The formation of a transient network of wormlike micelles analogous to polymer solutions can be observed with dynamic light scattering (DLS). A stretched exponential approach was applied to fit the correlation functions.  相似文献   

10.
We have studied the rheology and structure of a mixed long polyoxyethylene chain phytosterol (PhyEO30) and monoglyceride (monolaurin (ML) or monopalmitin (MP)) surfactants in an aqueous system. Both ML and MP are insoluble in 10 wt.% PhyEO30 solution at normal room temperature, but their solubility is found to increase with the rise of temperature and an isotropic solution is formed at higher temperature. A maximum viscosity as a function of temperature appears as ML or MP is solubilized in the micellar solution of PhyEO30. With increasing temperature, viscosity increases rapidly for higher monoglyceride content and forms viscoelastic solution. The oscillatory rheological behavior of the viscoelastic solution can be described by Maxwell model at low-frequency region, which is the typical pattern of entangled wormlike micelles. Upon successive increase in temperature, the viscosity decreases and ultimately a phase separation occurs. Small-angle X-ray scattering measurements were performed to provide a supportive structural evidence for the rheological data.  相似文献   

11.
Rheological behavior of viscoelastic wormlike micelles in an aqueous system of mixed sodium dodecyl trioxyethylene sulfate (SDES)–monolaurin (ML) is presented. Dilute aqueous solution of SDES has a high fluidity and follows Newtonian liquid-like behavior due to formation of small globular type of micellar structure. Addition of lipophilic nonionic cosurfactant ML to dilute or semidilute solution of SDES decreases the interfacial curvature of the aggregates favoring one dimensional micellar growth, and hence, viscosity increases. After a certain concentration of ML, the elongated micelles get entangled with each other leading to the formation of viscoelastic wormlike micelles. The viscoelastic solution follows Maxwell model of a single stress relaxation mode at low-frequency region. Further addition of ML decreases the viscosity of the solution due to formation of micellar joints in the network structure. The viscosity of the viscoelastic wormlike micelles decreases upon heating, and the system with poor viscoelastic character is observed at higher temperatures.  相似文献   

12.
The influence of polyethylene oxide (PEO) on the rheological properties of equimolar wormlike micellar solutions of hexadecyltrimethylammonium chloride (HTAC) and sodium salicylate (NaSal) is investigated, above the concentration where a micellar entanglement network is formed. PEO is known to have a temperature-dependent binding affinity for HTAC micelles. The influence of temperature, PEO concentration, and HTAC concentration is explored. Within the concentration and temperature range examined (25-100 mM HTAC and 25-50 degrees C), HTAC/NaSal solutions exhibit rheological characteristics of an entanglement network. Application of transient network theory provides information in the form of the plateau modulus, G(infinity)', the terminal viscoelastic relaxation time, tau(R), the reptation time, tau(rep), the micellar breaking time, tau(br), the mean micellar length, L , and the entanglement length, l(e). Consistent with literature data, increase of HTAC concentration results in an evolution from slow-breaking to fast-breaking behavior, accompanied by an increase in G(infinity)' and tau(rep), and decreases in tau(R), and tau(br), l(e) and L . Addition of PEO results in a substantial decrease in G(infinity)' (increase in l(e)), and corresponding increases in tau(R) and L . These observations are consistent with the idea that binding of HTAC micelles to PEO in aqueous solution decreases the number of surfactant molecules available to contribute to the entanglement network of wormlike micelles.  相似文献   

13.
We have studied the rheology and structure of a mixed nonionic fluorinated surfactant, perfluoroalkyl sulfonamide ethoxylate, C(8)F(17)SO(2)N(C(3)H(7))(CH(2)CH(2)O)(n)H abbreviated as C(8)F(17)EO(10), and perfluorodecalin (C(10)F(18)) or perfluoropolyether oil, (C(3)F(6)O)(n)COOH, in an aqueous system using rheometry and small-angle X-ray scattering (SAXS) techniques. In the absence of oil, the viscosity of surfactant solutions (10 and 15 wt %) first decreases slightly and then more strongly with temperature. Addition of a small amount of fluorinated oil to the wormlike micellar solution disrupts the network structure and decreases the viscosity sharply at lower temperature indicating a rod-sphere transition. The trend of the viscosity curve changes gradually and an anomalous viscosity maximum as a function of temperature appears. It is found that perfluoropolyether oil decreases the viscosity more effectively than perfluorodecalin. The generalized indirect Fourier transformation (GIFT) analysis of the SAXS data confirmed the formation of long rod-like particles in an oil-free, surfactant/water system at 20 degrees C. Addition of a trace amount of fluorinated oils induces modulation in the structure of the micelles and eventually short rods or spherical particles are formed. The decreasing trend in the viscosity with oil concentration is thus attributed to the microstructure changes induced by the added oils.  相似文献   

14.
Amino acid-based anionic surfactant, N-dodecanoylglutamic acid, after neutralizing by 2, 2′, 2″-nitrilotriethanol forms micellar solution at 25 °C. Addition of cationic cosurfactants hexadecyltrimethylammonium chloride (CTAC), hexadecylpyridinium chloride (CPC), and hexadecylpyridinium bromide (CPB) to the semi-dilute solution of anionic surfactant micellar solutions favor the micellar growth and after a certain concentration, entangled rigid network of wormlike micelles are formed. Viscosity increases enormously ~4th order of magnitude compared with water. With further addition of the cosurfactants, viscosity declines and phase separation to liquid crystal occurs. The wormlike micelles showed a viscoelastic behavior and described by Maxwell model with a single stress-relaxation mode. The position of viscosity maximum in the zero-shear viscosity curve shifts towards lower concentration upon changing cosurfactant from CPB to CTAC via CPC; however, the maximum viscosity is highest in the CPB system showing the formation of highly rigid network structure of wormlike micelles. In all the systems, viscosity decays exponentially with temperature following Arrhenius type behavior.  相似文献   

15.
The 22-carbon-tailed zwitterionic surfactant erucyl dimethyl amidopropyl betaine (EDAB) forms highly viscoelastic fluids in water at low concentrations and without the need for salt or other additives. Here, semidilute aqueous solutions of EDAB are studied by using a combination of rheological techniques, small-angle neutron scattering (SANS) and cryo-transmission electron microscopy (cryo-TEM). EDAB samples show interesting rheology as a function of temperature. At low temperatures (approximately 25 degrees C), a 50 mM EDAB sample behaves like an elastic gel with an infinite relaxation time and viscosity. Upon heating to approximately 60 degrees C, however, the sample begins to respond like a viscoelastic solution; that is, the relaxation time and zero-shear viscosity become finite, and the rheology approaches that of a Maxwell fluid. The same pattern of behavior is repeated at higher EDAB concentrations. Cryo-TEM and SANS reveal the presence of giant wormlike micelles in all EDAB samples at room temperature. The results imply that, depending on temperature, EDAB wormlike micelles can exhibit either a gel-like response or the classical viscoelastic ("Maxwellian") response. The unusual gel-like behavior of EDAB micelles at low temperatures is postulated to be the result of very long micellar breaking times, which, in turn, may be due to the long hydrophobic tails of the surfactant.  相似文献   

16.
The mixed micellar system comprising the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-based triblock copolymer (EO)(20)(PO)(70)(EO)(20) (P123) and the anionic surfactant sodium dodecyl sulfate (SDS) has been investigated in aqueous media by small-angle neutron scattering (SANS) and viscosity measurements. The aggregation number of the copolymer in the micelles decreases upon addition of SDS, but a simultaneous enhancement in the degree of micellar hydration leads to a significant increase in the micellar volume fraction at a fixed copolymer concentration. This enhancement in the micellar hydration leads to a marked increase in the stability of the micellar gel phase until it is destroyed at very high SDS concentration. Mixed micellar systems with low and intermediate SDS concentrations form the micellar gel phase in much wider temperature and copolymer concentration ranges than the pure copolymer micellar solution. A comparison of the observed results with those for the copolymers (EO)(26)(PO)(40)(EO)(26) (P85) and (EO)(99)(PO)(70)(EO)(99) (F127) suggests that the composition of the copolymers plays a significant role in determining the influence of SDS on the gelation characteristics of the aqueous copolymer solutions. Copolymers with high PO/EO ratios show an enhancement in the stability of the gel phase, whereas copolymers with low PO/EO ratios show a deterioration of the same in the presence of SDS.  相似文献   

17.
The phase behavior and self-assembled structures of perfluoroalkyl sulfonamide ethoxylate, C8F17SO2N(C3H7)(CH2CH2O)20H (abbreviated as C8F 17EO20), a nonionic fluorocarbon surfactant in an aqueous system, has been investigated by the small-angle X-ray scattering (SAXS) technique. The C8F17EO20 forms micelles and different liquid crystal phases depending on the temperature and composition. The fluorocarbon micellar structure induced by temperature or composition change and added fluorocarbon cosurfactant has been systematically studied. The SAXS data were analyzed by the indirect Fourier transformation (IFT) and the generalized indirect Fourier transformation (GIFT) depending on the volume fraction of the surfactant and complemented by plausible model calculations. The C8F17EO20 forms spherical type micelles above critical micelle concentration (cmc) in the dilute region. The micelle tends to grow with temperature; however, the growth is not significant on changing temperature from 15-75 degrees C, which is attributed to the higher clouding temperature of the surfactant (>100 degrees C). On the other hand, the micellar structure (shape and size) is apparently unaffected by composition (1-25 wt %) at 25 degrees C. Nevertheless, addition of fluorocarbon cosurfactant of structure C8F17SO2N(C3H7)(CH2CH2O)H (abbreviated as C8F17EO1) to the semidilute solution of C8F17EO20 (25 wt %) favors micellar growth, which finally leads to the formation of viscoelastic wormlike micelles, as confirmed by rheometry and supported by SAXS. The onset sphere-to-wormlike transition in the structure of micelles in the C8F17EO20/water/C8F17EO1 system is due to the fact that the C8F17EO1 tends to go to the surfactant palisade layer so that the critical packing parameter increases due to a decrease in the effective cross-sectional area of the headgroup. As a result, spherical micelles grow into a cylinder, which after a certain concentration entangle to form a rigid network structure of wormlike micelles.  相似文献   

18.
The rheological and mass transport properties of phenol in micellar solutions of hexadecyltrimethylammonium bromide (CTAB) were studied by rheometry and spectrophotometry. The presence of phenol located between headgroups of the CTAB diminishes the repulsive forces between the cationic groups and induces a sharp increase in viscosity that is attributed to the one-dimensional micellar growth favoring the formation of worm-like micelles. It is found that the mass transfer of phenol between two immiscible phases is significantly retarded by the presence of CTAB. The transfer is particularly slow when the diffusion takes place from a surfactant solution phase to an organic phase. This behavior is attributed to the phenol–surfactant interaction that leads to micellar growth and viscoelastic behavior. However, at elevated temperature, viscosity decreases and mass transfer increases. This particular rheological behavior offers the possibility of regulating the mass transfer, which might be interesting for applications.  相似文献   

19.
Micellization behavior of an amphiphilic ethylene oxide-propylene oxide-ethylene oxide tri-block copolymer Pluronic P85 [(EO)(26)(PO)(39)-(EO)(26)] in aqueous solution and in the presence of a hydrophobic C(14)diol (also known as Surfynol104) was examined by physico-chemical methods such as viscometry, cloud point (CP) and scattering techniques viz. dynamic light scattering (DLS) and small angle neutron scattering (SANS). The addition of diol decreases the cloud point and gelation temperature of aqueous Pluronic P85 copolymer solution. DLS and SANS measurements of the polymer in aqueous solution indicated micellar growth and sphere to rod transition in the presence of diol. Surfynol 104 is a sparingly water soluble diol surfactant with a solubility of approximately 0.1 wt%. However, up on addition to Pluronic solution, diol gets incorporated in the block copolymer micelles and leads to structural transition of the micelles. An increase in the temperature and the presence of added sodium chloride in the solution further enhances this effect. The addition of hydrophobic C(14)diol increases the hydrodynamic size and aggregation numbers of the micellar system. The micellar parameters for the copolymer in the presence of C(14)diol are reported at different temperatures and added sodium chloride concentrations.  相似文献   

20.
用流变学方法研究了无机电解质KBr存在时,阴离子表面活性剂十二烷基聚氧乙烯(3)硫酸钠(SDES)水溶液中胶束的生长和结构。通过测量体系的稳态剪切粘度(η)和应力(σ)关系,得到零剪切粘度(η0)、复合粘度(|η^*|)、动态模量[储能模量(G')和损耗模量(G")、平台模量(G0)、结构松驰时间(τ)等流变学参数,并应用Cox-Merz规则和Cole-Cole图,发现在SDES/KBr体系中可以形成蠕虫状胶束网络结构,体系为假塑性流体,偏离Maxwell模型,具有非线性粘弹性,没有单一的结构松驰时间。  相似文献   

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