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1.
Although electrical properties of nonionogenic hydrophobic surface (solid or liquid) in water and/or electrolyte solutions have been studied for many decades, they are still not well recognized, especially as for the nature of the charge and potential origin. Similarly, water structure at such a surface is still extensively studied. One such system is paraffin wax/water (electrolyte). The zeta potentials and the particle diameters of this system were investigated in this paper. To obtain the suspension of paraffin in water or electrolyte solution (NaCl or LaCl3), the mixture was heated to ca. 70 degrees C and then stirred during cooling. For thus obtained suspensions, the zeta potential was determined as a function of time at 20 degrees C. Also the pH effect on the zeta potentials was investigated. The zeta potentials were calculated from Henry's equation. The results obtained by us are in agreement with those obtained earlier by others. They confirm that although H+/OH- are not surface charge creating ions, OH- ions to some extent are zeta potential determining for the paraffin surface. By use of the potentials and diameters, the electric charge for a spherical particle in the shear plane was calculated. These values are small in the range of 10(-3) C/m2. On the basis of the findings of water structure near hydrophobic surface and the calculated charges, it is concluded that in fact the potential may be created by immobilized and oriented water dipoles.  相似文献   

2.
The interaction of inorganic ions with low-energy hydrophobic surfaces was examined using model systems of solid polymers without ionizable functional surface groups in aqueous electrolyte solutions. Low-rate dynamic contact angle measurements with captive bubbles in conjunction with axisymmetric drop shape analysis (ADSA) were performed to study the influence of electrolyte ions (in the aqueous test solutions) on the wettability of the polymers. When various types of ions were used, no significant change in advancing and receding contact angles was observed. The contact angle hysteresis was small. The zeta potential of the model polymers in aqueous electrolyte solutions was determined from streaming potential measurements. The variation of the zeta potential at different pH levels indicates preferential adsorption of hydroxyl ions at this interface. However, the presence of electrolytes at the interface between water and the different model polymers did not influence the macroscopic contact angle. The results may suggest the absence of any specific interaction between the ions and the solid polymer, as this should result in changes of hydrophobicity. Similar to the air/water interface, the composition and the potential of the polymer/water interface are obviously determined predominantly by the aqueous phase with only slight influence from the solid phase.  相似文献   

3.
The effect of Triton X-100 on the colloidal dispersion stability of CuPc-U (unsulfonated and hydrophobic) and CuPc-S (surface sulfonated and hydrophilic) particles in aqueous solutions (water and NaNO(3)) was investigated at 25 °C. Its adsorption density was determined from surfactant concentrations analyzed by an HPLC method with a UV detector. The experimental dispersion stability ratios of the particles were determined from dynamic light scattering (DLS) data, with the Rayleigh-Debye-Gans (RDG) light scattering theory. The adsorption densities of Triton X-100 on both the CuPc-U and CuPc-S increase with increasing concentration of surfactant up to the critical micelle concentration (cmc), and then reach a plateau. The maximum adsorption density Γ(m) is higher for the CuPc-U (d(h)=160 nm) than that for the CuPc-S (d(h)=90 nm). The hydrophobic chains are inferred to be adsorbed onto the surfaces, and the hydrophilic ethylene oxide chains are in a coil conformation. The W(app)-values for the CuPc-U dispersions are affected mainly by the surfactant fractional surface coverage θ. Adding NaNO(3) has no significant effect on the dispersion stability. The stabilization mechanism for the CuPc-U is inferred to be primarily steric, as expected. The stability ratios for the CuPc-S in solutions with NaNO(3) are higher than those for CuPc-U, and decrease with increasing concentration of NaNO(3), indicating that the stabilization is affected by the screening of electrostatic repulsive forces. The zeta potential is not a good predictor of the electrostatic stabilization, pointing to the need for new and improved theories.  相似文献   

4.
The adsorption of cetylpyridinium chloride (CPC) and sodium dodecylbenzenesulfonate (SDBS) onto a ceramic glaze mixture composed of limestone, feldspar, quartz, and kaolin has been investigated. Both adsorption isotherms and the average particle zeta potential have been studied in order to understand the suspension stability as a function of pH, ionic strength, and surfactant concentration. The adsorption of small amounts of cationic CPC onto the primarily negatively charged surfaces of the particles at pH 7 and 9 results in strong attraction and flocculation due to hydrophobic interactions. At higher surfactant concentrations a zeta potential of more than +60 mV results from the bilayered adsorbed surfactant, providing stability at salt concentrations < or = 0.01 M. At 0.1 M salt poor stability results despite substantial zeta potential values. Three mechanisms for SDBS adsorption have been identified. When anionic SDBS monomers either adsorb by electrostatic interactions with the few positive surface sites at high pH or adsorb onto like charged negative surface sites due to dispersion or hydrophobic interactions, the magnitude of the negative zeta potential increases slightly. At pH 9 this increase is enough to promote stability with an average zeta potential of more than -55 mV, whereas at pH 7 the zeta potential is lower at about -45 mV. The stability of suspensions at pH 7 is additionally due to steric repulsion caused by the adsorption of thick layers of neutrally charged Ca(DBS)2 complexes created when the surfactant interacts with dissolved calcium ions from the calcium carbonate component.  相似文献   

5.
The adsorption of a surfactant, sodium di-2-ethylhexyl sulfosuccinate (SDES), [C4H9CH(C2H5)CH2OCO][C4H9CH(C2H5)CH2OCOCH2]CHSO3- Na+, in an aqueous solution on an atomically flat H-terminated Si(111) [abbreviated as H-Si(111)] surface with a hydrophobic property was investigated by in-situ FTIR measurements. Immersion of the H-Si(111) surface in a solution of 1.0 x 10(-2) M SDES for more than 2 h led to formation of a self-assembled monolayer (SAM) with the alkyl chains having a tendency to be assembled perpendicular to the Si surface. The in-situ FTIR observation revealed that the adsorption was nearly complete about 60 min after the start of the immersion, and after that the adsorbed molecules changed their arrangement into an ordered mode. The Si-H peak in the FTIR spectrum remained unchanged with time in aqueous surfactant solution, in contrast to the case of immersion in pure water, indicating that the adsorbed surfactant protects the H-Si(111) surface from oxidation. No structural change in the SAM was observed when a negative potential of -700 mV vs Ag/AgCl was applied to the Si, whereas the adsorbed molecules changed their arrangement, accompanied by their substantial desorption and oxidation of the Si surface, when a positive potential of +700 mV was applied.  相似文献   

6.
测定了一系列有机铵盐与一种全氟烷磺酸盐1:1混合体系水 溶液的表面张力,由此研究有机铵盐对碳氟表面活性剂表面活性及溶度的影响,导出应用于此种混合体系的Gibbs吸附公式,并讨论了混合体系中两表面活性组分的表面分子相互作用和表面层的结构。  相似文献   

7.
The zeta potentials and dispersion properties of precipitated calcium carbonate suspensions adsorbed with alkyl polyglycosides in aqueous medium were investigated. Within the investigated pH ranges, the adsorption curves of alkyl polyglycosides on calcium carbonates show sigmoidal shapes, and the zeta potential decreases as the amount of adsorption increases. At positively charged surfaces of low pH, the adsorption amounts were greater than those at negatively charged surfaces, indicating that alkyl polyglycosides were negatively charged in aqueous solutions. At low concentrations of alkyl polyglycosides, the dispersion stabilities of suspensions were very poor and showed no linearity with zeta potentials over the entire range of pHs, which may be attributed to the onset of hydrophobic interaction between particles due to the adsorption of surfactant molecules. This destabilization continued until monolayer coverage by the surfactant layer was complete. Based on the classical DLVO theory, there may be a strong hydrophobic interaction between particles. Beyond monolayer adsorption, the dispersion stability increases, probably by the formation of hemimicelle or admicelle. Therefore, it is believed that ionization of alkyl polyglycosides and admicelles of surfactants on particle surface plays a key role in the stability of dispersions and the abrupt increase in adsorption. Copyright 2000 Academic Press.  相似文献   

8.
This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis. The surface properties of the materials were assessed by water contact angles (CAs) and by BET C constants. The results showed that, while loadings of the alkyl groups (%C) were comparable, the surface properties and pore ordering of the materials prepared through different methods were quite different. The best quality hydrophobic surfaces were prepared for SBA-15 grafted with CAMs of alkylsilanes. For these materials, the water CAs were above ~120°/100° (adv/rec) and BET C constants were in the range of ~15-25, indicating uniform low-energy surfaces of closely packed alkyl groups on external and internal surfaces of the pores respectively. Moreover, surfaces grafted with the long-chained (C(12)-C(18)) silanes showed super-hydrophobic behavior (CAs~150-180°) and extremely low adhesion for water. The pore uniformity of parental SBA-15 was largely preserved and the pore volume and pore diameter were consistent with the formation of a single layer of alkylsilyl groups inside the pores. Post-synthesis grafting of SBA-15 with SAMs worked not as well as CAMs: the surfaces prepared demonstrated lower water CAs and higher BET C constants, thereby indicating a small amount of accessible polar groups (Si-OH) related to packing constrains for SAMs supported on highly curved surfaces of mesopores. The co-condensation method produced substantially more disordered materials and less hydrophobic surfaces than any of the grafting methods. The surfaces of these materials showed low water CAs and high BET C constants (~100-200) thereby demonstrating a non-uniform surface coverage and presence of unmodified silica. It is concluded that CAMs chemistry is the most efficient approach in preparation of the functionalized OMS materials with uniform surfaces and pores.  相似文献   

9.
The C-H stretch vibrational spectra of the trisiloxane superspreading surfactant Silwet L-77((CH3)3Si-O-Si(CH3)(C3H6)(OCH2CH2)7-8OCH3)-O-Si(CH3)3) at the air/water interface are measured with the surface Sum Frequency Generation Vibrational Spectroscopy (SFG-VS). The spectra are dominated with the features from the –Si-CH3 groups around 2905 cm-1 (symmetric stretch or SS mode) and 2957 cm-1 (mostly the asymmetric stretch or AS mode), and with the weak but apparent contribution from the -O-CH2- groups around 2880 cm-1 (symmetric stretch or SS mode). Comparison of the polarization dependent SFG spectra below and above the critical aggregate or micelle concentration (CAC) indicates that the molecular orientation of the C¡H related molecular groups remained unchanged at different surface densities of the Silwet L-77 surfactant. The SFG-VS adsorption isotherm suggested that there was no sign of Silwet L-77 bilayer structure formation at the air/water interface. The Gibbs adsorption free energy of the Silwet surfactant to the air/water interface is -42.2±0.8kJ/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant  相似文献   

10.
A quantitative model for the kinetics of adsorption of ionic surfactants to an expanding liquid surface is presented for surfactant concentrations below and above the critical micelle concentration (cmc). For surfactant concentrations below the cmc, the electrostatic double layer is accounted for explicitly in the adsorption isotherm. An overflowing cylinder (OFC) was used to create nonequilibrium liquid surfaces under steady-state conditions. Experimental measurements of the surface excess for solutions of cationic surfactants CH3(CH2)n-1N+(CH3)3 Br- (CnTAB, n = 12, 14, 16) and the anionic fluorocarbon surfactant sodium bis(1H,1H-nonafluoropentyl)-2-sulfosuccinate (di-CF4) in the OFC are in excellent agreement with the theoretical predictions for diffusion-controlled adsorption for all concentrations studied below the cmc. For surfactant concentrations above cmc, the diffusion ofmicelles and monomers are handled separately under the assumption of fast micellar breakdown. This simplified model gives excellent agreement for the system C14TAB + 0.1 M NaBr above the cmc. Agreement between theory and experiment for C16TAB + 0.1 M NaBr is less good. A plausible explanation for the discrepancy is that micellar breakdown is no longer fast on the time scale of the OFC (ca. 0.1 s).  相似文献   

11.
Atomic force microscopy was used to characterize an anatase TiO2 surface, prepared by the helical vapor preparation method. The forces between two bare TiO2 surfaces were measured in the presence of water at various pH values. This TiO2 isoelectric point (iep) was characterized by the presence of only a van der Waals attraction and was measured at pH 5.8; this value is similar to that for a rutile TiO2 surface. The adsorption mechanism of a nonionic surfactant molecule to this anatase TiO2 surface was investigated by measuring the forces between two such TiO2 surfaces at their iep pH in the presence of linear dodecanol tetraethoxylate (C12E4), a poly(ethoxylene oxide) n-alkyl ether. C12E4 was seen by the presence of steric forces to adsorb to the uncharged TiO2 surface. For low surfactant concentrations, C12E4 adsorbed with its hydrophobic tail facing the TiO2 substrate, to reduce its entropically unfavorable contacts with water. Additional surfactant adsorption occurred at higher surfactant concentrations by the hydrophobic and hydrophilic interactions between the surfactant tails and heads, respectively, and gave sub-bilayers. A two-step adsorption isotherm was subsequently proposed with four regions: (1) submonolayer, (2) complete monolayer, (3) sub-bilayer, and (4) bilayer. The absence of a long-range repulsive force between the two TiO2 surfaces in the presence of the C12E4 surface aggregates indicated that a C12E4 nonionic surfactant aggregate did not possess charge.  相似文献   

12.
研究Ta掺杂六方相氧化钨(hex-WO3)材料在吸附Sr2+过程中其表面zeta电位的变化情况,并进一步探讨了吸附过程的热力学及吸附机理。结果表明:(1)在实验pH值范围内,Ta掺杂hex-WO3悬浮液的zeta电位值随溶液中电解质的价态增大而增大;(2)且zeta电位随体系中离子强度的增加而增大;(3) Ta掺杂hex-WO3对Sr2+的吸附容量随着温度降低而增大,随着离子强度的增加而减少;(4)吸附过程的吸附焓为-47 kJ·mol-1,且Sr2+离子与材料表面之间主要为化学相互作用;(5) Ta掺杂hex-WO3对Sr2+吸附过程主要为材料表面吸附及材料孔道内离子交换共同作用。  相似文献   

13.
14.
Super-spreading trisiloxane surfactants are a class of amphiphiles which consist of nonpolar trisiloxane headgroups ((CH3)3-Si-O)2-Si(CH3)(CH2)3-) and polar parts composed of between four and eight ethylene oxides (ethoxylates, -OCH2CH2-). Millimeter-sized aqueous drops of trisiloxane solutions at concentrations well above the critical aggregate concentration spread rapidly on very hydrophobic surfaces, completely wetting out at equilibrium. The wetting out can be understood as a consequence of the ability of the trisiloxanes at the advancing perimeter of the drop to adsorb at the air/aqueous and aqueous/hydrophobic solid interfaces and to reduce considerably the tensions of these interfaces, creating a positive spreading coefficient. The rapid spreading can be due to maintaining a positive spreading coefficient at the perimeter as the drop spreads. However, the air/aqueous and solid/aqueous interfaces at the perimeter are depleted of surfactant by interfacial expansion as the drop spreads. The spreading coefficient can remain positive if the rate of surfactant adsorption onto the solid and fluid surfaces from the spreading aqueous film at the perimeter exceeds the diluting effect due to the area expansion. This task is made more difficult by the fact that the reservoir of surfactant in the film is continually depleted by adsorption to the expanding interfaces. If the adsorption cannot keep pace with the area expansion at the perimeter, and the surface concentrations become reduced at the contact line, a negative spreading coefficient which retards the drop movement can develop. In this case, however, a Marangoni mechanism can account for the rapid spreading if the surface concentrations at the drop apex are assumed to remain high compared to the perimeter so that the drop is pulled out by the higher tension at the perimeter than at the apex. To maintain a high apex concentration, surfactant adsorption must exceed the rate of interfacial dilation at the apex due to the outward flow. This is conceivable because, unlike that at the contact line, the surfactant reservoir in the liquid at the drop center is not continually depleted by adsorption onto an expanding solid surface. In an effort to understand the rapid spreading, we measure the kinetic rate constants for adsorption of unaggregated trisiloxane surfactant from the sublayer to the air/aqueous surface. The kinetic rate of adsorption, computed assuming the bulk concentration of monomer to be uniform and undepleted, represents the fastest that surfactant monomer can adsorb onto the air/aqueous surface in the absence of direct adsorption of aggregates. The kinetic constants are obtained by measuring the dynamic tension relaxation as trisiloxanes adsorb onto a clean pendant bubble interface. We find that the rate of kinetic adsorption is only of the same order as the area expansion rates observed in superspreading, and therefore the unaggregated flux cannot maintain very high surface concentrations at the air/aqueous interface, either at the apex or at the perimeter. Hence in order to maintain either a positive spreading coefficient or a Marangoni gradient, the surfactant adsorptive flux needs to be augmented, and the direct adsorption of aggregates (which in the case of the trisiloxanes are bilayers and vesicles) is suggested as one possibility.  相似文献   

15.
The properties of n-tetradecane/electrolyte emulsions with DPPC or DPPC vesicles in the electrolyte solution were investigated. The DPPC molecules form different aggregates, which possess different surface affinity, size and structure, and therefore we assumed some differences in the adsorption at the oil droplet/water interface. The n-tetradecane emulsions in 1:1, 1:2 and 1:3 electrolytes were prepared by mechanical stirring in the presence of DPPC at natural pH. Electrokinetic properties of the systems were investigated taking into account the effective diameter and multimodal size distribution of the droplets as well as the zeta potentials using the dynamic light scattering technique. The zeta potential of the droplets was negative in all systems with NaCl. In the emulsions with CaCl(2) at a higher concentration of electrolyte and emulsions with LaCl(3) with all investigated concentrations, positive values were observed. Similar measurements were performed for DPPC vesicles in the electrolyte solution. The pH and ionic strength changes induce those in the electrical charge of DPPC layer or vesicle surface. This is due to the fact that the DPPC molecule contains -PO(-) and -N(CH(3))(3) groups, which are in equilibrium with H(+) and OH(-), as well as other ions present in the solution, i.e. Na(+), Ca(2+), La(3+) or Cl(-). In the n-tetradecane/electrolyte emulsion stabilized by DPPC or DPPC vesicles the zeta potential may be also related to acid-base interactions. The effect of the ions from the solution on the DPPC layer adsorbed on n-tetradecane droplets or DPPC vesicles is discussed.  相似文献   

16.
Interfacial properties of cationic surfactants show strong dependence on the type of surfactant counterion or on the type of anion of a salt added to the surfactant solution. In the paper, the models of ionic surfactant adsorption that can take into account ionic specific effects are reviewed. Model of ionic surfactant adsorption based on the assumption that the surfactant ions and counterions undergo nonequivalent adsorption within the Stern layer was selected to describe experimental surface tension isotherms of aqueous solutions of a number of cationic surfactants. The experimental isotherms for: n-alkyl trimethylammonium cationic surfactants, namely: C(16)TABr (CTABr or CTAB), C(16)TACl, C(16)TAHSO(4), C(10)TABr and C(12)TABr as well as decyl- and dodecylpyridinium salts with and without various electrolyte anions as Cl(-), Br(-), F(-), I(-), NO(3)(-), ClO(4)(-) and CH(3)COO(-) were described in terms of the model and a good agreement between the theory and experiment was obtained for a wide range of surfactants and added electrolyte concentrations. A very pronounced Hofmeister effect in dependence of surface tension of cationic surfactants on the type of anion was found. Analysing this dependence in terms of the proposed model of ionic surfactant adsorption, strong correlation between "anion surface activity" (the model parameter accounting for ion penetration into the Stern layer), and the ion polarizability was obtained. That suggests that the mechanism related to the dispersive interaction of polarized ion with electric field at interface is responsible for Hofmeister series effects in surface activity of cationic surfactants. The same mechanism was proposed recently to explain the dependence of surface tension increase with electrolyte concentration on anion and cation type.  相似文献   

17.
不对称Gemini表面活性剂在气/液界面的吸附动力学   总被引:3,自引:0,他引:3  
合成出由1个亚甲基联接羟基和季铵基头基, 且带两根不同长度烷烃链的不对称Gemini表面活性剂CmH2m+1OCH2CH(OH)CH2N+(CH3)2C8H17Br(记为CmOhpNC8, m=10, 12, 14). 用最大泡压法研究了浓度低于临界胶团浓度时, CmOhpNC8在气/液界面上的吸附动力学. 结果表明, CmOhpNC8表现出很明显的吸附动力学效应. CmOhpNC8向新鲜气/液界面吸附时由扩散过程控制; 当界面上已具有一定吸附量时, 显示出吸附能垒Ea. 随着烷烃链的增长而明显降低, 表明长烷烃链的分子到达亚层后更容易插入表面层,这被归结为分子烷烃链间的疏水相互作用随着链增长而增强所致.  相似文献   

18.
Controlling zeta potential of PDMS surface coated with a layer of PEG is important for electroosmosis and electrophoresis in PDMS made microfluidic chips. Here, zeta potentials of PDMS surfaces modified by simple physisorption of PEG of different concentrations in phosphate buffer solutions, pure water, and PEG solution were reported. Coating PEG on PDMS surfaces was achieved by immersing a PDMS layer into the PEG solution for 10 min and then taking it out and placing it in an oven at 80℃ for 10 h. To avoid damaging the PEG layer on the PDMS surface, an induction current method was employed for zeta potential measurement. Zeta potentials of PEG modified PDMS in electrolyte solutions were measured. The results show that 2.5% PEG can effectively modify PDMS surface with positive zeta potential value in phosphate buffer solutions, pure water and 10% PEG solution. Further increase in PEG solution beyond 5% for surface modification has no obvious effect on zeta potential change.  相似文献   

19.
The wetting properties of surfactants on solid surfaces form the basis of many industrial and biological processes. The preferential adsorption of the surfactants from aqueous solutions onto solid surfaces alter the adhesion tension of the surface and this behavior may cause partial to complete wetting of the surfaces by the aqueous surfactant solutions. However, different types of surfactants show different wetting characteristics. To study the wetting properties of biologically produced rhamnolipids (RL), advancing contact angles of the aqueous solutions of the RL mixture of R1 and R2 in a ratio of R2/R1=1.1 were measured as a function of surfactant concentration. For a comparison of the wetting performance, sodium dodecyl sulfate (SDS) was chosen as the reference surfactant. A hydrophilic glass surface, a hydrophobic polymer, polyethylene terephthalate (PET), and gold surface were used as the solid surfaces to determine the wetting characteristics of rhamnolipids. At low surfactant concentrations (RL concentration <3x10(-5)M, SDS concentration<3x10(-4)M) contact angle (Theta) varied in a certain range depending on the character of the surfactant interactions with the surface. This was followed by a decrease in contact angle. Parallel to this behavior, at low surfactant concentrations the adhesion tension decreased, then remained constant and an increase at higher surfactant concentrations was obtained on hydrophobic surfaces. On hydrophilic surfaces a steady decrease in adhesion tension was observed with both surfactant solutions.  相似文献   

20.
Polypropylene surfaces were rendered cationic by hydrophobic implantation and by grafting a quaternized polyvinyl pyridine onto a plasma treated surface. The polypropylene surface with the grafted polymer showed a strong adsorption of an anionic surfactant, corresponding to about ten monomolecular layers. High concentration of electrolyte caused a reduction of the adsorption at low concentrations of surfactant.  相似文献   

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