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1.
The role of stabilizing agents in the interaction between styrene/butadiene latex and calcium carbonate particles has been studied using isothermal titration calorimetry (ITC) and an electrokinetic sonic amplitude (ESA) technique. It is demonstrated that the polyacrylate sodium salt (dispersing agent, referred to as NaPA) used as stabilizing agent for the calcium carbonate suspensions principally affects the interfacial properties of the calcite surface. An electrostatic barrier is created and this decreases the attractive interactions between the latex and the negatively charged mineral surface. The total enthalpy change observed when an emulsion of styrene/butadiene particles substantially free from surfactant was added to the dispersed calcium carbonate could be described via a relatively complex path. The process included (i) an exothermic response from the association of the latex particles (adsorption process) with the dispersed calcium carbonate surface and (ii) an endothermic bulk phase effect due to the adsorption on the latex particles of dissolved species originating from the calcium carbonate. Stabilization of the latex particles with sodium dodecyl benzene sulfonate (SDBS) or a non-ionic fatty alcohol ethoxylate surfactant did not significantly change the enthalpy of interaction. It was further demonstrated that SDBS had a very weak affinity for the dispersed calcium carbonate particles and that dissolution of species, such as calcium ions, from the calcium carbonate surface, allows further adsorption of SDBS onto the latex particles.  相似文献   

2.
Effect of the concentration of water-soluble polyanion (sodium carboxymethylcellulose, NaCMC) on the interaction between a cationic surfactant (1-dodecyl-3-methylimidazolium bromide, C12mimBr) and NaCMC in aqueous solution has been studied by isothermal titration microcalorimetry (ITC), conductivity, surface tension, and rheological measurements. From the surfactant/polymer interacting enthalpy, it can be deduced that the electrostatic attraction between the cationic surfactant and anionic polyelectrolyte causes an endothermic process, and the C12mimBr monomers binding to the NaCMC chains to form micelle-like aggregates through hydrophobic interaction is an exothermic process. Increasing the NaCMC concentration causes the interaction between C12mimBr and NaCMC to decrease, and the characteristic surfactant concentrations, including the critical aggregation surfactant concentration (CAC), the surfactant concentration to form free micelles (Cm), and the saturation concentration of surfactant on the NaCMC chains (CS) to increase. Because of the strong electrostatic interaction between C12mimBr and NaCMC, the formation of C12mimBr/NaCMC complexes can lead to precipitation or redissolution depending on solution composition, so the critical precipitation concentration (CP) and the onset of a redissolution concentration (CR) has been determined by the electrical conductivity. The rheological results reveal a dramatic increase in solution viscosity around the CAC, attributed to interpolymer cross-linking through the formation of mixed micelles involving the carboxylic acid groups of NaCMC and the surfactant.  相似文献   

3.
Adsorption of fluoride ions onto carbonaceous materials   总被引:9,自引:0,他引:9  
The characteristics of fluoride ion adsorption onto carbonaceous materials were derived as adsorption isotherms at different temperatures and in different pH solutions. The fluoride ion was adsorbed into pores in carbonaceous materials produced from wood; the larger the specific surface area, the more fluoride ions adsorbed. Bone char was the most effective adsorbent. The composition of bone char includes calcium phosphate, calcium carbonate, and so on. This suggests that the phosphate ion in bone char was exchanged with a fluoride ion. Moreover, the mechanism of fluoride ion adsorption onto bone char is clearly chemical in nature because the amount of fluoride ion adsorbed onto bone char increased with increasing temperature and decreasing pH. The amount of fluoride ion adsorbed onto bone char was also shown to depend on the concentration of sodium chloride in solution because of the "salting-out" effect. The adsorption of fluoride ion onto bone char is endothermic. Bone char can be utilized to remove fluoride ions from drinking water.  相似文献   

4.
Complexation between sodium carboxymethylcellulose (NaCMC) and ellipsoidal particles of oppositely charged beta-FeOOH is studied using electric light scattering and electrophoresis. We focus on the complex behavior for overcharging of the particle surface. In this case, the fraction of condensed counterions on NaCMC is found to remain unchanged during polymer adsorption onto a weakly charged particle surface. Using the theory of Sens and Joanny, we evaluate the fraction of condensed counterions and compare it with results for nonadsorbed NaCMC. The polarization of condensed counterions along the chain of the adsorbed macromolecule is proved to create the electro-optical effect in suspensions stabilized by NaCMC adsorption.  相似文献   

5.
The origin of the surface potential of calcium carbonate in aqueous dispersions and the dissolution of calcite in systems containing excess Ca(2+) and CO(3)(2-) have been the subjects of this study. In addition, stabilization of calcite particles with an anionic polyelectrolyte (sodium polyacrylate (NaPA)) and the effect on surface potential and dissolution of calcite have been studied. Preferential dissolution of either Ca(2+) or CO(3)(2-) from the surface, which is governed by the partial pressure of CO(2) in solution and the pH of the solution, mainly determines the surface potential. Both lattice ions (Ca(2+) and CO(3)(2-)) adsorb onto the surface and thus alter the surface potential. NaPA adsorbs strongly onto the calcite surface regardless of background electrolyte concentration, and reverses the surface potential to negative values. Chelation of the surface due to NaPA can be partly prevented by adding Ca(2+) to the dispersion.  相似文献   

6.
Adsorption of anionic polyelectrolytes, sodium salts of carboxymethyl celluloses (CMCs) with different degrees of substitution (DS = 0.9 and 1.2), from aqueous electrolyte solutions onto regenerated cellulose surfaces was studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) experiments. The influence of both calcium chloride (CaCl(2)) and sodium chloride (NaCl) on CMC adsorption was examined. The QCM-D results demonstrated that CaCl(2) (divalent cation) caused significantly greater CMC adsorption onto regenerated cellulose surfaces than NaCl (monovalent cation) at the same ionic strength. The CMC layers adsorbed onto regenerated cellulose surfaces from CaCl(2) solutions exhibited greater stability upon exposure to flowing water than layers adsorbed from NaCl solutions. Both QCM-D and SPR results showed that CMC adsorption onto regenerated cellulose surfaces from CaCl(2) solutions increased with increasing CaCl(2) concentration up to the solubility limit (10 mM). Voigt-based viscoelastic modeling of the QCM-D data indicated that the CMC layers adsorbed onto regenerated cellulose surfaces had shear viscosities of η(f) ≈ 10(-3) N·s·m(-2) and elastic shear moduli of μ(f) ≈ 10(5) N·m(-2). Furthermore, the combination of SPR spectroscopy and QCM-D showed that the CMC layers contained 90-95% water. Adsorption isotherms for CMCs in CaCl(2) solutions were also obtained from QCM-D and were fit by Freundlich isotherms. This study demonstrated that CMC adsorption from CaCl(2) solutions is useful for the modification of cellulose surfaces.  相似文献   

7.
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   

8.
At ultralow shear rate (~0.01 s?1), acting below the yield stress of the aqueous gel, adsorption of calcium carbonate nanoparticles (<~100 nm) onto cellulose nanofibrils is induced without pigment–pigment preflocculation. Dispersant-free and polyacrylate treated dispersed carbonate particles are compared. Initially, it is seen that the polyacrylate dispersed material does not adsorb, whereas the dispersant-free carbonate adsorbs readily under the controlled ultralow shear conditions. However, repeated cycles of ultralow shear with intermittent periods in the rest state eventually induce the effect as initially seen with the dispersant-free calcium carbonate. The fibril suspension in the bulk is slightly acidic. The addition of buffer to a controlled pH in the case of the dispersant treated particles maintained a similar delay in the onset of adsorption, but adsorption occurred eventually after repeated cycles. During this cycling process, in parallel, the pH gradually drops under repeated cycles of ultralow shear, opposite to expectation, given the buffering capacity of calcium carbonate. The conductivity, in turn, progressively increases slightly at first and then significantly. The action of surface bound water on the nanofibril is considered key to the action of adsorption, and the condition of ultralow shear suggests that the residence time of the particle in contact with the nanofibril, acting under controlled strain against diffusion in the gel, is critical. It is proposed that under these specific conditions the calcium carbonate nanoparticles act as a probe of the nanofibril surface chemistry. The hydrogen bonded water, known to reside at the nanofibril surface, is thus considered the agent in the carbonate-surface interaction, effectively expressing an acid dissociation, and the calcium carbonate nanoparticles act as the probe to reveal it. An important phenomenon associated with this acid dissociation behaviour is that the adsorbed calcium carbonate particles subsequently act to flocculate the otherwise stable cellulose material, leading to release of water held in the aqueous gel matrix structure. This latter effect has major implications for the industrial ease of use of micro and nanofibrillar cellulose at increased solids content. This novel mechanism is also proposed for use to enhance the dewatering capability in general of complex cellulose-containing gel-like water-holding suspensions.  相似文献   

9.
The effect of potassium, sodium, calcium, magnesium, and hydrogen cations on adsorption of guar gum onto quartz was investigated at natural pH. The role of the background ions was analyzed in terms of their water-structure making or breaking capabilities. In dilute solutions (0.01 mol/L) of structure-makers (NaCl, HCl, CaCl2, and MgCl2), the guar gum adsorption density did not change compared to the adsorption densities obtained in distilled water. Potassium, the only structure-breaking ion (chaotrope) among the tested cations, significantly enhanced guar gum adsorption. The results obtained in mixed electrolytes demonstrate that the strong structure-breaking properties of K+ overcome any contributions from weak structure making ions (kosmotropes), and guar gum adsorption remains at the levels observed in KCl alone. Only when strongly hydrated Mg2+ ions are mixed with KCl, the overall effect becomes additive and the influence of potassium is proportionally reduced by increasing concentrations of magnesium cations. In this approach, guar gum adsorption on quartz is viewed as a competition between polysaccharide and water molecules for silanol surface sites. The hydration of the quartz surface inhibits the adsorption process but the competition equilibrium, and hence polysaccharide adsorption, can be affected by the presence of chaotropes or kosmotropes.  相似文献   

10.
The adsorption of sodium polyacrylate (NaPAA) in slurries with up to 75 wt.% calcium carbonate was investigated with the use of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and adsorption of probe molecules. Analysis of the IR spectra demonstrated that the carboxylate groups of NaPAA adsorbed onto ground calcium carbonate (GCC) in three different modes. These modes were shown to be dependent on the solids loading and age of the slurry. Further investigation lead to the determination of the chelating ability of NaPAA at high solids loading.  相似文献   

11.
Upon reverse flotation of iron ore, the surface of the iron ore concentrate may become partially hydrophobized due to adsorption of flotation collector, which is facilitated by the calcium ions present in the process water. Hydrophobic areas on the concentrate surface may introduce problems in subsequent pelletization of the concentrate. A possible way to restore the wettability of the surface could be by modifying the surface with a hydrophilic polymer. The effect of hydrophilic polymers of different types, viz. cationic, anionic, and non-ionic, on the wettability of the magnetite surface after adsorption of a surfactant was investigated. Although all the polymers could adsorb on magnetite at pH 8.5, the contact angle measurements revealed that only anionic ammonium polyacrylate could decrease the contact angle of synthetic magnetite after surfactant adsorption to a level close to that of as-synthesized magnetite. Such effect was probably achieved due to shielding of the hydrophobic surfactant chains from the aqueous phase by hydrophilic polyacrylate molecules. The fact that polyacrylate adsorption on magnetite occurred via calcium ions makes polyacrylate suitable for application in calcium-rich process water. The results presented in this work illustrate that ammonium polyacrylate could be successfully used to improve the wettability of magnetite after adsorption of surfactants.  相似文献   

12.
2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position α to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of ~6. The role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.  相似文献   

13.
The surface adsorption of calcium hydroxide onto kaolin and metakaolin was investigated by monitoring with atomic emission spectroscopy and pH measurements the amounts of ions left in solution after exposing clays to calcium hydroxide solutions of various concentrations. Both clays adsorb calcium and hydroxyl ions but differently. Kaolin adsorbs calcium hydroxide not only at the edges of the clay particles but also onto the basal faces. The adsorbed hydrated calcium ions form a layer on the clay particle surfaces, preventing further dissolution of the clay mineral platelet. Metakaolin shows high pozzolanic activity, which provides the quick formation of hydrated phases at the interfaces between metakaolin and lime solutions. The nature of the hydration products has been investigated using X-ray diffraction (XRD) and differential thermal analysis (DTA). The most important hydrated phases like CSH (hydrated calcium silicate) and C2ASH8 (gehlenite) have been identified.  相似文献   

14.
A previous study on electrodialysis of calcium and carbonate high concentration solutions demonstrated that calcium migrated through the cation-exchange membrane (CEM) was blocked by the anion-exchange membrane (AEM) where it formed another fouling. The aim of the present work was to complete the identification of the deposit formed on AEM during electrodialysis and to characterize its physical structure at the interface of the membrane. No fouling was found on the anionic membranes treated without calcium chloride in presence of sodium carbonate, while membranes used during ED process of solutions containing calcium chloride and sodium carbonate were slightly fouled. A thin layer of precipitates was observed on the anionic membrane surface. The appearance of precipitates was typical of a crystalline substance. The size and form of crystal increased in proportion to the concentration of calcium chloride in solution. Large and cubic crystals were the best defined on the membrane treated at 1600 mg/L of CaCl2. The precipitate was identified as calcium hydroxide. However, this fouling was not found to affect significantly the electrical conductivity and the thickness of the membranes. Furthermore, the fouling formed was reversible.  相似文献   

15.
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   

16.
A detailed in situ scattering study has been carried out on the formation of amorphous calcium carbonate (ACC) particles modulated by the presence of small amounts of sodium polyacrylate chains. The work is aiming at an insight into the modulation of ACC formation by means of two polyacrylate samples differing in their molecular weight by a factor of 50. The ACC formation process was initiated by an in situ generation of CO(3)(2-) ions via hydrolysis of 10 mM dimethylcarbonate in the presence of 10 mM CaCl(2). Analysis of the formation process by means of time-resolved small-angle X-ray and light scattering in the absence of any additives provided evidence for a monomer addition mechanism for the growth of ACC particles. ACC formation under these conditions sets in after a lag-period of some 350 s. In the presence of sodium polyacrylate chains, calcium polyacrylate aggregates are formed during the lag-period, succeeded by a modulated ACC growth in a second step. The presence of anionic polyacrylate chains changed the shape of the growing particles toward loose and less homogeneous entities. In the case of low amounts (1.5-7.5 mg/L) of the long chain additive with 97 kDa, the size of the aggregates is comparable to the size of the successively formed hybrid particles. No variation of the lag-period has been observed in this case. Use of the short chain additive with 2 kDa enabled increase of the additive concentration up to 100 mg/L and resulted in a significant increase of the lag-period. This fact, together with the finding that the resulting hybrid particles remained stable in the latter case, identified short chain sodium polyacrylates as more efficient modulators than long chain polyacrylates.  相似文献   

17.
The flocculation performance of cationic starches on calcite pretreated with anionic sodium polyacrylate (NaPA) was investigated by measuring the mean particle size and the dynamic mobility of the calcite dispersions. Cationic starches of different molecular weight and degree of substitution were used. By varying the amount of anionic sodium polyacrylate, which has a strong affinity to the calcium carbonate surface, one is able to anionically modify the particles and reverse the charge character of the originally cationic calcium carbonate. By such modification of the charge character of the calcium carbonate dispersion, it is possible to approach the mechanisms of flocculation caused by cationic macromolecules like starch. The importance of different mechanisms of flocculation, such as bridging, charge neutralization, and flocculation induced by polyelectrolyte complexes (PEC), was further investigated in this work. It was found that when the NaPA is completely absorbed at the calcite surfaces the mechanism of the flocculation induced by the starch is mainly bridging flocculation. Excess NaPA in the calcium carbonate dispersion will result in polyelectrolyte complexes formed between the non-absorbed NaPA and the oppositely charged starch polymers. These complexes will in most cases strongly enhance the flocculation due to mainly charge neutralization. Depending on the ratio of non-absorbed NaPA and the starch in the aqueous phase, the calcite dispersion is either re-stabilized or more strongly flocculated due to the formed polyelectrolyte complexes. Both the mobility and the particle size measurements support the mechanisms described. It was further demonstrated that the molecular weight and degree of substitution of the starches might be adjusted to control the flocculation behavior.  相似文献   

18.
Adsorption of cations (Na(+), Ca(2+), Ba(2+)) onto negatively charged (pH 10.4) hematite (alpha-Fe(2)O(3)) particles has been studied. The oxide material was carefully prepared in order to obtain monodisperse suspensions of well-crystallized, quasi-spherical particles (50 nm in diameter). The isoelectric point (IEP) is located at pH 8.5. Adsorption of barium ions onto oxide particles was carried out and the electrophoretic mobility was measured throughout the adsorption experiment. Comparison with calcium adsorption at full coverage reveals a higher uptake of Ba(2+). In both cases it shows also that chloride ions coadsorb with M(2) ions. Simultaneous uptake of the positive and negative ions explains why the electrophoretic mobility does not reverse to cationic migration. A theoretical study of the surface speciation has been carried out, using the MuSiC model. It reveals the presence of negative as well as positive sites on both sides of the point of zero charge (PZC) of the hematite particles, which may explain the coadsorption of Ba(2+) and Cl(-) at pH 10.4. The effective charge of the oxide particles, calculated from the electrophoretic mobility, is in very good agreement with the results found with the MuSiC modelization and the chloride/barium adsorption ratio. It also verifies the theory of ionic condensation. Calorimetric measurements gave a negative heat for the overall reaction occurring when Ba(2+)/Cl(-) ions adsorb onto hematite. Despite the fact that anions (Cl(-) and OH(-)) adsorption onto mineral oxides is an exothermic phenomenon, it is likely that barium and calcium adsorption is endothermic, denoting the formation of an inner-sphere complex as reported in the literature.  相似文献   

19.
Suspensions of calcium carbonate in water with an indifferent background electrolyte (NaCl) have been investigated using several techniques. Particular attention was paid to the dissolution of calcite at equilibrium and as a function of sodium polyacrylate (NaPA) concentration. Also of interest was how this affects the magnitude of the surface charge and the zeta potential. The development of the interfacial charge is discussed with respect to the dissolved species and with regard to the kinetics of dissolution. The partial pressure of CO(2) in solution is believed to play a major role in determining the sign of the charge at equilibrium. In addition to effectively stabilizing calcite suspensions, NaPA was also found to act as a chelating agent at the calcite surface, enhancing the dissolution. The order of addition of NaPA to the suspensions was found to be important.  相似文献   

20.
FTIR-ATR was used to examine in situ the interaction of polyacrylate and hematite at pH 13. Static light scattering and mobility measurements were used to assess solution polyacrylate dimensions and hematite surface charge, respectively. Polyacrylate adsorption occurred only with the addition of electrolyte (e.g., NaCl), and it was found that excess cations, up to approximately 1 M, facilitated adsorption, above which the effect was found to plateau. At pH 13 and at low ionic strength, adsorption of polyacrylate onto hematite is facilitated by cations in solution shielding both the negative acrylate functionality of the polymer and the negative hematite surface. The shielding of the hematite surface continues to increase with increasing salt concentration up to a measured 3 M. Similarly, the shielding of the polymer increased with electrolyte concentration up to approximately 1 M salt, beyond which no further increase in shielding was observed. At this concentration the polymer assumes a finite minimum size in solution that ultimately limits the amount adsorbed. The dimension of the polymer in solution was found to be independent of monovalent cation type. Thus, at high pH and high ionic strength adsorption is determined by the degree of hematite surface charge reduction. The cation-hematite surface interaction was found to be specific, with lithium leading to greater polyacrylate adsorption than sodium, which was followed by cesium. The stronger affinity of lithium for the hematite surface over sodium and cesium is indicative of the inverse lyotropic adsorption series and has been rationalized in the past by the "structure-making-structure-breaking" model. These results provide a useful insight into the likely adsorption mechanism for polyacrylate flocculants at high pH and ionic strength onto residues in the Bayer processing of bauxite.  相似文献   

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