Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles

Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles were investigated. The state of dispersion was evaluated in terms of zeta potential, apparent viscosity and the mean particle size of solid phase in the solution. Zeta potential, apparent viscosity and the mean particle size as a function of pH were performed in absence of dispersant. The result showed that electrostatic stabilization of the aqueous suspension of barite nanoparticles can be accomplished in low acidic and high basic range of pH. In presence of sodium polyacrylate (PAA-Na) dispersant, the isoelectric point (IEP) of the barite nanoparticles was shifted to lower pH and the negative zeta potential was increased in a large range of pH above the (IEP). The optimum amount of PAA-Na dispersant is discussed in the light of zeta potential and viscosity. It is found that the adsorption of PAA is correlated to the net surface charge of the barite nanoparticles and the fraction of dissociated polymer at pH 4, 8.5 and 10. At pH 4, the state of dispersion was achieved at higher amount of electrolyte due to the low fraction of negatively charged dissociated polymer and the positively charge particles. At basic pH, the fraction of dissociated polymer was high and the surface charge of particle was highly negative, therefore, the lowest viscosity was obtained at a small amount of PAA. In addition, the optimum amount of polymer decreased with the increase in pH of the suspension.     

Biosorption of Pb(II) ions from aqueous solution by pine bark (Pinus brutia Ten.)

The biosorption potential of pine (Pinus brutia Ten.) bark in a batch system for the removal of Pb(II) ions from aqueous solutions was investigated. The biosorption characteristics of Pb(II) ions on the pine bark was investigated with respect to well-established effective parameters including the effects of solution pH, initial Pb(II) concentration, mass of bark, temperature, and interfering ions present, reusability, and desorption. Initial solution pH and contact time were optimized to 4.0 and 4 h, respectively. The Langmuir and Freundlich equilibrium adsorption models were studied and observed to fit well. The maximum adsorption capacity of the bark for Pb(II) was found to be 76.8 mg g⁻¹ by Langmuir isotherms (mass of bark: 1.0 g L⁻¹). The kinetic data fitted the pseudo-second-order model with correlation coefficient greater than 0.99. The thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were also calculated, and the values indicated that the biosorption process was spontaneous. Reutilization of the biosorbent was feasible with a 90.7% desorption efficiency using 0.5 M HCl. It was concluded that pine bark can be used as an effective, low cost, and environmentally friendly biosorbent for the removal of Pb(II) ions from aqueous solution.     

Stabilization and Processing of Aqueous BaTiO3 Suspension with Polyacrylic Acid

Polyacrylic acid (PAA) has been chosen to stabilize BaTiO₃ powder in aqueous solution. Zeta potential studies show that the Ba-rich particle surface is positively charged in the pH range from 2 to 11 without PAA. Adsorption of PAA decreases the zeta potential in acidic solution and changes the surface to a negative charge in basic solution. Adsorption of PAA onto BaTiO₃ surfaces is found to be related to the pH-dependent PAA conformation in solution. The amount of PAA adsorbed at pH 1.5 is one order of magnitude more than at pH 10.5, due to a more compact polymer conformation. Colloid stability of aqueous BaTiO₃ suspension is related to the dissociation of PAA as a function of pH. BaTiO₃ suspensions can be stabilized at pH values higher than 7, where more than 99% of carboxylic groups are ionized. At pH 10.5, suspension stability is related to the PAA coverage on BaTiO₃ particle surface. Stabilization can be achieved only when conditions of both PAA ionization and BaTiO₃ surface coverage are satisfied, suggesting an electrosteric stabilization mechanism. Green density of 62% can be achieved by slip casting at a pH above 10, compared to the best density of 58.6% by isostatic pressing at 242 MPa.     

高取代度阳离子淀粉改性棉纤维用于活性染料无盐染色的研究

本文以取代度为0.6的高取代度季铵型阳离子淀粉为阳离子化试剂,对棉纤维进行阳离子化改性,用于活性染料无盐染色.通过改性棉纤维表面Zeta电位变化和染料等温吸附曲线对无盐染色促染机理进行研究,对有盐染色和无盐染色中的染料色光、色牢度和染色纤维折皱回复性和强度性能进行比较,从而对高取代度季铵型阳离子淀粉的应用性能进行综合评...     

Interactions between Nanoclay,CTAB and Linear/Star Shaped Polymers

The influence of star-shaped (PAA-SS) and linear polyacrylic acid (PAA) with different molecular weights (high—PAA-HMW and low—PAA-LMW) on the structure of the adsorption layer, adsorption amount, electrokinetic and stabilizing properties of the PAA/CTAB/nanoclay suspensions was studied. The properties of the systems containing one of these polymers, the cationic surfactant—hexadecyltrimethylammonium bromide (CTAB) and the surface-modified nanoclay (N-SM) were analyzed using the following techniques: BET, CHN, FT-IR, ED-XRF, XRD, HRTEM, UV-Vis, tensiometry and zeta potential measurements. It was proved that PAA could be used as an effective stabilizer of N-SM. Moreover, the addition of CTAB caused a significant increase in the stability of the systems but decreased the adsorption of PAA on the N-SM surface and changed the structure of the adsorption layers. The largest stability was observed in the PAA-HMW/CTAB system. The PAA polymers and PAA/CTAB complexes adsorbed, especially on the clay surface, influenced the primary distribution of the layered sheets but kept the same basal d-spacing. The adsorption of PAA and the PAA/CTAB complexes took place mainly at the plate edges and on the contact space between the sheets. The obtained results will be used for the preparation of the PAA/CTAB/nanoclay composite for water purification.     

Acoustophoretic studies of aqueous suspensions of alumina and 8 mol% yttria stabilised zirconia powders

The iso electric points (IEPS) of four alumina powders and three 8 mol% yttria stabilised zirconia powders were investigated using acoustophoresis to measure the zeta potential as a function of pH. All the powders were characterised by X-ray fluorescence spectroscopy for elemental composition and BET nitrogen adsorption for surface area. Initial experiments revealed that the IEPS of the alumina powders were independent of the volume fraction of the alumina suspensions. Further experiments investigated the effect of adjusting the pH with different bases, i.e. NaOH, KOH, and NH₄OH, on the IEPS of the alumina powders. The IEP of an individual powder was independent of the base used, however, the degree of hysteresis varied depending on the polarisability of the cation. The smallest degree of hysteresis was recorded with additions of NaOH. The differences in IEP between the alumina powders were attributed to the different surface chemistries of the powders. For the zirconia powders the IEP of each suspension was identified using HCl and NaOH to adjust the pH. Again the differences in the IEP were attributed to different surface chemistries of the powders. Two of the powders demonstrated an IEP of approximately 6.5; however the Tosoh powder suspension demonstrated considerable hysteresis and an IEP of 9.3. This was due to its natural pH being an approximate pH unit lower than the other two powders. At this lower natural pH, yttria dissolved out of the Tosoh powder, generating yttrium ions in solution. These precipitated onto the powder surface and altered the surface chemistry with time; i.e increased the zeta potential. Atomic absorption experiments on the supernatant confirmed the dissolution of the yttria from the Tosoh powder.     

pH主导磷在磁铁矿-针铁矿混合相上的吸附

采用废弃贴式取暖物(商业名为热力贴)为原料制得一种吸附剂,通过静态批式实验考查了pH与吸附效果、zeta电位、离子强度等因素间的相互作用规律,探讨了不同pH下该吸附剂去除水中磷酸盐的机理。结果表明,该吸附剂的物相以磁铁矿-针铁矿混合相(magnetite-goethite mix phase,MGM)为主,其对水中磷酸盐的吸附等温线符合Langmuir方程。当温度为25℃,pH=2时,其饱和吸附量达12.57 mg·g^-1。研究还表明,磷在MGM上的吸附受溶液pH主导。pH较低时,内层络合,静电吸引,表面直接沉淀驱动磷的吸附;pH较高时,静电吸引渐变为静电排斥,内层络合减弱,不利于磷的吸附,而内层络合共吸附、表面间接沉淀促进了磷的吸附,但两者作用的综合结果表现为除磷效果下降。     

不同pH环境下CMS改性纳米铁在异质多孔介质中的迁移

纳米铁在污染土壤和地下水的修复中受到广泛关注。为进一步探究其在多孔介质的迁移行为,本研究采用羧甲基淀粉钠（CMS）对纳米零价铁（nZVI）进行包覆,进行了改性纳米零价铁的沉降试验,测量zeta电位与粒径分布探究其分散性;进行了不同pH条件下改性纳米零价铁在酸洗砂与水洗砂的柱实验,分析了化学异质性与pH对纳米铁在多孔介质迁移的影响。结果表明,CMS包覆纳米铁不仅使纳米颗粒本身稳定,而且还减少其在多孔介质表面沉积,大大提高了迁移性。pH=6～8时,nZVI的zeta电位由18.3mV减小到2.9mV,有效粒径由685nm增大到880nm,稳定性变差;而CMS-nZVI的zeta电位值由-19.7mV增大到-53.5mV,颗粒间静电排斥力增强稳定性变好。经能量色散X射线光谱（EDS）分析,水洗砂表面存在碳、铝、铁等氧化物杂质,这些杂质带有正电荷,会增强与带负电的CMS-nZVI的吸附作用,不利于其迁移;而经过酸洗后的石英砂,其表面杂质大大减少,在pH=8时,CMS-nZVI在酸洗砂最大迁移率为77.0%要好于水洗砂的63.0%。此外较高pH环境有助于增加石英砂介质的表面负电荷,减少颗粒与介质的吸附,促进纳米颗粒的迁移。     

Interaction and dispersion stability of alumina suspension with PAA in N,N′-dimethylformamide

The alumina suspension in N,N′-dimethylformamide (DMF) was studied in the presence of a polyacrylic acid (PAA) dispersant. The sedimentation measurements of the suspensions show that PAA can impart favorable dispersion stability to alumina in DMF over a wide apparent pH (pH_a) range. The adsorption of PAA on alumina and the zeta potential of the suspension are pH_a dependent. FTIR-ATR spectroscopic studies reveal that the different interaction mechanisms between PAA and alumina work as a function of pH_a. But the observable difference of dispersion between pH_a values of 2.6–12.7 is small according to the sedimentation experiments. This can be explained by a combination of the static effect of PAA dispersant and different sizes of steric barrier resulting from the configurational variation of PAA with changing pH_a values.     

Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from water using modified pine bark

This paper describes the removal of Cd(II), Pb(II), Cu(II), and Ni(II) ions from aqueous solutions using chemically modified pine barks (Pinus nigra). In this article, effects of chemical modification methods on the adsorption capacity have been investigated. Changes of the surface properties were examined by the FTIR, SEM and zeta potential analyses. HCl, NaOH, Fenton reactive, polymerization, acetone, ethanol, chloroform, tetra ethylene glycol, diethyl ether and glycol were used for modification processes. Maximum adsorption capacities were obtained by modification with NaOH (13-20 mg/g), Fenton (12-17 mg/g) and polymerization (12-16.5 mg/g). These modification processes also decreased Chemical Oxygen Demand of water from 1820 mg/L for raw pine barks to 35 mg/L for NaOH modified barks. Adsorption capacities of adsorbents increased from 2 mg/g to 20 mg/g as a result of modification that accordingly increase adsorbent surface activity.     

Silicon Nitride Colloidal Probe Measurements: Interparticle Forces and the Role of Surface-Segment Interactions in Poly(acrylic acid) Adsorption from Aqueous Solution

Direct measurements of forces between silicon nitride surfaces in the presence of poly(acrylic acid) (PAA) are presented. The force-distance curves were obtained at pH > pH_iep with an atomic force microscopy (AFM) colloidal-probe technique using a novel spherical silicon nitride probe attached to the AFM cantilever. We found that PAA adsorbs onto the negatively charged silicon nitride surface, which results in an increased repulsive surface potential. The steric contribution to the interparticle repulsion is small and the layer conformation remains flat even at high surface potentials or high ionic strength. The general features of the stabilization of ceramic powders with PAA are discussed; we suggest that PAA adsorbs onto silicon nitride by sequential adsorption of neighboring segments ("zipping"), which results in a flat conformation. In contrast, the long-range steric force found in the ZrO₂/PAA system at pH > pH_iep arises because the stretched equilibrium bulk conformation of the highly charged polymer is preserved via the formation of strong, irreversible surface-segment bonds on adsorption.     

Polyamic acid: nanoprecipitation and electrophoretic deposition on porous supports

Polyamic acid (PAA, a precursor of polyimide) was synthesized from 4,4′-oxydiphthalic anhydride and 4,4′-oxydianiline. PAA, dissolved in dimethylsulfoxide (DMSO), was precipitated into colloidal particles after its injection into acetone. The resulting particle size distribution was found to depend on aging time of PAA solutions, their concentration, and the manner in which the solutions were mixed with acetone. PAA particles of any size down to 10 nm appeared to be achievable by decreasing the acetone/DMSO ratio. Particles in DMSO/acetone suspensions were found to have a significant negative zeta potential. Therefore, there was no need to add organic bases to form PAA anions, in contrast to all previously published studies on the PAA electrodeposition. EPD was performed onto porous stainless-steel or alumina disks, which are suitable supports (reinforcements) for membranes. The slow evaporation of DMSO residue yielded dried polymer layers, comprised of 50–100 nm PAA globules. The outer surface of layers was usually covered with a very thin, continuous PAA skin. Such supported PAA layers—after a simple imidization step via a heat treatment—could be applied as thermally resistant membranes for gas separation.     

Electrophoresis of pH‐regulated particles in the presence of multiple ionic species

An electrophoresis model taking account of the pH‐regulated nature of particles and the presence of multiple ionic species is proposed for arbitrary surface potential and double‐layer thickness. It successfully simulated the electrophoretic behavior of Fe₃O₄ nanoparticles in an aqueous NaCl solution with pH adjusted by HCl and NaOH. The estimated zeta potential is compared with those from the conventional models, Smoluchowski's, Hückel's, and Henry's formulas. Due to the violation of the assumption of low and constant surface potential, these formulas yielded appreciable deviations (e.g., 23–30 mV at pH 9). With the surface charge density measured by titration and the zeta potential by electrophoresis, the true surface potential is estimated through a triple‐layer model. The estimated true potential is typically 1.5–10 times larger than the zeta potential, implying that using the latter in relevant calculations (e.g., stability and critical coagulation concentration) might yield appreciable deviation. © 2013 American Institute of Chemical Engineers AIChE J 60: 451–458, 2014     

Extraction of tungsten as polyoxometalate anion using a layered double hydroxide: Selectivity and regeneration

Extraction of tungstate species as highly charged polyoxometalates has been performed with hydrotalcite. An optimum pH around 5 has been determined, correlated with the stability domain of heptatungstate species. Two mechanisms have been shown from in situ infrared spectroscopy and zeta potential measurements: exchange of carbonate ions by heptatungstate species and adsorption as inner-sphere surface complexes. The presence of nitrate, chloride, and sulfate has no effect on the extracted fraction and it was concluded that the extraction is selective toward these anions. The regeneration of the solid was performed with a solution of carbonate sodium at pH 10.     

Synthesis of two novel acenaphthyl-quinoxaline based low-band gap polymers and its electrochromic properties

Dispersion stability and electrokinetic properties of TiO₂ nanoparticles, dispersed in aqueous solution of polyallylamine hydrochloride (PAAm.HCl) and polyvinyl alcohol (PVA) blends was examined. The electrophoresis method was employed to study electrokinetic properties of nanodispersion by varying pH and temperature with an emphasis on dispersion stability. The measurements were performed over a wide range of pH from 2–12 and temperature from 25–65 °C and the isoelectric points (IEPs) of nanodispersions were determined. The concentration of TiO₂ was varied from 2–12 wt%. The dispersions were found to be quite stable (no sedimentation) over a period of two months. The zeta potential of nanodispersions decreases as the pH increases. When temperature increases, a more distinct decrease in the zeta potential was observed. Such behavior may be due to the changes occurring in the linear dimension of adsorbing macromolecules with increasing temperature. As temperatures increases, the adsorption of polymers causes a decrease in the diffuse layer charge, which leads to a decrease in zeta potential. Also, the increase in ionic strength leads to a compression of the diffuse layer and reduction in the zeta potential. The conductivity of nanodispersions increases for all pH and temperatures studied.     

Protein–polymer interaction: Transfer loading at interfacial region of PES-based membrane and BSA

The adsorption of proteins onto polymeric surfaces is encountered in many natural and industrial processes and is a prerequisite to their efficient identification, separation, and purification by methods such as chromatography, and filtration. Nevertheless, the exact nature of the adsorption mechanisms and interfacial interactions is not easy to identify for a given protein–polymer system. Here, we aim to document the adsorption mechanism of a protein–polymer system by investigating the adsorption as well as desorption phenomenon of a protein [bovine serum albumin (BSA)] from the polymeric surface [polyethersulfone (PES)]. The analyses performed to document the adsorption mechanism of the BSA–PES system include scanning electron microscope (SEM), attenuated total reflection-Fourier transform infrared (FTIR), contact angle, zeta potential, surface charge density measurement, and Derjaguin–Landau–Verwey–Overbeek (DLVO). Here, SEM and FTIR identified the physical and chemical properties of pure PES and PES–BSA membranes. The low water contact angle of the PES–BSA membrane confirms its applicability for tissue engineering applications. Further, the zeta potential, surface charge density measurement, and DLVO analyses were performed to document the adsorption mechanism. The adsorption of BSA particles on the PES surface was carried out for pH values that ranged from 4 to 10 for contact times that ranged from 1 to 3 days. A monotonic increase in the zeta potential of the PES–BSA system indicated considerable adsorption of BSA particles on the PES surface. Further, BSA adsorption was very strong for pH values greater than 4.7 which confirms to strong electrostatic interactions between BSA and PES. The strong electrostatic interaction is also collaborated by low desorption rate, which was only ∼22% for pH 10 after 3 days of contact. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47931.     

Effects of poly(acrylic acid) and poly(ethylene oxide) adsorption on the stability of alumina suspension

The effect of adsorbed polymer on the stability of alumina suspension was investigated. Poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA) and similar kinds of polymer salts were used as a dispersant. The amount of polymer adsorbed on alumina surface and the suspension stability was measured. The pH, molecular weight, and concentration were considered as experimental parameters. PEO shows low affinity on the alumina surface while PAA has high affinity. In the case of PAA adsorption, the surface charge change by polymer adsorption influences suspension stability strongly, but not in the case of PEO adsorption. In simultaneous adsorption of PEO and PAA, the PAA concentration was fixed and PEO concentration was varied. The stability of suspension increased with increasing PEO concentration, and this is partly due to the steric stabilization by adsorption of PAA-PEO complex or adsorption of PEO through pre-adsorbed PAA and the depletion effect of non-adsorbed polymer. Suspension adsorbing sodium salts of PAA and poly(methacrylic acid) (PMA) each showed similar stability. But, when the PEO and these kinds of salts were added together to the suspension, the one with PAA sodium salt could keep a higher stability even with lower molecular weights of PEO compared with suspension with PMA sodium salt.     

Aqueous Dispersion and Slip Casting of Boron Carbide Powder: Effect of pH and Oxygen Content

The effect of pH and oxygen content on the zeta potential, viscosity, and casting performance of fine (>3 μm) boron carbide powder is presented. X-ray photoelectron spectroscopy of the powder revealed a surface layer of adsorbed water and oxides of boron and carbon. The soluble boric acid impurity was removed by washing the powder with water or alcohols. Electrophoresis indicated that the B₄C surface was negatively charged in water above pH 1, but the presence of dissolved boric acid suppressed the zeta potential at high pH. Stable, low-viscosity dispersions of >30 vol% solids were prepared and slip cast at pH >6, but boric acid was destabilizing for dispersions prepared above pH 7. The green density of slip-cast parts was more reproducible and about 3% to 5% higher for washed powders than for high-oxygen-content powders.     

Limiting flux in skimmed milk ultrafiltration: impact of electrostatic repulsion due to casein micelles

The variations of the limiting flux during skimmed milk ultrafiltration were studied under various physicochemical environments (pH, ionic strength, chemical nature of added salts). The evolutions were explained taking into account the physicochemical characteristics (size distribution, zeta potential) of the casein micelles, that is the main components of the fouling layer formed at the membrane surface. It was shown than in the pH range from 5.6 to 6.7, the limiting flux was linearly related to the zeta potential of the casein micelles regardless of the way used to obtain the zeta potential variation (addition of HCl, CaCl₂ or NaH₂PO₄): the higher the zeta potential of casein micelles (neutral pH), the greater the limiting flux. Under these operating conditions, the variations of hydrophobic interactions were negligible. The variation of the permeability of the deposit layer, composed of retained casein micelles, was therefore mainly governed by electrostatic interactions due to the casein micelles.     

Surface modification of ilmenite by a novel surfactant dodecyliminodimethylenediphosphoinc acid and its sequent influence on ilmenite floatability

ABSTRACT

In the study, a novel compound of dodecyliminodimethylenediphosphoinc acid was synthesized, and its adsorption mechanism onto ilmenite surface was investigated by zeta potential, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscop (XPS) measurements. The zeta potential measurement results indicated that dodecyliminodimethylenediphosphoinc acid (DDDA) could adsorb onto ilmenite surface, and the optimum pH range for adsorption was 4–8 (similar to the flotation behavior). The FTIR analyses further confirmed that DDDA chemisorbed onto ilmenite surface and formed metal–DDDA complex, rendering the hydrophobic media for flotation. The XPS results provided strong evidences that DDDA species chemisorbed onto ilmenite surface and reacted with Fe ions rather than Ti ions.