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• Molecularly designed polymeric inhibitor effectively mitigates silica scaling in solution. • Background salts significantly diminish the efficiency of silica scaling inhibition. • MD simulations elucidate inhibition mechanisms in the presence of background salts. • MD simulations uncover the distinctive role of divalent cations in inhibiting silica scaling. • The effectiveness of inhibitors significantly improves with increasing solution temperatures. High concentrations of dissolved silica in saline industrial wastewaters and brines cause silica scale formation, significantly hampering the efficacy of diverse engineered systems. Applying functional polymers as scale inhibitors in process feedwater is a common strategy to mitigate silica scaling. However, feedwater characteristics often vary widely, depending on the specific processes, making the inhibition of silica scaling challenging and complex. In this study, we systematically investigate the role of ionic composition, specifically ionic strength and divalent ions, and solution temperature, in inhibiting silica scaling using molecularly designed amine/amide polymers. The inhibitor demonstrates effective stabilization of silicic acid, with inhibition efficiency of 74 and 55 % in the absence and presence of 20,000 ppm NaCl, respectively. However, further increasing the ionic strength of oversaturated silicic acid solutions significantly diminishes inhibition performance, rendering it ineffective at 180,000 ppm NaCl. Divalent inorganic cations exhibit a stronger impact on reducing inhibition efficiency compared to sodium ions. Molecular dynamics simulations reveal a competition mechanism between anionic silicic acid reactants (i.e., H 3 SiO 4 −) and chlorides for binding to ammonium groups within the polymeric inhibitor. Additionally, cations form clusters with H 3 SiO 4 − ions, hindering their stabilization with polymeric inhibitor. Notably, at elevated temperatures, the inhibitor achieves near-perfect inhibition for 500 ppm silicic acid solutions. This comprehensive assessment provides important insights into the effectiveness of silica scaling inhibitors under solution conditions relevant to real-world applications, addressing the challenges posed by varying solution parameters in diverse industrial processes. [Display omitted] [ABSTRACT FROM AUTHOR]

Aggregation kinetics and surface charging properties of rod-like sulfated cellulose nanocrystals (CNCs) have been investigated in aqueous suspensions containing monovalent, divalent, or trivalent inorganic salts. Electrophoresis and time-resolved dynamic light scattering (DLS) were used to characterize the surface charge and colloidal stability of the CNCs, respectively. The surface charge and aggregation kinetics of the sulfated CNCs were found to be independent of solution pH (pH range 2–10). For the monovalent salts (CsCl, KCl, NaCl, and LiCl), the critical coagulation concentration (CCC) followed the order of Cs+ < K+ < Na+ < Li+, which follows the direct Hofmeister series, indicating specific interaction of the cations with the CNCs surface. The experimental aggregation kinetics of CNCs were in very good agreement with predictions based on the classic Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. A Hamaker constant of 3.6 × 10−20 J for the CNCs in aqueous medium was derived, for the first time, from the colloidal stability curves with monovalent salts. This value is consistent with a previous value determined by direct force measurements for cellulose surfaces in aqueous solutions. For the divalent salts (MgCl 2 , CaCl 2 , and BaCl 2), the CCC values followed the order Mg2+ > Ca2+ > Ba2+, which is in the reverse order of the counterion ionic size. For the trivalent salts (LaCl 3 , AlCl 3 , and FeCl 3), the CNCs suspension was destabilized much more effectively. The observed complex stability curves with AlCl 3 and FeCl 3 are attributed to charge neutralization and charge reversal imparted by the adsorption of aluminum and ferric hydrolysis species on the CNC surface. The significant charge reversal induced by the ferric hydrolysis species led to the restabilization of suspensions. Our results on the colloidal stability of CNCs are of central importance to the nanotechnology and materials science communities working on various applications of CNCs. [ABSTRACT FROM AUTHOR]

Homoaggregation and heteroaggregation involving amidine and sulfate latex particles in the presence of the anionic surfactant octyl sulfate (OS) is studied by light scattering. This surfactant causes a charge reversal of the amidine particles. This reversal induces a rapid homoaggregation near the charge reversal point. In the presence of the same surfactant, the sulfate particles remain negatively charged and stable. The heteroaggregation process is probed in mixed suspensions of amidine and sulfate latex particles with multi-angle time-resolved dynamic light scattering. This technique allows differentiating between the contributions of homoaggregation and heteroaggregation, and permits to measure the heteroaggregation rate. By optimally choosing the sizes of the particles, one can optimize the contrast and extract heteroaggregation stability ratio over a wide range. The heteroaggregation rate is fast at low OS concentrations, where the two particles are oppositely charged. This rate slows down at higher OS concentrations due to double layer repulsion between the negatively charged particles. However, the onset of this slow heteroaggregation occurs at lower OS concentrations than for homoaggregation. The reason for this shift is that the double layer repulsion between two OS-decorated amidine particles is weaker than between one sulfate particle and one OS-decorated amidine particle. These measurements compare favorably with calculations with the theory by Derjaguin, Landau, Verwey, and Overbeek (DLVO). These calculations suggest that constant potential boundary conditions are more appropriate than the ones of constant charge. In the system studied, the present light scattering technique permits to extract heteroaggregation stability ratios over almost three orders of magnitude. This study is the first of its kind, where such a large range is being probed. [ABSTRACT FROM AUTHOR]

Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions. [ABSTRACT FROM AUTHOR]

Shiftsof the critical coagulation concentration (CCC) in particlesuspensions in salt solutions containing multivalent co-ions and monovalentcounterions are rationalized. One observes that the CCC is inverselyproportional to the valence, and this behavior is referred to as theinverse Schulze–Hardy rule. This dependence is establishedby means of measurements of the stability ratio for positively andnegatively charged latex particles with time-resolved light scattering.The same dependence is equally suggested by calculations of the CCCwith the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, wherebythe full Poisson–Boltzmann equation for the asymmetric electrolyteshas to be used. The latter aspect is essential, since in the caseof multivalent co-ions the surface charge is principally neutralizedby monovalent counterions. This rule complements the classical Schulze–Hardyrule, which applies in the case of multivalent counterions, and statesthat the CCC is inversely proportional to the sixth power of the valence. [ABSTRACT FROM AUTHOR]

• The impacts of humic acid and colloidal particles on gypsum crystallization are investigated. • Humic acid increases the induction time of gypsum crystallization. • Humic acid alters the morphology of formed calcium sulfate crystals. • Colloidal particles may decrease or increase the induction time of gypsum crystallization. Gypsum scaling via crystallization is a major obstacle limiting the applications of membrane-based technologies and heat exchangers in engineered systems. Herein, we perform the first comparative investigation on the impacts of natural organic matter (Suwannee River humic acid, SRHA) and colloidal particles on the gypsum crystallization process in terms of induction time and crystal morphology. Results show that the presence of SRHA significantly increases the induction time of gypsum crystallization. Specifically, at a solution saturation index of 4.92, the induction time increases 6.5-fold in the presence of 6 mg/L SRHA, compared to the case without SRHA. SRHA also alters the morphology of the formed calcium sulfate crystals, resulting in a polygon-like shape, differing from the characteristic needle-like shape of gypsum in the absence of additives. These changes in crystal morphology are attributed to the adsorption of SRHA on the gypsum crystal surface, blocking the active sites for gypsum growth. In contrast, in the presence of colloidal particles, the observed induction time of gypsum crystallization either decreases or increases, depending on the competitive interplay between the enhancement effect in the nucleation step and the inhibition effect in the subsequent crystal growth step. Furthermore, the formed gypsum crystals in the presence of colloidal particles exhibit a needle-like morphology similar to the crystals formed in the absence of any additives. Our study provides fundamental understanding of gypsum crystallization in feedwaters containing natural organic matter and colloidal particles, highlighting the importance of feedwater composition in gypsum scaling. [Display omitted] [ABSTRACT FROM AUTHOR]

Very recently, we report a facile preparation and strong UV-shielding function of poly(ethylene terephthalate) (PET) nanocomposites using 4,4′-diaminostilbene-2,2′-disulfonic acid anion-intercalated layered double hydroxide (LDH_DDA). Herein, the effect of the photofunctional organo anion-intercalated LDH nanoparticles on nonisothermal crystallization kinetics of PET is reported by differential scanning calorimetry technique. First, the nonisothermal crystallization behaviour is discussed by several basic parameters including crystallization peak temperature, relative degree of crystallinity with temperature or time, and half-time of crystallization. Then, Avrami and Jeziorny method, as well as Mo model were applied for the PET/LDH_DDA nanocomposites. Finally, the crystallization activation energy was investigated by Kissinger method and Flynn conversion. The results reveal that the incorporation of LDH_DDA nanoparticles acted as nucleating agent and significantly accelerated the PET nonisothermal crystallization process, whereas had little effect on the three-dimensional growth pattern of spherulites. [ABSTRACT FROM AUTHOR]

Abstract: Ion‐selective optical microsensors based on surface‐modified polystyrene (PS) beads with positively charged lipophilic solvatochromic dye (SD) on the surface were studied with K+ as model ion. Water‐soluble SDs are expelled into the aqueous phase by ion exchange with the cationic analyte of interest, resulting in a detectable color change. In contrast, lipophilic SDs are more attractive, as they appear to remain anchored to the surface after expulsion from the sensing phase. This transfers just the ionic chromophore functionality into the aqueous phase and allows the system to act as a reversible, truly self‐contained sensor. In this work this mechanism was evaluated with ζ‐potential measurements on microsensor suspensions. It indeed provides experimental evidence for the mechanism of SD transfer, as a reversal of the ζ‐potential of the PS microsensors was observed for higher potassium concentrations with valinomycin‐doped microspheres. For a discriminated ion such as sodium, the ζ‐potential change occurs at much higher electrolyte concentrations, in agreement with sensor selectivity. Undoped microspheres showed no apparent dependence of ζ‐potential on electrolyte concentration. The study also shows that the effective range of microsensor surface charge is tunable and depends on the concentration of the SD on the coating phase. [ABSTRACT FROM AUTHOR]