Sáringer Szilárd, Rouster Paul, Szilágyi István
Institute of Condensed Matter and Nanosciences-Bio and Soft Matter , Université Catholique de Louvain , B-1348 Louvain-la-Neuve , Belgium.
Langmuir. 2019 Apr 9;35(14):4986-4994. doi: 10.1021/acs.langmuir.9b00242. Epub 2019 Mar 27.
Charging and aggregation processes of titania nanosheets (TNS) were extensively studied in the presence of oppositely charged or like-charged polyelectrolytes in aqueous dispersions. The surface charge of the TNS was systematically varied by the pH; therefore, positive nanosheets were obtained at pH 4 and negative ones at pH 10. Strong adsorption of poly(styrene sulfonate) (PSS) of high negative line charge density on the TNS was observed at pH 4, leading to charge neutralization and reversal of the original sign of charge of the nanosheets. The adsorption of like-charged poly(diallyldimethylammonium chloride) (PDADMAC) was also feasible through a hydrophobic interaction. The predominating interparticle forces were mainly of the DLVO-type, but additional patch-charge attraction also took place in the case of PSS at low surface coverage. The TNS was found to be hydrophilic at pH 10 and no adsorption of like-charged PSS was possible because of strong electrostatic repulsion between the polyelectrolyte and the surface. The PDADMAC showed high affinity to the oppositely charged TNS surface in alkaline dispersions, giving rise to neutral and positively charged nanosheets at appropriate polyelectrolyte doses. Formation of a saturated PDADMAC layer on the TNS led to high resistance against salt-induced aggregation through the electrosteric stabilization mechanism. These results shed light on the importance of polyelectrolyte concentration, ionic strength, and charge balance on the colloidal stability of TNS, which is especially important in applications, where the nanosheets are dispersed in complex solution containing polymeric compounds and electrolytes.
在水性分散体系中,在带相反电荷或相同电荷的聚电解质存在下,对二氧化钛纳米片(TNS)的充电和聚集过程进行了广泛研究。TNS的表面电荷通过pH值系统地变化;因此,在pH 4时获得正电荷纳米片,在pH 10时获得负电荷纳米片。在pH 4时观察到高负线电荷密度的聚(苯乙烯磺酸盐)(PSS)在TNS上的强烈吸附,导致电荷中和并使纳米片的原始电荷符号反转。通过疏水相互作用,带相同电荷的聚(二烯丙基二甲基氯化铵)(PDADMAC)的吸附也是可行的。主要的颗粒间作用力主要是DLVO型,但在低表面覆盖率的PSS情况下也会发生额外的补丁电荷吸引。发现在pH 10时TNS是亲水的,由于聚电解质和表面之间的强烈静电排斥,不可能吸附带相同电荷的PSS。在碱性分散体系中,PDADMAC对带相反电荷的TNS表面表现出高亲和力,在适当的聚电解质剂量下产生中性和带正电荷的纳米片。在TNS上形成饱和的PDADMAC层通过电空间稳定机制导致对盐诱导聚集的高抗性。这些结果揭示了聚电解质浓度、离子强度和电荷平衡对TNS胶体稳定性的重要性,这在纳米片分散在含有聚合物化合物和电解质的复杂溶液中的应用中尤为重要。