Daab Matthias, Eichstaedt Natalie J, Edenharter Andreas, Rosenfeldt Sabine, Breu Josef
Bavarian Polymer Institute and Department of Chemistry, University of Bayreuth D-95440 Bayreuth Germany
RSC Adv. 2018 Aug 13;8(50):28797-28803. doi: 10.1039/c8ra05318a. eCollection 2018 Aug 7.
To date delamination of organo-clays is restricted to highly charged, vermiculite-type layered silicates (-butylammonium vermiculites) while - counterintuitively - low charged, smectite-type layered silicates do not delaminate although their Coulomb interactions are much weaker. Guided by previous findings, we now identified organo-cations that allowed for extending the delamination of organo clays to charge densities in the regime of low charged smectites as well. Upon intercalation of protonated amino-sugars like -methyl-d-glucamine (meglumine) robust delamination of 2 : 1 layered silicates repulsive osmotic swelling in water is achieved. This process is stable over a wide range of charge densities spanning from smectites (layer charge ∼ 0.3 charges per formula unit SiOF, p.f.u.) to vermiculites ( ∼ 0.7 p.f.u.). It is evidenced that a combination of first, a sufficiently large charge equivalent area (bulkiness) of meglumine with second, a significant hydrophilicity of meglumine leads to swelling above a threshold -spacing of ≳17.5 Å in moist air (98% r.h.). Hereby, electrostatic attraction is critically weakened, causing the onset of repulsive osmotic swelling which leads to utter delamination. Moreover, meglumine renders delamination tolerant to charge heterogeneities typically found in natural and synthetic clays.
迄今为止,有机粘土的分层仅限于高电荷的蛭石型层状硅酸盐(如丁基铵蛭石),而与之相反的是,低电荷的蒙脱石型层状硅酸盐尽管其库仑相互作用要弱得多,但却不会分层。根据先前的研究结果,我们现在确定了一些有机阳离子,它们能够使有机粘土的分层扩展到低电荷蒙脱石范围内的电荷密度。在插入质子化氨基糖(如甲基 - d - 葡甲胺)后,实现了2:1层状硅酸盐在水中的强烈分层和排斥性渗透膨胀。这个过程在从蒙脱石(层电荷约为每式单元SiOF 0.3个电荷,p.f.u.)到蛭石(约0.7 p.f.u.)的广泛电荷密度范围内都是稳定的。有证据表明,首先,甲基 - d - 葡甲胺具有足够大的电荷等效面积(体积),其次,甲基 - d - 葡甲胺具有显著的亲水性,这两者相结合导致在潮湿空气中(相对湿度98%),当层间距超过约17.5 Å的阈值时发生膨胀。由此,静电吸引力被显著削弱,导致排斥性渗透膨胀的开始,进而导致完全分层。此外,甲基 - d - 葡甲胺使分层能够耐受天然和合成粘土中常见的电荷不均匀性。