Volume 65 - Issue 6 - December 2017
Article
Molecular Dynamics Simulation of Alkylammonium-Intercalated Vermiculites
- Cheng Chen, Xiandong Liu, Yingchun Zhang, Chi Zhang, Xiancai Lu
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 378-386
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In order to understand the microscopic properties of alkylammonium-intercalated vermiculites, molecular dynamics simulations employing the clayff-CVFF force field were performed to obtain the interlayer structures and dynamics. The layering behavior of alkyl chains was uncovered. With the model used in the present study (1.2 e per unit cell), the alkyl chains formed monolayers with carbon-chain lengths of C6, bilayers from C7 to C10, and pseudo-trimolecular layers from C15 to C18. Intermediate states also existed between bilayer and pseudo-trimolecular layer states from C11 to C14. The ammonium groups had two locations: most ammonium groups were located over the six-member rings (~90%), and the rest above the substitution sites (~10%). The ammonium groups interacted with the vermiculite surface through H bonds between ammonium H atoms and surface O atoms. The ammonium groups were fixed firmly on surfaces and, therefore, had very low mobility. The alkyl chains were slightly more mobile. The similarities and differences between alkylammonium-intercalated vermiculites and smectites were revealed. The layering behaviors of alkyl chains were similar in alkylammonium-intercalated vermiculites and smectites: the alkyl chain behavior was controlled by both the amount of layer charge and the carbon chain length. The distributions of ammonium groups, however, were different, caused by the layer-charge distribution in vermiculites being different from that in smectites. The atomic-level results derived in the present study will be useful for future research into and the applications of organo-vermiculites.
Influence of Montmorillonite Nanoclay Content on the Optical, Thermal, Mechanical, and Barrier Properties of Low-Density Polyethylene
- Nattinee Bumbudsanpharoke, Wooseok Lee, Jae Chun Choi, Se-Jong Park, Meekyung Kim, Seonghyuk Ko
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 387-397
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Although low density polyethylene (LDPE) has long been widely used in packaging applications, some limitations in its use still exist and are due to its relatively poor gas barrier properties and low mechanical strength which can restrict its extensive use for more advanced applications, such as electronic and pharmaceutical packaging. The purpose of this study was to investigate the possibility of using montmorillonite (MMT) nanoclay as a means to enhance the thermal, mechanical, and barrier properties of LDPE prepared via melt extrusion. The level of exfoliated dispersion of the MMT nanoclay in the prepared LDPE-MMT composite was confirmed using transmission electron microscopy (TEM). The relationship between the resulting morphology and the thermal, mechanical, and barrier properties as a function of the MMT content was evaluated. The results showed that incorporating >3 wt.% of MMT nanoclay produced significant changes in the morphology of the LDPE-MMT nanoclay composite in that the segregated matrix adopted an oriented arrangement of exfoliated clay platelets. Thermogravimetric analysis (TGA) showed that the thermal stability of LDPE improved significantly as a result of MMT nanoclay incorporation. Furthermore, differential scanning calorimetry (DSC) analysis indicated that increasing clay content above 3 wt.% effectively reduces the crystallinity of LDPE-MMT composites through the suppression effect. The tensile strength of LDPE increased gradually with an increased content of MMT nanoclay and the maximum value of 16.89 N/mm2 was obtained at 10 wt.% MMT content. This value represents a 40.87% increase relative to the tensile strength of the pristine LDPE. Barrier properties of LDPE and LDPE-MMT nanoclay composites were assessed by examining the permeability with respect to oxygen and water vapor. As the content of MMT nanoclay was increased to 10 wt.%, the permeability of the nanocomposite films to oxygen and water vapor notably decreased to 42.8% and 26.2%, respectively.
Molecular Simulation Study on the Interaction of Nanoparticles with Clay Minerals: C60 on Surfaces of Pyrophyllite and Kaolinite
- Huijun Zhou, Meng Chen, Lifang Zhu, Lin Li, Runliang Zhu, Hongping He
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 398-409
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Buckminsterfullerene (C60) is one of the most important carbon-based nanoparticles (CNPs). Industrial-scale production of C60 has reached the level of tons; release to the environment has been confirmed (Tremblay, 2002; Qiao et al., 2007). The present study was devoted to study of the effect of clay minerals on the migration process of C60. Molecular dynamics (MD) simulations were used to study the interaction of CNPS with clay minerals through study of the adsorption of C60 on various surfaces of kaolinite and pyrophyllite in vacuum and aqueous environments. Two kinds of surfaces, hydrophobic siloxane surfaces and hydrophilic hydroxyl surfaces, were investigated. C60 is mainly adsorbed onto the vacancy of the six-membered ring, composed of SiO4 tetrahedra or AlO6 octahedra, on clay-mineral surfaces. A single adsorption layer consisting of C60 molecules with an ordered hexagonal arrangement is presented for all surfaces in vacuum. In aqueous environments, however, the monolayer appears on the siloxane surfaces only, while a cluster of C60 molecules is formed on the hydroxyl surfaces. Free energies prove that the attachment of two C60 molecules is stronger than the adsorption of C60 onto the hydroxyl surface in water, which is the reason for unfavorable formation of C60 monolayer. On the other hand, the adsorption free energy is more negative on the hydrophobic siloxane surface, explaining the monolayer formation. The existence of water, which forms hydration layers on the surfaces of clay minerals, produces energy barriers, and reduces the adsorption affinity to some extent. Because clay minerals act as geosorbents in the environment, the present study is significant in terms of understanding the migration and fate of CNPS in nature.
The Effects of Biogeochemical Modification of Fe-Rich Smectite on the Fate of Pb
- Tae-hee Koo, Jee-young Kim, Jong-woo Choi, Jin-wook Kim
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 410-416
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Fe-rich smectite is ubiquitous in soil environments and closely linked to the fate and mobility of hazardous trace metals and particularly to the variations in the biogeochemical redox reactions of structural Fe that determine the sorption and desorption properties of clay minerals. The biotic/abiotic redox reactions of a Fe-rich smectite, nontronite (NAu-1), were performed at various reaction times using the Fe-reducing bacterium Shewanella oneidensis MR-1 at 30°C and Na-dithionite (Na2S2O4), respectively. The extent of biotic Fe-reduction of NAu-1 after 30 days of incubation reached up to 10.7% of total Fe and the range of abiotic Fe-reduction varied from 4.9–46.6% at reaction times of 5 min, 30 min, 1 h, and 4 h. The biotically and abiotically Fe-reduced NAu-1 samples were spiked with Pb concentrations of 0.07, 0.2, 0.5, and 1.0 mg/kg and incubated under aerobic or anaerobic conditions for 24 h.
The amounts of Pb in the supernatants were analyzed using an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) and Multi-collector (MC)-ICP-MS. The amounts of Pb removed from the supernatants were negatively related to the extent of Fe(III) reduction in the abiotically Fe-reduced NAu-1 samples. In contrast, less Pb (~15%) was removed from the biotically Fe-reduced NAu-1 samples with a similar extent of Fe(III) reduction. Changes in the isotopic 208/204Pb ratio indicated that the lighter 204Pb isotope was preferentially adsorbed to the NAu-1 samples with less Fe reduction and indicated that variations in the net layer charge affected isotopic fractionation. Significant differences in the 208/204Pb ratios for NAu-1 samples that were biotically Fe-reduced under anaerobic conditions were measured and indicate that the reversibility of the structural/chemical modifications that occur under redox conditions can affect Pb removal and, thus, isotope fractionation. These results collectively infer that the biogeochemical properties of clay minerals should be considered in order to understand the fate of trace metals in natural environments.
Preparation of Organo-Montmorillonites and the Relationship Between Microstructure and Swellability
- Wei Hua Yu, Ting Ting Zhu, Dong Shen Tong, Min Wang, Qi Qi Wu, Chun Hui Zhou
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 417-430
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Hydrophobicity, swellability, and dispersion are important properties for organo-montmorillonites (OMnt) and have yet to be fully characterized for all OMnt configurations. The purpose of the present work was to examine the preparation of OMnt from the reaction of Ca2+-montmorillonite (Ca2+-Mnt) with a high concentration of surfactant and to reveal the relevant properties of hydrophobicity and dispersion of the resultant OMnt. A series of OMnt samples were prepared using a small amount of water and cetyltrimethylammonium bromide (CTAB) with a concentration more than the CTAB critical micelle concentration (CMC). The relationship between OMnt microstructure and the hydrophobicity and swellability properties was investigated in detail. The resulting OMnt samples were characterized using powder X-ray diffraction patterns (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric and differential thermogravimetry (TG-DTG), water contact angle tests, swelling indices, and transmission electron microscopy (TEM). The addition of CTAB and water in the OMnt preparation affected the OMnt microstructure and properties. An increase in CTAB concentration led to a more ordered arrangement of cetyltrimethylammonium (CTA+) cations in the interlayer space of the OMnt and a large amount of CTA+ cations on the outer surfaces of the OMnt. The swelling indices and the water contact angles of OMnt samples depended on the distribution of the CTAB surfactant on OMnt and the orientation of the surfactant hydrophilic groups on the inner and on the outer surfaces of OMnt. A maximum swelling index of 39 mL/g in xylene was achieved with an average water contact angle of 62.0° ± 2.0° when the amount of CTAB added was 2 times the cation exchange capacity (CEC) of Mnt and the lowest water to dry Mnt mass ratio was 3 during the preparation of OMnt samples. The platelets of OMnt aggregated together in xylene by electrostatic attraction and by hydrophobic interactions.
An Experimental Study on Transforming Montmorillonite to Glauconite: Implications for the Process of Glauconitization
- Xiaoke Zhang, Yuanfeng Cai, Dongmei Jiang, Yang Zhang, Yuguan Pan, Lijuan Bai
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 431-448
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The objective of this study was to explore the geological origin of glauconite, which is believed to precipitate and mature very slowly (~1 Myr) in neritic environments (shallow water, oceanic coastal zones, at water depths of 100–200 m) with very low sedimentation rates. A series of simulation experiments was designed and carried out in sealed tubes placed in an oven and heated to a constant temperature of 50°C (±2°C) for 60 or 150 d. The parent materials used for these experiments were two low-Fe montmorillonites with different crystallinities. The montmorillonites were introduced to solutions with concentrations of 0.02–0.1 mol/L Fe3+ and 0.05–0.2 mol/L K+ with various values of pH and Eh. The products were analyzed using X-ray powder diffraction (XRD), Fourier-transform infrared (FTIR) spectrometry, electron spin resonance (ESR) spectrometry, scanning electron microscopy (SEM), and Mössbauer spectroscopy. The morphological changes from parent material to product were observed under SEM, which revealed the formation of a flaky mineral (e.g. a product formed in the interstitial spaces between montmorillonite crystals). The formation of a flaky mineral indicates that the product is a layer silicate. Qualitative analysis of XRD patterns revealed that the main product phase was a mica group mineral and the d060 value was consistent with the presence of glauconite (0.152 nm) and/or Fe-illite (0.150 nm). A glauconite and Fe-illite mineral assemblage formed in a weakly acidic solution, while Fe-illite, mixed-layer Fe-illite, and montmorillonite formed in neutral and alkaline solutions. Stretching vibrations of Fe(III)Fe(III)OH-AlFe(II)OH and/or MgFe(III)OH were observed in FTIR spectra (3550–3562 cm−1) of the products formed in acidic solutions, which along with the g = 1.978 ESR signal indicated that Fe(III) entered octahedral positions in the tetrahedral/octahedral/tetrahedral layer (TOT) platelets. The AlFe(II)OH-MgFe(III)OH (3550–3562 cm−1) and AlFe(III)OH (870 cm−1) vibrations were only observed in products formed in neutral and alkaline solutions. Analysis of the Mössbauer spectra showed that Fe(III) substituted for Al and Mg in the cis octahedral sites of montmorillonite. The simulation experiments demonstrated that the pH and redox conditions (Eh) of the environment controlled the nature of the product mineral species. Results of the present study revealed that glauconitization and illitization occurred under different conditions, where glauconitization preferentially occurred in an acidic environment and illitization preferentially occurred in a nearly neutral to alkaline environment.