• Korean Journal of Mineralogy and Petrology
• /
• v.33 no.3
• /
• pp.143-152
• /
• 2020

Birnessite is a layered manganese oxide mineral with ~7 Å of d-spacing. Because of its high cation exchange capacity, birnessite greatly impacts the chemical compositions of ground water and fluids in sediment pores. Understanding the cation exchange mechanisms requires atomistic investigations of the crystal structures and coordination environments of hydrated cations in the interlayer. In this study, we conducted classical molecular dynamics (MD) simulations, an atomistic simulation method of computational mineralogy, for triclinic Na-birnessite and K-birnessite whose chemical formula are from previous experiments. We report our MD simulation results of the crystal structures, coordination environments of Na⁺ and K⁺, and the polytypes of birnessite and compare them with available experimental results. The simulation results well reproduced experimental lattice parameters and provided atomic level information for the interlayer cation and water molecule sites that are difficult to distinguish in X-ray experiments. We also report that the polytype of the Mn octahedral sheets is identical between Na- and K-birnessite, but the cation positions differ from each other, demonstrating a correlation between the coordination environment of the interlayer cations and the crystal lattice parameters. This study shows that MD simulations are very promising in elucidating ion exchange reactions of birnessite.

• Journal of the Korean Ceramic Society
• /
• v.33 no.8
• /
• pp.909-914
• /
• 1996

In this research [RCOOH]-$\varepsilon$-Caprolactam-Montmorillonite was synthesized by reaction between Na-Mont-morillonite (10-Carboxy-n-decyl)dimethylethylammonium (=RCCOH) ion and $\varepsilon$-Caprolactame-Motmorillonite ob-tained was 3.62$\AA$ After heat treatment of this intercalations complex at 37$^{\circ}C$ in high vacuum for 12 h 24 h, 40 h and 90 h the basal spacing was reduced to 35.8$\AA$, 34.2, 17.5 $\AA$ and 16.6$\AA$ respectively. The calculated amount of free $\varepsilon$-caprolactame included int he intercaltions complex and that of $\varepsilon$-caprolactame which is interca-lated into the interlayer space of montomorillonite and still remained after heat treatment are 4.6~4.9 and 0.5 molecules per unite cell of montmorillonite respectively.

• The Transactions of The Korean Institute of Electrical Engineers
• /
• v.57 no.9
• /
• pp.1572-1578
• /
• 2008

The effect of the organoclay_10A nanoparticles on the DSC and Structural and Dielectrics Properties(1Hz-1MHz) for epoxy/Organoclay_10A Nanocomposites has been studied. Dielectric properties of epoxy-Organoclay nanocomposites were investigated at 1, 3, 5, 7, 9 filler concentration by weight. Epoxy nanocomposites samples were prepared with good dispersion of layered silicate using power ultrasonic method in the particles. As structural analysis, the interlayer spacing have decreased with filled nanoparticles contents increase using power ultrasonic dispersion. The maximum increase interlayered spacing was observed to decease for above 5wt% clay loading. The other hand, as decrease with concentration filler of the layered silicate were increased dispersion degree of nanoparticles in the matrix. The interesting dielectric properties for epoxy based nanocomposites systems are attributed to the large volume fraction of interfacesin the bulk of the material and the ensuring interactions between the charged nanoparticle surface and the epoxy chains.

• Journal of the Korean Ceramic Society
• /
• v.22 no.6
• /
• pp.53-57
• /
• 1985

Korean montmorillonite from Youngil district was characterized by Alkylammonium derivatives. This method was very sensitive to the basal plane spacing d and the charge in the layer charge. The result include the values of average layer charge, charge distribution, equivalent area. interlayer cationic exchange capacity (C, E, C) and total C. E. C.

• Journal of the Mineralogical Society of Korea
• /
• v.15 no.4
• /
• pp.305-314
• /
• 2002

The dehydration of hexadecyltrimethylammonium (HDTMA)-exchanged montmorillonite has been studied using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The dehydration in HDTMA-montmorillonite seems to influence the swelling behavior of the organo-clay during heating. The basal d(001) spacing vs temperature curve of the HDTMA-montmorillonite has one broad swelling edge with a shoulder on the low-temperature side. We believe that the shoulder at $100^{\circ}C$ for the HDTMA-montmorillonite is due to interlayer swelling induced by the initial rearrangement of surfactants, and the second edge at $200^{\circ}C$ is caused by interlayer swelling resulting from the secondary vertical reorientation of alkyl chains. It seems that the dehydration of organo-clay induces a reorientation of the alkyl chains by transition to more vertical position relative to the silicate sheets, allowing instantly greater d-spacing.

• Journal of the Korean Chemical Society
• /
• v.21 no.4
• /
• pp.246-255
• /
• 1977

The adsorption of methylmethacylate on layer silicates containing various interlayer cations has been studied by means of infrared spectroscopy and X-Ray. Several characteristic carbonyl bands of adsorbed methylmethacrylate appeared differently at the region of 1723∼1547$cm^{-1}$depending on the species of cation and the dehydration temperature. The carbonyl stretching band shifted about 190$cm^{-1}$ to lower frequencies has been observed only for polyvalent cations, which has been attributed to $>C=O{\cdot}{\cdot}{\cdot}M^{n+}$ complex formation. The band appeared at 1703∼1640$cm^{-1}$ is responsible for hydrogen bonding between carbonyl oxygen and cationic water or cationic hydroxyl group, and the degree of shift indicates good correlation with the polarizing power of the interlayer cations. However, the band appeared at 1723$cm^{-1}$ has not been correlated with the species of cation but assigned to the carbonyl stretching which reacted with the surface hydroxyl group. On the basis of interlamellar spacing, it is suggested that the molecular plane of MMA molecule is parallel to silicate layers.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.7
• /
• pp.2041-2043
• /
• 2013

A layered perovskite of Dion-Jacobson phase, $RbLaTa_2O_7$, was successfully exfoliated into colloidal suspension via successive ion-exchange and intercalation reaction. The pristine perovskite $RbLaTa_2O_7$ was synthesized by conventional solid-state reaction, and then, it was ion-exchanged with hydrochloric acid to obtain a protonic form of perovskite. The resulting proton-exchanged perovskite was reacted with ethylamine to increase interlayer spaces for further intercalation reaction. Finally, the ethylamine-intercalated form was exfoliated into nanosheets via an intercalation of bulky organic cations (tetrabutylammonium). According to X-ray diffraction (XRD) analysis, the TBA-intercalated form showed remarkably increased interlayer spacing (${\Delta}d$ = 1.67 nm) in comparison with that of the pristine material. Transmission electron microscopic image of exfoliated perovskite clearly revealed that the present exfoliated perovskite were composed of very thin layers. This exfoliated perovskite nanosheets could be applicable as building blocks for fabricating functional nanocomposites.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.29 no.1
• /
• pp.19-23
• /
• 2019

The PMMA (polymethyl methacrylate)/clay nanocomposites were synthesized by in situ radical polymerizations with different clay contents (3 and 7 wt%) using microwave heating. The nanostructure, optical, and thermal properties of the synthesized PMMA/clay nanocomposites were measured by XRD, TEM, AFM, UV-vis, and TGA. It was found that the intercalated- or exfoliated structure of PMMA/clay nanocomposites was strongly dependent on the content of clay. Thus, the imposition of microwave-assisted polymerization facilitated a delamination process of layered silicates to achieve exfoliation state of interlayer distance. The PMMA/3 wt% C10A nanocomposite with well-dispersed and exfoliated clay nano-layers showed the good optical transparency similar to pure PMMA in this study. The thermal decomposition rates of the PMMA/clay nanocomposites become to be lower compared to that of the pure PMMA, indicating the intercalated- or exfoliated inorganic silicate has high thermal stability. A possible reason is that the thermally segmental motion of PMMA polymer into inorganic silicate interlayer spacing has increased the thermal stability of the PMMA/clay nanocomposites.

• Journal of the Mineralogical Society of Korea
• /
• v.30 no.2
• /
• pp.71-81
• /
• 2017

Rock properties and the effects of chemicals that were used for conservation were studied for effective conservation treatment of Seated Buddha rock carving, which is composed of grayish white tuff, at Golguram Hermitage, Gyeongju. The rocks contain 3-5% montmorillonite, a swelling mineral and reacting with water, the d spacing of swelling minerals was increased (1.54-2.69%). On the one hand, the physical properties of the rock samples, such as surface hardness, water absorption rate, and porosity improved after the application of ethyl silicate-based stone strengthener. On the other, the interlayer of swelling minerals decreased and greater the of swelling mineral content, the greater is the extent of swelling (4.23-12.12%). When the ethyl silicate-based stone strengthener was applied after pretreatment with a swelling inhibitor, the physical properties were similar to those of the stone strengthener alone. There was no interlayer spacing change of swelling minerals due to swelling inhibition treatment; however, when the stone strengthener was applied after the swelling inhibitor, interlayer changes were similar to those when only the stone strengthener was treated (4.10-11.85%). Though the peak intensity of swelling minerals in X-ray diffraction pattern decreased, the effect of the swelling inhibitor was almost negligible. Therefore, it is not appropriate to use ethyl silicate-based stone strengthener for Golgulam rock containing swelling minerals and supplementing them with a swelling inhibition system is not effective. Because weathering rapidly progresses when swelling minerals contact moisture, for now, measures to prevent water contact, such as expansion of the canopy, are needed in the lower and side parts of the carving.

• Journal of the Mineralogical Society of Korea
• /
• v.15 no.4
• /
• pp.243-257
• /
• 2002

Ca-type and Na-type bentonites show the great difference of some physicochemical properties. Na exchanged bentonite is mainly used for the foundry and construction materials in domestic utilization. This study tries to identify in detail the differences of some physicochemical properties and thermal properties between Ca-type and Na-type bentonites. Also the adsorption behavior and interlayer expansion for the HDTMA (Hexadecyltrimethylammonium) exchanged and CP (Cetylprydinium) exchanged Ca-type and Na-type bentonites were compared. Na-type bentonite shows the strong alkaline property, high viscosity and swelling compared to Ca-type bentonite. However, two types are very similar for the cation exchange capacity and MB (Methylene Blue) adsorption. The decomposition of adsorbed and interlayer water of Na-type bentonite is caused in the lower temperature than Ca-type bentonite. And Ca-type bentonite shows the decomposition of structural water in the lower temperature than Na-type bentonite. The interlayer expansion of montmorillonite resulted to the intercalation of HDTMA and CP into bentonite is so strongly caused from 12～15 $\AA$ to $40\AA$ (basal spacing). HDTMA-bentonite is almost expanded to $37～38\AA$ when 200% CEC equivalent amount of HDTMA is added, and CP-bentonite is fullly expanded to 40 $\AA$ in the 140% CEC equivalent amount of CP It means that CP causes the stronger interlayer expansion of montmorillonite and easier adsorption than HDTMA. Adsorption behaviors of CP into bentonite is so stable and continuously sorbed in the proportion to the treatment of amount until 200% of the CEC equivalents. CP-bentonite shows the same adsorption behavior regardless of Ca-type or Na-type montmorillonite.