Solid-State Nuclear Magnetic Resonance Spectroscopy on Synthetic Ammonium/Aluminum-Saponites

Kloprogge, J. Theo; Breukelaar, Johan; Wilson, A.E.; Geus, J.W.; Jansen, J. Ben H.

doi:10.1346/ccmn.1994.0420406

Cited by 26 publications

(28 citation statements)

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“…For this reason, different methods have been developed to prepare synthetic saponites with well-controlled chemical composition and property (Farmer et al 1991(Farmer et al , 1994Kloprogge et al 1993Kloprogge et al , 1994aKloprogge et al , 1994bVogels et al 1997Vogels et al , 2005bKawi and Yao 1999;Yao et al 2005;Higashi et al 2007;Bisio et al 2008;Vicente et al 2010;Xue and Pinnavaia 2010). For instance, Farmer et al (1991Farmer et al ( , 1994 synthesized well-formed saponite in hydrazine-water mixtures and found that the presence of Fe 2+ in a calcareous environment may promote the formation of saponite.…”

Section: +mentioning

confidence: 99%

“…In this respect, Kloprogge and co-workers have conducted a series of investigations during the last two decades, by using a combination of various characterization techniques (Kloprogge et al 1993(Kloprogge et al , 1994a(Kloprogge et al , 1994bVogels et al 1997Vogels et al , 2005b. Al ions could occupy both tetrahedral and octahedral sites and the Al(IV)/ Al(VI) ratio increased with increasing synthesis temperature (Kloprogge et al 1994a(Kloprogge et al 1994b.…”

Section: +mentioning

confidence: 99%

“…Al ions could occupy both tetrahedral and octahedral sites and the Al(IV)/ Al(VI) ratio increased with increasing synthesis temperature (Kloprogge et al 1994a(Kloprogge et al 1994b. A muscovite substitution (2Al 3+ + vacancy → 3Mg 2+ ) was proposed for the substitution of Al 3+ for Mg 2+ in the octahedral sheet of synthetic saponites (Vogels et al 2005b).…”

Section: +mentioning

confidence: 99%

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Aluminum ion occupancy in the structure of synthetic saponites: Effect on crystallinity

He¹,

Li²,

Tao³

et al. 2014

American Mineralogist

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Two series of saponites with fixed (Si+Al)/Mg and Si/Mg ratios, respectively, were synthesized by using hydrothermal methods. The obtained products were characterized by XRD, XRF, 27 Al, and 29 Si MAS NMR, SEM, and TEM. XRD patterns showed that well-ordered saponites were obtained in the initial Si/Al ratio range of 5. 43-7.89. Beyond this Si/Al ratio range, poorly crystallized saponites were obtained with small crystallized particles, which can be seen from TEM images. When intercalating saponite with surfactant, the intercalated products displayed strong and well-ordered (00l) reflections, indicating that layered saponite has been successfully synthesized in the present study. 27Al MAS NMR spectra demonstrated that well-crystallized synthetic saponites had a higher Al(IV)/Al(VI) ratio than the poorly crystallized samples, which is an important factor affecting the crystallinity of synthetic saponite. A one-to-one substitution (i.e., 1 Al 3+ → 1 Mg 2+) actually occurred in the octahedral sheet and this substitution had a negative effect on the crystallinity of the synthetic saponites. After grafting the synthetic saponites with silane, the decreased intensity of the 29 Si NMR signal at -86 ppm and the increased intensity of Q 3 Si(0Al) and Q 3 Si(1Al) signals strongly suggested that the signal at ca. -86 ppm corresponded to Q 2 Si at the layer edges of saponite.

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confidence: 99%

Section: +mentioning

confidence: 99%

Section: +mentioning

confidence: 99%

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Aluminum ion occupancy in the structure of synthetic saponites: Effect on crystallinity

He¹,

Li²,

Tao³

et al. 2014

American Mineralogist

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“…The range of different sites for Mg 2+ and A13+ prevents control of the composition and the layer charge of the composites during synthesis as demonstrated by Kloprogge et al (1993aKloprogge et al ( , 1994aKloprogge et al ( , 1994b and Vogels et al (1995). Harder (1972) claimed to have synthesized trioctahedral smectite (i.e., saponite) from Mg-containing Al(OH)3-silica precipitates at 20~…”

Section: Saponitementioning

confidence: 99%

“…Even in monometallic systems (e.g., Fe) a wide range of hydroxide, oxide, or oxyhydroxide Neumann (1971Neumann ( , 1972, Neumann and Sansom (1976) Torii et al (1983), Torii (1985, Iwasaki (1986, 1987) Roy (1963a, 1963b) 800~ 24 h; 850~ 2 Li-fluorhectorite, h Na~CO3, Li2CO 3 silica sand, MgO, 925~ Na2CO3, Na2SiF6 Mg-, AI-, Na-nitrates, Sil-mostly -<575~ and 1 saponite ica sol (Ludox) kbar, some syntheses at 600-900~ or > 1 kbar quartz, Li2SiO3, fluoramphiboles fluorhectorite Hickson (1974Hickson ( , 1975 hydrous silica sol, AI(OH)3, Mg(OH)2 NH4OH or NH4F Granquist (1966), Kuchta hydrous oxides of Si, A1, and Fajnor (1988) Mg, and Na Cohen et aL (1980) igneous rocks Suquet et al (1977Suquet et al ( , 1981aSuquet et al ( , 1981b, Hamilton and Henderson (1968), Booij (1992) Breukelaar et aL (1989, Kloprogge et al (1993aKloprogge et al ( , 1994aKloprogge et al ( , 1994b Noll (1936) kaolin, H4SiO4, Na-, K-, Ca-hydroxides Sand et al (1953Sand et al ( , 1957 Eberl and Hower (1977), Eberl (1978) De Kimpe (1976) Granquist (1966), Capell and Granquist (1966), Jaffe (1974), Gaaf et al (1983, R6bschl~i-ger et al (1984R6bschl~i-ger et al ( ), van Santen et al (1985, Heinerman (1985) Komarneni and Roy (1983), Komarneni and Breval (1985…”

Section: Synthetic Approachesmentioning

confidence: 99%

Synthesis of Smectite Clay Minerals: A Critical Review

Kloprogge

Komarneni

Amonette

1999

Clays and clay miner.

318

153

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Abstract--Smectites are one of the most important groups of phyllositicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature (< 100~(2) under moderate hydrothermal conditions (100-1000~ pressures to several kbars), (3) under extreme hydrothermal conditions (>1000~ or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrothermal conditions are the most numerous and the most successful in terms of smectite yield and phasepurity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The presence of Mg 2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temperatures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from underand over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermodynamically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.

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Nuclear Magnetic Resonance of Geological Materials and Glasses

Moran

Howe

2000

Encyclopedia of Analytical Chemistry

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This article concerns the application of nuclear magnetic resonance (NMR) spectroscopic techniques to the analysis of geological materials and glasses. It includes inorganic minerals and glasses, but does not cover soils and clay minerals to any extent. The first part presents an overview of solid‐state NMR experiments applicable to inorganic solids. The range of nuclei accessible by NMR and the particular requirements for obtaining good spectra of more difficult nuclei, including quadrupolar nuclei, are discussed. The experimental conditions under which solid‐state NMR can provide quantitative analytical measurements are also considered. NMR spectroscopy provides element‐specific speciation and structural information including coordination environment and bond distances. It is particularly valuable for the analysis of amorphous and partially crystalline materials not amenable to structure determination by X‐ray diffraction. NMR can detect and quantify materials containing multiple phases and can be used for in situ monitoring of phase transitions. It provides qualitative and quantitative speciation information for framework nuclei in glasses and is also capable of characterizing the dynamic behavior of mobile ions and solvent through relaxation, diffusion and chemical exchange experiments. Thus it has become an important technique for the study of hydrous minerals and gels and for ion‐conducting glasses. The sensitivity of NMR varies considerably, depending on the nucleus observed, its abundance and its chemical environment. NMR sensitivities and detection limits cannot compete with elemental analytical techniques such as X‐ray fluorescence. In addition, quantitation in solids requires careful control of experimental parameters and careful calibration to avoid artifacts. However, the selectivity of NMR as an analytical technique is unsurpassed and the development of specialist pulse sequences to measure specific local interactions in solids makes it particularly well suited to the analysis of geological materials and glasses. NMR imaging enables structural information to be resolved in three dimensions, although resolution in solid‐state imaging is limited to tens of micrometers at best owing to the broader line widths and lower signal‐to‐noise ratios compared with liquids. However, capabilities in this field are being extended all the time and the application of NMR imaging techniques in materials analysis is expanding steadily. An alternative to conventional imaging is NMR force microscopy, which shows potential for surface mapping at higher resolutions. The applications section is organized on the basis of the materials being analyzed. Within each section, NMR techniques are classified according to the observed nuclei. The emphasis is on more recent applications and on developments leading to enhanced resolution and sensitivity. Silicates and aluminosilicates represent the largest class of applications, followed by phosphate, borate and other oxide glasses. Sol–gel materials and the reactions leading to gel formation are also discussed, as are hydrous materials more generally. The other important areas of application reviewed are minerals, ceramics, high‐temperature melts and ion‐conducting glasses. Finally, the applications of NMR imaging in this field, although sparse at present, are potentially very great. This is illustrated by two major areas of application to date, namely the imaging of bone minerals and cement and concrete.

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Solid-State Nuclear Magnetic Resonance Spectroscopy on Synthetic Ammonium/Aluminum-Saponites

Cited by 26 publications

References 10 publications

Aluminum ion occupancy in the structure of synthetic saponites: Effect on crystallinity

Aluminum ion occupancy in the structure of synthetic saponites: Effect on crystallinity

Synthesis of Smectite Clay Minerals: A Critical Review

Nuclear Magnetic Resonance of Geological Materials and Glasses

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