The Christiansen effect appears in the i.r. spectrum of powders embedded in a solid, liquid or air matrix as an apparently anomalous transmittance (Christiansen peak) of the incident electromagnetic radiations. The peak appears at wavelengths for which the refractive index of the sample and the refractive index of the matrix are equal (Christiansen wavelength: λChr).

On account of the great variation of the sample refractive index in the immediate neighborhood of the absorption bands (anomalous dispersion curve), one often observes the occurrence of a transmittance peak or of a band deformation in this spectral range. A change in the position of this transmission peak with the value of the matrix refractive index is indicative of the Christiansen effect.

The equality of the refractive indices of the sample and of the matrix for μChr has been used to determine some points of the anomalous dispersion curve in the neighborhood of the hydroxyl stretching band (3678 cm−1).

Spectral distortions caused by the Christiansen effect can be reduced by preparing the sample in such a manner that the width at half-maximum (Δν1/2) of the Christiansen peak is several times greater than this of the absorption band itself. Clarke’s theoretical formula, which gives an estimation of Δν1/2, has been qualitatively verified and thus gives an appropriate guide in the choice of the parameters which one can optimize during the sample preparation. One can reduce the Christiansen effect spectral modifications, without running the risk of modifying the sample itself, particularly by overly severe grinding.

The migration of small cations into the empty octahedral sites of dioctahedral clays allows one to study the local effects in the trioctahedral structure and the consequences of the exchange capacity decrease on the solvation properties. The results concern essentially the montmorillonite saturated by lithium. Computations based on a point charge model shows the necessity for the OH groups to undergo a reorientation when the lithium ions are within the octahedral sites. This change of orientation was studied by i.r. spectroscopy which permits one to estimate the amounts of lithium present in the structure. By analogy with i.r. results obtained for the Li, Mg, Ca and K montmorillonites, one can say that the non-exchangeable lithium which is not within the octahedral sites must be in the bottom of the hexagonal cavities. Moreover, it is shown that the solvation properties of the clay depend on the number of exchangeable cations and on the nature of the solvent. The clay does not swell with water when the amount of exchangeable cation is lower than 50 per cent of the exchange capacity. This limit is 30 per cent with glycerol, and 20 per cent with ethylene glycol.

Infrared (IR) spectra in the fundamental and near-IR regions were obtained for Na-saturated Wyoming montmorillonite and reduced-charge Na/Li-saturated Wyoming montmorillonites hydrated under water vapor at 50% RH and dehydrated under vacuum. For the Na-montmorillonite, changes in the intensities of the structural OH-bending modes, particularly that of the MgAlOH group, were observed as the clay was dehydrated. This result was interpreted as evidence that exchangeable Na ions lose solvation water and settle into the ditrigonal cavities on the clay surface as it becomes desiccated. For the Na/Li-montmorillonites, the structural OH-bending modes also decreased in IR intensity because of Li+ migration into the octahedral sheet. The fundamental IR spectra of D2O adsorbed by the montmorillonites showed characteristic absorptions at 2685, 2510, 2400, and 1205 cm-1 that decreased in intensity proportionally to the cation-exchange capacity. This result, along with corroborating data from X-ray powder diffractograms and from near-IR diffuse reflectance spectra of H2O adsorbed by the clays, suggest that the exchangeable cations on Na-montmorillonite dissociated from the clay surface as it hydrated and played a significant role in organizing the structure of adsorbed water at low water contents.

The characterization of cations associated with clay materials has generally been approached by the sequential use of specific chemical reagents. To avoid the disturbing effect of the chemical reagents on the state and location of compensating cations of clays and to get information in situ, far-infrared spectroscopy was used. The far-infrared vibrational spectra of the potassium cation in muscovite, phlogopite, and biotite were recorded before and after heating at the dehydroxylation temperature. The vibrational frequency of K in micas before dehydroxylation was found to be a function of the di- or trioctahedral character and of the Fe content. After dehydroxylation or deprotonation, shifts of the K absorption band to lower frequencies were observed for the heated muscovite, in which K exchangeability increased, and to higher frequencies for the heated biotite, in which K exchangeability decreased. These results suggest that the vibrational frequency of potassium is characteristic of the state of K in these minerals and of its ability to be exchanged.

The resolution of the infrared spectra of structural OH in kaolin-group minerals increases with decreasing temperature. Poorly crystalline kaolinite gives typical infrared spectra, which suggest the existence of kaolinite-, dickite-, and nacrite-like configurations. The relative amount dickite- and nacrite-like configurations compared with kaolinite-like configurations increases with decreasing crystallinity. Low-temperature infrared spectroscopy is a more sensitive means of estimating the degree of order of poorly crystalline kaolinite than is X-ray powder diffraction.

To identify the far-infrared (FIR) absorption bands related to K cations in micas, spectra of muscovite, phlogopite, and biotite were compared with the spectra of pyrophyllite and talc, which have no compensating cations, and to the spectra of micas in which K is substituted by mono- and divalent cations. Dichroic experiments using single crystals of these micas showed that some of the bands or components related to K have a strong in-plane and out-of-plane dichroic character. These experimental data led to the assignment of the FIR bands at 110, 91, and 83 cm−1 for muscovite, phlogopite, and biotite, respectively, which have no in-plane and out-of-plane dichroic character, to the vibration of the double ring of oxygen atoms that constitutes the cage in which K is located (mode III).

Bands at 146, 136, and 152 cm−1 for muscovite, phlogopite, and biotite, respectively, which have a strong out-of-plane dichroic character, were assigned to the out-of-plane vibrations of K atoms (mode IV). Some of the components at 190, 158–153, and 145–124 cm−1 for muscovite, phlogopite, and biotite, respectively, which have a strong in-plane dichroic character, are possibly related to the in-plane vibrations of K atoms (modes I and II). The 165-cm−1 band of muscovite is a lattice mode of vibration. Frequencies of modes III and IV of the compensating cations of micas in which K was substituted by mono- and divalent cations exchanged as a function of $\sqrt{Z/m}$ where Z is the charge and m the mass of the cation. Modes III and IV were well resolved and very sensitive to the crystallochemical properties of the structure (di- or trioctahedral character, Fe content, etc.). FIR spectroscopy may therefore be an important tool that uses compensating cations as probes to study the interactions between the cations and the structure of mica minerals.

The application of the Frenkel-Halsey-Hill (FHH) formalism to the water desorption isotherms obtained for the whole range of the activity of water with the pressure membrane device (0.98 < aw < 1) and with the desiccator (0 < aw < 0.98) gives information concerning the nature and the relative importance of the 2 mechanisms involved in the dehydration—hydration processes: adsorption and capillary condensation. The state and location of water are described in each domain. An equation that gives the thickness t of the film of water adsorbed on the walls of pores versus the activity of water is developed. This t-curve is used to get, from the desorption isotherm, the pore size distribution curve of the studied hydrated materials. Then concepts of surface and fabric of clay pastes are discussed as a function of hydration and a mechanism is proposed to explain swelling and shrinkage of finely divided materials. Three kinds of surfaces, related to the aggregate fabric, are defined as a function of their capacity to adsorb water. Each kind of surface is determined by a specific technique: the total surface area (St) by ethylene glycol adsorption, the external surface area of particles (Ss) by nitrogen adsorption and the external surface area of aggregates (Se) by hydraulic conductivity measurements. As a consequence it is only with completely dispersed clays that swelling is a function of St. With unwell-dispersed clays, water adsorption, which induces swelling, successively occurs on St, Ss and Se surfaces.

We report the first application of 39K solid-state NMR to the study of tecto- and phyllosilicates. Under high field (11.7 Tesla) and with the application of a spin-echo sequence, informative 39K spectra can be obtained for several compounds of interest to the geologist and the agronomist. Tectosilicates and phyllosilicates can be distinguished from the uncorrected frequency (δCG) of the observed NMR peak. A series of montmorillonites submitted to increasing numbers of wetting and drying cycles was studied in order to discriminate between mobile and “fixed” forms of K+: when the spectra are run on hydrated samples, two different signals are observed corresponding to K+ in different hydration states, and NMR data can be correlated with the amount of exchangeable K+ measured by ion exchange. Thus, it appears that NMR can provide useful information on K fixation complementary to classical chemical methods.

To assign far infrared (FIR) absorption bands of K+ in muscovite, dichroic experiments were performed. For a muscovite crystal rotated about a crystallographic axis, c*, a, or b, two bands corresponding to vibration modes of K+ appear, respectively, at 107 and 110 cm−1 (rotation about c*), 107 and 143 cm−1 (rotation about a), and 110 and 143 cm−1 (rotation about b). Two in-plane modes at 107 and 110 cm−1 and one out-of-plane mode at 143 cm−1 are identified for the vibrations of K+ in muscovite. Each of these transition moments are near the crystallographic axes b, a, and c, respectively. These observations match well predictions based on the approximate C3i symmetric environment of K+, although the site symmetry in the space group of muscovite is only C2.

To get a better understanding of the mechanisms of selective retention of cations by clay minerals, we have studied the physicochemical state and the location of immobilized cations. The approach developed is based on the concomitant study of the exchange isotherms and the compensating cations/clay structure interactions, using far infrared (FIR) spectroscopy. For that, cations are used as spectroscopic probes to characterize the selective sites.

Exchanged K, Rb-, K, Cs-, K, NH4- and NH4, Cs-Llano vermiculite samples were prepared. The exchange isotherms illustrate the higher selectivity of Llano vermiculite in the following order: K+ < Rb+ < Cs+. Desorption experiments show that a 2 N MgCl2 solution can extract a small fraction of immobilized Cs+. The concomitant analyses of the exchange phenomena at microscopic (X-ray diffraction) and molecular (far and middle IR spectroscopy) levels show that: (1) only ∼65% of the interlamellar hydrated Mg2+ of Llano vermiculite is exchanged; (2) cations are randomly distributed in the interlamellar spaces; and (3) retention is strongly related to the distance between compensating cations and oxygen atoms of the ditrigonal cavity.

The low hydration energy of selectively retained cations induces strong cation/clay interactions, which give FIR absorption bands of compensating cations. The FIR absorption bands of smaller cations shift towards lower wavenumbers when the proportion of the larger cations increases, whereas the wavenumber of the larger ones is constant. This reproducible scenario shows that larger cations act as wedges and expand layers, thus increasing the distance between the smaller cations and the layers. Calculation of the distances dM-O inner and dM-O outer shows that selectively-retained cations are six-coordinated in these dehydrated systems. The decrease of the difference between dM-O outer and dM-O inner from K+ to Cs+ may explain the observed selectivity of Llano vermiculite.

All the exchange isotherms of Na+ or Ca2+ in vermiculite for K+, Rb+ or Cs+ show two kinds of exchanges sites: the first corresponds to sites located in phlogopite-like interlamellar spaces and the second to sites located in smectite-like interlamellar spaces. During the exchange, three mineralogical phases are formed: Na- or Ca-vermiculite; K-, Rb- or Cs-vermiculite and a mixed-layer phase. Far infrared absorption bands of K+, Rb+ and Cs+ located in the phlogopite-like interlamellar spaces are at 72, 59 and 53 cm–1, respectively. These frequencies are characteristic of a trioctahedral mixed-layer phase. Selectivity is greater for cations with a low hydration energy (K+, Rb+, Cs+) than for cations with a high hydration energy (Na+, Ca2+). On the other hand, for cations with a low hydration energy, structural parameters such as the tetrahedral rotation angle, α, have to be taken into account.

The infrared spectrum of water adsorbed on K-hectorite has been studied in the frequency range 2600–4000 cm−1 on samples equilibrated with relative humidities of 0% to 100%. The model proposed by J. Mamy for the molecular array of water upon the mineral surface has been used as a starting assumption. A ‘unit cell’ made of two H2O molecules is then considered as a possible theoretical basis for the interpretation of the infrared spectrum. When taking into account this unit cell six stretching frequencies may be anticipated. The six components of the OH stretching band are clearly resolved at −95°C at room temperature a Curve Resolver was used to analyse the composite band, which was recorded at various incident angles (0–45°). From the variation of the integrated absorption of each component band given by the curve resolver, the orientation of the dipolar moment is calculated, and compared with the theoretical one deduced from the model.

K+ ⇋ Ca2+ exchange was performed on a mixed-layer (phlogopite-vermiculite) sample from Palabora, Republic of South Africa. Exchange isotherms, X-ray diffraction patterns and far infrared (FIR) spectra of the mineral were obtained. Different mineralogical phases were identified during the exchange process: K-vermiculite, Ca-vermiculite and a regular mixed-layer (VK–VCa) phase. Two types of exchange sites for K+ were identified by FIR during the exchange process. The first type, dominant in the K-vermiculite, gives an absorption band at 76 cm–1. The other, which was the most pronounced site in the mixed-layer phase, gives an absorption band at 72 cm–1. The mixed-layer phase was formed only when oxidation of Fe2+ resulted in the internal compensation of part of the negative charge of vermiculite. This study shows that the high selectivity displayed by vermiculite for K+ is enhanced by the formation of the mixed-layer phase.

Le spectre de réflexion diffuse de pâtes de kaolinite obtenues pour des teneurs en eau croissantes a été étudié en séparant la part due au phénomène d'absorption de celle due à d'autres phénomènes comme la diffusion. On montre que l'intensité des bandes d'absorption varie linéairement avec la teneur en eau jusqu'à ce que le point d'entrée d'air dans le système soit atteint. Au-delà du point d'entrée d'air, quand le système est saturé en eau, l'intensité des bandes d'absorption semble tendre vers une limite. On montre de même que l'intensité réfléchie-diffusée en dehors des bandes d'absorption tend elle aussi vers une limite quand le système est saturé en eau. Il en résulte: (i) que la détermination des teneurs en eau à partir des données de réflexion diffuse est possible grâce à l'existence de courbes d'étalonnage linéaires dans le domaine d'hydratation pour lequel le système n'est pas saturé en eau, (ii) que l'analyse quantitative des données de réflexion diffuse est plus facile lorsque le milieu est saturé en eau. Les résultats obtenus montrent en outre que la relation générale proposée par P. F. Low: J = J0eα/θ; où où J est une propriété de l'eau associée avec l'argile, J0 une même propriété pour l'eau liquide, θ; la teneur en eau et α un coefficient, ne s'applique que sur un domaine limité de teneurs en eau.

Les substrats argile-alkylammonium sont utilisés dans ce travail comme des modèles de sol, dans le but d'étudier les interactions entre un pesticide neutre peu soluble dans l'eau, le dinoseb, et des substrats dont les surfaces ont été rendues hydrophobes. Les spectrométries infrarouge (IR), Raman et de réflexion diffuse dans l'UV-visible sont utilisées de façon complémentaire aux isothermes d'adsorption pour préciser la localisation et l'état des molécules pesticide retenues sur les substrats. Dans le cas de la vermiculite-décylammonium, la fixation du dinoseb est observée à la fois sur les surfaces externes et dans les espaces interfoliaires, les molécules de pesticide sont directement en interaction avec les atomes d'oxygène de la surface des feuillets et avec les cations ammonium, par liaisons hydrogène. Le taux de molécules de dinoseb retenues sur l'hectorite-décylammonium est beaucoup plus faible. Les molécules fixées ont alors une structure voisine de celle des molécules libres. Ces analyses montrent que le caractère hydrophobe de la surface des complexes organominéraux est une condition nécessaire, mais non suffisante, pour la fixation de molécules peu solubles dans l'eau. Notre étude souligne l'importance des interactions spécifiques par liaison hydrogène entre le pesticide et le feuillet de vermiculite dans le processus de rétention.

Les hydrates à deux couches et à une couche d'une saponite calcique ont été étudiés par infrarouge. Les résultats expérimentaux indiquent que dans l'hydrate à deux couches les molécules d'eau directement coordinées à l'ion calcium sont liées par liaisons hydrogène fortes d'une part aux atomes d'oxygène de surface chargés négativement et d'autre part à d'autres molécules d'eau. En revanche, dans l'hydrate à une couche où chaque ion calcium est solvaté par un minimum de 2 molécules d'eau, il n'y a pas de liaison hydrogène intermoléculaire. La plupart des molécules d'eau donnent une seule liaison hydrogène forte. Chacune des molécules d'eau forme un pont hydrogène, l'une avec le feuillet supérieur et l'autre avec le feuillet inférieur.

La prise en compte simultanée des résultats de diffraction des RX et de spectrométrie infrarouge a permis de préciser la nature des interactions entre l'eau, les cations compensateurs et les feuillets dans les phases à 14.6, 12.2 et 10.1 Å d'une saponite-Li de synthèse. En effet, la diffraction des RX renseigne sur l'espace interfeuillet disponible à l'eau et aux cations compensateurs alors que les perturbations observées sur les fréquences de vibration de valence des hydroxyles de structure apportent des indications sur la nature et la position des atomes situés à l'aplomb des cavités hexagonales. Cette étude a permis de confirmer la présence de cations hydratés (Li-H2O)+ dans les cavités ditrigonales des feuillets de la saponite-Li amené àun état d'hydratation correspondant à la phase à 10.1 Å.

De-intercalation of DMSO from well-crystallised kaolinites induced disorder. SEM, XRD and low-temperature IR were used to probe changes in morphology, layer stacking, and the environment of OH groups, respectively. The degree and type of disorder depended on the starting material and on the method of removing the intercalate. Rapid removal by heating at 250°C caused smaller changes than more prolonged heating at lower temperature, or washing with water.

L'arrangement des cations décylammonium échangés entre les feuillets de la vermiculite et de l'hectorite a été précisé à l'aide des spectrométries infrarouge (IR) et Raman. Les expériences de deutération et de dichroïsme faites par spectrométrie IR montrent que l'axe C3 du groupe NH3+ est confondu avec l'axe de la cavité hexagonale sous-jacente, dans le cas de la vermiculite comme dans celui de l'hectorite, et que dans la vermiculite, les groupes NH sont engagés dans des liaisons hydrogène avec les atomes d'oxygène des tétraèdres substitués. La spectrométrie Raman permet de comparer l'arrangement des chaînes alkyles dans les deux phyllosilicates. En effet, cette technique donne accès à des modes de vibration très sensibles à la conformation des chaînes carbonées, en particulier grâce à la décomposition des bandes de vibration de valence des groupements CH2 et CH3. Ainsi, dans la vermiculite, on montre que les chaînes sont linéaires, et que leur arrangement interdigité est proche de celui du chlorure de décylammonium cristallisé. Les spectres Raman obtenus pour l'hectorite mettent en évidence l'existence de conformations gauches dans les chaînes alkyles, qui caractérisent une rotation de la chaîne autour de la liaison C-C voisine du groupe NH3+ terminal. Les résultats obtenus en Raman montrent par ailleurs que les interactions entre les chaînes alkyles sont beaucoup plus faibles que dans le cas de la vermiculite et confortent le modèle proposé ici pour le complexe hectorite-décylammonium, pour lequel les chaînes sont parallèle aux surfaces des feuillets.