Lattice Expansion and Rheological Behavior Relationships in Water-Montmorillonite Systems
01 Feb 1954-Clays and Clay Minerals (Springer Science and Business Media LLC)-Vol. 3, Iss: 1, pp 296-316
TL;DR: In this paper, a recording Couette-type viscometer designed to provide a wide spectrum of shear rates and shearing stresses has been used to examine the rheological transformations which occur in passing from states of maximum dispersion to states of varying degrees of agglomeration as a result of interactions between LiCl, NaCl, KCl, and CaCl2.
Abstract: Some divergent experimental data have been reported on the swelling behavior of sodium montmorillonite. At water contents above 50 percent (based on the weight of dry clay) the basal reflection of sodium montmorillonite at 19.2 A becomes weak and very diffuse; some workers have stated that it disappears altogether while others report a persistent weak line even at very high water content. The pronounced differences in physical properties of sodium and calcium montmorillonite suggest that their lattice expansions should also be dissimilar. This paper describes some X-ray diffraction experiments using purified lithium, sodium, and potassium montmorillonites dispersed in water and in salt solutions which were conducted for the purpose of resolving some of these disputed points. The X-ray diffraction instrument employed was a General Electric geiger counter spectrometer unit with a copper tube and nickel filters. The knowledge thus gained has provided some insight into other properties of these clays, such as their rheological behavior. A recording Couette-type viscometer designed to provide a wide spectrum of shear rates and shearing stresses has been used to examine the rheological transformations which occur in passing from states of maximum dispersion to states of varying degrees of agglomeration as a result of interactions between LiCl, NaCl, KCl, and CaCl2, and the Li, Na, K, and Ca salts of montmorillonite in terms of certain ideal rheological models. Filtration characteristics of these systems have also been explored using a standard technique.
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TL;DR: In this paper, the authors provide a comprehensive understanding of the mechanism by which clay minerals swell and what steps have been taken in the development of effective and environmentally friendly clay swelling inhibitors.
492 citations
TL;DR: In this paper, the influence of single-species salt solutions of various concentration, cation valence, and pH on swelling and hydraulic conductivity of non-prehydrated GCLs was examined.
Abstract: The influence of single-species salt solutions of various concentration, cation valence, and pH on swelling and hydraulic conductivity of nonprehydrated GCLs was examined. At similar concentration, swell was largest with NaCl, KCl, and LiCl solutions (monovalent cations Na+, K+, and Li+) and smallest with LaCl3 solutions (trivalent cation La3+). Intermediate swell volumes were obtained with divalent solutions (CaCl2, MgCl2, ZnCl2, and CuCl2). Analogous results were obtained from hydraulic conductivity tests. GCL specimens permeated with solutions containing divalent or trivalent cations had higher hydraulic conductivity than GCLs permeated with monovalent solutions or deionized water, unless the divalent or trivalent solutions were very dilute (≤0.01 M). Hydraulic conductivity increased as the concentration increased, and at high concentration (1 M) only small differences existed between hydraulic conductivities measured with all solutions. Swelling and hydraulic conductivity were related to size of the h...
356 citations
01 Jan 1980
278 citations
TL;DR: In this paper, the authors show that at equilibrium, the swelling pressure, II, is equal to the applied pressure, thus, it is possible to determine II as a function of λ for each montmorillonite.
178 citations
TL;DR: A review of the literature on adsorbed water can be found in this paper, where the authors present a re-interpretation of data that may lead to inferences or conclusions not intended by the original author.
Abstract: Current knowledge of clay mineralogy and changing concepts of clay behavior have suggested a re-examination of the experimental data concerning adsorbed water. Data published between 1935 and 1959 have been studied and evaluated. In some instances this requires a reinterpretation of data that may lead to inferences or conclusions not intended by the original author. The intention of the re-evalution of data is to clarify understanding of the nature of adsorbed water and to suggest fruitful avenues for future research. While all literature on the subject has not been included, a concerted effort has been made to include representative data from all viewpoints and experimental methods. Data reviewed come under the following headings: X-ray and electron diffraction, density, dielectric and magnetic, thermodynamic, diffusion and fluid flow, freezing, and rigid water films. Utilizing present knowledge of crystal and surface chemistry of clay leads to the following conclusions: (a) Positions of the oxygen atoms of the adsorbed water molecules have been established by X-ray diffraction of vermiculite. These positions preclude both the ice structure and the Hendricks-Jefferson net structure even after modification to accommodate the exchangeable ions, (b) Density of water sorbed on Na montmorillonite has a minimum value of about 0.97 g/cm3 at a water content of 0.7 g H2O/g clay (approximately the plastic limit). For water contents less than 0.7 the density rapidly rises to about 1.4, and for water contents greater than 0.7 the density gradually rises until at about 6.5 g H2O/g clay the density of the adsorbed water equals that of normal liquid water. (c) The differential entropy of water adsorbed on kaolinite has a minimum value approximately that of ice; however, (1) this minimum occurs at about 0.7 of a monolayer, and (2) the integral entropy is greater than that for normal liquid water up to at least two molecular layers. The apparently contradictory entropy of sorbed water on montmorillonitic clay has not been resolved but is believed to be at least partially associated with clay swelling. (d) Diffusion and fluid flow phenomena are shown to be extremely sensitive to clay fabric; therefore, it is the writer's opinion that diffusion and fluid flow data on loosely compacted clay are of little help in ascertaining the structure of the adsorbed water phase. (e) Adsorbed water is easily supercooled and an appreciable fraction of the adsorbed water remains unfrozen after ice has once formed. The two major hypotheses indicate that the nature of the adsorbed water is: (1) a solidlike substance, or (2) a two-dimensional fluid. In the writer's opinion the only data that cannot be adequately explained by both of the hypotheses are the integral entropy data on kaolinite. The integral entropy data favor the two-dimensional fluid hypothesis; however, the paucity of data requires that this be a very tentative conclusion. The major difficulty encountered in the re-examination of data for this review was that a, rather poorly defined clay surface was employed by various investigators. If progress is to be made in unraveling the water-clay complex, it is deemed absolutely essential that experiments be carried out on very carefully defined and controlled clay surfaces. The nature of adsorbed water as interpreted from physico-chemical data on water-clay systems is no better than the purity of the clay surface regardless of the accuracy and precision of the measurements.
139 citations
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145 citations
"Lattice Expansion and Rheological B..." refers background in this paper
...Mering (1946, p. 205) has stated that it disappears altogether and that crystalline expansion ceases above 20/X,....
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TL;DR: Montmorillonit is the selten vorkommende reine Mineral, Bentonit das häufig vorkomende, meist with feinverteiltem Quarz vermengte Gestein this article.
Abstract: Als wesentliche Substanz der in der Natur vorkommenden Tone sind bisher hauptsächlich zwei Mineralien bekannt geworden, der • A l ^ ^ a l s Hauptbestandteil der keramischen Tone^) und der M o n t m o r i l l o n i t mit dem stöchiometrischen Verhältnis S'i02,'A l ß ^ ^ i als der Hauptbestandteil der sog. B o d e n k o l lo ide oder Ben ton i t e^ ) . Montmorillonit ist das selten vorkommende reine Mineral, Bentonit das häufig vorkommende, meist mit feinverteiltem Quarz vermengte Gestein. Die E n t s t e h u n g der Montmorillonit enthaltenden Bentonittone scheint an die Zersetzung basischer Eruptivgesteine gebunden zu sein. Die nordamerikanischen Bentonite sind meist aus Lipariten entstanden und bleiben in Gegenden mit aridem Klima erhalten. Auch in einem aus Lipariten entstandenen Ton aus Java konnten wir als Tonmineral Montmorillonit feststellen. Im Anschluß an seine früheren Arbeiten®) gelang es einem von uns, unter Führung von Herrn Dr. Wenz vom Senckenberg-Museum im Basaltbruch von Dietesheim bei Frankfurt a. M. unter einer jetzt fortgeschlämmten Braunkohle eine zersetzte Basal t tonl inse zu finden, die außerordentlich plastisch war und gleichfalls Montmorillonit als wesentliches Tonmineral enthielt. Infolge des leichten Zerfalls des Montmorillonits durch Hydrolyse werden hochprozentige Montmorillonittone
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TL;DR: In this article, a sample of the whole clay was dispersed with Na2C2Oi and the fraction consisting of particles between 0.1 and 0.05 μ effective settling diameter were recovered centrifugally.
Abstract: Recently reported studies of the swelling of montmorillonite (1) (2) (3), have left open to question the actual relationship between the \"pyrophyllite\" foundation and the water absorbed. It would seem well agreed that gently ignited montmorillonite possesses a structure of octahedral and tetrahedral layers related as in pyrophyllite, but the positions of the water in the wet specimens have not been defined. The present authors have previously been interested in the improved X-ray diffraction effects produced when clay specimens exhibiting preferred orientation were irradiated (4). From these studies, it appeared likely that, if water molecules have any place in the montmorillonite lattice, a study of flakes oriented with the 001 directions of the individual particles parallel should permit their detection. For such a study a Wyoming bentonite was selected. The material has been widely recognized on the basis of optical, chemical, and X-ray diffraction data as montmorillonite, and is sold commercially as such. In the natural state it includes small amounts of quartz and of kaolinite. For the diffraction experiments to be reported here a sample of the whole clay was dispersed with Na2C2Oi and the fraction consisting of particles between 0.1 and 0.05 μ effective settling diameter were recovered centrifugally. This whole procedure has been described elsewhere (5). The material so collected was electrodialyzed to free it from electrolytes. Petrographic and X-ray examination of this material yielded no evidence of impurities. The air dried material had this composition:
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"Lattice Expansion and Rheological B..." refers background in this paper
...Hofmann and Bilke (1936, p. 239) reported a reflection in excess of 30 _A. Recently Collis-George and Bodman (1954) reported a persistent 19.2 .A. line for sodium montmorillonite at very high water content....
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