0000000000040103
AUTHOR
Pierre Bracconi
Structural properties of magnesium stearate pseudopolymorphs: effect of temperature.
A thorough review of the relevant literature reveals that the interaction between water vapour and magnesium stearate, in contrast to many other metal soaps, is not properly understood. The structural modifications associated with the up-take or loss of water of vegetable-derived commercial magnesium stearate powders exposed to humid air or vacuum at room temperature are investigated using standard powder X-ray diffractometry. It is found that in such conditions magnesium stearate reacts reversibly with the vapour phase with structural consequences very similar to the high temperature transition between the crystalline and rotator phases of other anhydrous metal soaps. When temperature is i…
On the difficulty of assessing the specific surface area of magnesium stearate
Abstract The water content of as-received commercial magnesium stearate batches from animal and vegetable sources have been modified by ageing in humid air at room temperature or by vacuum treatment. The complete adsorption–desorption isotherms of nitrogen and krypton vapours by samples of these as received and modified materials have been measured at liquid nitrogen temperature after standardised vacuum degassing. They are greatly affected by the initial water content of the material. In particular: (a) the BET surface area values computed from the adsorption branch vary widely and is increasing with increasing water content; (b) anomalous hysteresis of varying amplitude is observed in all…
Electronic microdiffraction study of structural modifications resulting from the dehydration of gypsum. Prediction of the microstructure of resulting pseudomorphs
Abstract Endothermic decomposition reactions (solid 1→solid 2+gas) generally affect only part of the inter-atomic bonds of the solid 1 structure. In consequence, the morphology and external dimensions of particles remain unchanged (the particles of solid 2 are referred to as pseudomorphs of those of solid 1). The gas release normally leads to a decrease of the molar volume of the precursor solid, resulting in cracking and formation of intra-particle porosity. This work deals with such a reaction: the dehydration of gypsum into sub-hydrated and anhydrous phases. Ultrathin (010) gypsum cleaved plates have been dehydrated under controlled conditions and studied by electron microdiffraction. Al…
Thermal analyses of commercial magnesium stearate pseudopolymorphs
Abstract Two commercial magnesium stearate powders in two well-characterised structural states are investigated using DSC and coupled TGA–DTA under dry nitrogen flow. They consist of either a mixture of crystalline hydrates or a poorly crystallised so-called anhydrate. Following the degassing of unbound water, 1 or 3 weight-loss peaks are observed below about 100 °C, each associated with one heat loss peak at the same temperature. The present results and a review of graphical data from literature show that the so-called anhydrate always contains a significant amount of water. At the beginning of the dehydration process, the heat loss is the same as the standard heat of vaporisation of water…
Irreversible modifications of the porous microstructure of soluble anhydrite β-CaSO4 induced by hydration-dehydration cycles
26 pages; The internal surface area of hexagonal (soluble) primary anhydrite CaSO4 produced by dehydration of gypsum decreases by about 70 % when the anhydrite is successively subjected to rehydration and dehydration at room temperature in humid air and in vacuum respectively. In the rehydration step, the hemihydrate is formed; its dehydration yields secondary anhydrite. Additional hydration-dehydration cycles in the same conditions have a much smaller effect. The first cycle also brings about a modification of the t-plot, which reveals that the micropores of primary anhydrite are irreversibly healed. Mercury intrusion porosimetry shows that the primary dehydration of gypsum also generates …
Theory of mercury intrusion in a distribution of unconnected wedge-shaped slits
Effective mercury intrusion in a wedge-shaped slit is gradual, the intruded depth increasing with applied pressure. The Washburn equation must be modified accordingly. It relates the distance, e, separating the three-phase contact lines on the wedge faces to the hydrostatic pressure, P, wedge half-opening angle alpha, mercury surface tension gamma, and contact angle theta: e=(-2gamma/P)cos(theta-alpha) if theta-alpha>pi2. The equations relating the volume of mercury in a single slit to hydrostatic pressure are established. The total volume of mercury V(Hg)(tot)(E(0),e) intruded in a set of unconnected isomorphous slits (same alpha value) with opening width, E, distributed over interval [E(0…
Comparison of different methods for evaluating the transmission function of a two-stage cylindrical mirror analizer in XPS applications
Three different evaluations of the energy dependence of the transmission-detection function of a two-stage cylindrical electron analyzer have been obtained by resorting to three established procedures. Their relative merits have been tested as follows. First they have been used to correct raw XPS spectra of clean Cu, Ag and Au surfaces. Next, the secondary electron background has been subtracted using Tougaard's method. Finally, the primary electron spectra so obtained have been reanalyzed by peak area measurement in the frame of the modern formalism for quantitative XPS analysis. Ideally a constant residual value should thus be obtained. The variability of these residuals with peak energy …
Microstructural modifications resulting from the dehydration of gypsum
Various faces of dehydrated gypsum-cleaved blocks and single crystals have been investigated using optical microscopy, SEM, and TEM. The orientation of the cracks with respect to the initial gypsum structure and the Miller indices of all possible crack planes have been determined. These crack planes have been found to be few and to correspond to planes of high atomic density in the initial and final structures, therefore characterised by a low surface tension. These observations allow us to propose cracking criteria based on general concepts of crystal growth. The cracks' dimensions measured on different faces of the pseudomorph are distributed over several orders of magnitude and seems to …
Quantitative phase analysis and thickness measurement of surface-oxide layers in metal and alloy powders by the chemical-granular method
The principles of the chemical-granular analysis of metal and alloy powders are reviewed and the results are compared with those provided by the spectroscopic analytical techniques XPS, AES and SIMS, including ion etching in their depth-profiling mode, when they are applied to the same materials. Several examples are analysed and it is shown that the chemical-granular method alone can provide the very same information as depth profiling. However, it is averaged over a macroscopic powder sample in contrast to one or a few single particles. Nevertheless, it is the combination of the chemical-granular and depth-profiling analyses that really provides an unparalleled description in quantitative…
Assessing the particle size of a broadly dispersed powder by complementary techniques
The experimental determination of reliable particle size distribution curves and statistical parameters of broad distributions is known to be a difficult task. This problem is addressed here in an attempt to characterize the granularity of three distinct batches of a pharmaceutical powder (fenofibrate from Fournier Laboratories). The methodology consists in comparing the results, expressed in terms of surface based mean diameter, as obtained by three complementary techniques, namely optical microscopy image analysis, laser light low angle diffraction and surface area measurement by krypton physisorption. These techniques are applied in parallel to the material of interest and to a certified…
Heterogeneous kinetics: from solid–gas reaction to solid–liquid dissolution
Abstract The extension of the formal kinetics of solid–gas reactions to solid–liquid dissolution is investigated theoretically. The work is based on modelling the dissolution of a solid in a closed system by a stoichiometrically simple chemical reaction A solid ⇄A liquid proceeding up to either an equilibrium state if the solid phase is initially in excess or exhaustion in the reverse situation. The initial amount of solid compared to the capacity of the liquid phase appears as a major factor of complexity. First, the rate equation is formulated in terms of the intensive variables without any assumption about the mechanism and the rate-limiting step. The resulting equations are compared to …
Physical chemistry of the powder metallurgy of beryllium: Chemical characterization of the powder in relation to its granularity
Combining the systematic quantitative chemical analysis of the light impurities H, C, N, and O, the quantitative thermal desorption of molecular H2O and H2, and X ray diffractometry of various size fractions of a commercial Be powder (SP-65 grade from Brush-Wellman) allowed the precise de-termination of the mean composition and equivalent mean thickness of the surface impurity phases in the passivation-contamination layer on the surface of the particles. The overall surface stoichi-ometry is as follows: 0.2 BeOcrystallized, 0.8 [BeO - 0.59 H2O]amorphous, 0.14 H2Oads The result of the elemental analysis by X-ray photoelectron spectroscopy of the unetched surface of a powder pellet is compare…