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The collector for separating diasporic bauxite serves as a type of flotation reagent by adsorbing selectively on diaspore to make it hydrophobic enough to separate it from the aluminosilicates. Although the flotation process is considered economical in the desilication of Chinese diasporic bauxite, the existing collectors fail to separate these ores because of their poor adsorption selectivity over other minerals. The present study was an attempt to seek a collector for selective flotation of diaspore over aluminosilicates. A novel carboxyl hydroxamic acid compound, 2,2-bis(hydroxycarbamoyl) decanoic acid (BHDA), was designed and synthesized, and the flotation behavior of diaspore, kaolinite, and illite was investigated by flotation tests with BHDA. The interactions between the BHDA and the minerals were also explored by Fourier-transform infrared spectroscopy (FTIR), zeta-potential measurement, and density functional theory (DFT) calculation. Using BHDA as the collector, the pulp pH value affected the floatability of diaspore significantly while the floatability of kaolinite or illite was unaffected or only slightly affected. The dosage of BHDA had little effect on the floatability of the three minerals. The greatest difference in floatability between diaspore and aluminosilicates occurred at mid-range pulp pH (7). Large shifts in characteristic absorption peaks and new absorption peaks were observed for BHDA-treated diaspore but were absent from BHDA-treated aluminosilicates. The change in the negative zeta potential of diaspore was also greater than those of aluminosilicates in the presence of BHDA. The O atoms in the carboxyl and hydroxycarbamoyl of BHDA have highly negative charges, and favorable stereo conditions existed to form five- or six-membered rings, resulting in their coordination with the Al atoms of diaspore, leading to chemisorption in chelate rings; the adsorption of BHDA on kaolinite or illite, on the other hand, was mainly physical in nature. The BHDA was, therefore, highly selective in the flotation between diaspore and aluminosilicates and possibly suitable for the separation of diasporic bauxite.

The persistence of many seemingly metastable mineral assemblages in sediments and soils is commonly attributed to their sluggish transformation to the stable-phase assemblage. Although undoubtedly kinetics plays a major role, this study shows that thermodynamic factors, particularly surface energy, significantly influence the free energy. Enthalpies of formation of boehmite samples with variable surface area were derived using high-temperature oxide-melt calorimetry. The average surface enthalpy for all faces terminating boehmite particles was calculated at +0.52 ± 0.12 J/m2. This value represents the surface enthalpy for surfaces exposed to vacuum assuming that H2O adsorbed on the surface of boehmite is loosely bound. These results show that the enthalpy of formation of boehmite may vary by ≤8 kJ/mol as a function of particle size. An overview of published values of surface energies of gibbsite, γ-Al2O3, corundum, and the results here indicates that the hydrated phases (boehmite, gibbsite) have lower surface energies than the anhydrous phases (corundum, γ-Al2O3). Lower surface energies allow the hydrated phases to maintain high surface area, i.e., small particle size. Similar surface energies of boehmite and gibbsite suggest kinetic control favoring the crystallization of boehmite or gibbsite from aqueous solution. The enthalpy of formation of bulk boehmite from the elements was calculated at −994.0 ±1.1 kJ/mol. Combining this result with the data in existing thermodynamic databases, we confirm that bulk boehmite is metastable with respect to bulk diaspore at ambient conditions.

The solubilities of HCl-treated samples of corundum, gibbsite, boehmite, and diaspore in aqueous solutions at 298 K and one atmosphere pressure were determined from undersaturated and supersaturated initial conditions. Solution characteristics at apparent equilibrium were measured and used to calculate equilibrium constants (Kr) for mineral dissolution reactions: $$\begin{array}{l} A{l_2}{O_3}\left( {corundum} \right) + 3{H^ + } = A{l^3} + 1.5\,{H_2}O,\\ Al{\left( {OH} \right)_3}\left( {gibbsite} \right) + 3{H^ + } = A{l^3} + 3\,{H_2}O,\\ and\\ AlOOH\left( {boehmite\,or\,diaspore} \right) + 3{H^ + } = A{l^3} + 2{H_2}O, \end{array}$$ Assuming solid phase and water activities of unity, log Kr = 3pH - pAl3+ for all three equations. The calculated log Kr values were: 9.01 ± 0.05 (corundum), 7.76 ± 0.14 (gibbsite), 7.49 ± 0.09 (boehmite), and 6.75 ± 0.24 (diaspore), indicating that the relative thermodynamic stabilities under the experimental conditions were: corundum < gibbsite < boehmite < diaspore. The gibbsite value agreed well with that determined independently by another research group using acid-treated subsamples of the same source mineral (7.70 ± 0.02). The calculated Gibbs free energies of formation (kJ/mole) were: -1587.4 ± 2.1 (corundum), -1156.7 ± 1.6 (gibbsite), -921.0 ± 1.5 (boehmite), and -925.1 ± 2.0 (diaspore). The Δ G f o values of the acid-treated minerals were 1.8 to 12.4 kJ/mole more negative than values recently compiled for untreated mineral samples. This result is attributed to the removal of reactive surface coatings that isolated the bulk mineral phases from the solution phase.

During the epigenetic alteration of boehmitic karstic bauxite in the Vlasenica region of Yu- goslavia, which was caused by siliceous water descending through the deposit by means of cracks, fissures, etc., oolites were less altered compared with the coexisting matrix material, which was intensely kaolinized. The following zonal alteration pattern of the oolites was identified: a diaspore enrichment zone, followed by a diaspore-boehmite enrichment zone, and then the original bauxite. Considering this alteration pattern and that determined previously for the matrix material, the following overall pattern of alteration was established: a kaolinite-diaspore zone, followed by a boehmite-diaspore zone, and then the original bauxite. The alteration solutions reacted with the bauxite to form solution-matrix and solution-oolite subsystems, which were characterized by different types of diffusion and geochemistry. In the kaolinite-diaspore zone Si-metasomatism kaolinized the matrix, and excess A1 partly migrated into the oolites, forming diaspore, and outward into the bauxite. The latter Al-remobilization resulted in a transition zone, in which new boehmite was formed in both the matrix and the oolites, and diaspore only in the oolites. Thermodynamic models of oolites and whole bauxite alterations were established, on the basis of stability diagrams calculated for the mineral assemblages of both the oolites and the matrix, in the alteration zones and in the deposit as a whole. Based on these models, the genesis of the diaspore and the relationship of diaspore-boehrnite-kaolinite assemblages in natural systems at low temperature and low pressure can be described. Rezime--Tokom epigenetske alteracije bemitskih karsnih boksita u podru~ju Vlasenice, izazvane per- kolacijom voda obogarenih rastvorenom silicijom koje su ponirale kroz pukotine, rasedne zone i sl., ooliti su slabije alterisani u poredjenju sa koegzistentnom osnovom kojaje intenzivno kaolinisana. Identifikovan je slederi tip zonarne alteracije za oolite: zona obogarenja dijasporom, iza koje slede zona obogarenja dijasporom i bemitom i zatim originalni boksit. Na osnovu razmatranja ovog tipa alteracije i tipa alteracije za materijal osnove, ustanovljen je slederi tip alteracije boksita kao celine: kaolinitsko-dijasporska zona, iza koje slede bemitsko-dijasporska zona i zatim originalni boksit. Alteracioni rastvor je reagovao sa boksitom obrazujuri kompleksan sistem, koji se sastojao od dva podsistema: rastvor-materijal osnove i rastvor-ooliti, koji su se medju sobom razlikovali kako po modelima difuzije tako i po geohemijskim karakteristikama. U kaolinsko-dijasporskoj zoni Si-metasomatizam je doveo do kaolinizacije materijala osnove, a vi~ak A1 je delom migrirao kako u koegzistentne oolite, obrazujuri u njima dijaspor, tako i dublje u boksit. Remobilizacija A1 dublje u boksit dovela je do obrazovanja prelazne zone, u kojoj se obrazovao bemit i u osnovi i u oolitima, i dijaspor samo u oolitima. Postavljeni su termodina~irki modeli za alteraciju oolita i boksita kao celine, a na osnovu dijagrama stabilnosti prorarunatih za mineralne asocijacije i oolita i osnove, u zonama alteracije i u samom le~i~tu. Na osnovu svega ovoga razmotreni su tarnije i pouzdanije geneza dijaspora i odnos dijaspor-bemit-kaolinit u prirodnim sistemima na niskim temperaturama i niskim pritiscima.

Sedimentologic zones that are differentiated by changes in lithology, mineralogy, chemical composition, and crystal morphology observable in scanning electron micrographs occur in Missouri high-alumina clay deposits. These properties and changes suggest that the high-alumina materials originated from Pennsylvanian-age, paludal sediments deposited in depressions underlying Paleozoic carbonate rocks. Alumina was relatively enriched in zones of the deposits by leaching of silica and of alkali and alkaline earth metals from the sediments. The most intense leaching occurred on the highest parts of the Ozark Dome.

Flint clay is denned as a sedimentary, microcrystalline to crystalline clay (rock) composed dominantly of kaolin, which breaks with a pronounced conchoidal fracture and resists slaking in water. Additional ceramic (refractory) properties are implied, but not expressed, in the definition. Flint clay first given recognition in the U.S.A., has been observed on all continents; it will probably be found to be more abundant than its occurrences reported to date. It occurs in rocks mainly Carboniferous or Cretaceous in age, and is invariably associated with plant- or coal-bearing measures. The environment of deposition is commonly lowlying paludal, in basins in either clastic silicate rocks or in karstic carbonates. It is inferred that parent illitic and/or kaolinitic clay colloids were transported into the swamps and there under-went further dialysis, alteration, and eventual crystallization in situ, producing a notably homogeneous kaolinite clay possessing interlocking crystallinity. Some occurrences were further desilicated to high-alumina minerals, particularly to diaspore and boehmite. Flint clay is interpreted as being an intermediate member of a so-called flint-clay facies which is a claystone sequence ranging from high-alumina minerals (or potentially so) formed on the highest part, structurally and/or topographically, of the depositional area, and grading down-structure and/or lower in elevation through flint clay to iliite-kaolinite plastic clay and thence to marine illitic shale, all being equivalent stratigraphically. The geochemical reactions are depotassification of parent clay by substitution of K+ by H+, and desilication, especially where high-alumina minerals are formed.

The term “flint clay” used in USA and several other countries, corresponds very closely to the term “toasted bread (sukhar) clay”. In both USA and U.S.S.R., the typical occurences of “toasted clays” are confined to deposits of the lower Carboniferous. In their properties and occurrence the well-studied toasted clays of the Borovichy deposit (Novgorod province) are highly similar to the flint clays of Missouri, differing significantly only in having lower bulk specific gravity and higher porosity than do Missouri flint clays. Varieties with excess free alumina (diaspore, boehmite) are observed both among “toasted” and flint clays. The author suggests the term “toasted complex” (sukharnii kompleks) which corresponds to W. D. Keller’s term “flint clay facies”. The clays of the “toasted complex” are sediments of ancient swamps and lakes which contained rich vegetation. Their source material was finaly dispersed silicate particles transported from dry land. The structure and properties of toasted clays are explained by the precipitation of kaolinite as colloidal clumps in which crystallization occurred with formation of intimate intergrowths and variously oriented segregations.

High-alumina minerals refer, in this paper, to Al-rich, normal sedimentary phases, including gibbsite, boehmite, diaspore, possibly “proto-diaspore” and “proto-alunite”, “Al-chlorite”, and corundum, in association with kaolin minerals. They may be derived from any common Al-containing rock. Processes of origin include direct bauxitization of non-clay silicate minerals and rocks, and the desilication of any of the common clay minerals, particularly of the kaolin group. Apparently aluminous gels were formed within certain marshy basins, and/or were transported into basins, giving rise to concretionary masses of high-alumina minerals. Concretionary deposits were formed by dissolution of Al and reprecipitation.

An experimental study has been made of the effect of neutral fluoride solutions on typical clay minerals, both at room temperature and elevated temperatures. The fractionated samples of boehmite, diaspore, kaolinite, chrysotile, muscovite, etc. were equilibriated with neutral NaF solutions over a period of three months. The extent of F-OH exchange was measured by three independent methods: (a) Back-titration of developed alkalinity due to OH liberation, (b) Direct F-analysis, and (c) Infra-red absorption measurements. Extensive release of OH from the lattice (from 20–50% at between 25°C and 60°C) was found for several common clay minerals. Neither cation content (e.g. dioctahedral vs. trioctahedral) nor type of structure (e.g. two-layer vs. three-layer) appeared to affect the magnitude of exchange greatly. Definite identification (and rough estimation) of Na3AlF6 in the product shows that not all F enters the lattice in all cases.