X-ray intensity ratios of Si/Al, Si/Fe, and Al/Fe in micron-sized particles of geochemical standards were found to vary linearly with the composition ratio. The same linear relationship was found for samples of the clay minerals kaolinite and illite.

The reaction of phlogopite with a trimethylsilylating reagent yielded organosilicate compounds which are soluble in various organic solvents. Gas chromatographic analysis of the soluble products indicates that they consist of the trimethylsilylated derivatives of silicic acids which have been formed in the decomposition of phlogopite by hydrochloric acid and that silicic acids formed by the acid attack are monomelic and also oligomeric. The increase of the ratio of GC peak areas of monomer derivative to dimer one with an increase of the reaction time shows that silicic acids in the reaction system tend to depolymerize. The difference between phlogopite and biotite in the ease of trimethylsilylation also is discussed.

The rate of dissolution of phlogopite in an open system was measured at low temperature and pressure and at pH 3–5. The maximum dissolution rate was achieved by maintaining extremely low ionic concentrations in the solution using a cation-exchange resin (hydrogen form) as a trap for released cations. The resin also served as a source of hydrogen ions and acted as a buffer. The concentrations of ions adsorbed on the resin and remaining in solution were measured, along with surface area and cation-exchange capacity. The amount of phlogopite dissolved after 1010 hr was 67 times that dissolved using a CO2-buffered, closed-system method. During the first hour of the experiment, dissolution was incongruent, but later became congruent from 1 to 1010 hr. From 1 to 200 hr the reaction had linear kinetics. The dissolution rate for the first 200 hr of the reaction was 2.0 × 10−14 mole KMg3AlSi3O10(OH)2/cm2/sec. Since no evidence of parabolic kinetics was found, there is no reason to postulate the formation of a “protective layer.”

Dry ground phlogopite was placed in deionized water saturated with CO2 at room temperature and pressure. The bulk solution was buffered between a pH of 5 and 6 which is close to the pH of natural weathering systems. The conditions simulated a closed system. After 1010 hr, 2.0% of the total K, 0.95% of the Mg, 0.54% of the Si, and 0.74% of the F had been released, indicating that the dissolution was incongruent. Most of the K was released within 3 min, apparently by a rapid surface exchange with hydrogen ion. One-third of the cation-exchange capacity of this phlogopite arises from cations released from the outer surfaces, while two-thirds arises from the release of more deeply seated cations. All cations exhibited decreasing release with time, the slowest being Si. The rate-controlling “factor” in the later stages is related to the release of Si. It is difficult to distinguish linear from parabolic kinetics in the later stages because of the slow rate of dissolution; however, linear kinetics is most likely. If linear kinetics is applicable, the dissolution rate of Si was 3.8 × 10−17 mole/cm2/sec. Conclusions may be affected by the length of the experimental run.

The crystal structures of a reddish-purple, Mn-bearing muscovite-2M1 (alurgite variety) and a reddish-brown, Mn-bearing phlogopite-1M (manganophyllite variety) were refined to final residuals of 2.7% and 3.1%, respectively. The refinements were carried out in space groups C2/c and C1 for alurgite and C2/m and C2 for manganophyllite. The C1 and C2 subgroup refinements gave atomic coordinates consistent with the parent space group refinements. No cation ordering was found in either specimen, and the structures are very similar to those of muscovite and phlogopite. Residual areas of positive electron densities were found between the tetrahedral cations and neighboring oxygens in difference maps of both minerals. Those of alurgite were examined in detail to show the correlation between the residual densities and covalent bonding in the tetrahedra. The valence of the Fe present was determined by Mössbauer spectra as Fe3+ in both samples and of the Mn by optical spectra as Mn3+ in the alurgite but as Mn2+ in the manganophyllite.

The sorption of U and Ra on finely ground biotite, muscovite, and phlogopite was adequately described by the Freundlich adsorption equation, (x/m) = KCn, at low U and Ra concentrations despite Ra precipitation at the higher temperature. Radium and U sorption-efficiency curves derived from the Freundlich constants generally showed decreased distribution coefficients in response to increasing temperature and increasing Ra or U concentrations. Temperatures investigated were 5°C, 25°C, and 65°C. Solution compositions used were 0.1 M NaCl and 0.01 M NaHCO, for U, and 0.01 M NaCl for Ra. Uranium initial solution concentrations ranged from 1.00 × 10−4 M to 4.00 × 10−7 M; the Ra initial solution concentration range was 6.80 × 10−7 M to 8.60 × 10−9 M.

In 0.01 M NaHCO3 solutions, anionic uranyl carbonate complexes were prevalent, and because they are weakly sorbed relative to free uranyl ion and uranyl hydroxy complexes, the result was a relatively low U sorption efficiency on biotite and phlogopite and excellent sorption efficiency on muscovite. Uranyl carbonate complexes decreased in solubility with increasing temperature, so that U sorption efficiency on biotite increased with increasing temperature. Sorption of uranyl ion and uranyl hydroxy cations on biotite decreased with incresaing temperature.

A low-charge corrensite, i.e., a regular 1:1 interstratified smectite/chlorite was found in veins and fissures of an extensively fractured dolomite south of Perth, Ontario, Canada. Total chemical analysis indicated that the mineral was trioctahedral, having a structural formula corresponding to:

$({\text{Ca}}_{0.17}){({\text{Mg}}_{7.36}{\text{Al}}_{0.90}{\text{Fe}}^{3+}{\hspace{0.17em}}_{0.45}{\text{Fe}}^{2+}{\hspace{0.17em}}_{0.42})}^{\text{VI}}{({\text{Si}}_{6.06}{\text{Al}}_{1.94})}^{\text{IV}}{\text{O}}_{20}{(\text{OH})}_{10}.$

The coefficient of variation (CV) of the d(00l) spacings calculated for the mineral from X-ray powder diffraction data was 0.42, well below the maximum recommended value for corrensite, 0.75. The corrensite coexists with phlogopite, which is present as small (~0.5 mm) crystals throughout the rock and locally as large (~5 cm) crystals in pegmatitic veins. Microscopic observatiofls of large phlogopite crystals partially altered to corrensite suggest that corrensite formed at the expense of phlogopite by hydrothermal alteration.

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.

An X-ray diffraction study of vermiculitized micas in ultramafic and mafic intrusive rocks from Cheongyang, Korea, shows the following weathering sequence: mica → ordered mica/vermiculite interstratification → vermiculite. Electron microprobe analyses show the general trends of K leaching and Ca enrichment with increased weathering. The vermiculitization of phlogopite from ultramafic rocks proceeds by means of a continuous decrease in Al-for-Si tetrahedral substitutions and a progressive increase in Al-for-(Fe2+ + Mg) octahedral substitutions in the early stage of weathering. These substitutions occur to compensate for the excess of negative charge in the mica-like layer, in agreement with currently accepted vermiculitization mechanisms. They change to a slight increase of Al-for-Si tetrahedral substitutions in the late stage of the vermiculitization of phlogopite, owing to the oxidation of Fe despite its low content. However, the behavior of Fe in the late stage of the transformation of biotite into vermiculite is significantly different; that is, Fe increases substantially. The reason for this Fe increase in the late stage remains unresolved. Recalculations of the structural formulas on the basis of several assumptions indicate that the oxidation of Fe is necessary for the vermiculite derived from biotite to form the reasonable structural formulas.

Dioctahedral vermiculite occurs in an isolated metagabbro klippe (Kurançalı Metagabbro) that belongs to the Central Anatolian Ophiolites from central Turkey. Both the metagabbro and the structurally underlying high-grade metamorphic rocks are intruded by granitic rocks. The Kurançalı Metagabbro is characterized by its well-developed compositional layering, and the presence of vermiculitized phlogopiterich layers. Petrographic and mineralogie studies show that the primary mineral phases in the host rock are diopside, tschermakitic hornblende, Fe-rich phlogopite, and plagioclase. Secondary minerals are hornblende, actinolitic hornblende, Fe-rich phlogopite, and vermiculite. A two-phase history of alteration involving acidic weathering and alkaline metasomatism is suggested for the dioctahedral vermiculite and secondary Fe-rich phlogopite, respectively. The alteration of phlogopite to dioctahedral vermiculite proceeded both along cleavage planes and at crystal edges. The vermiculite is colorless to pale yellow with weak pleochroism and shows optical continuity with the parent mineral. Vermiculite flakes, analyzed semi-quantitatively by scanning electron microscope-energy dispersive analysis (SEM-EDS) and electron microprobe (EMP), are characterized by partially expanded interlayers, K depletion, and Mg and/or A1 enrichment. X-ray diffraction (XRD) and differential thermal analysis-thermal gravimetric (DTA-TG) analyses indicate that phlogopite is not a pure phase, although it is the dominant one. The XRD patterns show the presence of both dioctahedral vermiculite having dehydrated interlayers and hydroxy-Al interlayers, and interstratified phlogopite-vermiculite. The transformation of phlogopite to vermiculite is thought to represent an initial stage of weathering in an acidic environment.

The alteration experiments of phlogopite with 0.01 N HCl solution containing 0.1 M NaCl at 50°, 80° and 120°C have been carried out to aid in the understanding of the dissolution process of mica and the formation of secondary phases such as vermiculite and interstratified mica/vermiculite. Twenty milligrams of phlogopite samples were suspended in 20 ml or 100 ml of leaching solution.

In these experiments, the dissolution ofphlogopite occurred incongruently, where the preferential release of K occurred in almost all stages of the alteration reaction. In the 100 ml experiments, the priority in dissolution in the initial stage was in the order; K > Fe > Mg, Al > Si. This supports that phlogopite leaching is controlled by the mineral structure. At 80° and 50°C in the 20 ml experiments, the release of all elements except for K was nearly congruent. At 120°C in the 20 ml experiments, the dissolution was outwardly incongruent, which Fe decreased remarkably after six days and Al was released most slowly compared with all other elements in phlogopite. This is probably due to the precipitation of secondary phases such as aluminum and iron oxides and/or hydroxides.

Vermiculite and R1-type interstratified mica/vermiculite, containing 70 ∼ 50% mica, were formed in the alteration process of phlogopite. The following two processes were confirmed for the formation of interstratified structure: Interstratified structure was formed (1) directly from phlogopite or (2) from vermiculite which was produced earlier from phlogopite by regaining of K from the ambient solution. It may depend on the release rate of K from phlogopite whether mica-vermiculite layer sequences develop or vermiculite-vermiculite sequences do.

Cation exchange experiments were carried out on phlogopite, biotite, and muscovite using cryptand [222] as a complexing agent, dioxane as solvent, and Li as the exchanging cation. The results indicate greater than 90% exchange of the analyzed cations K+, Rb+, and Sr++ in phlogopite and biotite after two days. Similar results for the exchange in muscovite are observed but it is apparently slower. The amount of exchange observed for mica depends mainly on pH, time and the exchanging cation at a constant temperature. Residues of the mineral phase were also investigated by X-ray diffraction and a significant change of the interlayer spacing was detected. Some samples of the residue were analyzed for Li content. The compositions of the treated samples were in good agreement with the determined exchange of K+.

The acid hydrolysis products of trioctahedral fluorohectorite and phlogopite have been investigated by XRD, MAS NMR spectroscopy and nitrogen BET surface area analysis in an effort to assess the relative importance of edge attack and gallery access mechanisms. A dramatic loss of X-ray crystallinity and the formation of Q3 and Q4 SiO4 sites accompanied the depletion of Mg2+ from the octahedral sheet of both 2:1 layered structures. Depending on the extent of hydrolysis, the products derived from fluorohectorite exhibited surface areas up to 208 m2/g, whereas phlogopite hydrolysis products gave values <20 m2/g. The dramatic differences in surface areas were not related to differences in hydrolysis mechanisms. 19F MAS NMR studies indicated that the hydrolysis of fluorohectorite occurred primarily by an edge attack mechanism equivalent to the hydrolysis pathway for phlogopite. A gallery access mechanism contributed to the hydrolysis of fluorohectorite only at the later stages of octahedral Mg2+ depletion. Solvation effects appeared to be important in determining the surface areas of the reaction products derived from the swelling (fluorohectorite) and non-swelling (phlogopite) precursors.

Porous silica products obtained by selective leaching of phlogopite using an acid solution were investigated by XRD, MAS NMR, SEM, TEM, DTA/TG, and N2 and Ar gas adsorptions. The phlogopite powder was leached by a nitric acid solution at various concentrations (0.01–10 M) at 5–150°C for 10 min–480 h. Selective leaching of the phlogopite powder became extensive when the concentration of nitric acid was >1 M. Only SiO2 remained after the treatment, the other components (MgO, Al2O3, K2O and Fe2O3) being selectively leached from the product. At higher leaching temperatures, the leaching rate became faster and the resulting maximum specific surface area of the porous silica product became larger at each leaching temperature. The porous silica products were found by SEM and TEM, to maintain their original platy particle shape even after the selective leaching. The 29Si MAS NMR spectra of the products, however, revealed that the linkage structure of SiO4 tetrahedra converted to a framework type from a layered type in the original phlogopite. The porous silica product with the maximum specific surface area (532 m2/g) was obtained by leaching in a nitric acid solution with concentration of 5 M at 90°C for 15 min. The pore-size distribution of the porous silica product was bimodal with micropores of ∼0.7 nm and mesopores of ∼4 nm. The pore size of the products changed from 0.7 nm to 4 nm and further to 6 nm with increased leaching time. The present results are discussed in relation to those reported for phlogopite by other workers.

South Africa is a net importer of fertilizer products, importing all of its potassium, as well as 60–70% of its nitrogen requirements. Thus, domestic prices are impacted significantly by international prices, shipping costs, and exchange rates. Producing these fertilizers locally would be far more economical. Phlogopite, a rich source of potassium, is discarded in large quantities during mining operations; the objective of the present study, therefore, was to determine the acid-leaching characteristics and behavior of phlogopite as a means of releasing potassium. Phlogopite samples were leached with nitric acid (source of nitrogen for fertilizers) at various concentrations, temperatures, and reaction times. The feed phlogopite and leached residue samples corresponding to conversions of 14% (LP1), 44% (LP2), and 100% (LP3) were collected and analyzed using X-ray fluorescence spectroscopy (XRF), X-ray diffractometry (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), Brunauer–Emmett–Teller surface area and porosity analysis (BET), thermogravimetric analysis (TGA), and field emission gun-scanning electron microscopy (FEG-SEM). The feed phlogopite was highly crystalline. The absence of defects in the lattice meant that the motion of H+ atoms penetrating into the lattice was restricted, suggesting internal diffusion-controlled leaching. Furthermore, results obtained from the various analytical techniques corroborated each other in terms of the release of cations during leaching. All leaching experiments were conducted batchwise, in a closed system. The gravimetric data from the experiments were used to identify a suitable model which predicts accurately the leaching behavior. The reaction was found to be internal diffusion-controlled, and the D1 model, which represents one-dimensional diffusion through a flat plate, predicts the leaching behavior most accurately. The observed activation energies (Ea) and pre-exponential constants (k0) varied with initial nitric acid concentration ([H+]0).

Vermiculites and phlogopites can be exfoliated by chemical and thermal treatment methods to obtain chemically inert, adsorbent, fire-resistant, low-density materials with excellent thermal and acoustic insulation properties. The water content of the clay generally determines the extent of exfoliation and the presence of interstratification is claimed to increase the rate of exfoliation. Considering the strong interaction between water and microwaves, the effect of microwave power on exfoliation characteristics of vermiculites and phlogopites after treatment with water and hydrogen peroxide solution were studied at 600, 950 and 1300 W for microwave exposure times of 10, 20, 30, 60, 120 and 300 s. It was observed that the water molecules in the interlayers of the individual flakes were driven off quickly by microwave treatment causing layer separation in the samples. The vermiculite sample showed 2.8 and 5.6 times, respectively, the exfoliation ratio of the phlogopite samples, in accord with their water contents.

Micaceous layer silicate clay minerals are attractive materials for applications involving non-linear optics because of their low cost and ability to form well ordered, platy aggregates, but such applications require precise knowledge of the dielectric behavior of the clay. The purpose of the present study was to use Terahertz time-domain spectroscopy (THz-TDS) to determine the dielectric properties of certain cleavable layered clay minerals, including muscovite, vermiculite, phlogopite, and biotite. The samples were characterized by X-ray diffraction and Fourier transform infrared spectroscopy as well as chemical analysis by Energy dispersive X-ray spectroscopy. The THz frequency window investigated was the far-infrared region of 3.3 to ∼40.0 cm−1 corresponding to 0.1 and 1.2 THz, respectively. The samples were selected so that the hydrated form of the interlayer cation, e.g. Mg2+ present in the interlayer gallery of vermiculite, could be compared to species such as phlogopite, biotite, and muscovite with the dehydrated form of interlayer cations such as K+ or Na+. The frequency-dependent complex index of refraction of these natural materials was determined to vary between 2.50 and 2.80. The presence of water in the interlayer space of vermiculite was reflected in the detection of increased values of the absorption index in comparison with the muscovite, phlogopite, and biotite.

Far-infrared (FIR) analysis of synthetic Mg-, Ni-, Co-, and Fe-phlogopites coupled with structural data from X-ray diffraction revealed that the K interlayer environments are directly related to octahedral sheet composition and geometry. The general phlogopite formula, KM32+(Si3Al)O10(OH)2, was varied according to octahedral compositions, where M2+ = Mg2+, Fe2+, Co2+, and Ni2+. Octahedral substitutions have a direct effect on the b lattice parameter, which is related to the tetrahedral-octahedral sheet misfit and manifested by change in the tetrahedral rotation angle (α). The ditrigonal interlayer cavity geometry and the potential for retention of the compensating cations therefore varies according to the ionic size and the types and oxidation state of octahedral cations. These structural features appear as frequency shifts on FIR spectra. When Mg2+ is replaced by a smaller cation, Ni2+, the b parameter decreases and the tetrahedral rotation angle, α, increases, inducing the collapse of the ditrigonal ring. When this happens, the local anisotropy of the interlayer site increases, resulting in every other six out of 12 K-O bonds becoming shorter and the in-plane K-O vibration band shifts slightly to greater wavenumbers. Synthetic phlogopites with octahedral substitutions by cations of larger ionic radii (i.e. Co2+ and Fe2+) exhibit b parameter increases, where in the case of the annite end-member, α decreases to almost 0°. As α decreases, compensating cation sites become more hexagonal like and the nearest K-O bond increases in length. The K-O vibration bands move toward much smaller wavenumbers. Far infrared offers the potential for a new approach to study the retention of interlayer cations in other phyllosilicates and the mechanisms by which they are altered, such as heating or by weathering reactions in the environment.

The Marepalli dyke of the Vattikod cluster of the Ramadugu Lamproite Field, Nalgonda district, Telangana, India consists of pseudomorphed leucite, phlogopite (Al-poor, Ti-rich zoned phlogopite micas), pseudomorphed olivine, fluorapatite and Al-poor diopside embedded in groundmass consisting mainly of poikilitic Fe-rich titanian phlogopite and potassic amphibole. Other groundmass minerals are Al-Na-poor diopside, Al-poor spinels (titanian magnesian chromites to titanian chromites), Sr-rich fluorapatite and late-stage interstitial anhedral crystals of titanite and K-feldspar. The late-stage deuteric minerals present are REE-rich allanite, pyrite, magnetite, chalcopyrite, galena, hydro-zircon, carbonates (calcite, witherite and strontianite), baryte and cryptocrystalline SiO2. Apatite is an early crystallising phase and is present as inclusions in phlogopite and pyroxene. Phlogopite and amphibole occur as inclusions in titanite and K-feldspar. The compositional trends of phlogopite are of almost constant Al2O3 content with FeOT and TiO2 enrichment, and are typical of lamproitic micas. The FeOT enrichment is accompanied additionally by MgO depletion (reflecting VIFe2+ enrichment) from core to rim together with a slight increase in the tetraferric iron component. Diopside is characterised by <0.4 wt.% alumina and <0.6 wt.% sodium contents and exhibits typical lamproitic affinity. The spinels are alumina-poor with un-evolved titanian magnesian chromite to titanian chromite compositions. The presence of K-richterite, as an abundant amphibole, indicates a lamproite affinity, and on the basis of the typomorphic mineralogy, this rock is classified as a ‘pseudoleucite-amphibole-phlogopite lamproite’. The Marepalli lamproite shows significant difference in compositional ranges of phlogopite, amphibole, pyroxene and spinel in comparison to those reported from the Vattikod, Gundrapalli, Ramadugu, Somavarigudem and Yacharam lamproites of Ramadugu Lamproite Field. These lamproites are considered to form from a common parent magma under reducing conditions as evidenced from: (1) low tetraferric iron content in phlogopite; (2) low Fe3+# and Ti# in spinels; and (3) high F content in phlogopite and apatite.