The effect of acid type and concentration on the reaction rate and products of dissolution of hectorite in inorganic acids was investigated. The dissolution of hectorite in hydrochloric (HCl), nitric (HNO3) and sulphuric (H2SO4) acids was characterized using quantitative chemical analysis, infrared (IR) and multinuclear MAS NMR spectroscopies. The rate of dissolution increased with acid concentration and decreased in the order HCl ≥ HNO3 = H2SO4 at the same molar concentration. No differences were found in the reaction products of hectorite treated with the three acids. The rate of Li dissolution was slightly greater than that of Mg at lesser acid concentrations (0.25 M), indicating that protons preferentially attack Li octahedra. The gradual changes in the Si-O IR bands reflects the extent of hectorite dissolution. The analysis of 29Si MAS NMR spectra relative peak intensities with dissolution time and acid concentration provided direct dissolution rates for tetrahedral (Q3) Si. After acid dissolution, most Si was bound in a three dimensional framework site (Q4), but a substantial part also occurred in the Si(OSi)3OH (Q31OH) and Si(OSi)2(OH)2 (Q220H) environments. These three sites probably occur in a hydrous amorphous silica phase. Both AlJV and AlVt rapidly disappeared from 27Al MAS NMR spectra of the dissolution products with acid treatment. The changes in IR and MAS NMR spectra of hectorite due to acid dissolution are similar to those of montmorillonite.

This report consists of a study of l-ornithine hydrochloride-vermiculite and of benzylammonium hydrochloride-vermiculite complex. The evolution of these organo-vermiculite structures upon heating is studied by X-ray diffraction (XRD) as well as infrared spectroscopy.

After heating vermiculite saturated with 1-ornithine cations, it shows condensation of interlayer ornithine molecules (peptide complexes). The stacking mode, opposing ditrigonal cavities, is not modified between aminoacid complex and peptide complex.

For vermiculite saturated with benzylammonium cations, the stacking sequence changes through heating by changing benzylammonium to NH4+. This transformation implies a sliding of the layers over each other. The ditrigonal surface cavities become face to face, as in the original mica. There are no random translations as in the starting complex.

Two clay minerals, a dioctahedral, Na-montmorillonite from Wyoming and a trioctahedral, synthetic Na-laponite, were exchanged by cupric (Cu(II)) ions and subsequently heated at 100 °C intervals up to 500 °C. The resulting materials were analyzed by chemical analysis, X-ray diffraction (XRD), cation exchange capacity (CEC) measurements, combined thermogravimetric and differential thermal analysis (TGA-DTA), infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). Montmorillonite exhibits a well-known Hoffmann-Klemen effect in that, when heated, cupric (Cu) ions migrate into the lacunae of the octahedral sheet, where they compensate the negative charge deficit of the clay layer. In the case of laponite, CEC measurements and spectroscopic measurements reveal that Cu ions migrate into the octahedral sheet where they replace Li and Mg ions. After heating at 200 °C, approximately half the interlayer Cu ions are exchanged. The exchange appears to be 1 Cu for 1 Li, resulting in a slight decrease of the negative charge of the layer. After heating at 300 °C, the remaining Cu ions are exchanged by either 1 Mg or 2 Li, which does not result in any further charge reduction. At 400 °C, some of the extracted Mg remigrates into the structure and exchanges some Li (1 Mg for 2 Li). The final product at 400 or 500 °C is then a Li-laponite with Cu(II) in the octahedral sheet.

The crystallochemical features of Co in Co-substituted goethite solid-solutions prepared by two different procedures have been studied using infrared, X-ray photoelectron and electron energy loss spectroscopies. It was found that the path followed for the synthesis of Co-substituted goethite determines the oxidation state of Co in the goethite structure. Thus, in the solid-solution prepared by precipitation with Na2CO3 of an Fe(II) aqueous solution containing Co(II) cations, followed by the aerial oxidation of the precipitate, the Co cations were found to be divalent, whereas trivalent Co was incorporated into the goethite obtained by ageing a solution containing Fe(III) and Co(II) cations precipitated by the addition of KOH. This different behavior is explained by the higher pH of goethite formation in the latter case, which favors the oxidation of the Co(II) cations.

Bentonite from the ‘Bogovina’ coal mine in Serbia, was characterized. The influence of acid treatment on its composition, as well as mathematical descriptions of this influence are reported. The purpose of this work was to correlate the concentration of the acid used for the treatment with the resulting bentonite composition. X-ray diffraction (XRD), infrared spectroscopy and quantitative chemical analysis were employed to define the changes caused by acid treatment.

The contents of all the cations, except Si, decreased exponentially with increasing concentration of the HCl used for the treatment of the bentonite. This approach was tested on previously published data and was shown to be valid.

The basal reflections of smectite decreased gradually and eventually disappeared after intense treatment, while the other reflections remained in the XRD patterns of all the samples, but decreased slightly with increasing acid strength. In addition, the amount of X-ray amorphous matter formed increased rapidly with increasing acid concentration up to 4.5 M. With further increase in the acid strength, the amount of X-ray amorphous matter remained virtually constant.

In recent years KAlSiO4 polymorphs have become minerals of interest from an industrial point of view; they have various applications in technological and medical fields. The costs of synthesis processes are often significant and so, in the present study, an attempt was made to develop a new synthesis protocol using a widely available and inexpensive, natural starting material. The KAlSiO4 polymorphs synthesized here were kalsilite and KAlSiO4-01 — 01 refers to the high-temperature polymorph of KAlSiO4 (Cook et al., 1997; Gregorkiewitz et al., 2008; Kremenovic et al., 2013). KAlSiO4 polymorphs were synthesized using kaolin; the effects of time and temperature on the synthesis process were investigated. A solid-state synthesis protocol was developed which required the mixing of the calcined kaolin with K2CO3 in stoichiometric proportions at temperatures of 700 and 800°C at atmospheric pressure. Crystallization of kalsilite at 700°C was demonstrated while that of KAlSiO4-01 was revealed at 800°C. Synthetic kaliophilite H2 was found in both of the experiments as a metastable phase. The products of synthesis were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR), and 29Si magic-angle spinning solid-state nuclear magnetic resonance spectroscopy (29Si MAS NMR). Calculation of cell parameters (through Rietveld refinement) and the density and specific surface area of the phases synthesized was also achieved. The amount of amorphous phase in the synthesis powders was estimated by means of quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. In particular, the results of the spectroscopic, chemical, and morphological characterizations are in agreement with the data available for these minerals in the literature, thus confirming the effectiveness of the experimental protocol. The quantitative phase analysis (QPA) also indicated the high purity of the powders synthesized, thus allowing for industrial applications.

The paper argues that education is relevant for both domestic and international reasons and without an incorporation of the international within the national it is not possible to understand education's changes and transformations in post-conflict and conflict-affected contexts. The paper aims to connect the local to the global by investigating their dynamic interaction through the peculiar lenses of international assistance to education reform in post-conflict Kosovo. It asks two questions: (1) how do global agendas of peace and security affect education reforms in conflict-affected contexts? and (2) how does education reform in conflict-affected contexts interacts with and is related to broader, international dynamics, processes, and actors? More specifically, the paper analyses the role of international actors in traditionally national sectors and the multi-layered, hybrid governance of education reform within a broader statebuilding, peacebuilding, and stabilization perspective. The analysis is divided into two empirical instances: (i) education for liberal multicultural peace (1999–2013) and (ii) education against violent extremism and radicalization (2014–2019). The paper sheds light on the globalization and securitization of education as well as the changing forms and practice of statehood and sovereignty in times of post-war-reconstruction and fragility. A threat-containment and security-based logic has dictated priorities and determined choices in education reform and content.

Metal Ir films were prepared by spray chemical vapor deposition (CVD) in air from an Ir precursor, (1,3-cyclohexadiene)(ethylcyclopentadienyl)iridium, Ir(EtCp)(CHD). Film deposition was ascertained at 270–430°C on a SiO2/Si substrate and the deposition rate increased with the deposition temperature but was saturated above 330°C. The obtained films consisted of Ir metal without any iridium oxide impurity irrespective of the deposition temperature. Films tended to orient to (111) with increasing deposition temperature. Resistivity of these Ir films decreased with increasing film thickness and reached to values on the order of 10-6 Ω・cm, which was the same order of the values for bulk Ir metal. Good step coverage was observed for the Ir metal films deposited at 270°C and 330°C. This shows that the simple spray CVD process in air is a good candidate for depositing Ir metal films with good conductivity and step coverage.

We demonstrated that single-walled carbon nanotubes (SWCNTs) grew from Ir catalysts by an alcohol catalytic chemical vapor deposition (ACCVD) method using a gas source-type CVD system. At an ethanol pressure of 1×10−1 Pa at 800°C, vertically aligned SWCNTs (VA-SWCNTs) were grown on SiO2/Si substrates. As the growth time became longer, the VA-SWCNT became thicker, and it reached almost 5 μm for a growth time of 180 min. The Raman spectroscopy results showed that the diameters of the grown SWCNTs were mainly distributed below 1.1 nm, indicating that the SWCNTs grown from Ir catalysts had small diameters compared with those from other metal catalysts.

This article draws on a Kleinian psychoanalytic reading of Hegel’s theory of the struggle for recognition to explore the role of international misrecognition in the creation of state subjectivity. It focuses on Ghana’s early years, when international relations were powerfully conceptualised and used by Kwame Nkrumah in his bid to bring coherence to a fragile infant state. Nkrumah attempted to create separation and independence from the West on the one hand, and intimacy with a unified Africa on the other. By creating juxtapositions between Ghana and these idealised international others, he was able to create a fantasy of a coherent state, built on a fundamental misrecognition of the wider world. As the fantasy bumped up against the realities of Ghana’s failing economy, fractured social structures, and complex international relationships, it foundered, causing alienation and despair. I argue that the failure of this early fantasy was the start of Ghana’s quest to begin processes of individuation and subjectivity, and that its undoing was an inevitable part of the early stages of misrecognition, laying the way for more grounded struggles for recognition and the development of a more complex state-subjectivity.

The structure of an illite-smectite (I-S) sample (HSI) from the Tertiary–Cretaceous boundary layer at Stevns, Denmark, i.e. the so-called Fish Clay, is investigated in order to discuss the origin of this clay and its similarity to clays from Maastrichtian-Danian chalk of Denmark and the North Sea. The phase compositions and layer sequences have been determined by X-ray diffraction. The structural formulae are determined from chemical analysis and solid-state 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The octahedral vacancy pattern has been determined by thermal analysis and the particle shape by atomic force microscopy. The HSI sample I-S consists of two phases, a high-smectitic (HS) phase (70%) having 95% smectite and 5% illite (leucophyllite) layers, and a low-smectitic (LS) phase (30%) having 50% smectite and 50% illite (leucophyllite) layers. Both phases have trans-vacant dioctahedral sheets and contain only traces of IVAl, the charge of the illite (leucophyllite) layers being provided predominantly by octahedral Mg for Al substitution. The structure of the tetrahedral and octahedral sheets for the HSI are compared to the structure of an I-S sample (GRI) from the Maastrichtian chalk at Stevns below the Tertiary-Cretaceous boundary and to the standard smectite SAz-1 from Arizona. For all three samples the 27Al MAS NMR spectra show the presence of two resolved IVAl resonances, which indicate the presence of two different IVAl sites. The NMR, infrared spectroscopy and chemical data show that both HSI and GRI have highly ordered Mg for Al substitution in the octahedral sheet, each Al having one Mg and two Al neighbours, whereas substitution of Mg for Al in SAz-1 is random. For the HSI sample, both the HS and LS phases are probably formed from volcanic ash. The structural similarity of the phases in HSI and GRI shows that GRI formed from a material similar to HSI by illitization of the HS phase and chloritization of the LS phase.

The clay mineralogy of sediments collected from the San Simón inlet, the Ría de Vigo, the Galician Platform, the Galician Margin and the Celtic Sea has been studied using XRD, IR and TEM with a microanalytical attachment. All samples consisted largely of dioctahedral mica and kaolin minerals, in addition to significant amounts of gibbsite, chloritic and smectitic minerals. The clay mineralogy of the sediments is generally consistent with terrigenous inputs from soils and weathered rocks of the Galician granitic hinterland. It is of particular interest that gibbsite, which is not a common constituent of soils of temperate climates, has previously been shown to occur in weathering profiles in this region and may therefore be regarded as an indicator of ‘‘continentality’’, as suggested by Macías Vásquez and co-workers. The smectitic mineral is Fe-rich and also contains significant amounts of K. This mineral is likely to be ultimately of an authigenic origin and may possibly be important as a precursor mineral in a diffuse, non-granular glauconitization process.

The Capim Kaolin District (eastern Brazilian Amazon), is one of the largest kaolin deposits in the world; with the kaolin used mainly for paper coating. The kaolin developed at the expense of Cretaceous sandy-clayey sediments of the Ipixuna formation, through intense lateritization from the Mesozoic to Cenozoic times.

This work describes the morphological, mineralogical, crystallochemical and geochemical evolution of the Capim kaolin facies. Based on the profile analysis in the open pit fronts, it encompasses X-ray diffraction, thin-section optical analysis, EDS-assisted scanning electron microscopy and transmission electron microscopy, chemical analysis, infrared and Mössbauer spectroscopies.

Six facies were defined as different stages of the supergene process. Ferruginization led to a thick duricrust on the soft kaolin, which in turn evolved from sandy-clayey sediments of the Ipixuna Formation. A subsequent deferruginization event degraded the duricrust, resulting in the flint kaolin facies.

The physical properties of three montmorillonites before and after heating were studied by reflectance colorimetry, X-ray diffraction (XRD) and infrared (IR) and Mössbauer spectroscopies. Colorimetric data, though not directly relatable to sample mineralogy, provide cheap and rapid information on the temperatures of sample breakdown. X-ray diffraction provides information on sample mineralogy and the transformations that develop during firing and allows the major phases formed in the course of firing to be identified, whereas IR data provide information on water and hydroxyl loss and the final breakdown of the montmorillonite structure. Mössbauer spectroscopy gives information on Fe2+ oxidation (where applicable) and reveals subtle variations in Fe site coordination and Fe mineralogy, including the formation of Fe oxides – that can be quantified in proportions as low as 0.1% – following structural breakdown of the montmorillonites.

Goethite, lepidocrocite, magnetite and akaganeite were synthesized in 0.8 M, 2 M and 5 M NaCl solutions at various temperatures (25, 40, 60°C) under slightly acidic to slightly alkaline pH with or without Si additions. Elevated temperatures prevent complete oxidation of initial Fe2+ solutions and magnetite and siderite precipitate, accompanied by goethite and lepidocrocite. At higher salinity, O2 solubility is reduced and its distribution is limited, leading to coprecipitation of lepidocrocite, akaganeite and goethite.

Lepidocrocite morphology changes from plates at pH 5.5 through rods at pH 7 to multi-domainic crystals at pH 8.2, due to enhanced crystal growth along the c axis. Salinity and temperature have opposite effects on lepidocrocite crystallinity.

Goethite crystals are multi-domainic and twinning appears only at elevated temperatures. Increases in temperature and salinity improve goethite crystallinity as observed by IR spectra. Addition of Si up to Si/Fe = 0.1 retards crystal growth and Si-OH-stretching bands appear. At Si/Fe = 1 most of the precipitate is short range ordered.

Platy and rod-shaped lepidocrocite from the Thetis and Atlantis II Deeps, were probably formed under the slightly acidic conditions of the hydrothermal brines. The Si concentration was greater in Atlantis II Deep than in Thetis Deep, leading to larger lepidocrocite and goethite crystals in the latter.

Multi-domainic goethite could have precipitated throughout. Pure phase goethite might have precipitated in the less concentrated brine, whereas mixtures of goethite and lepidocrocite might have precipitated in the more concentrated brine, depending mainly on oxidation rate and oxygen mobility within the brine.

Eleven Oxisols with high clay contents, 2.6–59.7 wt.% Fe2O3, and containing hematite, goethite, magnetite and maghemite, from São Paulo, Minas Gerais and Goiás, Brazil, were studied for the purpose of microwave remote sensing applications in the 0.3 to 300 GHz range. Of special interest are: the pseudosand effect caused by Fe-oxide cementation of clusters of soil particles; the mineralogy; and whether the soil magnetic susceptibility affected by ferromagnetic magnetite and maghemite interferes with microwave propagation. Quantitative mineralogical analyses were conducted using X-ray diffraction with Rietveld refinement. Visible, near infrared and short wave infrared spectroscopic analyses were used to characterize the samples qualitatively for comparison with published spectral radiometry results. Quartz (3–88%), hematite (2–36%) and gibbsite (1–40%) occurred in all soils, whereas kaolinite (2–70%) and anatase (2–13%) occurred in nine samples. Ilmenite (1–8%) was found in eight soils and goethite (2–39%) in seven. Of the ferromagnetic minerals, maghemite occurred in seven soils (1–13%) and three contained magnetite (<2%). These results will be applied to the interpretation of the effect of Fe oxides, particularly the ferromagnetic oxides, on microwave interaction with high-Fe soils, with ultimate application to the monitoring of soil water content by microwave remote sensing.

The results of EPR, UV-VIS and IR spectral studies show that benzimidazole forms various complexes with Cu(II) exchanged in the interlayer space of montmorillonite, depending on the acidity of the reaction medium during synthesis. In a nearly neutral solution a bis(benzimidazole)bis(aqua) Cu(II) cationic complex is formed. In a strongly basic solution, benzimidazole is bound to Cu(II) in the form of an anionic bifunctional ligand and a planar intercalated bis(benzimidazolate) Cu(II) complex is formed, where the benzimidazolate anion acts as a bridging ligand in the polymeric complex. The treatment in basic solution leads to partial illitization of the smectite. In a strongly acid solution, a nearly stoichiometric ionic exchange of benzimidazolium ion for Cu(II) ions takes place in the interlayer space of montmorillonite.

Ammoniation of montmorillonites pillared with polyhydroxo-complexes of Al was performed in flow conditions at 773–1073 K and monitored by IR spectroscopy. Interaction of the clay with ammonia revealed exchange of terminal and bridging -OH groups by NH2-, NH- and N- species depending on the reaction temperature. Amination begins at 773 K while formation of NH groups starts at 873 K. Transformation of NH- into N-species occurs at 973 K. A mechanism for the ammoniation reaction is proposed and the series of the relative reactivity of OH groups was established: Si–OH > Mg–OH–Mg > Al–OH–Mg > Al–OH–Al. This series was rationalized in terms of accessibility of the OH groups.

57Fe Mössbauer spectra of the Na+- and Ca2+-saturated forms of four ferruginous smectites,displaying a range of compositions, have been fitted with Voigtian profiles to represent (principally) two correlated distributions of isomer shifts and quadrupole splittings for the Fe3+ sites. Correlating the areas and hyperfine parameters of these distributions with simulations of the octahedral array of cations based on chemical analyses and infrared spectroscopy has enabled identification of the Fe3+ ions that contribute to the outer quadrupole doublet. The octahedral Fe3+ sites are characterized as having at least one Mg2+ nearest-cation neighbour and probably a cisconfiguration with respect to the OH– ions.