Super‐Hydrated Zeolites: Pressure‐Induced Hydration in Natrolites

High‐pressure synchrotron X‐ray powder diffraction studies of a series of alkali‐metal‐exchanged natrolites, A₁₆Al₁₆Si₂₄O₈₀ ? n H₂O (A=Li, K, Na, Rb, and Cs and n=14, 16, 22, 24, 32), in the presence of water, reveal structural changes that far exceed what can be achieved by varying temperature and chemical composition. The degree of volume expansion caused by pressure‐induced hydration (PIH) is inversely proportional to the non‐framework cation radius. The expansion of the unit‐cell volume through PIH is as large as 20.6 % in Li‐natrolite at 1.0 GPa and decreases to 6.7, 3.8, and 0.3 % in Na‐, K‐, and Rb‐natrolites, respectively. On the other hand, the onset pressure of PIH appears to increase with non‐framework cation radius up to 2.0 GPa in Rb‐natrolite. In Cs‐natrolite, no PIH is observed but a new phase forms at 0.3 GPa with a 4.8 % contracted unit cell and different cation–water configuration in the pores. In K‐natrolite, the elliptical channel undergoes a unique overturn upon the formation of super‐hydrated natrolite K₁₆Al₁₆Si₂₄O₈₀ ? 32 H₂O at 1.0 GPa, a species that reverts back above 2.5 GPa as the potassium ions interchange their locations with those of water and migrate from the hinge to the center of the pores. Super‐hydrated zeolites are new materials that offer numerous opportunities to expand and modify known chemical and physical properties by reversibly changing the composition and structure using pressure in the presence of water.     

Adsorption-energetic and IR spectroscopic studies of NH4 natrolite

The ammonium form of natural zeolite, natrolite, obtained by vapor phase ion exchange is similar to calcium-containing zeolites of the natrolite group in its de- and rehydration characteristics and the heats of immersion in water. The adsorption capacity and the heat of immersion in water are maximum after evacuation of the zeolite at 200 °C. The irreversible sintering of NH₄ natrolite occurs above 200 °C (up to 45% at 500 °C), accompanied by the formation of hydroxyl groups. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 359–361, February, 1998.     

Isoconversional Kinetics of Thermal Processes in Mixtures Based on Metakaolin and Sodium Hydroxide

This study investigated the thermal behavior of the mixtures 6Al₂Si₂O₇: 12NaOH and 6Al₂Si₂O₇: 12NaOH: 2Al₂O₃ which are designed for synthesis of LTA (Linde type A) zeolite. XRD, SEM, and Synchronous thermal analysis (STA) have been used. It was found that after evaporating suspensions, molding pellets, and drying, small amounts of LTA and sodium hydroaluminates have been formed in the sample. The removal of crystallization water occurs on heating up to 400°C. In the temperature range from 400 to 850°C, Na₆Al₄Si₄O₁₇ and Na₈Al₄Si₄O₁₈ are synthesized by interaction of metakaolin with sodium hydroxide. The formation of mullite and nepheline is also observed. It was shown that preactivation of powders in the vibratory mill allows reducing the starting temperature of synthesis at 50–100°C. For the range 400–850°C using Ozawa–Flynn–Wall analysis, the values of apparent activation energy and preexponential factor have been calculated. It was established that the apparent activation energy for mixtures without preactivation made 200–290 kJ mol⁻¹. After preactivation, E values decreased to 130–170 kJ mol⁻¹. Also it was shown that alumina excess inhibits nepheline and mullite formation.     

Production of Granulated NaP Zeolite without Binder

Possibility was examined of synthesizing zeolites granulated without a binder with the use of a preliminary ultrasonic treatment of the suspension at a frequency of 22 kHz from mixtures of sodium metasilicate and aluminum and silicon oxides with various Si: Al ratios. It was found that, after the preliminary treatment, extrusion of grains, and calcination at 650°C, crystalline phases Na₆Al₄Si₄O₁₇, Na₈Al₄Si₄O₁₈, Na₂Al₂O₄, and Na₂SiO₃ phases are formed in the sample with Si: Al = 1. These phases are precursors for synthesis of NaA and NaP zeolites and sodalite via hydrothermal crystallization in a NaOH solution with concentration of 2 M. Upon a similar treatment of a sample with Si: Al = 2, there are crystalline phases α- and β-Na₂Si₂O₅, from which only NaP zeolite is formed in the course of crystallization. The hydrothermal crystallization in a 6 M alkali solution yields sodalite, irrespective of the Si: Al ratio. It was shown that an ultrasonic treatment gives a gel-like system at Si: Al = 1 and a powdered material at Si: Al = 2, which yields by the end of synthesis samples with cactus-like or wool-like morphology, respectively.     

Structural evolution of Li-exchaned natrolite at pressure-induced over-hydration: An X-ray diffraction study

The behavior of Li-exchanged natrolite Li_1.92Na_0.10[Al_2.02Si_2.98O₁₀]?2H₂O at compression in penetrating (water-containing) medium was studied by in situ synchrotron powder diffraction in diamond anvil cell up to 2.5 GPa. Within 0-1.3 GPa the compression is almost isotropic, and upon the further pressure increase the sample undergoes additional hydration, leading to abrupt volume expansion by 22%, a record value for natrolite. In the proposed model for the high-pressure phase Li₂[Al₂Si₃O₁₀]?6H₂O the Li⁺ cations have no contact with the framework O-atoms and are surrounded by “water-jacket” in the form of semi-octahedron (tetragonal pyramid) composed of five H₂O molecules. Such polyhedra, lining up along the channel axis, are joined through their edges and create a “water” column expanding the structure.     

Microwave absorption and structure of zeolite water in heulandite and clinoptilolite by <Superscript>1</Superscript>H NMR

The structure of zeolite water in single crystals of natural zeolites represented by clinoptilolite Na₂K₂Ca[Al₆Si₃₀O₇₂]·22H₂O and heulandite Ca₃Mg[Al₈Si₂₈O₇₂]·24H₂O is studied with ¹H NMR. Below 170 K the distribution of H₂O over the structural positions is shown to be fixed but different for the two minerals. Above 290 K translational and orientational diffusion of zeolite water molecules is observed and the structure of water is almost identical in both heulandite and clinoptilolite. Diffusion mechanism may be associated with the interaction between librational modes of H₂O and high-frequency oscillations of aluminosilicate framework. The microwave absorption is shown to be caused in certain conditions by this type of interaction.     

Dynamic and controlled rate thermal analysis of halotrichite

Three halotrichites namely halotrichite Fe²⁺SO₄·Al₂(SO₄)₃·22H₂O, apjohnite Mn²⁺SO₄·Al₂(SO₄)₃·22H₂O and dietrichite ZnSO₄·Al₂(SO₄)₃·22H₂O, were analysed by both dynamic, controlled rate thermogravimetric and differential thermogravimetric analysis. Because of the time limitation in the controlled rate experiment of 900 min, two experiments were undertaken (a) from ambient to 430 °C and (b) from 430 to 980 °C. For halotrichite in the dynamic experiment mass losses due to dehydration were observed at 80, 102, 319 and 343 °C. Three higher temperature mass losses occurred at 621, 750 and 805 °C. In the controlled rate thermal analysis experiment two isothermal dehydration steps are observed at 82 and 97 °C followed by a non-isothermal dehydration step at 328 °C. For apjohnite in the dynamic experiment mass losses due to dehydration were observed at 99, 116, 256, 271 and 304 °C. Two higher temperature mass losses occurred at 781 and 922 °C. In the controlled rate thermal analysis experiment three isothermal dehydration steps are observed at 57, 77 and 183 °C followed by a non-isothermal dehydration step at 294 °C. For dietrichite in the dynamic experiment mass losses due to dehydration were observed at 115, 173, 251, 276 and 342 °C. One higher temperature mass loss occurred at 746 °C. In the controlled rate thermal analysis experiment two isothermal dehydration steps are observed at 78 and 102 °C followed by three non-isothermal dehydration steps at 228, 243 and 323 °C. In the CRTA experiment a long isothermal step at 636 °C attributed to de-sulphation is observed.     

Temperature effect on hydrothermal synthesis of wairakite and hsianghualite

The zeolite minerals wairakite (Ca₈(Al₁₆Si₃₂O₉₆)x16H₂O) and hsianghualite (Li₁₆Ca₂₄(Be₂₄Si₂₄O₉₆)xF₁₆) were synthesized in a temperature range between 150°C and 500°C by hydrothermal treatment of artificial glasses of the respective same composition at one kbar H₂O pressure. The crystal symmetry of wairakite varied systematically with temperature under the given experimental conditions starting from orthorhombic symmetry at low synthesis temperatures, tetragonal at medium, leading to cubic symmetry at highest zeolite formation temperatures. In contrast, the crystal symmetry of hsianghualite remained cubic in the whole temperature range of synthesis. The crystal sizes varied between 500 nm and 100 μm. The investigations showed the direct correlation between chemical composition of the starting materials and the formed zeolite phase under the given pressure-temperature conditions.     

Hydroxidgruppen an Zeolithen. II. Zahl und Eigenschaften von Hydroxidgruppen an CeNaY- und HNaY-Zeolithen unterschiedlichen Austauschgrades

Hydroxide Groups on Zeolites. II. Number and Properties of Hydroxide Groups on CeNaY and HNaY Zeolites of Different Exchange Degree The number of hydroxide groups on CeNaY and HNaY zeolites was examined by D₂ exchange, and their properties in dependence of the cation exchange degrees were studied by IR spectroscopy. On CeNaY zeolites there exist six kinds and on HNaY zeolites at least seven kinds of hydroxide groups. On the CeNaY zeolites, the hydroxide groups are produced by dissociative chemisorption of water on Ce³⁺ ions. Their total number increases continuously with increasing exchange degree. Some of the hydroxide groups are acid BRÖNSTED centers whose number increases with increasing exchange degree and decreases with the temperature of preheating increasing to about 600°C. On the HNaY zeolites, the hydroxide groups are produced by thermal decomposition of the NH⁺₄ ions, by dealumination and interaction of the Al³⁺ ions produced in this way in the place of cations with water. Above the threshold value of 35% the total number of the hydroxide groups increases very rapidly with increasing exchange degree. One part of the hydroxide groups decreasing with increasing exchange degree acts as acid BRÖNSTED centers. The number of these centers does not decrease until at preheating temperatures above 450°C.     

Use of drinking water sludge in the production process of zeolites

This study reports the synthesis of zeolites A, X, and P, cancrinite, and sodalite using sludge generated in a drinking water plant. Two experimental steps were carried out: (1) fusion and (2) hydrothermal treatment. Crystallization was achieved by means of a 2³ experimental design with central point with the following factors: temperature, time, and solid/liquid ratio. The sludge presented Si and Al contents (SiO₂/Al₂O₃ = 1.7) which allow the synthesis of zeolites with high cation exchange capacity. The content of organic matter was considerable (loss on ignition 26.1 %), but is eliminated in the fusion step at 550 °C. This process also permits the conversion of the initial aluminosilicates into zeolite precursors (sludge–NaOH mix of 1:0.785 g/g). Hydrothermal treatment then permits the crystallization of the aforementioned zeolites. These materials showed high cation exchange capacities as compared to other commercial and experimentally synthesized zeolites, and can be used in the removal of heavy metals such Cd²⁺, Pb²⁺, Cu²⁺, Fe²⁺, and ammonium present in water, providing an interesting new option in wastewater treatment and remediation of soils.     

Thermal decomposition of the hydrotalcite

Summary A combination of thermogravimetry and hot stage Raman spectroscopy has been used to study the thermal decomposition of the synthesised zinc substituted takovite Zn₆Al₂CO₃(OH)₁₆·4H₂O. Thermogravimetry reveals seven mass loss steps at 52, 135, 174, 237, 265, 590 and ~780°C. MS shows that the first two mass loss steps are due to dehydration, the next two to dehydroxylation and the mass loss step at 265°C to combined dehydroxylation and decarbonation. The two higher mass loss steps are attributed to decarbonation. Raman spectra of the hydroxyl stretching region over the 25 to 200°C temperature range, enable identification of bands attributed to water stretching vibrations, MOH stretching modes and strongly hydrogen bonded CO₃^2--water bands. CO₃^2- symmetric stretching modes are observed at 1077 and 1060 cm^-1. One possible model is that the band at 1077 cm^-1is ascribed to the CO₃^2- units bonded to one OH unit and the band at 1092 cm^-1is due to the CO₃^2- units bonded to two OH units from the Zn-takovite surface. Thermogravimetric analysis when combined with hot stage Raman spectroscopy forms a very powerful technique for the study of the thermal decomposition of minerals such as hydrotalcites.</o:p>     

Synthesis of Ca<Subscript>3</Subscript>Al<Subscript>6</Subscript>Si<Subscript>2</Subscript>O<Subscript>16</Subscript>: Ce<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript> phosphors by sol–gel method and optical properties

Ca₃Al₆Si₂O₁₆: Ce³⁺, Tb³⁺ phosphors have been prepared by sol–gel method. The structure and photoluminescence properties were studied with careful. The results indicated that the single-phased Ca₃Al₆Si₂O₁₆ phosphors crystallize at 1,000 °C for 2 h in conventional furnace. With appropriate concentrations of Ce³⁺ and Tb³⁺ ions into Ca₃Al₆Si₂O₁₆ matrix, these materials exhibit blue phosphors and white light under ultraviolet radiation. White-light emission can be achieved because of a 400 nm emission ascribed to transitions of Ce³⁺ ions and three sharp peaks at 487, 543, 585 nm, respectively, resulting from transitions of Tb³⁺ ions.     

On the oxidation behaviour of monolithic TiB2 and Al2O3-TiB2 and Si3N4-TiB2 composites

In view of the susceptibility of TiB₂ to oxidation, the thermal stability of monolithic TiB₂ and of Al₂O₃-30 vol% TiB₂ and Si₃N₄-20 vol% TiB₂ composites was investigated. The temperature at which TiB₂ ceramic starts to oxidize is about 400°C, oxidation kinetics being controlled by diffusion up toT≈900°C and in the first stage of the oxidation at 1000°C and 1100°C (up to 800 min and 500 min respectively), and by a linear law at higher temperatures and for longer periods. Weight gains in the Al₂O₃-TiB₂ composite can be detected only at temperatures above ≈700°C and the rate governing step of the oxidation reaction is characterized by a one-dimensional diffusion mechanism atT=700°C andT=800°C and by two-dimensional diffusion at higher temperatures. Concerning the Si₃N₄-TiB₂ composite, three different oxidation behaviours related to the temperature were observed, i.e. up to ≈1000°C the reaction detected regards only the second phase; at ≈1000<T<≈1200°C, the diffusion of O₂ or N₂ through an oxide layer is proposed as the rate-governing step; atT〉=1200°C, a linear kinetic indicates the formation of a non protective scale.     

Reconstructive and displacive transformations of tectosilicates

By using the thermally induced phase transformation initial zeolites were converted into pure carnegieite, stuffed derivative of cristobalite. The polymorphs obtained from Na-LTA are stoichiometric (NaAlSiO₄), since those obtained from Na-FAU zeolite are non-stoichiometric (Na_1-xAl_1-xSi_1+xO₄). Stoichiometric carnegieite have cubic structure, while non-stoichiometric carnegieite crystallized in cubic and orthorhombic forms. ²⁹Si MAS NMR spectra show a very large but expecting difference between stoichiometric and non-stoichiometric carnegieite. The spectrum of stoichiometric carnegieite has only one peak Si(4Al), while the spectrum of non-stoichiometric carnegieite consist few superimposed peaks assigned to Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al). DTA study indicates the occurrence of displacive phase transition of all synthesized carnegieite. The transition temperature is depending on silicon aluminum order: T _m=690°C for stoichiometric, T _m=565 and 660°C for non-stoichiometric, low-temperature and high-temperature carnegieite, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Ionic Conductivity of Ultrafine Solid Electrolytes for Li4.4Al0.4Si0.6O4‐xY2O3 Systems

The Li_4.4Al_0.4Si_0.6O₄‐xY₂O₃ (x = 0 to 0.5) ion conductors were prepared by the Sol‐Gel method and examined in detail. The powder and sintered samples were characterized by DTA‐TG, XRD, SEM, and AC impedance techniques. The experimental results show that the conductivity and sinterability increased with the amount of excess Y₂O₃ in the silicate. The particle size of the powder samples is about 0.12 μm. The maximum conductivity at 16 °C is 2.925 × 10^?5s·cm^?1 for Li_4.4Al_0.4Si_0.6O₄‐0.3 Y₂O₃.     

Structural relationships in tetrahedral frameworks: Reflections on cristobalite

Twinning on the unit cell level of the idealized cristobalite structure, using a mirror plane as the twin and composition plane, provides a simple relationship between 14 tetrahedral frameworks. Of these, 9 are found among the aluminosilicates with examples ranging from (stuffed) silicas to zeolites and include the framework types of nepheline hydrate I, zeolite LiA(BW), gismondine, phillipsite, merlinoite, tridymite, paracelsian, and monoclinic CaAl₂Si₂O₈. Similar twinning relates the frameworks of natrolite, thomsonite, and edingtonite.     

Untersuchungen zum Existenzgebiet des CaAl2Si2-Strukturtyps bei ternären Siliciden

Investigations about the Stability Range of the CaAl₂Si₂ Type Structure in the Case of Ternary Silicides Five compounds LnAl₂Si₂ (Ln: trivalent rare-earth metal, Y) were synthesized by heating the elements at 800°–1000 °C. They are isotypic and crystallize in the CaAl₂Si₂ type structure (P 3 m1; Z = 1) (lattice constants see “Inhaltsübersicht”). The electronic structures (LMTO band structure calculations) of CaAl₂Si₂ and YAl₂Si₂, the latter one is in accordance to Ln³⁺(Al³⁺)₂(Si^4–)₂ not electrovalent, are discussed with regard to the bondings and the electrical conductivity respectively. Investigations of GdAl_2–xMn_xSi₂ mixed crystals showed, that the structure type already at low Mn content (x ≈ 0,3) changes from CaAl₂Si₂ (GdAl₂Si₂) to ThCr₂Si₂ type structure (GdMn₂Si₂).     

Phase equilibria in the Sm–Al–Si system at 500 °C

The isothermal section at 500 °C of the Sm–Al–Si system has been experimentally investigated by using scanning electron microscopy, electron microprobe analysis and X-ray powder diffraction. Four intermetallic compounds have been confirmed: τ₁-SmAl₂Si₂ (hP5-CaAl₂Si₂ type), τ₂-SmAl_xSi_1?x (tI12-Th₂Si type), τ₄-SmAl_0.5Si_0.5 (oS8-CrB type) and τ₅-Sm₆Al₃Si (tI80-Tb₆Al₃Si type). A new ternary intermediate has been found: τ₃-Sm₄Al₃Si₃ that crystallizes orthorhombic isostructural with Pr₄Al₃Ge₃.     

Spin-lattice relaxations study of water mobility in natural natrolite

The mobility of water molecules in natural natrolite (Na₂Al₂Si₃O₁₀?2H₂O) is investigated by the ¹H NMR method. The spin-lattice relaxation times in the laboratory and rotating frames (T₁ and T_1ρ) are measured as a function of the temperature for a polycrystalline sample. From experimental T₁ data it follows that at T > 286 K the diffusion of water molecules along channels parallel to the c axis is observed. From experimental T_1ρ data it follows that at T > 250 K the diffusion of water molecules in transversal channels of natrolite is also observed. At a low temperature (T < 250 K) the dipolar interaction with paramagnetic impurities (presumably Fe³⁺ ions) becomes significant as a relaxation mechanism of ¹H nuclei.     

Thermal properties of Y-type zeolites

The thermal and structural properties of two parent NaY zeolites and of those modified by ion exchange (ReNaY, HNaY, FeNaY) were investigated by simultaneous thermal analysis (TG-DTA-DTG) and by X-ray diffraction spectroscopy. Both the intracrystalline water and the zeolite framework were in our attention. The impurities (Fe) located in the lattice as well as the ions which entered by ion exchange (Re, H, Fe) influence the properties of the zeolites. The values of the activation energy of the dehydration process prove that the water molecules are more strongly bonded in all modified samples than in the parent ones. As compared to the NaY zeolites, an increased thermal stability, of about 100°C was revealed for ReNaY or of about 180°C for HNaY, and a decreased stability, of about 50°C, for FeNaY samples. The temperature at which the lattice break-down beginsT _amf, estimated by following the X-ray diffraction patterns for samples heated in air at temperatures from 300 to 1100°C, is the temperature which may be related to the structural characteristics of the zeolites, i.e., to the lattice constant of the uncalcined materials. The XRD studies reveal the heterogeneity of the crystallites constituting the zeolite material from both the point of view of the lattice constant values and the thermal stability. As the temperatureT _amf, generally, does not coincide with the temperature of the first exothermic peak,T ₁, of the DTA curve, we suggest the temperatureT _amf to be taken as an unambiguous measure of the thermal stability.