Al-substituted tobermorite: shows cation exchange

It has been found that the tobermorite family--fundamental to cement chemistry can exhibit base exchange behavior. Several Al-substituted tobermorites were synthesized and these 11Å type tobermorites were discovered to have cation exchange as well as selective cation adsorption properties. For example, Al-substituted tobermorite (synthesized from a mixture of clinoptilolite and mortar) has a cation exchange capacity of 56 meq/100g and a selective Cs adsorption K_d of 3400 (ml/g). The cation exchange and selective properties of Al-substituted tobermorite are analogous to those of zeolites because of its rigid structure but unlike those of smectites or vermiculites where the basal spacing varies with the nature of the interlayer cation.     

Hydrothermal alkaline treatment of oil shale ash for synthesis of tobermorites

The hydrothermal alkaline activation of the oil shale fly ash was studied using SEM/EDX, XRD and ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. The silicon in the original fly ashes was completely converted into calcium-alumino-silicate hydrates, mainly into 1.1 nm tobermorite structure during 24 h treatment under hydrothermal conditions at 160 °C in the presence of NaOH. The local structure of synthesized tobermorite samples implies long silicate chains with small number of bridging sites. The results obtained in the study prove that the oil shale fly ash can be used for production of Al-substituted tobermorites.     

Synthesis and characterization of calcium–alumino-silicate hydrates from oil shale ash – Towards industrial applications

The influence of the alkaline medium on the hydrothermal activation of the oil shale fly ash with NaOH and KOH was studied using SEM/EDX, XRD, ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. In the presence of NaOH the silicon in the original fly ash was completely converted into calcium–aluminum–silicate–hydrates, mainly into 1.1 nm tobermorite structure during 24-h treatment at 160 °C. At similar reaction conditions, the activation with KOH resulted only to the formation of amorphous calcium–silica-hydrate gel on the surface of ash particles at temperature. The results obtained in this study indicate that the oil shale fly ash can be used for production of Al-substituted tobermorites when strongly alkaline media (NaOH) is applied. The synthesized product was used in a catalytic d-lactose isomerization reaction.     

Structural Degradation of Tobermorite during Vibratory Milling

Mechanochemistry of hydrothermally prepared Al-free and Al-substituted 1.1 nm tobermorite was studied using ²⁹Si NMR, XRD, and TGA-DTA. Tobermorite has a double-chain structure and Al/Si substitution occurs preferentially at bridging tetrahedra. By using the vibration mill, both tobermorites were observed to decompose as a function of milling time to form amorphous C-S-H-like phases. The decomposition rate was higher for the Al-substituted tobermorite. The decomposition process occurs mainly at the bridge portion of the silicate double chain. In the Al-substituted tobermorite, the breakage seems to occur preferentially at the points where Al has replaced Si. On heating the amorphous C-S-H-like phase, wollastonite is formed. However, no decrease was observed at the wollastonite formation temperature.     

Substituted Tobermorites: 27Al and 29Si MASNMR, Cation Exchange, and Water Sorption Studies

²⁷Al and ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy revealed that the maximum amount of Al that can be substituted for Si in the tobermorite structure is 15 to 20 mol%. Powder X-ray diffraction and cation exchange studies corroborate the above finding. Anomalous tobermorite structures resulted in all cases, and hydrogarnet appeared beyond the 15 to 20 mol% Al substitution limit for Si. The sorption of water molecules by synthetic [Al³⁺+ Na⁺]-substituted tobermorites and their cation-exchanged forms heated at 200°C under vacuum (≥10⁻³ torr) was measured at 25°C in order to probe the nature of the ion-exchange cavity. Samples with ≤30 mol% of Al substitution for Si showed isotherms of Brunauer, Demming, Demming, Teller (BDDT) type I and gave better linearity with the Langmuir plot than with the BET plot. Samples with ≥35 mol% of Al substitution for Si showed BDDT type II isotherms and gave better linearity with the BET than with the Langmuir equation. The Langmuir monolayer capacity was found to depend on the Al content and on the cationic form. The Li⁺- and Na⁺-exchanged tobermorites with about 20 mol% of Al substitution for Si showed the highest Langmuir monolayer water sorption capacity. The Cs⁺-exchanged tobermorites showed a smaller capacity than the Li⁺- or Na⁺-exchanged samples, which can be ascribed to clogging of the ion-exchange cavity by the large Cs⁺ ions.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

Selective Cation Exchange in Substituted Tobermorites

Selective cation exchange in tobermorites with three levels of Al³⁺ and Na⁺ substitution for Si⁴⁺ has been investigated. The cation exchange selectivity for a tobermorite with 2 mol% Al³⁺ and 0 mol% Na⁺ substitution increased as follows: Mg²⁺ > Ba²⁺ > Sr²⁺. Cation exchange in the above tobermorite is postulated to take place mainly from edge and planar surface sites and apparently from interlayer Ca²⁺ sites. Tobermorites with 10 and 15 mol% Al³⁺ (and Na⁺) substitution have additional Na⁺ exchange sites in the interlayers and show the following selectivity: Ba²⁺ > Sr²⁺ > Mg²⁺. The cation exchange selectivity in the substituted tobermorites can be explained by the hydrated radii of cations and the steric limitations of the ion exchange cavity in tobermorite; the latter was determined by ²⁷Al and ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy. These basic selective cation exchange studies of substituted tobermorites are of relevance in nuclear waste treatment and disposal.     

Hydrothermal reaction between CSH and kaolinite for the formation of tobermorite at 180°C

11 Å tobermorites were made from C---S---H (Ca/Si = 1.14) and kaolinite with Ca/(Si+Al) = 0.8 and Al/(Si+Al)= 0.15 at 180°C. The C---S---H was prepared from colloidal silica and lime at 130°C and 180°C for 2 h. Reaction gives in succession C---S---H, poorly crystalline Al-substituted tobermorite, and highly crystalline Al-substituted tobermorite. The addition of kaolinite markedly accelerates the formation of tobermorite within 4 h, more effectively with C---S---H prepared at 130°C than with that prepared at 180°C. X-ray fluorescence diffractometry shows that the Al coordination number is a mixture of 4 and 6 in the initial products and shifts to 4 with an increase in processing time. This agrees with the results for the degree of reaction of the kaolinite.     

Hydrothermal reaction between C6S6H and kaolinite for the formation of tobermorite at 180°C

11 Å tobermorites were made from CSH (Ca/Si = 1.14) and kaolinite with Ca/(Si+Al) = 0.8 and Al/(Si+Al)= 0.15 at 180°C. The CSH was prepared from colloidal silica and lime at 130°C and 180°C for 2 h. Reaction gives in succession CSH, poorly crystalline Al-substituted tobermorite, and highly crystalline Al-substituted tobermorite. The addition of kaolinite markedly accelerates the formation of tobermorite within 4 h, more effectively with CSH prepared at 130°C than with that prepared at 180°C. X-ray fluorescence diffractometry shows that the Al coordination number is a mixture of 4 and 6 in the initial products and shifts to 4 with an increase in processing time. This agrees with the results for the degree of reaction of the kaolinite.     

Activation of Pozzolanic Reaction of Hydrated Portland Cement Fly Ash Pastes in Sulfate Solution

The activation of the pozzolanic reaction of fly ash in portland cement paste immersed in sulfate solution has been studied. Mixtures of two Spanish fly ashes (ASTM class F) with 0%, 15%, and 35% replacement of portland cement by fly ash were immersed in Na₂SO₄ solution, of 2880 ppm SO₄²⁻ concentration, for a period of 90 days. The resistance of the different mixtures to the sulfate attack was evaluated using the Koch-Steinegger test. The results showed that all of the mixtures were sulfate resistant, despite the high Al₂O₃ content of the fly ash. The diffusion of SO₄²⁻ and Na⁺ ions through the pore solution activated the pozzolanic reactivity of the fly ashes, causing microstructural changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Crystal Chemistry of Hydrous Calcium Silicates: II, Characterization of Interlayer Water

Examination of tobermorite, 4–SCaO.5SiO₂.-5H₂O, and xonotlite, 5CaO.5SiO₂.H₂O, by infrared absorption revealed striking structural similarities and differences in the two phases. In the 8- to 15- μ region, the absorption was the same for both; the differences arose from the manner in which water and hydroxyl ions were bonded. Tobermorite exhibited strong absorption at 6.2 μ , a band which is generally associated with interlayer water, and at 2.9 μ , a band generally attributed to bonded (OH). The mineral xonotlite did not show these two bands but contained the band at 2.75 μ generally associated with free (OH). Synthetic xonotlite prepared at 300°C. was essentially the same as the mineral, but samples prepared at progressively lower temperatures exhibited the 2.9- μ band in increasing intensity. The fibrous form of tobermorite showed a band at 6.5 to 7.0 μ which increased in intensity with increasing amount of CaO in the solid; this band was also found in the 14-a.u. 1.0 CaO: SiO₂ hydrate, but not in xonotlite. The great volume stability of xonotlite during drying and wetting is readily explained on the basis of the present results. Shrinkage of tobermorite during drying at temperatures up to 650°C. may be due to removal of both interlayer water and bonded (OH). The changes in absorption during drying at room temperature were too small, however, to permit drawing any conclusions. Similarities and differences between tobermorite and certain clays are discussed.     

粉煤灰形貌元素组成的SEM／EDS分析

文章用扫描电子显微镜／能量色散谱（SEM／EDS）的扫描电镜、元素组成分析功能和背散射找寻功能对粉煤灰进行了形貌、元素组成分桥。粉煤灰为富含SiO2、Al2O3的比较规则的球形玻璃微珠（SiO2和Al2O3的含量达57．64％和31．09％），元素组成为Si、Al、O、Fe、Cu、Zn、Mg、Ca、Ti、K、Na、Ba等，无其它对人体有重大影响的重金属离子，对环境友好。粉煤灰颗粒中也有极少柱状、条状、纤维状、扁平状的颗粒，其组成大部分与球形颗粒相差不大，但也存在几乎哭含有氧化硅或氧化铁豹颗粒。粉煤灰颗粒是各种氧化物的聚集体。     

Thermochemistry of Framework Titanosilicate A2TiSi6O15 (A=K, Rb, Cs)

A new family of framework titanosilicates, A₂TiSi₆O₁₅ (A=K, Rb, Cs) (space group Cc ), has recently been synthesized using the hydrothermal method. This group of phases can potentially be utilized for storage of radioactive elements, particularly ¹³⁷Cs, due to its high stability under electron radiation and chemical leaching. Here, we report the syntheses and structures of two intermediate members in the series: KRbTiSi₆O₁₅ and RbCsTiSi₆O₁₅. Rietveld analysis of powder synchrotron X-ray diffraction data reveals that they adopt the same framework topology as the end-members, with no apparent Rb/K or Rb/Cs ordering. To study energetics of the solid solution series, high-temperature drop-solution calorimetry using molten 2PbO·B₂O₃ as the solvent at 975 K has been performed for the end-members and intermediate phases. As the size of the alkali cation increases, the measured enthalpies of formation from the constituent oxides (     ) and from the elements (     ) become more exothermic, suggesting that this framework structure favors the cation in the sequence Cs⁺, Rb⁺, and K⁺. This trend is consistent with the higher melting temperatures of A₂TiSi₆O₁₅ phases with increase in the alkali cation size.     

Effect of Fly Ashes with High Total Alkali Content on the Alkalinity of the Pore Solution of Hydrated Portland Cement Paste

The influence of two Spanish fly ashes (ASTM class F) with high total alkali content (equivalent to 2.0% and 2.6% Na₂O) on the alkalinity levels of the pore solutions expressed from hydrated portland cement pastes was studied during a period of 90 days from mixing. Mixtures with 0%, 15%, and 35% replacement of cement by fly ash were prepared with a water/mixture ratio of 0. 4. The effect of the fly ash on the pore solution depended mainly on the age and fineness of the fly ash.     

粉煤灰动态水热合成纳米复合托贝莫来石晶须及其表征

以山西某地普通粉煤灰为原料,采用动态水热法合成纳米复合托贝莫来石晶须,考察了CaO/SiO2摩尔比、反应温度、液固比、反应时间的影响. 结果表明,以预活化的普通粉煤灰为原料,控制CaO/SiO2摩尔比为1.0、液固比为25 mL/g,在220℃下水热反应10 h,可制备出晶须长/径比大于20的纳米复合托贝莫来石晶须,优化条件下晶须可相互缠绕成中空球形颗粒,纯度达80%以上.     

Al-B2O3-CeO2-粉煤灰复合增强涂层成分设计及冲蚀磨损分析

为了提高粉煤灰作为增强材料在金属基复合材料中的应用和性能,通过热力学分析和正交优化试验确定Al-B₂O₃-CeO₂-粉煤灰复合增强涂层各成分之间可能发生的反应及最佳配方比例,采用等离子喷涂在ZG310-570基体制备了粉煤灰复合增强涂层,分析了粉煤灰复合增强涂层的表面形貌、物相和冲蚀磨损性能。结果发现,热力学分析和正交优化试验表明Al、B₂O₃、CeO₂和粉煤灰之间能发生固相反应,粉煤灰复合增强涂层配方最佳比例质量分数为粉煤灰55%、B₂O₃20%、Al20%、CeO₂5%;粉煤灰复合增强涂层呈凹凸不平的片层状结构,致密性好,存在纵向裂纹、未充分融化颗粒和孔隙;X射线分析表明粉煤灰复合增强涂层有Al₂O₃、CeB₆、2MgO·SiO₂、3CaO·B₂O₃等新相生成,与热力学分析结果一致;在一定冲蚀时间和冲蚀角度下,不同冲蚀转速时ZG310-570基体表面粉煤灰复合增强涂层的相对耐冲蚀磨损性能比基体分别至少提高了20.41倍、22.43倍和23.17倍。     

Extended X-ray Absorption Fine Structure Investigation of Calcium Silicate Hydrates

²⁹Si MAS-NMR, and Ca-EXAFS experiments have been conducted on calcium silicate hydrates (C-S-Hs) with structure derived from wollastonite. Crystalline compounds (wollastonite, xonotlite, hillebrandite, foshagite, 1.1 nm and 1.4 nm tobermorites, and jennite) and C-S-H were synthesized and characterized. ²⁹Si NMR provides information on silicate chains and EXAFS on calcium environment. The refined EXAFS values are in agreement with XRD data, except for tobermorite. The calcium order in C-S-H (C/S molar ratio from 0.7 to 1.4) is similar to that of tobermorite but different from that of jennite. Structural models of C-S-H are discussed.     

Fabrication and Characterization of a (100) Three-Axis-Oriented Single-Crystal (Ba0.7Sr0.3)TiO3 Thin Film Prepared by the Chemical Solution Deposition Method

Epitaxially grown single-crystal perovskite (100) three-axis-oriented (Ba_0.7Sr_0.3)TiO₃ thin films were prepared on a (100) platinum-coated (100) magnesium oxide (MgO) single-crystal substrate by the chemical solution deposition method using a solution derived from Ba(CH₃COO)₂, Sr(CH₃COO)₂, and Ti(O- i -C₃H₇)₄.
The growth of the film was found to depend on the annealing condition. A (Ba,Sr)TiO₃ thin film annealed at 1073 K was found to be a single crystal by transmission electron microscope. The single-crystal film exhibited a (100) three-axis orientation that followed the (100) orientation of the Pt substrate, as observed from an X-ray pole figure measurement and selected area electron diffraction patterns.     

HIPed Tailored Hollandite Waste Forms for the Immobilization of Radioactive Cs and Sr

Hot isostatically pressed tailored hollandite waste forms were used to demonstrate the immobilization of Cs and Sr are separable from spent nuclear fuel, as well as Ba and Rb. Four hollandite formulations were investigated, two samples with ∼12 wt% waste loading (on an oxide basis) and two with ∼18 wt% waste loading. Two of the samples were Al-substituted and the other two contained Mg. The hollandite in the Al-substituted samples contained all the waste cations, as designed, but this was not the case in the Mg-substituted samples. The hollandite in the Mg-substituted samples did not contain all the waste cations, with ∼50% of the Sr forming SrTiO₃ as a secondary phase. This resulted in waste forms that were not as durable, with respect to Cs, as their Al counterparts. The formation of SrTiO₃ had little effect on the Sr release rates and was not detrimental to the Mg-substituted hollandite waste form. For the Al-substituted samples, the MCC-1 normalized release rates were <0.06 g·(m²·day)⁻¹ at 0–28 days for all elements, while the Cs release rates remained at 2.0 g·(m²·day)⁻¹ at 0–28 days for the Mg-substituted samples.     

Preparation of Cubic Perovskites A(B2/5W3/5)O3 (A=Ba or Sr, B=Na or Li)

Pure cubic perovskites Ba(Na_2/5W_3/5)O₃, Sr(Na_2/5W_3/5)l5)O₃, and Sr(Li_2/5W_3/5)O₃ were prepared by solid-state reaction at 600° to 650°C in air, by starting with oxides or carbonates of the various elements. The cubic forms have an ordered arrangement of the B cations in the ABO₃ structure, and the lattice constants are a =0.8324 nm [Ba(Na_2/5W_3/5)O₃], 0.8136 nm Sr(Na_2/5W_3/5)O₃], and 0.7958 nm [Sr(Li_2/5W_3/5)O₃]