Authors:Ray Frost, Sara Palmer, János Kristóf, and Erzsébet Horváth
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.
Authors:Ray L. Frost, Sara J. Palmer, and Ross Pogson
Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral ardealite and to ascertain the thermal stability of this ‘cave’ mineral. The mineral ardealite Ca2(HPO4)(SO4)·4H2O is formed through the reaction of calcite with bat guano. The mineral shows disorder, and the composition varies depending on the origin of the mineral. Thermal analysis shows that the mineral starts to decompose over the temperature range of 100–150 °C with some loss of water. The critical temperature for water loss is around 215 °C, and above this temperature, the mineral structure is altered. It is concluded that the mineral starts to decompose at 125 °C, with all waters of hydration being lost after 226 °C. Some loss of sulphate occurs over a broad temperature range centred upon 565 °C. The final decomposition temperature is 823 °C with loss of the sulphate and phosphate anions.
Authors:János Kristóf, Ray Frost, Sara Palmer, Erzsébet Horváth, and Emma Jakab
Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6] where M+ is the cations K+, Na+ or NH4+. Thermal decomposition occurs in a series of steps: (a) dehydration, (b) well-defined dehydroxylation and (c) desulphation.
CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium
conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter
on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration
Authors:Frederick L. Theiss, Sara J. Palmer, Godwin A. Ayoko, and Ray L. Frost
The removal of the sulfate anion from water using synthetic hydrotalcite (Mg/Al LDH) was investigated using powder X-ray diffraction (XRD) and thermogravimetric analysis (TG). Synthetic hydrotalcite Mg6Al2(OH)16(CO3)·4H2O was prepared by the co-precipitation method from aluminum and magnesium chloride salts. The synthetic hydrotalcite was thermally activated to a maximum temperature of 380 °C. Samples of thermally activated hydrotalcite where then treated with aliquots of 1000 ppm sulfate solution. The resulting products where dried and characterized by XRD and TG. Powder XRD revealed that hydrotalcite had been successfully prepared and that the product obtained after treatment with sulfate solution also conformed well to the reference pattern of hydrotalcite. The d(003) spacing of all samples was found to be within the acceptable region for a LDH structure. TG revealed all products underwent a similar decomposition to that of hydrotalcite. It was possible to propose a reasonable mechanism for the thermal decomposition of a sulfate containing Mg/Al LDH. The similarities in the results may indicate that the reformed hydrotalcite may contain carbonate anion as well as sulfate. Further investigation is required to confirm this.
Authors:Ping Zhang, Huisheng Shi, Ruan Xiuxiu, Qian Guangren, and Ray L. Frost
Hydrocalumite (CaAl-Cl-LDH) has the similar structure to layered double hydroxide (LDH). The effects of Na-dodecylsulfate (SDS) on the structure, morphology, and thermal property of CaAl-Cl-LDH have been investigated. Through ion exchange, CaAl-Cl-LDH had been modified with SDS at two concentrations: 0.005 mol L−1 and 0.2 mol L−1. Two different adsorption behaviors were observed through Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) patterns. When the SDS concentration was 0.005 mol L−1, surface anion exchange was the major process. When the SDS concentration was 0.2 mol L−1, anion exchange intercalation occurs, with the interlayer distance expanded to 3.25 nm, and the particle morphology from regular hexagons to irregular platelets. The thermal analysis (TG–DTA) showed that dehydration and dehydroxylation occur at a lower temperature when hydrocalumite was intercalated with dodecylsulfate. All these observations revealed that the property of CaAl-Cl-LDH has been changed by SDS modification.
Authors:Hongfei Cheng, Jing Yang, Ray L. Frost, Qinfu Liu, and Zhiliang Zhang
The thermal behavior and decomposition of kaolinite–potassium acetate intercalation complex was investigated through a combination of thermogravimetric analysis and infrared emission spectroscopy. Three main changes were observed at 48, 280, 323, and 460 °C which were attributed to (a) the loss of adsorbed water, (b) loss of the water coordinated to acetate ion in the layer of kaolinite, (c) loss of potassium acetate in the complex, and (d) water through dehydroxylation. It is proposed that the potassium acetate intercalation complex is stability except heating at above 300 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the kaolinite intercalation complex when the temperature is raised. The dehydration of the intercalation complex is followed by the loss of intensity of the stretching vibration bands at region 3600–3200 cm−1. Dehydroxylation is followed by the decrease in intensity in the bands between 3695 and 3620 cm−1. Dehydration is completed by 400 °C and partial dehydroxylation by 650 °C. The inner hydroxyl group remained until around 700 °C.
Authors:Yuri Park, Godwin A. Ayoko, Janos Kristof, Erzsébet Horváth, and Ray L. Frost
In this study, mono- and di-alkyl cationic surfactants were used to prepare organoclays through ion exchange and the prepared organoclays were characterised by X-ray diffraction (XRD) and thermogravimetric analysis (TG). Larger basal spacings were observed in the interlayer of the organoclays intercalated with DDDMA than organoclays intercalated with DDTMA. The DTG curves identify the thermal stability of organoclays intercalated with two different types of surfactants (DDTMA and DDDMA) and the different arrangements of the surfactant molecules intercalated in the montmorillonite. Both organoclays intercalated with organic surfactant molecules proved to be thermally stable at high temperature. This study provides an understanding of the structure and properties of organoclays, which will enhance the potential applications of organoclays in environmental remediation.
Authors:Yuri Park, Godwin A. Ayoko, Janos Kristof, Erzsébet Horváth, and Ray L. Frost
High resolution thermogravimetric analysis (TG) has attracted much attention in the synthesis of organoclays and its applications. In this study, organoclays were synthesised through ion exchange of a single cationic surfactant for sodium ions, and characterised by methods including X-ray diffraction (XRD) and TG. The changes of surface properties in montmorillonite (MMT) and organoclays intercalated with surfactant were determined using XRD through the changes in the basal spacing. The TG was applied in this study to investigate more information of the configuration and structural changes in the organoclays with thermal decomposition. There are four different decompositions steps in differential thermogravimetric curves. The obtained TG steps are relevant to the arrangement of the surfactant molecules intercalated in MMT and the thermal analysis indicates the thermal stability of surfactant modified clays. This investigation provides new insights into the properties of organoclays and is important in the synthesis and processing of organoclays for environmental applications.