Authors:Kathleen Bakon, Sara Palmer, and Ray Frost
The mineral reevesite and the cobalt substituted reevesite have been synthesised and studied by thermal analysis and X-ray
diffraction. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co
0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules
intercalated into the structure. This increase in carbonate anion content is attributed to an increase in surface charge on
the brucite like layers. The maximum temperature of the reevesite decomposition occurs for the unsubstituted reevesite at
around 220 °C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal
decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the
formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted
reevesite is proposed.
The transition of cubic indium hydroxide to cubic indium oxide has been studied by thermogravimetric analysis complimented
with hot-stage Raman spectroscopy. Thermal analysis shows the transition of In(OH)3 to In2O3 occurs at 219 °C. The structure and morphology of In(OH)3 synthesised using a soft chemical route at low temperatures was confirmed by X-ray diffraction and scanning electron microscopy.
A topotactical relationship exists between the micro/nano-cubes of In(OH)3 and In2O3. The Raman spectrum of In(OH)3 is characterised by an intense sharp band at 309 cm−1 attributed to ν1 In–O symmetric stretching mode, bands at 1137 and 1155 cm−1 attributed to In-OH δ deformation modes, bands at 3083, 3215, 3123 and 3262 cm−1 assigned to the OH stretching vibrations. Upon thermal treatment of In(OH)3, new Raman bands are observed at 125, 295, 488 and 615 cm−1 attributed to In2O3. Changes in the structure of In(OH)3 with thermal treatment is readily followed by hot-stage Raman spectroscopy.
Authors:Laure-Marie Grand, Sara Palmer, and Ray Frost
Hydrotalcites based upon gallium as a replacement for aluminium in hydrotalcite over a Mg/Al ratio of 2:1 to 4:1 were synthesised.
The d(003) spacing varied from 7.83 Å for the 2:1 hydrotalcite to 8.15 Å for the 3:1 gallium containing hydrotalcite. A comparison
is made with the Mg/Al hydrotalcite in which the d(003) spacing for the Mg/Al hydrotalcite varied from 7.62 Å for the 2:1 Mg hydrotalcite to 7.98 Å for the 4:1 hydrotalcite.
The thermal stability of the gallium containing hydrotalcite was determined using thermogravimetric analysis. Four mass loss
steps at 77, 263–280, 485 and 828 °C with mass losses of 10.23, 21.55, 5.20 and 7.58% are attributed to dehydration, dehydroxylation
and decarbonation. The thermal stability of the gallium containing hydrotalcite is slightly less than the aluminium hydrotalcite.
Authors:Qi Tao, Hongping He, Ray Frost, Peng Yuan, and Jianxi Zhu
Anionic surfactant and silane modified layered double hydroxides (LDHs) were synthesized through an in situ coprecipitation
method. The structure and morphology were characterized by XRD and TEM techniques, and their thermal decomposition processes
were investigated using infrared emission spectroscopy (IES) combined with thermogravimetry (TG). The surfactant modified
LDHs (H-DS) shows three diffractions located at 1–7° (2θ), while there is only one broad reflection for silane grafted LDHs
(H–Si) in this region. The morphologies of the H-DS and H–Si show fibrous exfoliated layers and curved sheets, respectively.
The IES spectra and TG curves indicate that alkyl chain combustion and dehydroxylation are overlapped with each other during
heating from 373 to 723 K in H-DS and to 873 K in H–Si. Sulfate anion transformation process occurs at 473 K in H-DS and 523 K
in H–Si. The derivant of sulfate can exist even above 1073 K. After further decomposition, the metal oxides and the new type
of Si–O compounds are formed beginning at around 923 K in silane modified sample.
Authors:Ray L. Frost, Sara J. Palmer, and Ross E. Pogson
The mineral newberyite Mg(PO3OH)·3H2O is a mineral that has been found in caves such as the Skipton Lava Tubes (SW of Ballarat, Victoria, Australia), Moorba Cave, (Jurien Bay, Western Australia) and in the Petrogale Cave (Madura, Eucla, Western Australia). Since these minerals contain water, the minerals lend themselves to thermal analysis. The mineral newberyite is found to decompose at 145 °C with a water loss of 31.96%, a result which is very close to the theoretical value. The result shows that the mineral is not stable in caves where the temperature exceeds this value. The implication of this result rests with the removal of kidney stones, which have the same composition as newberyite. Point heating focussing on the kidney stone results in the destruction of the kidney stone.
Authors:Ray L. Frost, Sara J. Palmer, and Ross E. Pogson
Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl3(PO4)2(OH)5·(H2O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and identifies the products of the thermal decomposition. The mineral crandallite is formed through the reaction of calcite with bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139 °C and the dehydroxylation occurs over the temperature range 200–700 °C with loss of the OH units. The critical temperature for OH loss is around 416 °C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity occurs at 788 °C. This study shows the mineral is unstable above 139 °C. This temperature is well above the temperature in the caves of 15 °C maximum. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal decomposition is given.
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