Thermal analysis and hot stage Raman spectroscopy of the basic copper arsenate mineral : euchroite

The thermal analysis of euchroite shows two mass loss steps in the temperature range 100 to 105°C and 185 to 205°C. These mass loss steps are attributed to dehydration and dehydroxylation of the mineral. Hot stage Raman spectroscopy (HSRS) has been used to study the thermal stability of the mineral euchroite, a mineral involved in a complex set of equilibria between the copper hydroxy arsenates: euchroite Cu2(AsO4)(OH).3H2O → olivenite Cu2(AsO4)(OH) → strashimirite Cu8(AsO4)4(OH)4.5H2O → arhbarite Cu2Mg(AsO4)(OH)3. Hot stage Raman spectroscopy inolves the collection of Raman spectra as a function of the temperature. HSRS shows that the mineral euchroite decomposes between 125 and 175 °C with the loss of water. At 125 °C, Raman bands are observed at 858 cm-1 assigned to the ν1 AsO43- symmetric stretching vibration and 801, 822 and 871 cm-1 assigned to the ν3 AsO43- (A1) antisymmetric stretching vibration. A distinct band shift is observed upon heating to 275 °C. At 275 °C the four Raman bands are resolved at 762, 810, 837 and 862 cm-1. Further heating results in the diminution of the intensity in the Raman spectra and this is attributed to sublimation of the arsenate mineral. Hot stage Raman spectroscopy is most useful technique for studying the thermal stability of minerals especially when only very small amounts of mineral are available.

Thermal analysis of synthetic reevesite and cobalt substituted reevesite (Ni,Co)6Fe2(OH)16(CO3)•4H2O

The mineral reevesite and the cobalt substituted reevesite have been synthesised. 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. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is 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.

Thermoanalytical studies of natural potassium, sodium and ammonium alunites

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 and dehydroxylation.

Thermogravimetric analysis-mass spectrometry (TG-MS) of selected Chinese kaolinites

Thermogravimetric analysis-mass spectrometry, X-ray diffraction and scanning electron microscopy (SEM) were used to characterize eight kaolinite samples from China. The results show that the thermal decomposition occurs in three main steps (a) desorption of water below 100 °C, (b) dehydration at about 225 °C, (c) well defined dehydroxylation at around 450 °C. It is also found that decarbonization took place at 710 °C due to the decomposition of calcite impurity in kaolin. The temperature of dehydroxylation of kaolinite is found to be influenced by the degree of disorder of the kaolinite structure and the gases evolved in the decomposition process can be various because of the different amount and kinds of impurities. It is evident by the mass spectra that the interlayer carbonate from impurity of calcite and organic carbon is released as CO2 around 225, 350 and 710 °C in the kaolinite samples.

Synthesis and thermal analysis of Indium based hydrotalcites of formula Mg6In2(CO3)(OH)16•4H2O

Insight into the unique structure of layered double hydroxides has been obtained using a combination of X-ray diffraction and thermal analysis. Indium containing hydrotalcites of formula Mg4In2(CO3)(OH)12•4H2O (2:1 In-LDH) through to Mg8In2(CO3)(OH)18•4H2O (4:1 In-LDH) with variation in the Mg:In ratio have been successfully synthesised. The d(003) spacing varied from 7.83 Å for the 2:1 LDH to 8.15 Å for the 3:1 indium containing layered double hydroxide. Distinct mass loss steps attributed to dehydration, dehydroxylation and decarbonation are observed for the indium containing hydrotalcite. Dehydration occurs over the temperature range ambient to 205 °C. Dehydroxylation takes place in a series of steps over the 238 to 277 °C temperature range. Decarbonation occurs between 763 and 795 °C. The dehydroxylation and decarbonation steps depend upon the Mg:In ratio. The formation of indium containing hydrotalcites and their thermal activation provides a method for the synthesis of indium oxide based catalysts.

Transition of synthetic chromium oxide gel to crystalline chromium oxide : a hot stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be X-ray amorphous. The changes in the structure of the synthetic chromium oxide gel were investigated using hot-stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr2O3 as determined by the hot-stage Raman spectra. Two bands were observed at 849 and 735 cm-1 in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O-CrIII-OH and O-CrIII-O. With temperature increase, the intensity of the band at 849 cm-1 decreased, while the band at 735 cm-1 increased. These changes in intensity are attributed to the loss of OH groups and formation of O-CrIII-O units in the structure. A strongly hydrogen bonded water H-O-H bending band was found at 1704 cm-1 in the Raman spectrum of the chromium oxide gel, however this band shifted to around 1590 cm-1 due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm-1 attributed to the thermal decomposed product Cr2O3. The use of the hot-stage Raman microscope enabled low-temperature phase changes brought about through dehydration and dehydroxylation to be studied.

Thermal analysis and infrared emission spectroscopic study of halloysite-potassium acetate intercalation compound

The thermal decomposition of halloysite-potassium acetate intercalation compound was investigated by thermogravimetric analysis and infrared emission spectroscopy. The X-ray diffraction patterns indicated that intercalation of potassium acetate into halloysite caused an increase of the basal spacing from 1.00 to 1.41 nm. The thermogravimetry results show that the mass losses of intercalation the compound occur in main three main steps, which correspond to (a) the loss of adsorbed water (b) the loss of coordination water and (c) the loss of potassium acetate and dehydroxylation. The temperature of dehydroxylation and dehydration of halloysite is decreased about 100 °C. The infrared emission spectra clearly show the decomposition and dehydroxylation of the halloysite intercalation compound when the temperature is raised. The dehydration of the intercalation compound 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 was completed by 300 °C and partial dehydroxylation by 350 °C. The inner hydroxyl group remained until around 500 °C.

Diarrhoea risk factors in enterally tube fed critically ill patients : a retrospective audit

Objective: Diarrhoea in the enterally tube fed (ETF) intensive care unit (ICU) patient is a multifactorial problem. Diarrhoeal aetiologies in this patient cohort remain debatable; however, the consequences of diarrhoea have been well established and include electrolyte imbalance, dehydration, bacterial translocation, peri anal wound contamination and sleep deprivation. This study examined the incidence of diarrhoea and explored factors contributing to the development of diarrhoea in the ETF, critically ill, adult patient. ---------- Method: After institutional ethical review and approval, a single centre medical chart audit was undertaken to examine the incidence of diarrhoea in ETF, critically ill patients. Retrospective, non-probability sequential sampling was used of all emergency admission adult ICU patients who met the inclusion/exclusion criteria. ---------- Results: Fifty patients were audited. Faecal frequency, consistency and quantity were considered important criteria in defining ETF diarrhoea. The incidence of diarrhoea was 78%. Total patient diarrhoea days (r = 0.422; p = 0.02) and total diarrhoea frequency (r = 0.313; p = 0.027) increased when the patient was ETF for longer periods of time. Increased severity of illness, peripheral oxygen saturation (Sp02), glucose control, albumin and white cell count were found to be statistically significant factors for the development of diarrhoea. ---------- Conclusion: Diarrhoea in ETF critically ill patients is multi-factorial. The early identification of diarrhoea risk factors and the development of a diarrhoea risk management algorithm is recommended.

Application of infrared emission spectroscopy to the thermal transition of indium hydroxide to indium oxide nanocubes

Cubic indium hydroxide nanomaterials were obtained by a low temperature soft-chemical method without any surfactants. The transition of nano-cubic indium hydroxide to cubic indium oxide during dehydroxylation has been studied by infrared emission spectroscopy. The spectra are related to the structure of the materials and the changes in the structure upon thermal treatment. The infrared absorption spectrum of In(OH)3 is characterised by an intense OH deformation band at 1150 cm-1 and two O-H stretching bands at 3107 and 3221 cm-1. In the infrared emission spectra, the hydroxyl-stretching and hydroxyl-bending bands diminish dramatically upon heating, and no intensity remains after 200 °C. However, new low intensity bands are found in the OH deformation region at 915 cm-1 and in OH stretching region at 3437 cm-1. These bands are attributed to the vibrations of newly formed InOH bonds because of the release and transfer of protons during calcination of the nanomaterial. The use of infrared emission spectroscopy enables the low-temperature phase transition brought about through dehydration of In(OH)3 nanocubes to be studied.

Large-scale fabrication of H2(H2O)Nb2O6 and Nb2O5 hollow microspheres

Hollow micro-sized H2(H2O)Nb2O6 spheres constructed by nanocrystallites have been successfully synthesized via a bubble-template assisted hydrothermal process. In the reaction process, H2O2 acts as a bubble generator and plays a key role in the formation of the hollow structure. An in situ bubble-template mechanism has been proposed for the possible formation of the hollow structure. The spherelike assemblies of these H2(H2O)Nb2O6 nanoparticles have been transformed into their corresponding pseudohexagonal phase Nb2O5 through a moderate annealing dehydration process without destroying the hierarchical structure. Optical properties of the as-prepared hollow spheres were investigated. It is exciting that the absorption edge of the hollow Nb2O5 microspheres shifts about 18 nm to the violet compared with bulk powders in the UV/vis spectra, indicating its superior optical properties.

Thermal analysis and infrared emission spectroscopic study of kaolinite-potassium acetate intercalate complex

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 KAc 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.

Analysis of micro-structural changes and measurement of their parameters of a food material

Food microstructure represents the way their elements arrangement and their interaction. Researchers in this field benefit from identifying new methods of examination of the microstructure and analysing the images. Experiments were undertaken to study micro-structural changes of food material during drying. Micro-structural images were obtained for potato samples of cubical shape at different moisture contents during drying using scanning electron microscopy. Physical parameters such as cell wall perimeter, and area were calculated using an image identification algorithm, based on edge detection and morphological operators. The algorithm was developed using Matlab.

Heat strain, hydration status, and symptoms of heat illness in surface mine workers

The aim of the research program was to evaluate the heat strain, hydration status, and heat illness symptoms experienced by surface mine workers. An initial investigation involved 91 surface miners completing a heat stress questionnaire; assessing the work environment, hydration practices, and heat illness symptom experience. The key findings included 1) more than 80 % of workers experienced at least one symptom of heat illness over a 12 month period; and 2) the risk of moderate symptoms of heat illness increased with the severity of dehydration. These findings highlight a health and safety concern for surface miners, as experiencing symptoms of heat illness is an indication that the physiological systems of the body may be struggling to meet the demands of thermoregulation. To illuminate these findings a field investigation to monitor the heat strain and hydration status of surface miners was proposed. Two preliminary studies were conducted to ensure accurate and reliable data collection techniques. Firstly, a study was undertaken to determine a calibration procedure to ensure the accuracy of core body temperature measurement via an ingestible sensor. A water bath was heated to several temperatures between 23 . 51 ¢ªC, allowing for comparison of the temperature recorded by the sensors and a traceable thermometer. A positive systematic bias was observed and indicated a need for calibration. It was concluded that a linear regression should be developed for each sensor prior to ingestion, allowing for a correction to be applied to the raw data. Secondly, hydration status was to be assessed through urine specific gravity measurement. It was foreseeable that practical limitations on mine sites would delay the time between urine collection and analysis. A study was undertaken to assess the reliability of urine analysis over time. Measurement of urine specific gravity was found to be reliable up to 24 hours post urine collection and was suitable to be used in the field study. Twenty-nine surface miners (14 drillers [winter] and 15 blast crew [summer]) were monitored during a normal work shift. Core body temperature was recorded continuously. Average mean core body temperature was 37.5 and 37.4 ¢ªC for blast crew and drillers, with average maximum body temperatures of 38.0 and 37.9 ¢ªC respectively. The highest body temperature recorded was 38.4 ¢ªC. Urine samples were collected at each void for specific gravity measurement. The average mean urine specific gravity was 1.024 and 1.021 for blast crew and drillers respectively. The Heat Illness Symptoms Index was used to evaluate the experience of heat illness symptoms on shift. Over 70 % of drillers and over 80 % of blast crew reported at least one symptom. It was concluded that 1) heat strain remained within the recommended limits for acclimatised workers; and 2) the majority of workers were dehydrated before commencing their shift, and tend to remain dehydrated for the duration. Dehydration was identified as the primary issue for surface miners working in the heat. Therefore continued study focused on investigating a novel approach to monitoring hydration status. The final aim of this research program was to investigate the influence dehydration has on intraocular pressure (IOP); and subsequently, whether IOP could provide a novel indicator of hydration status. Seven males completed 90 minutes of walking in both a cool and hot climate with fluid restriction. Hydration variables and intraocular pressure were measured at baseline and at 30 minute intervals. Participants became dehydrated during the trial in the heat but maintained hydration status in the cool. Intraocular pressure progressively declined in the trial in the heat but remained relatively stable when hydration was maintained. A significant relationship was observed between intraocular pressure and both body mass loss and plasma osmolality. This evidence suggests that intraocular pressure is influenced by changes in hydration status. Further research is required to determine if intraocular pressure could be utilised as an indirect indicator of hydration status.

Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.