Raman and infrared spectroscopic characterization of beryllonite, a sodium and beryllium phosphate mineral : implications for mineral collectors

The mineral beryllonite has been characterized by the combination of Raman spectroscopy and infrared spectroscopy. SEM–EDX was used for the chemical analysis of the mineral. The intense sharp Raman band at 1011 cm-1, was assigned to the phosphate symmetric stretching mode. Raman bands at 1046, 1053, 1068 and the low intensity bands at 1147, 1160 and 1175 cm-1 are attributed to the phosphate antisymmetric stretching vibrations. The number of bands in the antisymmetric stretching region supports the concept of symmetry reduction of the phosphate anion in the beryllonite structure. This concept is supported by the number of bands found in the out-of-plane bending region. Multiple bands are also found in the in-plane bending region with Raman bands at 399, 418, 431 and 466 cm-1. Strong Raman bands at 304 and 354 cm-1 are attributed to metal oxygen vibrations. Vibrational spectroscopy served to determine the molecular structure of the mineral. The pegmatitic phosphate minerals such as beryllonite are more readily studied by Raman spectroscopy than infrared spectroscopy.

Catalytic cracking of tar derived from rice hull gasification over palygorskite-supported Fe and Ni

The catalytic performance of Fe–Ni/PG (PG: palygorskite) catalysts pre-calcined and reduced at 500 ◦C for catalytic decomposition of tar derived through rice hull gasification was investigated. The materials were characterized by using X-ray diffraction, hydrogen temperature reduction, and transmission electron microscopy. The results showed that ferrites with spinel structure ((Fe, Ni)3O4) were formed during preparation of bimetallic systems during calcination and reduction of the precursors (Fe–Ni/PG catalysts) and NiO metal oxide particles were formed over Fe6–Ni9/PG catalyst. The obtained experimental data showed that Fe–Ni/PG catalysts had greater catalytic activity than natural PG. Tar removal using Fe6–Ni9/PG catalyst was as high as Fe10–Ni6/PG catalyst (99.5%). Fe6–Ni9/PG showed greater catalytic activity with greater H2 yield and showed stronger resistance to carbon deposition, attributed to the presence of NiO nanoparticles. Thus, the addition of nickel and iron oxides played an important role in catalytic cracking of rice hull biomass tar.

Effect of aging time and Al substitution on the morphology of aluminous goethite

Goethite and Al-substituted goethite were synthesized from the reaction between ferric nitrate and/or aluminum nitrate and potassium hydroxide. XRF, XRD, TEM with EDS were used to characterize the chemical composition, phase and lattice parameters, and morphology of the synthesized products. The results show that d(020) decreases from 4.953 to 4.949 Å and the b dimension decreases from 9.951 Å to 9.906 Å when the aging time increases from 6 days to 42 days for 9.09 mol% Al-substituted goethite. A sample with 9.09 mol% Al substitution in Al-substituted goethite was prepared by a rapid co-precipitation method. In the sample, 13.45 mol%, 12.31 mol% and 5.85 mol% Al substitution with a crystal size of 163, 131, and 45 nm are observed as shown in the TEM images and EDS. The crystal size of goethite is positively related to the degree of Al substitution according to the TEM images and EDS results. Thus, this methodology is proved to be effective to distinguish the morphology of goethite and Al substituted goethite.

Effect of preparation method of palygorskite-supported Fe and Ni catalysts on catalytic cracking of biomass tar

In this study, the effect of catalyst preparation and additive precursors on the catalytic decomposition of biomass using palygorskite-supported Fe and Ni catalysts was investigated. The catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is concluded that the most active additive precursor was Fe(NO3)3·9H2O. As for the catalyst preparation method, co-precipitation had superiority over incipient wetness impregnation at low Fe loadings.

Recovery and reuse of ammonium from wastewater treatment plants : an application for agriculture

In wastewater treatment plants based on anaerobic digestion, supernatant and outflows from sludge dewatering systems contain significantly high amount of ammonium. Generally, these waters are returned to the head of wastewater treatment plant (WWTP), thereby increasing the total nitrogen load of the influent flow. Ammonium from these waters can be recovered and commercially utilised using novel ion-exchange materials. Mackinnon et al. have described an approach for removal and recovery of ammonium from side stream centrate returns obtained from anaerobic digester of a typical WWTP. Most of the ammonium from side streams can potentially be removed, which significantly reduces overall inlet demand at a WWTP. However, the extent of reduction achieved depends on the level of ammonium and flow-rate in the side stream. The exchange efficiency of the ion-exchange material, MesoLite, used in the ammonium recovery process deteriorates with long-term use due to mechanical degradation and use of regenerant. To ensure that a sustainable process is utilised a range of potential applications for this “spent” MesoLite have been evaluated. The primary focus of evaluations has been use of ammonium-loaded MesoLite as a source of nitrogen and growth medium for plants. A MesoLite fertiliser has advantage over soluble fertilisers in that N is held on an insoluble matrix and is gradually released according to exchange equilibria. Many conventional N fertilisers are water-soluble and thus, instantly release all applied N into the soil solution. Loss of nutrient commonly occurs through volatilisation and/or leaching. On average, up to half of the N delivered by a typical soluble fertiliser can be lost through these processes. In this context, use of ammonium-loaded MesoLite as a fertiliser has been evaluated using standard greenhouse and field-based experiments for low fertility soils. Rye grass, a suitable test species for greenhouse trials, was grown in 1kg pots over a period of several weeks with regular irrigation. Nitrogen was applied at a range of rates using a chemical fertiliser as a control and using two MesoLite fertilisers. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks, and dry plant mass and N concentrations were determined. At all nitrogen application rates, ammonium-loaded MesoLite produced higher plant mass than plants fertilised by the chemical fertiliser. The lower fertiliser effectiveness of the chemical fertliser is attributed to possible loss of some N through volatilisation. The MesoLite fertilisers did not show any adverse effect on availability of macro and trace nutrients, as shown by lack of deficiency symptoms, dry matter yield and plant analyses. Nitrogen loaded on to MesoLite in the form of exchanged ammonium is readily available to plants while remaining protected from losses via leaching and volatilisation. Spent MesoLite appears to be a suitable and effective fertiliser for a wide range of soils, particularly sandy soils with poor nutrient holding capacity.

A new database compilation of whole-rock chemical and geochronological data of igneous rocks in Queensland : a new resource for HDR geothermal resource exploration

The Geothermal industry in Australia and Queensland is in its infancy and for hot dry rock (HDR) geothermal energy, it is very much in the target identification and resource definition stages. As a key effort to assist the geothermal industry and exploration for HDR in Queensland, we are developing a comprehensive and new integrated geochemical and geochronological database on igneous rocks. To date, around 18,000 igneous rocks have been analysed across Queensland for chemical and/or age information. However, these data currently reside in a number of disparate datasets (e.g., Ozchron, Champion et al., 2007, Geological Survey of Queensland, journal publications, and unpublished university theses). The goal of this project is to collate and integrate these data on Queensland igneous rocks to improve our understanding of high heat producing granites in Queensland, in terms of their distribution (particularly in the subsurface), dimensions, ages, and controlling factors in their genesis.

Numerical Modelling of Mechanical Behaviour of Graphene

Graphene, one of the allotropes (diamond, carbon nanotube, and fullerene) of element carbon, is a monolayer of honeycomb lattice of carbon atoms, which was discovered in 2004. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov for their ground breaking work on the two-dimensional (2D) graphene [1]. Since its discovery, the research communities have shown a lot of interest in this novel material owing to its intriguing electrical, mechanical and thermal properties. It has been confirmed that grapheme possesses very peculiar electrical properties such as anomalous quantum hall effect, and high electron mobility at room temperature (250000 cm2/Vs). Graphene also has exceptional mechanical properties. It is one of the stiffest (modulus ~1 TPa) and strongest (strength ~100 GPa) materials. In addition, it has exceptional thermal conductivity (5000 Wm-1K-1). Due to these exceptional properties, graphene has demonstrated its potential for broad applications in micro and nano devices, various sensors, electrodes, solar cells and energy storage devices and nanocomposites. In particular, the excellent mechanical properties of graphene make it more attractive for development next generation nanocomposites and hybrid materials...

Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres : 13th Volume

"Seventeen peer-reviewed papers cover the latest research on the ignition and combustion of metals and non-metals, oxygen compatibility of components and systems, analysis of ignition and combustion, failure analysis and safety. It includes aerospace, military, scuba diving, and industrial oxygen applications. Topics cover: • Development of safe oxygen systems • Ignition mechanisms within oxygen systems and how to avoid them • Specific hazards that exist with the oxygen mixture breathed by divers in the scuba industry • Issues related to oxygen system level safety • Issues related to oxygen safety in breathing systems • Detailed investigations and discussions related to the burn curves that have been generated for metals that are burning in a standard test fixture This new publication is a valuable resource for professionals in the air separation industries, oxygen manufacturers, manufacturers of materials intended for oxygen service, and users of oxygen and oxygen-enriched atmospheres, including aerospace, medical, industrial gases, chemical processing, steel and metals refining, as well as to military, commercial or recreational diving."--- publisher website

Optimisation of bio-oil extraction process from Beauty Leaf (Calophyllum inophyllum) oil seed as a second generation biodiesel source

The Beauty Leaf tree (Calophyllum inophyllum) is a potential source of non-edible vegetable oil for producing future generation biodiesel because of its ability to grow in a wide range of climate conditions, easy cultivation, high fruit production rate, and the high oil content in the seed. This plant naturally occurs in the coastal areas of Queensland and the Northern Territory in Australia, and is also widespread in south-east Asia, India and Sri Lanka. Although Beauty Leaf is traditionally used as a source of timber and orientation plant, its potential as a source of second generation biodiesel is yet to be exploited. In this study, the extraction process from the Beauty Leaf oil seed has been optimised in terms of seed preparation, moisture content and oil extraction methods. The two methods that have been considered to extract oil from the seed kernel are mechanical oil extraction using an electric powered screw press, and chemical oil extraction using n-hexane as an oil solvent. The study found that seed preparation has a significant impact on oil yields, especially in the screw press extraction method. Kernels prepared to 15% moisture content provided the highest oil yields for both extraction methods. Mechanical extraction using the screw press can produce oil from correctly prepared product at a low cost, however overall this method is ineffective with relatively low oil yields. Chemical extraction was found to be a very effective method for oil extraction for its consistence performance and high oil yield, but cost of production was relatively higher due to the high cost of solvent. However, a solvent recycle system can be implemented to reduce the production cost of Beauty Leaf biodiesel. The findings of this study are expected to serve as the basis from which industrial scale biodiesel production from Beauty Leaf can be made.

A vibrational spectroscopic study of the phosphate mineral zanazziite - Ca2(MgFe2+)(MgFe2+Al)4Be4(PO4)6⋅6(H2O)

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piauí mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca2.00(Mg3.15,Fe0.78,Mn0.16,Zn0.01,Al0.26,Ca0.14)Be4.00(PO4)6.09(OH)4.00⋅5.69(H2O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm−1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm−1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and HPO4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm−1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.

The difference of thermal stability between Fe-substituted palygorskite and Al-rich palygorskite

Sedimentary palygorskite (SP) and hydrothermal palygorskite (HP) were characterized by XRF, TG/DSC, andXRD. The total iron and dissociative iron in palygorskite were detected using spectrophotometry. The results showed that about 3.57 wt% of Fe2O3 was detected in SP in contrast with 0.4 wt% in HP. SP was a Fe-substituted palygorskite, and HP was an Al-rich palygorskite. The occurrence of Fe substitution in SP resulted in two mass loss steps of coordinated water and resulted in a larger d spacing. The SP showed greater thermal stability than the HP. It was proposed the change of (200) diffraction peak and (240) diffraction peak reflect changes of tetrahedral and octahedral structures in palygorskite.

The molecular structure of matioliite – NaMgAl5(PO4)4(OH)6·2(H2O) : a pegmatite mineral from Minas Gerais, Brazil

Detailed spectroscopic and chemical investigation of matioliite, including infrared and Raman spectroscopy, scanning electron microscopy and electron probe microanalysis has been carried out on homogeneous samples from the Gentil pegmatite, Mendes Pimentel, Minas Gerais, Brazil. The chemical composition is (wt.%): FeO 2.20, CaO 0.05, Na2O 1.28, MnO 0.06, Al2O3 39.82, P2O5 42.7, MgO 4.68, F 0.02 and H2O 9.19; total 100.00. The mineral crystallize in the monoclinic crystal system, C2/c space group, with a = 25.075(1) Å, b = 5.0470(3) Å, c = 13.4370(7) Å, β = 110.97(3)°, V = 1587.9(4) Å3, Z = 4. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of matioliite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of matioliite.

Neutralization of acid sulfate solutions using bauxite refinery residues and its derivatives

This investigation has shown that by transforming free caustic in red mud (RM) to Bayer hydrotalcite (during the seawater neutralization (SWN) process) enables a more controlled release mechanism for the neutralization of acid sulfate soils. The formation of hydrotalcite has been confirmed by X-ray diffraction (XRD) and differential thermalgravimetric analysis (DTG), while the dissolution of hydrotalcite and sodalite has been observed through XRD, DTG, pH plots, and ICP-OES. Coupling of all techniques enabled three neutralization mechanisms to be determined: (1) free alkali, (2) hydrotalcite dissolution, and (3) sodalite dissolution. The mechanisms are determined on the basis of ICP-OES and kinetic information. When the mass of RM or SWN-RM is greater than 0.08 g/50 mL, the pH of solution increases to a suitable value for plant life with aluminum leaching kept at a minimum. To obtain a neutralization pH greater than 6 in 10 min, the following ratio of bauxite residue (g) in 50 mL with a known iron sulfate (Fe2(SO4)3) concentration can be determined as follows: 0.04 g:50 mL:0.1 g/L of Fe2(SO4)3.

Vibrational spectroscopic characterization of the phosphate mineral phosphophyllite – Zn2Fe(PO4)2·4H2O, from Hagendorf Süd, Germany and in comparison with other zinc phosphates

This research was undertaken on phosphophyllite sample from the Hagendorf Süd pegmatite, Bavaria, Germany. Chemical analysis was carried out by Scanning Electron Microscope in the EDS mode and indicates a zinc and iron phosphate with partial substitution of manganese, which partially replaced iron. The calculated chemical formula of the studied sample was determined to be: Zn2(Fe0.65, Mn0.35)P1.00(PO4)2- �4(H2O). The intense Raman peak at 995 cm�1 is assigned to the m1 PO3� 4 symmetric stretching mode and the two Raman bands at 1073 and 1135 cm�1 to the m3 PO3� 4 antisymmetric stretching modes. The m4 PO3� 4 bending modes are observed at 505, 571, 592 and 653 cm�1 and the m2 PO3� 4 bending mode at 415 cm�1. The sharp Raman band at 3567 cm�1 attributed to the stretching vibration of OH units brings into question the actual formula of phosphophyllite. Vibrational spectroscopy enables an assessment of the molecular structure of phosphophyllite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral hureaulite – (Mn, Fe)5(PO4)2(HPO4)2·4(H2O)

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn3.23, Fe1.04, Ca0.19, Mg0.13)(PO4)2.7(HPO4)2.6(OH)4.78. The Raman spectrum of hureaulite is dominated by an intense sharp band at 959 cm−1 assigned to PO stretching vibrations of HPO42− units. The Raman band at 989 cm−1 is assigned to the PO43− stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO42− and PO43− units. A set of Raman bands at 531, 543, 564 and 582 cm−1 are assigned to the ν4 bending modes of the HPO42− and PO43− units. Raman bands observed at 414, and 455 cm−1 are attributed to the ν2 HPO42− and PO43− units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.