Vibrational spectroscopic study of the minerals nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O : implications for the molecular structure

Nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O are both hydrated calcium silicates found respectively in contact metamorphosed limestone and in association with zeolites from the alteration of basalts. The minerals form two-Dimensional infinite sheets with other than six-membered rings with 3-, 4-, or 5-membered rings and 8-membered rings. The two minerals have been characterised by Raman, near-infrared and infrared spectroscopy. The Raman spectrum of nekoite is characterised by two sharp peaks at 1061 and 1092 cm-1 with bands of lesser intensity at 974, 994, 1023 and 1132 cm-1. The Raman spectrum of okenite shows an intense single Raman band at 1090 cm-1 with a shoulder band at 1075 cm-1.These bands are assigned to the SiO stretching vibrations of Si2O5 units. Raman water stretching bands of nekoite are observed at 3071, 3380, 3502 and 3567 cm-1. Raman spectrum of okenite shows water stretching bands at 3029, 3284, 3417, 3531 and 3607 cm-1. NIR spectra of the two minerals are subtly different inferring water with different hydrogen bond strengths. By using a Libowitzky empirical formula, hydrogen bond distances based upon these OH stretching vibrations. Two types of hydrogen bonds are distinguished: strong hydrogen bonds associated with structural water and weaker hydrogen bonds assigned to space filling water molecules.

Vibrational spectroscopic study of the copper silicate mineral ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O

Ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O is a mineral named after the Ajo district of Arizona. Raman and infrared spectroscopy were used to characterise the molecular structure of ajoite. The structure of the mineral shows disorder which is reflected in the difficulty of obtaining quality Raman spectra. The Raman spectrum is characterised by a broad spectral profile with a band at 1048 cm-1 assigned to the ν1 (A1g) symmetric stretching vibration. Strong bands at 962, 1015 and 1139 cm-1 are assigned to the ν3 SiO4 antisymmetric stretching vibrations. Multiple ν4 SiO4 vibrational modes indicate strong distortion of the SiO4 tetrahedra. Multiple AlO and CuO stretching bands are observed. Raman spectroscopy and confirmed by infrared spectroscopy clearly shows that hydroxyl units are involved in the ajoite structure. Based upon the infrared spectra, water is involved in the ajoite structure, probably as zeolitic water.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Vibrational spectroscopic study of the mineral creaseyite Cu2Pb2(Fe,Al)2(Si5O17)·6H2O – a zeolite mineral?

Vibrational spectroscopy has been used to characterise the mineral creaseyite Cu2Pb2(Fe,Al)2(Si5O17)·6H2O. The mineral is found in the oxidised zone of base metal deposits and interestingly is associated with copper silicate minerals including ajoite, kinoite, chrysocolla as well as wulfenite, willemite, mimetite and wickenburgite. Creaseyite is a mineral with zeolitic properties. A Raman band at 998 cm−1 is assigned to the SiO stretching vibration of SiO3 units. The Raman band at 1071 cm−1 is assigned to the SiO stretching vibrations of the Si2O5 units. Raman bands are found at 2750, 2902, 3162, 3470 and 3525 cm−1. The band at 3525 cm−1 is attributed to zeolitic water. Other bands are assigned to water coordinated to the metal cations. Vibrational spectroscopy enables aspects of the molecular structure of creaseyite to be determined.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

A spectroscopic comparison of YBCO superconductors synthesised by solid-state and co-precipitation methods

Raman spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) have been used to compare samples of YBa2Cu3O7 (YBCO) synthesised by the solid-state method and a novel co-precipitation technique. XRD results indicate that YBCO prepared by these two methods are phase pure, however the Raman and SEM results show marked differences between these samples.

SERS substrate for detection of explosives

A novel gold coated femtosecond laser nanostructured sapphire surface – an “optical nose” - based on surface-enhanced Raman spectroscopy (SERS) for detecting vapours of explosive substances was investigated. Four different nitroaromatic vapours at room temperature were tested. Sensor responses were unambiguous and showed response in the range of 0.05 – 15 uM at 25 °C. The laser fabricated substrate nanostructures produced up to an eight-fold increase in Raman signal over that observed on the unstructured portions of the substrate. This work demonstrates a simple sensing system that is compatible with commercial manufacturing practices to detect taggants in explosives which can undertake as part of an integrated security or investigative mission.

The borate mineral jeremejevite Al6(BO3)5(F,OH)3 – A vibrational spectroscopic study

Jeremejevite is a borate mineral of aluminium and is of variable colour, making the mineral and important inexpensive jewel. The mineral contains variable amounts of F and OH, depending on origin. A comparison of the vibrational spectroscopic data is made with the published data of borate minerals. Raman spectra were averaged over a range of crystal orientations. Two intense Raman bands observed at 961 and 1067 cm−1 are assigned to the symmetric stretching and antisymmetric stretching modes of trigonal boron. Infrared spectrum, bands observed at 1229, 1304, 1350, 1388 and 1448 cm−1 are attributed to BOH in-plane bending modes. Intense Raman band found at 372 cm−1 with other bands of significant intensity at 327 and 417 cm−1 is assigned to trigonal borate bending modes. A quite intense Raman band is found at 3673 cm−1 with other sharp Raman bands found at 3521, 3625 and 3703 cm−1 are assigned to the stretching modes of OH. Raman and infrared spectroscopy has been used to assess the molecular structure of the mineral jeremejevite. Such research is important in the study of borate based nanomaterials.

Vibrational spectroscopic study of the mineral penkvilksite Na2TiSi4O11·2H2O – a mineral used for the uptake of radionuclides

We have used vibrational spectroscopy to study the formula and molecular structure of the mineral penkvilksite Na 2TiSi 4O 11·2H 2O. Penkvilksite is a mineral which may be used in the uptake of radioactive elements. Both Raman and infrared spectroscopies identify a band at 3638 cm−1 attributed to an OH-stretching vibration of hydroxyl units. The inference is that OH units are involved in the structure of penkvilksite. The formula may be well written as Na 2TiSi 4O 10(OH)2·H 2O. The mineral is characterised by a very intense Raman band at 1085 cm−1 and a broad infrared band at 1080 cm−1 assigned to SiO-stretching vibrations. Raman bands at 620, 667 and 711 cm−1 are attributed to SiO and TiO chain bonds. Water-stretching vibrations are observed as Raman bands at 3197, 3265, 3425 and 3565 cm−1. Vibrational spectroscopy enables aspects of the molecular structure of the mineral penkvilksite to be ascertained. Penkvilksite is a mineral which can incorporate actinides and lanthanides from radioactive waste.

Is chrysocolla (Cu,Al)2H2Si2O5(OH)4·nH2O related to spertiniite Cu(OH)2? - a vibrational spectroscopic study

Chrysocolla (Cu, Al)2H2Si2O5(OH)4·nH2O is a hydrated copper hydroxy silicate and is commonly known as a semi-precious jewel. The mineral has an ill defined structure but is said to be orthorhombic, although this remains unproven. Thus, one of the few methods of studying the molecular structure of chrysocolla is to use vibrational spectroscopy. Chrysocolla may be defined as a colloidal mineral. The question arises as to whether chrysocolla is a colloidal system of spertiniite and amorphous silica. The main question addressed by this study is whether chrysocolla is (1) a mesoscopic assemblage of spertiniite, Cu(OH)2, silica, and water, (2) represents a colloidal gel or (3) is composed of microcrystals with a distinct structure. Considerable variation in the vibrational spectra is observed between chrysocolla samples. The Raman spectrum of chrysocolla is characterised by an intense band at 3624 cm−1 assigned to the OH stretching vibrations. Intense Raman bands found at 674, 931 and 1058 cm−1 are assigned to SiO3 vibrations. The Raman spectrum of spertiniite does not correspond to the spectrum of chrysocolla and it is concluded that the two minerals are not related. The spectra of chrysocolla correspond to a copper silicate colloidal gel.

Stichtite : a review

Stichtite is a naturally occurring layered double hydroxide (LDH) with the ideal chemical formula Mg6Cr2CO3(OH)16·4H2O. It has received less attention in the literature than other LDHs and is often described as a rare mineral; however, abundant deposits of the mineral do exist. In this article we aim to review a number of significant publications concerning the mineral stichtite, including papers covering the discovery, geological origin, synthesis and characterizsation of stichtite. Characterization techniques reviewed include powder X-ray diffraction (XRD), infrared spectroscopy (IR), near infrared spectroscopy (NIR), Raman spectroscopy (Raman), thermogravimetry (TG) and electron microprobe analysis.

Low temperature response of nanostructured tungsten oxide thin films toward hydrogen and ethanol

Semiconducting metal oxide based gas sensors usually operate in the temperature range 200–500 °C. In this paper, we present a new WO3 thin film based gas sensor for H2 and C2H5OH, operating at 150 °C. Nanostructured WO3 thin films were synthesized by thermal evaporation method. The properties of the as-deposited films were modified by annealing in air at 300 °C and 400 °C. Various analytical techniques such as AFM, TEM, XPS, XRD and Raman spectroscopy have been employed to characterize their properties. A clear indication from TEM and XRD analysis is that the as-deposited WO3 films are highly amorphous and no improvement is observed in the crystallinity of the films after annealing at 300 °C. Annealing at 400 °C significantly improved the crystalline properties of the films with the formation of about 5 nm grains. The films annealed at 300 °C show no response to C2H5OH (ethanol) and a little response to H2, with maximum response obtained at 280 °C. The films annealed at 400 °C show a very good response to H2 and a moderate response to C2H5OH (ethanol) at 150 °C. XPS analysis revealed that annealing of the WO3 thin films at 400 °C produces a significant change in stoichiometry, increasing the number of oxygen vacancies in the film, which is highly beneficial for gas sensing. Our results demonstrate that gas sensors with significant performance at low operating temperatures can be obtained by annealing the WO3 films at 400 °C and optimizing the crystallinity and nanostructure of the as-deposited films.

Synthesis and characterisation of titanium sol-gels in varied gravity environments

Sol-gel synthesis in varied gravity is only a relatively new topic in the literature and further investigation is required to explore its full potential as a method to synthesise novel materials. Although trialled for systems such as silica, the specific application of varied gravity synthesis to other sol-gel systems such as titanium has not previously been undertaken. Current literature methods for the synthesis of sol-gel material in reduced gravity could not be applied to titanium sol-gel processing, thus a new strategy had to be developed in this study. To successfully conduct experiments in varied gravity a refined titanium sol-gel chemical precursor had to be developed which allowed the single solution precursor to remain un-reactive at temperatures up to 50oC and only begin to react when exposed to a pressure decrease from a vacuum. Due to the new nature of this precursor, a thorough characterisation of the reaction precursors was subsequently undertaken with the use of techniques such as Nuclear Magnetic Resonance, Infra-red and UV-Vis spectroscopy in order to achieve sufficient understanding of precursor chemistry and kinetic stability. This understanding was then used to propose gelation reaction mechanisms under varied gravity conditions. Two unique reactor systems were designed and built with the specific purpose to allow the effects of varied gravity (high, normal, reduced) during synthesis of titanium sol-gels to be studied. The first system was a centrifuge capable of providing high gravity environments of up to 70 g’s for extended periods, whilst applying a 100 mbar vacuum and a temperature of 40-50oC to the reaction chambers. The second system to be used in the QUT Microgravity Drop Tower Facility was also required to provide the same thermal and vacuum conditions used in the centrifuge, but had to operate autonomously during free fall. Through the use of post synthesis characterisation techniques such as Raman Spectroscopy, X-Ray diffraction (XRD) and N2 adsorption, it was found that increased gravity levels during synthesis, had the greatest effect on the final products. Samples produced in reduced and normal gravity appeared to form amorphous gels containing very small particles with moderate surface areas. Whereas crystalline anatase (TiO2), was found to form in samples synthesised above 5 g with significant increases in crystallinity, particle size and surface area observed when samples were produced at gravity levels up to 70 g. It is proposed that for samples produced in higher gravity, an increased concentration gradient of water is forms at the bottom of the reacting film due to forced convection. The particles formed in higher gravity diffuse downward towards this excess of water, which favours the condensation reaction of remaining sol gel precursors with the particles promoting increased particle growth. Due to the removal of downward convection in reduced gravity, particle growth due to condensation reaction processes are physically hindered hydrolysis reactions favoured instead. Another significant finding from this work was that anatase could be produced at relatively low temperatures of 40-50oC instead of the conventional method of calcination above 450oC solely through sol-gel synthesis at higher gravity levels. It is hoped that the outcomes of this research will lead to an increased understanding of the effects of gravity on chemical synthesis of titanium sol-gel, potentially leading to the development of improved products suitable for diverse applications such as semiconductor or catalyst materials as well as significantly reducing production and energy costs through manufacturing these materials at significantly lower temperatures.

Vibrational spectroscopic characterization of the sulphate mineral khademite Al(SO4)F⋅5(H2O)

Vibrational spectroscopy has been used to characterize the sulphate mineral khademite Al(SO4)F∙5(H2O). Raman band at 991 cm-1 with a shoulder at 975 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode. The observation of two symmetric stretching modes suggests that the sulphate units are not equivalent. Two low intensity Raman bands at 1104 and 1132 cm-1 are assigned to the ν3 (SO4)2- antisymmetric stretching mode. The broad Raman band at 618 cm-1 is assigned to the v4 (SO4)2- bending modes. Raman bands at 455, 505 and 534 cm-1 are attributable to the doubly degenerate v2 (SO4)2- bending modes. Raman bands at 2991, 3146 and 3380 cm-1 are assigned to the OH stretching bands of water. Five infrared bands are noted at 2458, 2896, 3203, 3348 and 3489 cm-1 are also due to water stretching bands. The observation of multiple water stretching vibrations gives credence to the non-equivalence of water units in the khademite structure. Vibrational spectroscopy enables an assessment of the structure of khademite.

In situ observation of structural changes in polycrystalline silver catalysts by environmental scanning electron microscopy

Morphology changes induced in polycrystalline silver catalysts as a result of heating in either oxygen, water or oxygen-methanol atmospheres have been investigated by environmental scanning electron microscopy (ESEM), FT-Raman spectroscopy and temperature programmed desorption (TPD). The silver catalyst of interest consisted of two distinct particle types, one of which contained a significant concentration of sub-surface hydroxy species (in addition to surface adsorbed atomic oxygen). Heating the sample to 663 K resulted in the production of 'pin-holes' in the silver structure as a consequence of near-surface explosions caused by sub-surface hydroxy recombination. Furthermore, 'pin-holes' were predominantly found in the vicinity of surface defects, such as platelets and edge structures. Reaction between methanol and oxygen also resulted in the formation of 'pin-holes' in the silver surface, which were inherently associated with the catalytic process. A reaction mechanism is suggested that involves the interaction of methanol with sub-surface oxygen species to form sub-surface hydroxy groups. The sub-surface hydroxy species subsequently erupt through the silver surface to again produce 'pin-holes'.