Natural Corundum Research Articles

Sintered transparent polycrystalline ceramics: the next generation of fillers for clarity enhancement in corundum

A significant proportion of mined natural corundum (ruby and sapphire) contain fractures, which negatively affects a gemstone’s clarity and value. Over the past decades, heat treatment techniques have been developed for either fracture healing, or filling to make such gems marketable. The clarity enhancement processes are mainly based on techniques which are either not durable, as in the case of lead silicate fillers, or do not yield perfect transmittance through a fracture, as in the case of borax based fluxes. Therefore, the gemstone treatment community is actively in pursuit of better techniques for clarity enhancement in corundum. Given that application of pressure is a recent advancement in the heat treatment processes of natural sapphire, it is essential to explore the possibilities regarding different outcomes such treatments can have. In this perspective paper, we have briefly described how application of pressure during heat treatments can lead to in-situ sintering of transparent polycrystalline ceramics within the fractures of corundum, which can result in clarity enhancement. Spinel-structure based fillers can be tailored to mimic corundum in terms of tribological, chemical and optical properties. Therefore, gemstones treated with such fillers will be durable, unlike currently used glass-based filler material. We also provide a possible explanation for ghost-fissures in sapphires heated under pressure, as being a by-product of in-situ sintering process of ceramic fillers that are thermodynamically compatible with Al2O3. The prospect of transparent polycrystalline ceramics in the gem and jewelry industry opens a new field of research in this area, given that ceramic fillers can outperform currently used methods and material for clarity enhancement in gemstones. In essence, we present a novel application for sintered transparent polycrystalline ceramics.

Thermally and optically stimulated luminescence of natural red and blue corundum (Al2O3)

We report the thermoluminescence (TL) and optically stimulated luminescence (OSL) of natural corundum (Al2O3) of two varieties; one red and the other blue. X-ray fluorescence spectroscopy of the samples show that the concentration of Al2O3 in the red corundum is 43.05% and 46.87% in the blue corundum. TL measurements carried out on un-annealed samples and samples annealed at 700 °C, 900 °C and 1200 °C show that the TL sensitivity increases with annealing. The sensitivity of the red corundum reaches a maximum after annealing at 900 °C whereas that of the blue corundum increases with annealing up to the maximum annealing temperature of 1200 °C used in this study. Both samples have a complex glow curve between 30 °C and 500 °C. The composite nature of the glow curves is deduced to be due to a continuum in the trap distribution in the crystal. The activation energy of the traps vary between 0.70 eV and 1.15 eV. The dose response of the red corundum under TL is linear within 100‒1000 Gy whereas that of the blue corundum is superlinear for the same dose range. The TL of both samples is reproducible but the signal fades with time between irradiation and measurement. Both samples produce OSL under 470 nm blue light stimulation. The dose response of the OSL is superlinear within 100‒1000 Gy. It is found that the samples also produce thermally-assisted OSL (TA-OSL) at elevated temperature. The TA-OSL intensity of the red corundum increases with dose up to 400 Gy and saturates thereafter. On the other hand, the intensity of the blue corundum increases consistently with dose from 100 Gy to 1000 Gy.

The origin of needle-like rutile inclusions in natural gem corundum: A combined EMPA, LA-ICP-MS, and nano-SIMS investigation—Reply

The origin of needle-like rutile inclusions in natural gem corundum: A combined EMPA, LA-ICP-MS, and nano-SIMS investigation—Reply

The origin of needle-like rutile inclusions in natural gem corundum: A combined EPMA, LA-ICP-MS, and nano-SIMS investigation—Discussion

The origin of needle-like rutile inclusions in natural gem corundum: A combined EPMA, LA-ICP-MS, and nano-SIMS investigation—Discussion

The origin of needle-like rutile inclusions in natural gem corundum: A combined EPMA, LA-ICP-MS, and nanoSIMS investigation

Trace-element chemistry and microscopic observations of included gem corundum (α-Al2O3) suggests a new model of syngenetic growth of oriented rutile inclusions rather than the usual interpretation of their growth through exsolution. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is now a robust method for measuring trace elements in gem-quality corundum (ruby and sapphire). Nonetheless, the corundum structure is relatively unforgiving for substitutional components and typically only a small handful of minor to trace elements are measured by LA-ICP-MS (Mg, Ti, V, Cr, Fe, Ga). Less commonly, trace elements such as Be, Zr, Nb, Sn, La, Ce, Ta, and W are found in natural corundum. Their concentrations are typically correlated with high contents of Ti and silky or cloudy zones in the corundum that contain a high concentration of needle-like rutile or other oxide inclusions. Three metamorphic-type sapphires from Sri Lanka, Madagascar, and Tanzania were studied here using LA-ICP-MS, electronprobe microanalysis (EPMA), and nanoSIMS to document correlations between the various trace elements and their distribution between the corundum and included, oriented rutile TiO2 needles. NanoSIMS and EPMA measurements show concentration of Be, Mg, Fe, V, Zr, Nb, Ce, Ta, and W in the rutile needles. The relative atomic concentrations of Mg and Ti from LA-ICP-MS measurements suggest the corundum-rutile intergrowth grew as a mechanical mixture of the two phases as opposed to rutile formation through exsolution from the corundum host. This scenario is also suggested for the three magmatic-type sapphires studied here based on the presence of glassy melt inclusions in close association with included, oriented oxide needles. The preservation of a glassy melt inclusion requires fast cooling, whereas exsolution of the oxide inclusions would require slow cooling and annealing at a temperature lower than sapphire formation. The studied sapphires suggest the likely origin of the oriented, needle-like rutile inclusions to be syngenetic epitaxial coprecipitation of both rutile and corundum. The interpretation of such oriented oxide inclusions has important implications for understanding the geological formation conditions based on trace element data or using such data to separate sapphires and rubies based on their geographic origin.

The role of silicon in the color of gem corundum

Natural corundum is colored by a variety of trace-element impurities and by the chemical reactions among them. Important to nearly all of the colors is the role played by the reactions among silicon, titanium, and magnesium. Characterization of the interactions between these aliovalent ions has been hindered by the fact that the laser ablation–inductively coupled quadrupole–mass spectrometry equipment used in most gem labs does not resolve the interferences for silicon. Thus Si has not been measured at relevant concentrations. Recent development of ion implant standards and the application of secondary ion mass spectrometry has allowed the accurate measurement of silicon in corundum for the first time. As an example of its importance, detailed analyses of sapphire from Montana’s Yogo Gulch deposit are presented. These analyses show that without silicon, Yogo sapphire would not be blue.

Morphological and chemical evolution of corundum (ruby and sapphire): Crystal ontogeny reconstructed by EMPA, LA-ICP-MS, and Cr3+Raman mapping

The term “ ontogeny ,” which is commonly used in biology, was introduced into the Earth sciences in 1961 to include the genesis and evolution of single crystals and crystal aggregates. The term encompasses nucleation , growth , alteration , and destruction . We present results of studies concerning the ontogeny of natural corundum (rubies and sapphires), and the chemical and morphological evolution of corundum crystals from deposits in Africa (Kenya, Tanzania, Madagascar) and Southeast Asia (Vietnam). Trace-element compositions indicative for different corundum habits were determined by rim-to-rim LA-ICP-MS and electron microprobe analyses. Raman spectroscopy was applied for Cr 3+ photoluminescence mapping. Results traced the development of corundum crystals and the evolution of their chemistry and morphology, and helped to clarify the geological processes within particular deposits. These variations of corundum morphology are directly correlated with Cr and Fe contents and varying P-T conditions that prevailed during crystal growth. Dipyramidal habits combined with white color in corundum from two deposits in the Mangari area in Kenya have Cr concentrations of ~200–700 μg/g in crystals that grew under high P-T conditions. Prismatic habit of bright red ruby crystals was linked to Cr concentrations of ≥1500 μg/g in samples from Luc Yen (Vietnam) and Mangari (Kenya), formed under lower P-T . Concentrations of Cr between 700–1500 μg/g are associated with pink color and combinations of different habits (dipyramidal, prismatic, or dipyramidal-prismatic) in these samples. Contents of Fe ~700 μg/g and Cr ~1200 μg/g in sapphire crystals from the Morogoro area of Tanzania caused pink color that correlated with dipyramidal habit and elongation along the c axis. Rhombohedral habit and blue-violet color were observed at Cr ~600 μg/g and Fe ≥2000 μg/g in sapphires from Andranondambo in Madagascar, formed during the final stage of contact metamorphism.

Investigation on modification of ion implanted natural corundum by UV–Vis-NIR spectroscopy

Abstract Natural corundum, a crystalline form of aluminium oxide (Al 2 O 3 ) with impure elements, is an allochromatic mineral whose color varies based on the presence of impurities in the composition. Ion implantation technology can be utilized for enhancing the optical properties of corundum by selecting the implanted ion type leading to modification of the composition and defects. As for the appearance of corundum depending on many factors including brilliance, color, fire (light dispersion), and luster, this research attempted to find out an alternative method for improving the optical appearance and color enhancement of corundum by using ion implantation. Ion beam treatments with 70 keV nitrogen and argon ions and 23 keV oxygen ion at fluence of 10 17 ions/cm 2 were applied to ruby and sapphire from Thailand, Myanmar, Cambodia, Sri Lanka, Africa, and USA. Additionally, ion beam analysis techniques, i.e., particle-induced X-ray emission (PIXE), together with conventional gemological observations such as optical microscope and UltraViolet-Visible and Near Infrared (UV–Vis-NIR) spectroscopy were applied to understand the phenomena observed. The results revealed the possibility of color changing by ion beams resulting from variation in the ionic stage of trace elements as seen from UV–Vis-NIR absorption spectra. The advantages of ion implantation appear to be new and sustainable for improving corundum properties.

Vanadium-rich ruby and sapphire within Mogok Gemfield, Myanmar: implications for gem color and genesis

Rubies and sapphires are of both scientific and commercial interest. These gemstones are corundum colored by transition elements within the alumina crystal lattice: Cr3+ yields red in ruby and Fe2+, Fe3+, and Ti4+ ionic interactions color sapphires. A minor ion, V3+ induces slate to purple colors and color change in some sapphires, but its role in coloring rubies remains enigmatic. Trace element and oxygen isotope composition provide genetic signatures for natural corundum and assist geographic typing. Here, we show that V can dominate chromophore contents in Mogok ruby suites. This raises implications for their color quality, enhancement treatments, geographic origin, exploration and exploitation and their comparison with rubies elsewhere. Precise LA-ICP-MS analysis of ruby and sapphire from Mogok placer and in situ deposits reveal that V can exceed 5,000 ppm, giving V/Cr, V/Fe and V/Ti ratios up to 26, 78, and 97 respectively. Such values significantly exceed those found elsewhere suggesting a localized geological control on V-rich ruby distribution. Our results demonstrate that detailed geochemical studies of ruby suites reveal that V is a potential ruby tracer, encourage comparisons of V/Cr-variation between ruby suites and widen the scope for geographic typing and genesis of ruby. This will allow more precise comparison of Asian and other ruby fields and assist confirmation of Mogok sources for rubies in historical and contemporary gems and jewelry.

Development of vertical compact ion implanter for gemstones applications

Abstract Ion implantation technique was applied as an effective non-toxic treatment of the local Thai natural corundum including sapphires and rubies for the enhancement of essential qualities of the gemstones. Energetic oxygen and nitrogen ions in keV range of various fluences were implanted into the precious stones. It has been thoroughly proved that ion implantation can definitely modify the gems to desirable colors together with changing their color distribution, transparency and luster properties. These modifications lead to the improvement in quality of the natural corundum and thus its market value. Possible mechanisms of these modifications have been proposed. The main causes could be the changes in oxidation states of impurities of transition metals, induction of charge transfer from one metal cation to another and the production of color centers. For these purposes, an ion implanter of the kind that is traditionally used in semiconductor wafer fabrication had already been successfully applied for the ion beam bombardment of natural corundum. However, it is not practical for implanting the irregular shape and size of gem samples, and too costly to be economically accepted by the gem and jewelry industry. Accordingly, a specialized ion implanter has been requested by the gem traders. We have succeeded in developing a prototype high-current vertical compact ion implanter only 1.36 m long, from ion source to irradiation chamber, for these purposes. It has been proved to be very effective for corundum, for example, color improvement of blue sapphire, induction of violet sapphire from low value pink sapphire, and amelioration of lead-glass-filled rubies. Details of the implanter and recent implantation results are presented.

Identification of deposit types of natural corundum by PIXE

Natural corundum, one of the most important exports of Thailand, is a rare, durable and valuable gemstone. The value of these precious stones is determined by their visual appearances, including brilliance, color, fire (light dispersion) and luster. Corundum is an allochromatic mineral whose trace element concentration depends on the origin and has influence on price setting. This work attempts to use an alternative method to identify the geological deposits of rubies and sapphires found in the Thai market which came from various countries, e.g., Africa, Cambodia, Myanmar, Sri Lanka, Thailand and USA. Interrelations between most important major trace elements are the main results of this work. Quantitative analysis of trace elements were performed by particle-induced X-ray emission (PIXE) technique, using 2-MeV proton beam generated and accelerated by the 1.7MV tandem accelerator at Chiang Mai University. The trace elements of interest are Ti, Cr, Fe and Ga. We have found that the relationships between the ratios of trace element concentration can be used to classify the deposit type. Moreover, this method shows a clear separation between two main types of geological deposits, basaltic and metamorphic deposits, which further helps in determining the gemstone origin. For example, the gemstones from Cambodia, Thailand and the USA can be classified as the basaltic deposits with their high concentration in Fe but low in Ti, while the gemstones from Africa, Myanmar and Sri Lanka are metamorphic deposits because they have low Fe but high Ti concentrations. Both deposits required plots of pairs of trace elements and their ratios in population field appearance in order to distinguish their origins. The advantageous of these methods appear to be a new and a sustainable procedure for determining gemstone origins.

The High Temperature Annular Shear Cell: A modified ring shear tester to measure the flow properties of powders at high temperature

Although changes of cohesive behaviour of powders is observed at high temperature in several industrial process units, conventional testers and procedures are still not suited for testing powder flow properties at high temperature. In this work a High Temperature Annular Shear Cell was designed, built and set-up in order to directly measure the flow properties of powders up to 500°C. A temperature control system was also developed to establish a uniform temperature inside the powder sample.Yield loci at room temperature and 500°C were measured for samples of fluid catalytic cracking catalyst (FCC powder), fly ashes, natural corundum, synthetic porous α-alumina and glass beads. Experimental evidences did not reveal a univocal effect of temperature in the tested range.Finally, shear tests on glass beads mixed to with some high-density polyethylene (HDPE) (1% of the total weight) confirmed that a significant increase of the cohesive behaviour occurs at high temperature when liquid bridges form due to the melting of one of the solid phases.

Electronic properties and reactivity of simulated Fe(3+) and Cr(3+) substituted α-Al(2)O(3) (0001) surface.

Metal oxide based minerals naturally contain transition metal impurities isomorphically substituted into the structure that can alter the structural and electronic properties as well as the reactivity of these metal oxides. Natural α-Al(2)O(3) (corundum) can contain up to 9.17% (w/w) Fe(2)O(3) and 1.81% (w/w) of Cr(2)O(3.) Here we report on changes in the structural and electronic properties of undoped and doped α-Al(2)O(3) (0001) surfaces using periodic density functional theory (DFT) methods with spin unrestricted B3LYP functional and a local atomic basis set. Both structural and electronic properties are altered upon doping. Implications for doping effects on photochemical processes are discussed.As metal oxides are major components of the environment, including atmospheric mineral aerosol, DFT was also used to study the effect of transition metal impurities on gas/surface interactions of a model acidic atmospheric gas molecule, carbon monoxide (CO). The theoretical results indicated that the presence of Fe(3+) and Cr(3+) impurities substituted on the outer layer of natural corundum surfaces reduces the propensity toward CO adsorption relative to the undoped surface. However, CO-surface interactions resemble that of bulk α-Al(2)O(3) when the impurity is substituted below the first surface layer. The presence and location of the mineral dopant was found to significantly alter the structural and electronic properties and gas/surface interactions studied here.

New data for distinguishing between hydrothermal synthetic, flux synthetic and natural corundum

New data for distinguishing between hydrothermal synthetic, flux synthetic and natural corundum

Evidence of colour-modification induced charge and structural disorder in natural corundum: Spectroscopic studies of beryllium treated sapphires and rubies

Corundum α – Al2O3 single crystals is an important gemstone known by different names depending on the colour it exhibits which in turn depends on the impurities that are present. The colour depends on the valence state of the impurity element present in corundum (Cr3+ in ruby, Fe3+ in yellow sapphire and Fe-Ti complex in blue sapphire). There have been a number of reports of diffusion controlled high temperature chemical reactions to influence the colouration in these materials. Present paper deals with the Raman and FT-IR results on Be treated rubies/sapphires and gives evidence of the disorder brought about by such treatments. This can be effectively used for diagnostic purposes for detecting the treated stones.

Gemological modification of local natural gemstones by ion beams

Ion implantation was applied as an effective method to gemological modification of Thai local natural corundum including sapphire and ruby for enhancement of the essential qualities of the gemstones. Oxygen and nitrogen ions at medium and low energies to various fluences were implanted to the natural gemstones. The heavy ion irradiation modifies the color to desirable colors and improves the color distribution, transmission and lustre. These modifications lead to the improvement of quality of gemstones and thus the market value. Possible mechanisms of these modifications have been proposed. The main cause for these modifications could be the changes in oxidation states of impurity metals, induction of charge transfer from one metal cation to other and the production of color centres.

Towards the differentiation of non-treated and treated corundum minerals by ion-beam-induced luminescence and other complementary techniques

Differentiation of treated and non-treated gemstones is a chief concern for major jewellery import companies. Low-quality corundum specimens coming from Asia appear to be often treated with heat, BeO or flux in order to enhance their properties as precious minerals. A set of corundum samples, rubies and sapphires from different origins, both treated and non-treated has been analysed at the Centre Européen d'Archéométrie, with ion-beam-induced luminescence (IBIL) and other complementary techniques such as Raman, proton-induced X-ray emission (PIXE), and proton-induced gamma-ray emission (PIGE). IBIL, also known as ionoluminescence, has been used before to detect impurities or defects inside synthetic materials and natural minerals; its use for the discrimination of gemstone simulants or synthetic analogues has been elsewhere discussed (Cavenago-Bignami Moneta, Gemología, Tomo I Piedras preciosas, perlas, corales, marfil. Ediciones Omega, Barcelona, 1991). PIXE has been frequently applied in the archaeometric field for material characterisation and provenance studies of minerals (Hughes, Ruby & sapphire. RWH Publishing, Fallbrook, 1997; Calvo del Castillo et al., Anal Bioanal Chem 387:869-878, 2007; Calligaro et al., NIM-B 189:320-327, 2002) and PIGE complements the elemental analysis by detecting light elements in these materials such as-and lighter than-sodium that cannot be identified with the PIXE technique (Sanchez et al., NIM-B 130:682-686, 1997; Emmett et al., Gems Gemology 39:84-135, 2003). The micro-Raman technique has also been used complementarily to ion beam analysis techniques for mineral characterisation (Novak et al., Appl Surf Sci 231-232:917-920, 2004). The aim of this study is to provide new means for systematic analysis of corundum gemstone-quality mineral, alternative to the traditional gemmologic methods; for this purpose, a Spanish jewellery import company supplied us with a number of natural corundum samples coming from different places (part of them treated as explained above). The PIXE elemental concentrations of the samples showed large quantities of calcium and lead in some cases that can be linked to treatment with fluxes or lead oxide. The plot of the chromium and iron concentration grouped the samples in various aggregates that corresponded to the different types of corundum analysed. Micro-Raman complemented the PIXE analysis corroborating the presence of lead oxides but the use of the PIGE technique was not successful for the detection of beryllium due to the low cross section of the nuclear reaction chosen for its identification. IBIL was capable of distinguishing between treated and non-treated samples of the same type based on the luminescent features of the materials.

Micro‐Raman spectroscopy applied to the study of inclusions within sapphire

AbstractThe present research concerns the characterization of samples of corundum (Al2O3), varieties of sapphire, by micro‐Raman spectroscopy. Ten samples of natural corundum from Australia, Madagascar, Sri Lanka, Thailand, Tanzania, and Vietnam were studied. After standard gemmological analysis, micro‐Raman analysis was also performed in order to identify mineral inclusions within the sapphire samples and to obtain information on the geological genres of the minerals. Several inclusions were evidenced within the sapphires and identified by Raman spectroscopy thanks to a confocal spectrometer, which allowed detection also below the external surface of the gem. Finally, the Raman spectra are discussed taking into account the provenance of the samples and their optical absorption. Copyright © 2008 John Wiley & Sons, Ltd.

XPS and ToF-SIMS analysis of natural rubies and sapphires heated in an inert (N2) atmosphere

Advanced surface analysis techniques: X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, have been employed in the study of heat treatment of natural corundum as ruby and sapphire. The stones were heat treated in an inert (N2) atmosphere. The setting temperatures were: 1000, 1100, 1200, 1300, 1400, 1500 and 1600°C. The XPS studies and the parallel ToF-SIMS experiments revealed diffusion behavior of Fe and Ti in the as-mined stones as evidenced by surface observations. Both metals exhibited broad maxima in surface concentration near 1300°C. Owing to its superlative detection limit, ToF-SIMS spectra are able to provide the temperature-dependent concentration profiles of trace transition metals such as Cr, Cu and V at a level not detectable by XPS. Visible appearance of the stones is clearly affected by heat treatment. Interestingly, the ruby stones did not exhibit cloudy inclusion (“silk”) on heating, contrary to previous experiments under atmospheric conditions.

Characterization of Natural Corundum (rubies and sapphires) and Beryllium Diffused Corundum.

not Available.