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1.
The photoluminescence (PL) and optical excitation spectra of baratovite in aegirine syenite from Dara-i-Pioz, Tien Shan Mts., Tajikistan and katayamalite in aegirine syenite from Iwagi Islet, Ehime, Japan were obtained at 300 and 80 K. Under short wave (253.7 nm) ultraviolet light, baratovite and katayamalite exhibited bright blue-white luminescence. The PL spectrum of baratovite at 300 K consisted of a wide band with a peak at approximately 406 nm and a full width at half maximum (FWHM) of approximately 6.32k cm−1. The excitation spectrum of the blue-white luminescence from baratovite at 300 K consisted of a prominent band with a peak at approximately 250 nm. The PL and excitation spectra of katayamalite were similar to those of baratovite. The luminescence from these minerals was attributed to the intrinsic luminescence from the TiO6 center.  相似文献   

2.
Chabazite-Ca deposited on dacite laccolith from Osódi Hill, Dunabogdány, Hungary, exhibited bluish-white luminescence under ultraviolet (UV) light. The photoluminescence (PL) and optical excitation spectra of chabazite-Ca were obtained at 300 K. The PL spectrum under 300-nm excitation consists of (1) a Ce3+ band with a peak at 340 nm, (2) a broad main band with a peak at 453 nm and (3) five narrow bands at 592, 616, 650, 700 and 734 nm due to Eu3+. The main band is spread over the entire visible-wavelength region. The excitation spectrum obtained by monitoring green luminescence at 520 nm consists of a band at wavelengths shorter than 200 nm and an extremely broad band with a peak at 385 nm. The extremely broad band is spread over not only the UV region but also the blue region. The features of PL and excitation spectra suggest that the origin of bluish-white luminescence is luminescent organic matter incorporated into chabazite-Ca crystals during growth.  相似文献   

3.
The photoluminescence (PL) spectra, optical excitation spectra and PL decay curves of anthophyllite from Canada were obtained at 300 and 10 K. The MnO content in the sample, determined using an electron probe microanalyzer, was high at 5.77 wt%. In the PL spectra obtained under 410-nm excitation, bright red bands with peaks at 651 and 659 nm were observed at 300 and 10 K, respectively. The origin of the red luminescence was ascribed to Mn2+ in anthophyllite from the analysis of the excitation spectra and PL decay times of 6.1–6.6 ms. In the PL spectra obtained under 240-nm excitation at 300 K, a small violet band with a peak at 398 nm was observed. On the violet band at 10 K, a vibronic structure was observed. The origin of the violet luminescence was attributed to a minor impurity in anthophyllite.  相似文献   

4.
Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca3(Zr,Ti)Si2O9 crystals are synthesized. Synthetic Ca3(Zr,Ti)Si2O9 shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.  相似文献   

5.
Natural calcite from Kuerle, Xinjiang, China, shows orange-red fluorescence when exposed to short-wave ultraviolet (UV) light (Hg 253.7 nm). Photoluminescence (PL) emission and excitation spectra of the calcite are observed at room temperature in detail. The PL emission spectrum under 208 nm excitation consists of three bands: two UV bands at 325 and 355 nm and an orange-red band at 620 nm. The three bands are ascribed to Pb2+, Ce3+ and Mn2+, respectively, as activators. The Pb2+ excitation band is observed at 243 nm, and the Ce3+ excitation band at 295 nm. The Pb2+ excitation band is also observed by monitoring the Ce3+ fluorescence, and the Pb2+ and Ce3+ excitation bands, in addition to six Mn2+ excitation bands, are also observed by monitoring the Mn2+ fluorescence. These indicate that four types of the energy transfer can occur in calcite through the following processes: (1) Pb2+ → Ce3+, (2) Pb2+ → Mn2+, (3) Ce3+ → Mn2+ and (4) Pb2+ → Ce3+ → Mn2+.  相似文献   

6.
The photoluminescence and excitation spectra of sodalites from Greenland, Canada and Xinjiang (China) are observed at 300 and 10 K in detail. The features of the emission and excitation spectra of the orange-yellow fluorescence of these sodalites are independent of the locality. The emission spectra at 300 and 10 K consist of a broad band with a series of peaks and a maximum peak at 648 and 645.9 nm, respectively. The excitation spectra obtained by monitoring the orange-yellow fluorescence at 300 and 10 K consist of a main band with a peak at 392 nm. The luminescence efficiency of the heat-treated sodalite from Xinjiang is about seven times as high as that of untreated natural sodalite. The emission spectrum of the S2 center in sodalite at 10 K consists of a band with a clearly resolved structure with a series of maxima spaced about 560 cm−1 (20–25 nm) apart. Each narrow band at 10 K shows a fine structure consisting of a small peak due to the stretching vibration of the isotopic species of 32S34S, a main peak due to that of the isotopic species of 32S2 and five peaks due to phonon sidebands of the main peak.  相似文献   

7.
The optical luminescence excited with synchrotron radiation along a preferential orientation of a quartz crystal has been investigated. It is found that the crystal is composed of two distinct regions, only one of which luminesces upon X-ray excitation. This luminescence is generally uniform and exhibits emission bands in the blue (470 nm with a shoulder at 522 nm) and in the UV (340 nm) regions of the spectrum. The branching ratio for the intensity of these bands is sensitive to the excitation energy across the Si K-edge. XANES spectra collected by partial luminescence yield (PLY) suggest that both emission bands originate from the de-excitation of Si atoms in the quartz. The possible defect sites within the crystal structure that could account for the observed luminescence are investigated and discussed. Additional experiments are proposed to verify this assignment of the optical emission bands.  相似文献   

8.
The emission and excitation spectra of yellow luminescence due to S2 in scapolites (#1 from Canada and #2 from an unknown locality) were observed at 300, 80 and 10 K. Emission and excitation bands at 10 K showed vibronic structures with a series of maxima spaced 15–30 and 5–9 nm, respectively. The relative efficiency of yellow luminescence from scapolite #2 was increased up to 117 times by heat treatment at 1,000°C for 2 h in air. The enhancement of yellow luminescence by heat treatment was ascribed to the alteration of SO3 2− and SO4 2− to S2 in scapolite.  相似文献   

9.
Summary ?Feldspar specimens covering the whole Or–Ab–An ternary have been investigated by cathodoluminescence (CL), photoluminescence (PL), radioluminescence (RL) and radiophosphorescence (RP) spectrometry. A red luminescence emission, which is commonly explained by Fe3+ lattice defects, is a characteristic feature of all the spectra. Different shifts of the peak-wavelength between ∼680–750 nm (1.82–1.65 eV) were observed with varying feldspar composition. Despite the dependence of the peak position on the Ca/Na ratio, initially described for CL in the 1970s, there is also a shift induced by changing NaK composition. The observed effects can be explained by known relations that the peak position of the red luminescence emission in feldspars can be affected both by the structural state of the feldspar and the site occupancy of the trivalent iron. In the case of alkali feldspars another factor may influence the peak-shift. The incorporation of the larger potassium ion causes non-linear variations of the cell dimensions and therefore Fe–O bond distance. The behaviour of the red peak-shift dependent on the feldspar composition is not equal for all types of luminescence investigated. This is most likely caused by the different luminescence excitation mechanism. Received December 3, 2001; revised version accepted March 25, 2002  相似文献   

10.
Luminescence decay time data are presented for 17 samples of synthetic calcite and a natural calcite between room temperature and approximately 15 K. The majority of the samples have Mn concentration in the range 0.0001–0.01 atoms per formula unit (apfu). Their spectra are consistent with a single exponential decay. It was necessary to use a “stretched” exponential to obtain adequate fits to the spectra of two samples having Mn concentrations of 0.036 and 0.091 apfu. The decay time at room temperature ranges from approximately 40–57 ms. At low temperature the corresponding range is 51–120 ms, indicating that thermal quenching of the decay time takes place. The decay time is dependent on the concentration of Mn, reaching a maximum (at both room- and low-temperature) in the range 0.001–0.003 apfu. The composition dependence is greater at low temperature. The results are discussed in terms of the Mott-Seitz and multiphonon mechanisms of thermal quenching. It is concluded that the latter provides a better fit to the data and is more consistent with models of the luminescence process in calcite:Mn.  相似文献   

11.
Summary Investigations of natural and synthetic quartz specimens by cathodoluminescence (CL) microscopy and spectroscopy, electron paramagnetic resonance (EPR) and trace-element analysis showed that various luminescence colours and emission bands can be ascribed to different intrinsic and extrinsic defects. The perceived visible luminescence colours in quartz depend on the relative intensities of the dominant emission bands between 380 and 700 nm. Some of the CL emissions of quartz from the UV to the yellow spectral region (175 nm, 290 nm, 340 nm, 420 nm, 450 nm, 580 nm) can be related to intrinsic lattice defects. Extrinsic defects such as the alkali (or hydrogen)-compensated [AlO4/M+] centre have been suggested as being responsible for the transient emission band at 380–390 nm and the short-lived blue-green CL centered around 500 nm. CL emissions between 620 and 650 nm in the red spectral region are attributed to the nonbridging oxygen hole centre (NBOHC) with several precursors. The weak but highly variable CL colours and emission spectra of quartz can be related to genetic conditions of quartz formation. Hence, both luminescence microscopy and spectroscopy can be used widely in various applications in geosciences and techniques. One of the most important fields of application of quartz CL is the ability to reveal internal structures, growth zoning and lattice defects in quartz crystals not discernible by means of other analytical techniques. Other fields of investigations are the modal analysis of rocks, the provenance evaluation of clastic sediments, diagenetic studies, the reconstruction of alteration processes and fluid flow, the detection of radiation damage or investigations of ultra-pure quartz and silica glass in technical applications. Zusammenfassung Ursachen, spektrale Charakteristika und praktische Anwendungen der Kathodolumineszenz (KL) von Quarz – eine Revision Untersuchungen von natürlichen und synthetischen Quarzproben mittels Kathodolumineszenz (KL) Mikroskopie und -spektroskopie, Elektron Paramagnetischer Resonanz (EPR) und Spurenelementanalysen zeigen verschiedene Lumineszenzfarben und Emissionsbanden, die unterschiedlichen intrinsischen und extrinsischen Defekten zugeordnet werden k?nnen. Die sichtbaren Lumineszenzfarben von Quarz werden durch unterschiedliche Intensit?tsverh?ltnisse der dominierenden Emissionsbanden zwischen 380 und 700 nm verursacht. Einige der KL Emissionen vom UV bis zum gelben Spektralbereich (175 nm, 290 nm, 340 nm, 420 nm, 450 nm, 580 nm) stehen im Zusammenhang mit intrinsischen Defekten. Die kurzlebigen Lumineszenzemissionen bei 380–390 nm sowie 500 nm werden mit kompensierten [AlO4/M+]-Zentren in Verbindung gebracht. Die KL-Emissionen im roten Spektralbereich bei 620 bis 650 nm haben ihre Ursache im “nonbridging oxygen hole centre” (NBOHC) mit verschiedenen Vorl?uferzentren. Die unterschiedlichen KL-Farben und Emissionsspektren von Quarz k?nnen oft bestimmten genetischen Bildungsbedingungen zugeordnet werden und erm?glichen deshalb vielf?ltige Anwendungen in den Geowissenschaften und in der Technik. Eine der gravierendsten Einsatzm?glichkeiten ist die Sichtbarmachung von Internstrukturen, Wachstumszonierungen und Defekten im Quarz, die mit anderen Analysenmethoden nicht oder nur schwer nachweisbar sind. Weitere wesentliche Untersuchungsschwerpunkte sind die Modalanalyse von Gesteinen, die Eduktanalyse klastischer Sedimente, Diageneseuntersuchungen, die Rekonstruktion von Alterationsprozessen und Fluidmigrationen, der Nachweis von Strahlungssch?den oder die Untersuchung von ultrareinem Quarz und Silikaglas für technische Anwendungen. Received March 29, 2000 Accepted October 27, 2000  相似文献   

12.
The low-temperature isobaric heat capacities (C p) of β- and γ-Mg2SiO4 were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°298) of β- and γ-Mg2SiO4 are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg2SiO4 were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°298) in Mg2SiO4 are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°298 and ΔS°298 with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°298 and ΔS°298 of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg2SiO4 to MgSiO3 perovskite plus MgO was also calculated, using the optimized data on γ-Mg2SiO4 and available enthalpy and entropy data on MgSiO3 perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.  相似文献   

13.
Laboratory driven ionic thermal exchange of alkali feldspars from K to Na produces samples which are strongly luminescent in the ultraviolet region near 320 nm. The sites providing this luminescence are suggested as being correlated with the motion of Na atoms along interface-interphases of the material (i.e. with Na-O bond fracture). The thermoluminescence peaks show multi-order kinetics. Thermal preheatings of low albite sensitize the feldspar lattice with respect to thermoluminescence generated by exposure to UV irradiation and heating produces a strong blue luminescence spread over the range 350 nm to 500 nm band in feldspars. The upper temperature for thermoluminescence in feldspars is ∼300 °C, which is also the point where ionic conductivity of albite (010) begins, but the 300 °C region is also the starting point of a large second glow peak in adularia. Whilst it seems appropriate to link the Na motion to the 350–500 nm emission, it is unclear whether these changes are the result of the large anisotropic thermal vibration of Na atoms or the massive Na jumps that occur when the lattice reaches 300 °C. A speculative model is considered in which the UV TL emissions of natural minerals are linked to different interface-interphases (grain boundaries, exsolution limits, twinning planes, antiphase domains). Increased interface coherency energies are related to the kinetic order and the spectral position of luminescence emission peaks. Received: 3 December 1998 / Revised, accepted: 17 April 1999  相似文献   

14.
The aim of this work is to study the suitability of the use of fluorescence and UV–visible spectroscopies to evaluate the humification degree of different organic alkaline extracts obtained from diverse materials (humic substances, composted and non-composted materials). Our results indicate that the complementary utilization of the fluorescence index proposed by Milori et al. [Milori, D., Martin-Neto, L., Bayer, C., Mielniczuk, J., Vagnato, V., 2002. Humification degree of soil humic acids determined by fluorescence spectroscopy. Soil Science, 167, 739–749] (the total area of the emission spectra collected over a range of 460–650 nm using an excitation wavelength of 465 nm), the ratio between the electron-transfer band and benzenoid band of benzene UV light absorption, and the molar absorption coefficients at 600 nm and 280 nm proved capable of discriminating between extracts obtained from non-humified, partially humified and very humified materials.Likewise, our results suggest that humification is related to increments in the aromatic character of the molecules, which may be reflected in the presence of more aromatic rings and/or more condensed polyaromatic structures, and the degree of substitution in aromatic rings with polar functional groups, as well as to the possible increase in the conjugation degree in unsaturated aliphatic chains.  相似文献   

15.
Single-crystal electron paramagnetic resonance (EPR) spectra of a natural citrine quartz without any artificial irradiation, measured at W-band frequencies (∼94 GHz) and temperatures of 77, 110 and 298 K, allow better characterization of three previously-reported Centers (#6, #7 and B) and discovery of three new defects (B′, C′ and G′). The W-band EPR spectra reveal that Centers #6 and #7 do not reside on twofold symmetry axes, contrary to results from a previous X-band EPR study. The W-band spectra also show that the previously reported Center B is a mixture of two defects (B and B′) with similar g matrices but different-sized 27Al hyperfine structures. Center C′ has similar principal g values to the previously reported Center C but is distinct from the latter by a larger 27Al hyperfine structure with splittings from 0.10 to 0.22 mT. Also, Center G′ has a similar g matrix to the previously reported Center G but a different 27Al hyperfine structure with splittings from 0.41 to 0.53 mT. These spin-Hamiltonian parameters, together with observed thermal properties and microwave-power dependence, suggest that Centers #6 and #7 probably represent O23− type defects. Centers B and B′ are probably superoxide radicals (O2) with the unpaired spin localized on the same pair of oxygen atoms around a missing Si atom but linked to a substitutional Al3+ ion each at different neighboring tetrahedral sites. Similarly, Centers G and G′ are most likely superoxide radicals with the unpaired spin localized on another pair of oxygen atoms around a missing Si atom and linked to a substitutional Al3+ ion each at different neighboring tetrahedral sites. Center C′ is probably an ozonide radical associated with a missing Si atom and linked to a substitutional Al3+ ion at the neighboring tetrahedral site. This study exemplifies the value of  high-frequency EPR for discrimination of  similar defect centers and determination of  small local structural distortions that are often difficult to resolve in conventional  X- and Q-band EPR studies.  相似文献   

16.
Thermal behaviour of γ-anhydrite (γ-CaSO4, soluble anhydrite) has been investigated in situ real-time using laboratory parallel-beam X-ray powder diffraction data. Thermal expansion has been analysed from 303 to 569 K with temperature steps of 4 K. Lattice parameters and volume were fitted with a second-order polynomial to calculate thermal expansion coefficients. Thermal expansion of γ-anhydrite is anisotropic being larger along the c axis. Within the 343–383 K thermal range, γ-anhydrite has been found to partially re-hydrate to bassanite CaSO4·0.5H2O. At 455 K the transformation γ-CaSO4 → β-CaSO4, insoluble anhydrite, starts reaching completion at 653 K.  相似文献   

17.
从光致发光光谱角度探讨了海南蓬莱蓝宝石的呈色机理.结果发现:与蓝宝石吸收光谱的500~700 nm吸收宽带相比,在500~720 nm发光波段内存在566.8 nm锐峰、600 nm左右肩峰和Cr~(3+)的694.2 nm特征峰.600 nm肩峰与其吸收峰镜像对称,566.8 nm处锐峰的产生原因复杂.600 nm肩峰可能与Fe~(2+)-Fe~(2+)离子对的电子跃迁有关;566.8 nm锐峰因532 nm激光激发Fe~(2+)-Ti~(4+)或Fe~(2+)-Fe~(3+)间的电荷迁移带,通过晶格造成Si~(4+)、Mg~(2+)等微量杂质离子敏化而产生.光致发光谱中呈现更多谱峰,能呈现离子跃迁时不同离子间发生的相互作用,为500~700 nm吸收宽带由不同致色机制的叠加给出了直接证明,是一种能全面地研究宝石矿物中致色元素能级结构的有效方法.  相似文献   

18.
Plates made of diamonds from the Sao Luiz province (Brazil) were investigated by confocal scanning luminescence microscopy. The samples have many macroinhomogeneities (cracks and inclusions), but there is a quasi-uniform distribution of luminescence centers in the bulk. At all investigated points of the crystals, the same group of centers was observed: N3, H4, 575, and a red band with a maximum at 690-700 nm. The visible nonuniformities in the distribution of luminescence over the area of the plates are determined by relatively small fluctuations in the ratio of the intensities of individual bands in the spectra. Nitrogen centers of different degrees of aggregation (H4, N3, and 575 nm, with four, three, and one nitrogen atom, respectively) coexist in these crystals. In the same zones of the samples, the distribution of blue luminescence (N3 centers) is diffuse (uniform), but the distribution of yellow-green luminescence is characterized by layering on (111). This might be a consequence of the tangential growth of octahedron faces or a result of plastic deformation of the crystals and dislocations along (111).  相似文献   

19.
Calcite was synthesized by four methods, and the luminescence decay-time was measured for nine samples before and after heating hydrothermally in the temperature range 200–400°C. Decay-time data were collected between room temperature and approximately 15 K. The decay time at room temperature is approximately 50 ms, with little difference between a given calcite before and after hydrothermal treatment. The decay time at 15 K is always greater than at room temperature as the effect of thermal quenching diminishes. Differences in decay time before and after heating are more apparent at low temperature owing to this reduction in thermal quenching. The decay time decreased significantly in two samples, and an increase in decay time was observed in the remaining seven samples following heating. Among the latter group, the change in decay time was insignificant in three samples. The results are compared with previous data in which it was shown that the effect of heating is to increase the intensity of luminescence.  相似文献   

20.
Summary Among the oxides, spinels are relatively abundant constituents of stardust, as has been inferred from studies of presolar grains in meteorites. Up to now, only pure Mg–Al-spinels have been considered as a possible stardust component. However, cosmically abundant transition metals such as iron or chromium may well be incorporated in spinels in the process of their formation in stellar atmospheres. We have produced synthetic Cr-doped spinels in order to study their UV, visible and IR spectra. Mass absorption coefficients (MACs) have been derived from transmission spectroscopy over a large wavelength range. For a Cr content of 5%, a maximum MAC in the UV (close to 200 nm) of 1000 cm2/g was found. For a Cr content of 10%, the maximum UV-MAC of spinel exceeds the maximum IR-MAC of 2000 cm2/g. The MIR bands of Cr-doped spinels are shifted to longer wavelengths with increasing Cr content, namely by ∼0.1 μm per 5% Cr in the range covered by our measurements. We conclude that a Cr content of spinel amounting to a few percents (<10%) is compatible with astronomical observations of spinel-bearing dusty environments, while a larger chromium content of spinels is not consistent with the presently available astronomical data.  相似文献   

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