Coloration of natural beryl by iron ion implantation

Хайбуллин, Р. И.; Lopatin, O. N.; Vagizov, F. G.; Bazarov, V. V.; Bakhtin, A. I.; Хайбуллин, И. Б.; Aktaş, B.

doi:10.1016/s0168-583x(03)00744-4

Cited by 13 publications

(6 citation statements)

References 3 publications

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“…The authors reported that above ~1100 K, most of the Fe 2+ ions are oxidized. Khaibullin et al (2003) implanted colorless beryl crystals with 40 keV Fe + ions and then annealed them at 600°C for 30 m. Optical absorption, Mössbauer, and Rutherford back-scattering spectroscopies showed Fe 2+ replacing Be at the tetrahedrally coordinated Be positions and Fe 3+ substituting for Al at the octahedrally coordinated Al sites. Figueiredo et al (2008) used X-ray absorption spectroscopy at the Fe K-edge to study blue beryl crystals from the Licungo pegmatite in Mozambique.…”

Section: Previous Workmentioning

confidence: 99%

Crystal Chemistry of Dark Blue Aquamarine From the True Blue Showing, Yukon Territory, Canada

Groat¹,

Rossman²,

Dyar³

et al. 2010

The Canadian Mineralogist

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Dark blue aquamarine and beryl were discovered at the True Blue showing in the southern Yukon Territory in 2003. Electronmicroprobe-derived compositions show up to 5.39 wt.% FeO in the darkest material, which is among the highest Fe concentration known for true beryl. The Al site totals average 2.05, with a maximum of 2.10 apfu, which implies that there is more Fe present in the sample than can be accommodated at the Al position. Charge-balance considerations and Mössbauer spectra show that the Fe is present as both Fe 2+ and Fe 3+. Optical absorption and Mössbauer spectra and the results of the X-ray and neutron singlecrystal refinements suggest that there is very little Fe at the tetrahedral or channel sites. Previous investigators have proposed that the color of blue beryl is due to intervalence charge-transfer (IVCT) between Fe 2+ and Fe 3+ cations. The anisotropy of the optical absorption spectra suggest that if the mechanism responsible for the color in our samples is IVCT, the vector between the ions involved must be oriented approximately parallel to c. The only vectors that fulfill this condition and have a realistic length (2.300 Å) are 4d-Al and 6g-Be. Given the close proximity of the Si positions (closer than any anion sites), it is difficult to conceive of the substitution taking place at the interstitial 4d site. However, Fe could substitute at the interstitial 6g position, but likely only in very small amounts, because of the need to maintain local charge-balance. Unfortunately, there is no evidence of this in the Mössbauer spectra or in difference-Fourier maps of the X-ray-and neutron-diffraction data. For the former technique, it is likely that any doublet arising from Fe in the 6gO 6 polyhedron is too similar to the Fe in the AlO 6 octahedra to be resolved for either Fe 2+ or Fe 3+. Calculations suggest that the concentration of Fe involved in the IVCT process is 0.08 apfu Fe, of which half (0.04 apfu, 0.17 e-) would potentially be at the interstitial site. This amount of electrons and this nuclear density are likely too small to be seen on the difference-Fourier maps.

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Section: Previous Workmentioning

confidence: 99%

Crystal Chemistry of Dark Blue Aquamarine From the True Blue Showing, Yukon Territory, Canada

Groat¹,

Rossman²,

Dyar³

et al. 2010

The Canadian Mineralogist

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“…Образец характеризовал-ся высокой прозрачностью и имел бледно-голубоватый оттенок. Процентное содержание и валентное состояние примеси железа в природном образце были изучены нами ранее в работах [18,19]. Согласно элементному EDX-микроанализу (EDX -energy dispersive X-ray spectroscopy) и данным мeссбауэровской спектроскопии, содержание примеси железа в природном кристалле было значительно меньше, чем в его синтетическом аналоге (образце № 2), и составляло величину по-рядка 0.15 at.%.…”

Section: экспериментunclassified

“…При этом найдено, что большая часть примеси железа (∼ 80% от общего количества) былa в форме двухвалентных ионов железа, локализованных либо в октаэдрических (60%), либо в тетраэдрических (20%) узлах решетки, изоморфно замещающих катионы алюминия и бериллия соответственно (см. таблицу в работе [19]). …”

Section: экспериментunclassified

Субмиллиметровые спектры ЭПР иона Fe-=SUP=-2+-=/SUP=- в кристаллах синтетического и природного бериллов

Шакуров¹,

Хайбуллин²,

Томас³

et al. 2017

Физика Твердого Тела

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В синтетическом и природном кристаллах берилла с примесью железа в субмиллиметровом диапазоне длин волн при температуре жидкого гелия зафиксированы спектры ЭПР некрамерсового иона двухвалентного железа (Fe2+). Наблюдаемые сигналы ЭПР отнесены к резонансным переходам иона Fe2+ из основного (синглетного) состояния на возбужденные уровни (дублета) с расщеплением между ними, равным Delta=12.7 cm-1. Экспериментальные угловые и частотно-полевые зависимости величины резонансного поля сигнала ЭПР описаны в рамках спинового гамильтониана с эффективным спином S=1. Анализ данных ЭПР и оптических спектров поглощения указывает на то, что ионы Fe2+ находятся в тетраэдрических позициях и замещают катионы Be2+ в структуре берилла. Работа поддержана РФФИ (грант N 14-02-00255) и Министерством образования и науки РФ (программа 5топ100 и Госзадание N 3.9896.2017/ВУ). DOI: 10.21883/FTT.2017.08.44761.37

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“…The survey of publications indicates that ion implantation into a mineral matrix is not carried out systematically. Ohkubo et al (1986), Saito et al (1991), Lopatin et al (2001Lopatin et al ( , 2002Lopatin et al ( , 2005, and Khaibullin et al (2003) demonstrated the fundamental possibility to modify physical properties of minerals and their synthetic analogues, particularly coloration, with implantation of ions of the iron group elements.…”

Section: Setting Of Problem and Experimentalmentioning

confidence: 99%

Optical properties and crystal chemistry of synthetic rutile implanted with cobalt ions

et al. 2007

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Implantation of high-energy cobalt ions into plates of synthetic rutile has been studied, and absorption, luminescence, and luminescence excitation spectra have been recorded and interpreted. Long-wave luminescence (820 nm) of ions in rutile has been revealed; its intensity increased after the cobalt implantation. Analysis of luminescence and luminescence excitation spectra has allowed us to specify the scheme of electron energy levels of rutile and to establish the energy levels of impurity Ti 3+ ions occupying vacant octahedrons with the C 2 h symmetry in structure of the mineral.

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Coloration of natural beryl by iron ion implantation

Cited by 13 publications

References 3 publications

Crystal Chemistry of Dark Blue Aquamarine From the True Blue Showing, Yukon Territory, Canada

Crystal Chemistry of Dark Blue Aquamarine From the True Blue Showing, Yukon Territory, Canada

Субмиллиметровые спектры ЭПР иона Fe-=SUP=-2+-=/SUP=- в кристаллах синтетического и природного бериллов

Optical properties and crystal chemistry of synthetic rutile implanted with cobalt ions

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