OH point defects in olivine from Pakistan

The infrared (IR) spectra of gem-quality olivine crystals from Pakistan, formed in serpentinised dunitic rocks, are characterised by strongly pleochroic absorption bands at 3,613, 3,597, 3,580 and 3,566 cm^?1. These bands are assigned to O-H stretching vibrations of OH point defects corresponding to H₂O concentrations of about 35 wt ppm. Unlike other olivine spectra, the dominating bands are strongly polarised parallel to the b-axis. The unusual spectra type, excludes the presence of planar defects. This finding is supported by transmission electron microscopy. The 3,613 cm^?1 band is related to vacant Si sites, the slightly lower energetic bands preferentially to vacant M2 sites. The exclusive presence of these bands is not only a characteristic feature of olivines treated under high P,T conditions equivalent to mantle environment, the presence of these bands in untreated natural olivine also indicates formation conditions equivalent to crustal rocks.     

Application of the cBΩ model to the calculation of diffusion parameters of He in olivine

The validity of the thermodynamic cBΩ model is tested in terms of the experimentally determined diffusion coefficients of He in a natural Fe-bearing olivine (Fo₉₀) and a synthetic end-member forsterite (Mg₂SiO₄) over a broad temperature range (250–950 °C), as reported recently by Cherniak and Watson (Geochem Cosmochim Acta 84:269–279, 2012). The calculated activation enthalpies for each of the three crystallographic axes were found to be (134 ± 5), (137 ± 13) and (158 ± 4) kJ mol^?1 for the [100], [010] and [001] directions in forsterite, and (141 ± 9) kJ mol^?1 for the [010] direction in olivine, exhibiting a deviation of <1 % with the corresponding reported experimental values. Additional point defect parameters such as activation volume, activation entropy and activation Gibbs free energy were calculated as a function of temperature. The estimated activation volumes (3.2–3.9 ± 0.3 cm³ mol^?1) of He diffusion in olivine are comparable with other reported results for hydrogen and tracer diffusion of Mg cations in olivine. The pressure dependence of He diffusion coefficients was also determined, based on single experimental diffusion measurements at 2.6 and 2.7 GPa along the [001] direction in forsterite at 400 and 650 °C.     

High-temperature phase transition and local structure of a hydrous anorthoclase

The in situ Raman spectra of a hydrous anorthoclase at temperatures of 20–800 °C have been measured using a LABRAM-HR spectrometer and Linkam TS 1500 heating stage. The frequencies of modes at 54, 99, 130 and 162 cm^?1 related to M–O vibrations decrease sharply and then increase drastically or keep steady at temperatures above 200 °C. A knee point can be clearly seen at about 200 °C for those modes. The frequency of the mode at 282 cm^?1 shows little temperature dependence. However, for the two strongest modes at 471 and 512 cm^?1, the frequencies decrease linearly with increasing temperature. From evolution of the frequencies of modes at 54, 99, 130 and 162 cm^?1 with temperature, the following conclusions can be drawn: (1) The distance of the local M–O bond shortens rather than lengthens at temperatures above 200 °C; (2) The abrupt changes of the local structure of M site induce a collapse of the framework structure and displacive phase transition at 200 °C; and (3) The H atoms incorporated in anorthoclase are located at the M site. These results are indicative for the structure and properties of anorthoclase at deep earth conditions.     

Contribution of interstitial OH groups to the incorporation of water in forsterite

Water incorporation in forsterite samples synthesized under low to medium silica-activity conditions mostly occurs via a substitutional mechanism in which a Si vacancy is compensated by four protons. Corresponding IR absorption spectra display a cluster of narrow and weakly anharmonic OH-stretching bands at wavenumbers above 3,500 cm^?1. However, this diagnostic spectrum is often superimposed to one broader absorption band, rarely two, displaying pronounced temperature-dependent properties and tentatively assigned to H atoms in interstitial position (Ingrin et al. in Phys Chem Miner 40:499–510, 2013). Here, we investigate the structural and vibrational properties of selected interstitial H-bearing defects in forsterite using a first-principles modeling approach. We show that the broad bands discussed by Ingrin et al. (Phys Chem Miner 40:499–510, 2013) are most likely related to interstitial OH groups in the vacant octahedral sites alternating with the M2 sites along the c axis of the forsterite structure. The corresponding OH defects lead to the formation of fivefold coordinated Si species. Their peculiar thermal properties stem from the vibrational phase relaxation due to the anharmonic coupling of the high-energy local OH-stretching mode with a low-energy vibrational mode. This “exchange mode” corresponds to the hindered longitudinal translation of the OH group. These results suggest that at high pressure, hydrogen incorporation in forsterite is dominated by coexisting interstitial OH groups and (4H)_Si defects.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

Dehydration kinetics of antigorite using in situ high-temperature infrared microspectroscopy

The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm^?1 (band 1), 3,570–3,595 cm^?1 (band 2), and 3,450–3,510 cm^?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol^?1 for the total water band area, 245 ± 46 kJ mol^?1 for band 1, 243 ± 57 kJ mol^?1 for band 2, and 256 ± 53 kJ mol^?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10^?4 to 3 × 10^?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.     

OH in natural orthopyroxene: an in situ FTIR investigation at varying temperatures

In situ unpolarized and polarized Fourier transform infrared spectra of a natural orthopyroxene at varying temperatures were obtained using a heating stage attached on an Infrared microscope. The three main bands (3,595, 3,520 and 3,410 cm⁻¹) at room temperature are ascribed to OH fundamental stretching bands. With increasing temperature from room temperature to 500 °C, the 3,595 cm⁻¹ band shifts 20 cm⁻¹ to lower frequency. The total integral absorbance decreases with increasing temperature. These changes are reversible. Excluding the influences of dehydration, proton migration, thermal expansion, and changes in OH dipole direction, the change of integral absorbance with temperature reflects the temperature dependence of absorption coefficient due to the anharmonicity of OH vibration. Based on the integral absorption coefficient at room temperature (14.84 ppm⁻¹ cm⁻²) from Bell et al. (Am Mineral 80:463–474, 1995), the integral absorption coefficients at other temperatures are calculated. The variation of integral absorption coefficient between room temperature and 500 °C obtained in this study is about 18.5 % and may be greater at higher temperature according to the proposed linear relationship.     

Cation diffusion in olivine—I. Cobalt and magnesium

Cobalt and magnesium interdiffusion coefficients in synthetic crystals of olivine have been determined by a method of couple annealing. These coefficients increase with temperature and Co concentration. The coefficients in forsterite along the c crystallographic axis range from 1.13 × 10^?12 to 6.85 × 10^{?11 cm2sec?1} at temperatures ranging from 1150 to 1400°C. The calculated activation energies for Co-Mg interdiffusion in forsterite are 526 kJmol^?1 above approximately 1300°C and 196 kJmol^?1 at lower temperatures. These results indicate that the Co-Mg mobility in olivine is relatively low compared to published results for Fe-Mg interdiffusion.     

Diffusion and solubility of hydrogen and water in periclase

Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm^?1 indicating V _OH ^? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H₂O equivalent, was calculated to 3.5 wt ppm H₂O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H₂O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H₂O. Proton diffusion follows an Arrhenius law with an activation energy E _a = 280 ± 64 kJ mol^?1 and the logarithm of the pre-exponential factor logD_o (m² s^?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm^?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logD_H2O (m² s^?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.     

First-principles study of OH defects in zircon

The infrared spectroscopic properties of selected OH defects in zircon are investigated by first-principles calculations. The explicit treatment of the coupled nature of OH motions in the stretching modes, together with the calculation of the intensity and polarization of absorption bands, makes it possible to directly compare theoretical and experimental data. The bands observed at 3,420 cm^?1 (polarization parallel to c axis) and 3,385 cm^?1 (polarization perpendicular to c axis) in natural and synthetic samples correspond to the IR-active vibrational modes of the hydrozircon defect, that is, fully protonated Si vacancy. The broad band observed at 3,515 cm^?1 in the spectrum of zircon crystals grown in F-rich environments is consistent with the occurrence of composite (OH,F) tetrahedral defects. Calculations also show that the band observed at 3,200 cm^?1 in the spectrum of synthetic undoped samples can be ascribed to fully protonated Zr vacancies. The theoretical values of integrated absorption coefficients indicate that general correlations can be reasonably used to determine the concentration of OH groups in zircon.     

OH defects in quartz in the system quartz–albite–water and granite–water between 5 and 25?kbar

The incorporation of OH defects in quartz from the systems quartz–water, quartz–albite–water and granite–water at pressures between 5 and 25?kbar and temperatures between 800 and 1,000?°C was investigated by IR spectroscopy. The two most important OH absorption features can be assigned to hydrogarnet defects (absorption band at 3,585?cm^?1) and coupled substitutions involving Al³⁺ (Al–H defects, absorption bands at 3,310, 3,378 and 3,430?cm^?1). Al incorporation in quartz is controlled by mineral/melt partitioning (D _Al ^Qz/Melt ?=?0.01) and exhibits a negative pressure dependence. This trend is not clearly reflected by the concentration of Al–H defects, which shows positive deviations from the theoretical 1:1 correlation of Al/H for some samples. In contrast to the Al–H defects, formation of hydrogarnet defects appears to be positively correlated to pressure and water activity, and may be used a petrological indicator. The overall water concentration exhibits only minor changes with pressure and temperature, but a clear correlation of water activity (controlled by various amounts of dissolved salts) and hydrogarnet substitution could be established.     

OH defects in quartz in granitic systems doped with spodumene,tourmaline and/or apatite: experimental investigations at 5–20 kbar

The incorporation of OH defects in quartz as a function of Li content in the bulk system and pressures was investigated. Quartz crystals were grown in water-saturated granitic systems, containing various amounts Li, B and P, supplied as accessory phases such as spodumene, tourmaline or apatite in the starting mixtures. High pressure experiments were performed at temperatures between 900 and 1100 °C, and pressures between 5 and 20 kbar with a piston cylinder apparatus, and the synthesized quartz crystals were analyzed by IR spectroscopy, electron microprobe and LA-ICP-MS spectroscopy. All IR absorption spectra revealed absorption features that can be assigned to AlOH (3313, 3379 and 3431 cm^?1) and (4H)_Si defects (3585 cm^?1), whereas quartz grown in the Li and B systems exhibited two additional bands related, respectively, to LiOH (3483 cm^?1) and BOH defects (3596 cm^?1). It was further observed that LiOH incorporation increases with higher spodumene content in the starting material and decreases with pressure, until no LiOH defects are observed at pressure higher than 15 kbar. Specifically, the most pronounced reduction of LiOH defects occurs in a rather narrow pressure interval (10–15 kbar) close to the high-quartz/low-quartz transition. However, the link between the transition and the defect incorporation remains unclear. Li total concentrations always exceed the Li-coupled LiOH defects, suggesting the simultaneous presence of dry AlLi defects. Results of this study suggest that LiOH defects are detectable only in quartz crystals grown from middle and upper crustal sections (such as hydrothermal quartz) and not in quartz from deep roots of orogenic granitoids.     

Crystal chemistry, thermal expansion, and Raman spectra of hydroxyl-clinohumite: implications for water in Earth’s interior

Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg_8.674(14)Fe_0.374(4)(Si_0.99(1)O₄)₄(OH)₂ and sample SZ0411B with composition Mg₉(SiO₄)₄(OH)₂, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å³ for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å³ for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm^?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H₂O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10^?6 K^?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.     

Infrared spectroscopic properties of goethite: anharmonic broadening,long-range electrostatic effects and Al substitution

The infrared spectrum and its temperature dependence (20–320 K) were collected on a synthetic goethite sample (α-FeOOH). In addition, the infrared powder absorption spectrum of goethite and aluminum-substituted goethite was computed using ab initio quantum mechanical calculations based on density functional theory. This combined experimental and theoretical approach allows (1) the unequivocal assignment of absorption bands to the corresponding vibrational modes, (2) separate identification of the effects of the particle shape and of the aluminum substitution on the infrared spectrum, and (3) a discussion of the anharmonic properties and the origin of the line broadening in goethite. In particular, the two well-resolved OH bending absorption bands show different temperature evolution. Their detailed analysis suggests that the broadening of the band at ~800 cm^?1 cannot be described solely by a usual three-phonon process. The strong anharmonic behavior of this mode implies the addition of a four-phonon process, such as a pure dephasing process. In our calculations, the effect of the Hubbard U correction is also investigated and found to be most visible on the OH stretching and bending modes, in relation to the associated structural relaxation. The OH stretching frequencies decrease, leading to a better agreement with experimental frequencies, while the OH bending frequencies increase.     

The potential use of OH-defects in enstatite as geobarometer

In this study, single crystals of pure enstatite (Mg₂Si₂O₆) were synthesised under water-saturated conditions at 4 and 8 GPa and 1,150°C with variable silica activity, leading to phase assemblages enstatite + forsterite, enstatite or enstatite + coesite. Run products were investigated using an FTIR spectrometer equipped with a focal plane array detector enabling IR imaging with a lateral pixel resolution of 2.7 μm. IR spectra within the OH-absorption region show two different groups of absorption bands: group 1 (wavenumbers at 3,592 and 3,687 cm^?1) shows strongest absorptions for E||n _β, whereas group 2 (wavenumbers at 3,067 and 3,362 cm^?1) shows strongest absorptions for E||n _γ. The groups are related to different defect types, group 1 to tetrahedral defects (T-site vacancies) and group 2 to octahedral defects (M-site vacancies). The intensity ratio of the bands within one group (i.e. A ₃₀₆₇/A ₃₃₆₂ and A ₃₅₉₂/A ₃₆₈₇) and the intensity ratio of E||n _γ and E||n _α in group 2 bands remain constant within error. In contrast, the intensity ratio of group 2 to group 1 absorption bands [e.g. (A ₃₃₆₂)/(A ₃₆₈₇)] is sensitive to the SiO₂ activity and pressure. On the basis of the results of this and previous studies, a barometer for pure orthoenstatite coexisting with forsterite can be formulated:\( P\,[{\text{GPa}}] = 1.056 + \sqrt {{\frac{{1.025 - A_{{\left( {3362} \right)/\left[ {(3362) + (3687)} \right]}} }}{0.009}}} , \) where A ₍₃₃₆₂₎ and A ₍₃₆₈₇₎ are the integral absorbances of the component E||n _γ of the absorption bands at 3,362 cm^?1 and the component E||n _β of the absorption band at 3,687 cm^?1, respectively.     

In-situ IR measurements of OH species in quartz at high temperatures

The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour. At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm^–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration. This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational frequency from 3396 to 3386 cm^–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al) begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs. Received: 18 February 1998/ Accepted: 10 July 1998     

Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline

Polarized Raman spectra were collected for single crystal buergerite (NaFe₃Al₆(BO₃)₃Si₆O₁₈(O_0.92(OH)_0.08)₃F) from room temperature to near 1,375°C. Vibrational assignments to features in the room temperature spectra were determined by lattice dynamics calculations, where internal BO₃ motions dominate modes near 1,300 cm⁻¹, internal SiO₄ displacements dominate modes between 900 and 1,200 cm⁻¹, while less localized displacements within the isolated Si₆O₁₈ ring mix with motions within Na, Fe, Al, F, and BO₃ environments for fundamental modes below 780 cm⁻¹. At elevated temperatures, most buergerite Raman features broaden and shift to lower frequencies up to 900°C. Above this temperature, the lattice mode peaks evolve into broad bands, while OH stretch modes near 3,550 cm⁻¹ disappear. According to Raman spectroscopy, X-ray diffraction, differential thermal analysis, and scanning electron microscopy, buergerite undergoes a complex transition that starts near 700°C and extends over a 310°C interval, where initially, Al and Fe probably become disordered within the Y- and Z-sites, and most F and all OH are later liberated. A reversible crystal-to-amorphous transition is seen by Raman for buergerite fragments heated as high as 930°C. Buergerite becomes permanently altered when heated to temperatures greater than 930°C; after cooling to room temperature, these altered fragments are comprised of mullite and Fe-oxide crystals suspended in an amorphous borosilicate matrix.     

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002     

Characterization and properties of boron-doped aluminum hydroxide for Mn2+ adsorption and soil acidification

Al hydroxide was prepared by hydrolysis of Al(NO₃)_3, and oc-B-Al hydroxide was prepared by hydrolysis of Al(NO₃)₃ in the presence of boric acid solution. Curve-fitted B_1s XPS spectrum of oc-B-Al hydroxide demonstrated that the boron atom was probably incorporated with Al hydroxide to some extent. The IR band of Al–OH at 1,074 cm^?1 of oc-B-Al hydroxide was weaker than that of Al hydroxide. This indicated some surface hydroxyl groups of Al–OH of oc-B-Al hydroxide had disappeared. These peaks at 1,320 and 1,458 cm^?1 bands found in the oc-B-Al hydroxide were closer together than the salts containing boron, which are attributed to an interaction of aluminum hydroxide with boron. Analysis of XRD patterns indicated that Al hydroxide was very poorly crystalline boehmite, and oc-B-Al hydroxide appeared to have crystallite dimensions slightly smaller than those present in Al hydroxide. TEM showed that the presence of boron significantly decreased the size of Al hydroxide particles. The specific surface area of oc-B-Al hydroxide (556.0 m² g^?1) using BET method was larger than that of Al hydroxide (421.6 m² g^?1). This indicated the likelihood of Mn²⁺ adsorption ability of oc-B-Al hydroxide than the Al hydroxide. Boron-doped Al hydroxide always adsorbed more Mn²⁺, stabilized the sample solution pH to a higher value and slowed soil acidification than the Al hydroxide. It is suggested that boron in soils not only serves as a plant nutrient, but can also decrease the Mn²⁺ toxicity and slows soil acidification by formation of oc-B-Al hydroxide.