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1.
Methoxyphenols can be used as proxies for terrestrial biomass when investigating the chemical changes in lignin during hydrothermal alteration. The closed system microscale pyrolysis of 2-methoxyphenol (2-MOP) and 2,6-dimethoxyphenol (2,6-DMP), in the presence of water vapour, has been studied in borosilicate glass vessels. 2-MOP was heated isothermally at temperatures of 330°C for 96 h and 2,6-DMP was heated isothermally at 300°C for 118 h. Pyrolysis of the model compound 2-MOP gave a simple product distribution which was composed mainly of 1,2-dihydroxybenzene with lower amounts of 2-methylphenol and phenol. The prominent reaction products from heating 2,6-DMP were 1,2-dihydroxy-6-methoxybenzene and 2-methoxy-6-methylphenol, with minor amounts of 2-MOP, 1,2-dihydroxybenzene and 2-methylphenol. The decreasing amounts of 2,6-DMP with heating time and the concomitant increase in the amounts of 1,2-dihydroxy-6-methoxybenzene suggested that demethylation had occurred. 相似文献
2.
Muscovite-2M1 shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation
process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation
mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and
it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated
here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first
time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction
taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of
the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of
the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated
phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model
yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent
activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the
onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite,
the final product in the reaction pathway.
Received: 24 April 1998 / Revised, accepted: 12 October 1998 相似文献
3.
A.Yu. Likhacheva S. A. Veniaminov E. A. Paukshtis 《Physics and Chemistry of Minerals》2004,31(5):306-312
The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH4-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH4+ molecule onto NH3 and proton (framework OH group) and diffusion of NH3 out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH3 desorption is estimated to be 145(±13) kJ mol–1. This value is within the upper limit of the activation energy characteristic for the NH3 desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH3 and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol–1. 相似文献
4.
Chul-Min Chon Chul-Kyoo Lee Yungoo Song Sin Ae Kim 《Physics and Chemistry of Minerals》2006,33(5):289-299
The thermal response of the natural ferroan phlogopite-1M, K2(Mg4.46Fe0.83Al0. 34Ti0.22)(Si5.51Al2. 49)O20[OH3.59F0.41] from Quebec, Canada, was studied with an in situ neutron powder diffraction. The in situ temperature conditions were set up at ?263, 25, 100°C and thereafter at a 100°C intervals up to 900°C. The crystal structure was refined by the Rietveld method (R p=2.35–2.78%, R wp=3.01–3.52%). The orientation of the O–H vector of the sample was determined by the refinement of the diffraction pattern. With increasing temperature, the angle of the OH bond to the (001) plane decreased from 87.3 to 72.5°. At room temperature, a = 5.13 Å, b = 9.20 Å, c = 10.21 Å, β = 100.06° and V(volume) = 491.69 Å3. The expansion rate of the unit cell dimensions varied discontinuously with a break at 500°C. The shape of the M-octahedron underwent some significant changes such as flattening at 500°C. At temperatures above 500°C, the octahedral thickness and mean distance was decreased, while the octahedral flattening angle increased. Those results were attributed to the Fe oxidation and dehydroxylation processes. The dehydroxylation mechanism of the ferroan phlogopite was studied by the Fourier transform infrared spectroscopy (FTIR) after heated at temperatures ranging from 25 to 800°C with an electric furnace in a vacuum. In the OH stretching region, the intensity of the OH band associated with Fe2+(N B-band) begun to decrease outstandingly at 500°C. The changes of the IR spectra confirmed that dehydroxylation was closely related to the oxidation in the vacuum of the ferrous iron in the M-octahedron. The decrease in the angle of the OH bond to the (001) plane, with increasing temperature, might be related to the imbalance of charge in the M-octahedra due to Fe oxidation. 相似文献
5.
E. A. Kalinichenko A. S. Litovchenko A. M. Kalinichenko N. N. Bagmut N. T. Dekhtyaruk 《Physics and Chemistry of Minerals》1997,24(7):520-527
Dehydroxylation of muscovite in the form of small lamellae at 923 <T <1173 K was studied by Electron Spin Resonance (ESR) on Fe3+. The kinetics of the process has been established to be described by the model of continuous nucleation on the large surface
planes of the small plates. Determined by experimental data the rate constant of the process k is shown to be that of dehydroxylation itself. The activation energy obtained by data at T<1100 K is 97.5 KJ·mol−1. The nonlinear dependence of ln(k) on 1/T is explained by the theory of transitions induced by the fluctuative preparation of a potential barrier as a result of thermal
oscillations of ions in the lattice. At high temperatures the potential curve of the hydroxyl's proton is transformed so that
it can overcome the barrier from one potential well to the other (from one hydroxyl site to the adjacent one). Such transformations
of the curve can be caused by the oscillations of large structural clusters (∼1·10−22 kg) with the frequency ∼4.5·1012 s−1.
Received: 3 August 1995 / Accepted: 13 April 1997 相似文献
6.
Unit-cell dimensions of a natural phlogopite from Pargas, Finland, have been determined in the temperature interval of 27–1050 °C
by X-ray powder diffraction technique. Expansion rates vary discontinuously with temperature with a break at 412 °C. Below
this temperature, the linear expansions (α) for a, b and c axis lengths are 3.74 × 10−5 K−1, 1.09 × 10−5 K−1, and 1.19 × 10−5 K−1, respectively, and above that they are 0.86 × 10−5 K−1, 0.80 × 10−5 K−1, and 1.93 × 10−5 K−1. The volume thermal expansion coefficients are 6.26 × 10−5 K−1 and 3.71 × 10−5 K−1 for low-temperature and high-temperature intervals, respectively. The observed kink in the rate of thermal expansions with
temperature could be due to the different mode of structural changes. Thermogravimetric analysis of the sample indicates the
oxidation of iron in the temperature range of 500–600 °C and dehydroxylation as well as decomposition of phlogopite in the
temperature range of 900–1200 °C.
Received: 8 September 1998 / Accepted: 28 February 2000 相似文献
7.
The lattice constants of paragonite-2M1, NaAl2(AlSi3)O10(OH)2, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C,
were: αa = 1.51(8) × 10−5, αb = 1.94(6) × 10−5, αc = 2.15(7) × 10−5 °C−1, and αV = 5.9(2) × 10−5 °C−1. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements
of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion
along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged,
whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the
interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure
of the new phase, nominally NaAl2 (AlSi3)O11, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room
temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from
paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the
structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion
and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V
0 = 1 + 5.9(2) × 10−5
T(°C) − 0.00153(4) P(kbar).
Received: 12 July 1999 / Revised, accepted: 7 December 1999 相似文献
8.
Javier Garcia-Guinea E. Crespo-Feo V. Correcher J. Rubio M. V. Roux P. D. Townsend 《Physics and Chemistry of Minerals》2009,36(8):431-438
Natural hydrothermal ZnCO3 crystal aggregates are nominally anhydrous phases with interfacial water, with substitutional divalent cations and decarbonation
c. 300°C. All these common features must be involved during the experimental heating of a thermoluminescence (TL) glow curve
up to 500°C: dehydration–dehydroxylation, phase transition and ion transition of point defects in Zn2+ positions. A representative specimen of natural smithsonite was analysed by X-ray fluorescence spectrometry, field emission
scanning electron microscopy (FESEM) with a chemical probe of energy dispersive spectrometer, high temperature in situ X-ray
diffraction, differential scanning calorimetry, differential thermal analyses coupled to thermogravimetry, TL, radioluminescence
and high resolution spectra thermoluminescence (3DTL), to gain an overview of the spectra emission and defects linkages modified
by heating from room temperature up to 500°C. The ZnCO3 specimen contains minor amounts of Ca, Cu, Cr, Cd, Pb, Ce, Co, Ni, Mn and Fe. Under FESEM, it displays CaCO3 clusters and oscillatory zoning distribution with lamellae ranging from Ca0.11Zn0.89 to Ca0.19Zn0.81. The analytical results suggest assignments of defects and processes to measured 3DTL emission bands, as follows: (1) peak
at ~260°C, ~360 nm bonds, breaking during the thermal decarbonation process; (2) peak ~120°C, ~340 nm: non-bridging oxygen
centres associated to a complex dehydration–dehydroxylation process and (3) peak at ~170°C, ~650 nm, crystal field effects
on the thermoluminescence of Mn2+ centres and associated transitional elements in the ZnCO3 phase.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
9.
Mauro Gemmi Marco Merlini Alessandro Pavese Nadia Curetti 《Physics and Chemistry of Minerals》2008,35(7):367-379
Phengite samples (2M
1 and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray
diffraction. The measured volume thermal expansion of 2M
1 phengite (<α
V> ≈ 36.6 × 10−6 K−1) was systematically greater than <α
V> of the 3T polytype (≈33.3 × 10−6 K−1). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle
at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed
in 2M
1, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating
of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and
by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate
phase derived from 2M
1 is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H2O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect
to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows
two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not
proceed to completion.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
10.
The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum (P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application. 相似文献