Research on thermal shock resistance of mullite-bauxite-silicon carbide castable refractory

Effects of different silicon carbide contents on thermal shock resistance properties of mullite-bauxite castable refractory were analyzed respectively by taking the mullite,bauxite as main raw materials and taking calcium aluminate cement as a binding system.After 24 h curing in mould and another 24 h curing at 110℃ after demoulding,the samples were heated at 1000,1300 and 1500℃for 3 h in air,respectively.The bulk density,thermal expansion coefficient and thermal shock resistance were examined.The results showed that there was a great effect of content of SiC on bulk density,thermal expansion coefficient and thermal shock resistance of mullite-bauxite castable.Under the experimental conditions,the castable performed the best thermal shock resistance when w(SiC)=5%-10%.     

Electron microprobe measurement of pyroxenes coexisting with H2O-undersaturated liquid in the join CaMgSi2O6-Mg2Si2O6-H2O at 30 kilobars,with applications to geothermometry

Mixtures of synthetic crystalline enstatite and diopside were reacted with small water contents in sealed capsules in piston-cylinder apparatus at 30 kb between 1000° C and 1700° C. The compositions of coexisting enstatite and diopside solid solutions were measured with an ARL-EMX electron microprobe between 1000° C and 1500° C. Between 1100° C and 1500° C the pyroxenes coexisted with H₂O-undersaturated liquid which quenched to inhomogeneous pyroxene crystals. The presence of liquid facilitated growth of pyroxene crystals suitable for microprobe determinations. The solvus of Davis and Boyd (1966) is generally used in geothermometry; our enstatite solvus limb is a few mol-% richer in Mg₂Si₂O₆ in the temperature range 1000–1400° C; our diopside solvus limb is a few mol-% richer in Mg₂Si₂O₆ below 1100°C, in close agreement between 1100° C and 1200° C, but richer in CaMgSi₂O₆ between 1200° C and 1500° C. Estimated equilibration temperatures for a diopside with composition 78.7% Di is 1300° C according to our results compared with 1210° C for the Davis and Boyd solvus.     

Formation and kinetics of porous cordierite from fly ash

Porous cordierite ceramics were prepared from a mixture of coal fly ash and basic magnesium carbonate at 1100-1350℃. Porosity, flexural strength and thermal expansion coefficient of the samples sintered at 1300℃ were estimated to be 26%, 65 MPa and 4.21×10^-6/℃, respectively. The kinetics of the formation progress was investigated by stepwise isothermal dilatometry （SID） accompanied with XRD, SEM and porosity measurement. It was found that the isothermal shrinkage data from SID could be well analyzed to get kinetic parameters according to the erapirical rate equation developed by Makipirtti-Meng, dY/dt=nk（T）Y（1-Y）（Y/1-Y）^（1/n）,where Y is the fractional shrinkage during the sintering process and n is a dimensionless component. The apparent activation energy △E values for 900-1000℃ and 1050-1 150℃ were 1294 and 1778 kJ/mol, respectively.     

The oxygen isotope fractionation behaviour of kyanite in experiment and nature

The oxygen isotope fractionation between kyanite and calcium carbonate has been investigated experimentally at four temperatures in the range between 625 and 775 °C at 13 kbar. Because of low exchange rates, the isotopic reaction was enhanced by polymorphic transformation of andalusite to kyanite. With this experimental modification a close approach to equilibrium was reached in all runs. The temperature dependence of the equilibrium fractionation is described by the equation 1000 ln _ky-cc=−2.62×10⁶/T ². Application of the experimental results to natural quartz-kyanite-garnet assemblages indicates the preservation of the oxygen isotope composition of kyanite acquired during its formation, reflecting its extremely low oxygen diffusivity. This refractory behaviour restricts the use of kyanite for thermometry but opens the possibility to use its O-isotope composition as an indicator for recognition of polymetamorphic rock histories and reconstruction of the prograde evolution of a metamorphic sequence. Received: 8 June 1998 / Accepted: 24 August 1998     

Formation of the Fe,Mg-Silicates,Fe<Superscript>0</Superscript>, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

Experimental studies in the Fe₃C–SiO₂–MgO system (P = 6.3 GPa, T = 1100–1500°C, t = 20–40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe–C–O melt (1300–1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe–C–O) with oxides and silicates. The carbide–oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO₂ values near the iron–wustite buffer.     

On the thermal expansion of β-cristobalite

We have measured the temperature dependence of the cell parameter of cubic β-cristobalite up to 1300° C by high-precision X-ray powder diffraction. The thermal expansion coefficient decreases on heating, until above 1000° C the cell parameter is virtually constant in value. We discuss this change in the thermal expansion with reference to the behaviour of low-frequency rigid unit modes and fluctuations associated with the α-β phase transition.     

Experimental studies to constrain parental magma of Malangtoli volcanics from Singhbhum craton of the eastern Indian shield

Malangtoli volcanics of the Singhbhum craton of the eastern Indian shield is one of the important Proterozoic lava suites. Experimental studies on 1 atmosphere pressure constrain the parental magma type and temperature range of crystallization of the parent magma (deduced to be in the range of 1500°C to 1200°C). The experimental studies show that at 1500°C, plagioclase is the first phase to crystallize, followed by few opaques which join along with plagioclase at 1450°C. At subsequent lower temperature (1400°C-1300°C), plagioclase and opaque continue to crystallize. At 1250°C plagioclase and opaque still persist while pyroxene appears first and liquid (glass) still remains. Appearance of opaque minerals (magnetite and illmenite) at both ~1400°C and ~1300°C indicate oscillation of oxygen fugacity in the parent magma, petrographically documented by coarser phenocrysts as well as finer or peripheral tiny grains. Use of tectonic discrimination diagrams (based on discrimination factors F₁-F₂ and FeO^t/MgO vs. TiO₂) shows an island arc tholeiitic affinity for Malangtoli volcanic, suggests that the role of proto-plate convergence in Singhbhum architecture played an important role to build up Malangtoli volcanics during Proterozoic.     

Kyanite deformation in whiteschist of the ultrahigh-pressure metamorphic Kokchetav Massif, Kazakhstan

Microstructures in minerals from ultrahigh‐pressure metamorphic (UHPM) terranes are keys to understanding the rheological properties and the exhumation mechanisms of rocks from subduction zones. Kyanite‐bearing whiteschist, associated with eclogite lenses, is part of UHPM unit II located south‐west of Lake Zheltau in the Kulet region of the Kokchetav Massif. The equilibrium assemblage is kyanite + garnet + talc + phengite + coesite/quartz. Previously reported peak pressure–temperature (P–T) conditions are ～3.5 GPa at 750 °C. A strong foliation is defined by the talc and phengite, with a corresponding weak shape preferred alignment of kyanite. Crystallographic orientation maps and analysis of kyanite blades were performed using electron backscatter diffraction methods. The data are consistent with a (100)[001] slip system for the formation of undulose extinction and kink bands in kyanite. Rotations measured across individual kink bands are 10–50° about <010>, and rotations along kyanite with undulose extinction are up to 50° about <010> with variations between adjacent points typically <2°. The undulose extinction is interpreted to have developed through crystal plastic deformation by dislocation creep. Kink bands mark the development of high‐angle grain boundaries by dislocation climb. The deformation of kyanite occurred in the fault‐bounded terrane during the exhumation of the Kokchetav Massif.     

Specialized Methods of Thermal Treatment of Riverine and Marine Suspensions Preparatorily to Their Analysis for Trace Concentrations of Chemical Elements

The paper considerations of the possibility of the low-temperature (1000°C) and high-temperature (>1500°C) thermal decomposition of solid samples of suspensions and the selective fractional evaporation–condensation of elements in specialized electrothermal crucible and rod atomizers for the purposes of direct atomic-absorption analysis. The approach is applied to analyze samples of riverine and marine suspensions for Ag, Cd, and Tl.     

Aluminous reaction textures in orthoamphibole-bearing rocks: the pressure–temperature evolution of the high-grade Proterozoic of the Bamble sector, south Norway

Aluminous reaction textures in orthoamphibole-bearing rocks from the Froland area, Bamble, south Norway, record the prograde pressure–temperature path of the high-grade Kongsbergian Orogeny (c. 1600–1500 Ma) and the low–mid amphibolite facies overprint during the Sveconorwegian Orogeny (c. 1100–1000 Ma). The rocks contain anthophyllite/gedrite, garnet, cordierite, biotite, quartz, andalusite, kyanite, Cr-rich staurolite, tourmaline, ilmenite, rutile and corundum in a variety of parageneses. The P–T path is deduced from petrographic observations, mineral chemistry and zoning, geothermometry and (N)FMASH equilibria. The results indicate the sequence of metamorphic stages outlined below. (a) An M₁ phase characterized by the presence of strongly deformed andalusite, gedrite and tourmaline. (b) An M₂ phase with the development of kyanite after andalusite and the growth of staurolite associated with strong Na–Al–Mg zoning in orthoamphibole, indicating an increase in pressure (4 8 kbar) and temperature (500° 650°C). (c) Pressure decrease at high P (6–7 kbar) and high T (600–700 °C) during M_3a with the production of cordierite ° Corundum between kyanite, staurolite and orthoamphibole and cordierite growth between corundum and orthoamphibole. (d) Temperature increase to 740 ± 60 °C and 7 kbar; static growth of garnet (M_3b) at the metamorphic climax (peak T). The heat supply necessary to explain the temperature increase between the M_3a and M_3b phases is correlated with synkinematic enderbitic–charnockitic and basic intrusions in the Arendal granulite facies terrain. (e) M_3b metamorphic conditions were followed by an initial isobaric cooling path (early M₄) and late-stage pressure decrease (late M₄). Early M₄ conditions of 6–7 kbar and 550–600 °C, assuming P_H2O < P_total are indicated by a retrograde talc–kyanite–quartz assemblage in late quartz–cordierite veins. Late M₄ conditions of 3–4 kbar and 420–530 °C are inferred from a kyanite–andalusite–chlorite–quartz assemblage in vein-cordierite. The M₁–M₃ stages are interpreted as being the result of the same metamorphic P–T path, which was caused by both tectonic and magmatic thickening. A prolonged crustal residence time is proposed for the Bamble sector before uplift during the later stages of M₄ occurred.     

Supercooled diopside melt: confirmation of temperature-dependent expansivity using container-based dilatometry

The expansivity of supercooled diopside liquid has been determined using techniques of container-based dilatometry. Two thermal strategies have been employed, one in which the sample is brought to volumetric equilibrium by long-duration dwells at low temperatures (817 °C) and one in which scanning dilatometry of the sample has been performed at somewhat higher temperatures (890–913 °C). The results of both experiments yield a supercooled liquid expansivity for diopside liquid in the temperature range of 817–913 °C of 84.4 ± 2.8 × 10⁻⁴ cm³/mol K. The expansivity is 65% higher than that obtained for diopside melt obtained at superliquidus temperatures using the double bob Archimedean method. Combined fitting of the new low temperature, volume–temperature data from the present study and the superliquidus data from the literature has been performed. The combined fit yields the following equations for the volume–temperature relationship of diopside liquid (T=temperature in °C):

Unique mineral assemblages of shock-induced titanium-rich melt pockets in eucrite Northwest Africa 8003

Shock-induced Ti-rich melt pockets in a basaltic eucrite Northwest Africa (NWA) 8003 were studied using scanning and transmission electron microscopy. Unique mineral assemblages consisting of clinopyroxene, ilmenite, vestaite, corundum, and kyanite are observed. Among them, vestaite and corundum in NWA 8003 are first reported to occur in eucrite meteorites. Petrographic and chemical evidences indicate that the Ti-rich melt pockets have formed by in-situ melting of ilmenite, plagioclase, pyroxene, and possibly minor silica and apatite nearby. The temperature rise and melting were caused by the high shock impedance contrast at interfaces between ilmenite and other phases with a distinctly lower density. Crystallization pressure, temperature and cooling time of the Ti-rich melt pockets in NWA 8003 are constrained to be ˜0.9–˜10 GPa, ˜1300–˜1730 °C, and < 1 ms (5–50 μm in size), respectively.     

Experimental study of thermal effects on the mechanical behaviour of a clay

The paper presents the results of an experimental study of thermal effects on the mechanical behaviour of a saturated clay. The study was performed on CM clay (Kaolin) using a temperature-controlled triaxial apparatus. Applied temperatures were between 22 and 90°C. A comprehensive experimental program was carried out, including: (i) triaxial shear tests at ambient and high temperatures for different initial overconsolidation ratios; (ii) consolidation tests at ambient and high temperatures; and (iii) drained thermal heating for different initial overconsolidation ratios. The obtained results provide observations concerning a wide scope of the thermo-mechanical behaviour of clays. Test results obtained at 90°C were compared with tests performed at ambient temperature. Based on these comparisons, thermal effects on a variety of features of behaviour are presented and discussed. Focus is made on: (i) induced thermal volume change during drained heating; (ii) experimental evidence of temperature influence on preconsolidation pressure and on compressibility index; (iii) thermal effects on shear strength and critical state; and (iv) thermal effects on elastic modulus. Thermal yielding is discussed and yield limit evolution with temperature is presented. The directions of the induced plastic strains are also discussed. Several remarks on the difference in the mechanical behaviour at ambient and high temperatures conclude the paper. Copyright © 2004 John Wiley & Sons, Ltd.     

Reduction of Expansive Index,Swelling and Compression Behavior of Kaolinite and Bentonite Clay with Sand and Class C Fly Ash

Swelling behavior of expansive soil has always created problems in the field of geotechnical engineering. Generally, the method used to assess the swelling potential of expansive soil from its plasticity index, shrinkage limit and colloidal content. Alternative way to evaluate swelling behavior is from its expansive index (EI) and swelling pressure value. The present study investigates the reduction of EI and swelling pressure for kaolinite and bentonite clay when mixed with various percentages of Ottawa sand and Class C fly ash. The percentages of Ottawa sand and Class C fly ash used were 0–50 % by weight. The results show that there is a significant reduction in the swelling properties of expansive soil with the addition of Ottawa sand and Class C fly ash. The reduction in EI ranged approximately from 10 to 50 and 4 to 49 % for kaolinite and bentonite clay, respectively. Also the maximum swelling pressure of kaolinite and bentonite clay decreased approximately 93 and 64 %, respectively with the addition of various percentages of Ottawa sand and Class C fly ash. Standard index properties test viz., liquid limit, plastic limit and linear shrinkage test were conducted to see the characteristics of expansive soil when mixed with less expansive sand and fly ash. Also, for these expansive soils one dimensional consolidation test have been conducted with sand and fly ash mixtures and the results were compared with pure kaolinite and bentonite clay.     

Shock-induced formation of kyanite (Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript>) from sillimanite within a dense metamorphic rock from the Ries crater (Germany)

A dense (~3.34 g cm^–3) garnet–sillimanite-rich metamorphic rock from the suevite breccia of the Ries impact crater was studied by scanning-electron microscopy and Raman microprobe spectroscopy. In the strongly shocked rock clast kyanite was formed from sillimanite under momentary high pressures of natural shock waves. Kyanite aggregates were found as thin (~0.3–2.0 m) seams along grain boundaries between, and fractures within, sillimanite grains. Within these seams kyanite c-axes are oriented perpendicular to original grain boundaries and fractures. In addition, larger (up to 10 m) isolated kyanite grains were rarely found within host sillimanite. Filamentary kyanite aggregates and isolated crystals typically show shrinkage cracks due to volume decrease (~10%). Locally, broad interstices between sillimanite crystals are filled with aluminosilicate glass containing a high volume fraction of sub-micrometer-sized euhedral crystals. The silica-rich glass suggests incongruent melting of sillimanite at local post-shock temperatures significantly higher than 1,300°C. The edges of adjacent sillimanite grains are thermally and chemically altered. The local generation of temperature spikes is attributed to strong shock wave interactions due to very high shock impedance contrasts.     

Zur Stabilität von Margarit im System CaO-Al2O3-SiO2-H2O

An increasing number of occurrences of margarite have been reported in the last years. However, previous experimental investigations in the system CaO-Al₂O₃-SiO₂-H₂O are limited to the synthesis of margarite and to the upper stability limit according to the reaction (1) 1 margarite?1 anorthite +1 corundum +1 H₂O (Chatterjee, 1971; Velde, 1971). Since margarite often occurs together with quartz, the upper stability limit of margarite in the presence of quartz is of special interest. Therefore, the reactions (5) 1 margarite +1 quartz ?1anorthite +1 kyanite/andalusite +1 H₂O and (6) 4 margarite+3 quartz ? 2 zoisite+5 kyanite+3 H₂O were investigated experimentally using mixtures of natural margarite (from Chester, Mass., USA), quartz, kyanite, andalusite, zoisite, and synthetic anorthite. The indicated equilibrium temperatures at water pressures equal to total pressure are: 515± 25°C at 4 kb, 545 ±15°C at 5 kb, 590±10°C at 7 kb, and 650±10°C at 9 kb for reaction (5), and 651±11°C at 10 kb, 648 ± 8°C at 12.5kb, and 643±13°C at 15kb for reaction (6), respectively. Besides this, additional brackets for equilibrium temperatures were determined for the above cited reaction (1): 520±10°C at 3 kb, 580±10°C at 5 kb, and 640± 20°C at 7 kb. On the basis of these experimentally determined reactions (1), (5), and (6) and of the reactions (3) 2 zoisite +1 kyanite? 4 anorthite +1 corundum +1 H₂O (7) 2 zoisite +1 kyanite +1 quartz ? 4 anorthite +1 H₂O and (10) 1 pyrophyllite ? 1 andalusite/kyanite+3 quartz+1 H₂O for which experimental or, in the case of reaction (3), calculated data were already available, a pressure-temperature diagram with 3 invariant points and 11 univariant reactions was developed using the method of Schreinemakers. This diagram, summarizing both experimental and phase relation studies, allows conclusions about the conditions under which margarite has been formed in nature. Margarite is limited to low grade metamorphism at water pressures up to approximately 3.5 kb; in the presence of quartz, margarite is even limited to low grade metamorphism at water pressures up to 5.5 kb. Only at water pressures higher than the values stated before margarite, and margarite+quartz, respectively, can occur in medium grade metamorphism (as defined by Winkler, 1970 and 1973). For the combined occurrence of margarite+quartz and staurolite as reported by Harder (1956) and Frey (personal communication, 1973) it may be estimated that water pressure has been greater than approximately 5.5 kb, wheras temperature has been in the range from 550 to 650°C. Furthermore, the present study shows that the assemblage zoisite+kyanite (+ H₂O) is an indicator of both pressure [P _{H 2 O}> approximately 9kb]and temperature [T> approximately 640 to 650° Cat water Pressures up to 15 kb].     

The Genesis and Evolution of Alpine-Type Ultrabasic Rocks in Western Junggar, Xinjiang

The alpine-type ultrabasic rocks of the studied area have undergone plastic deformation under a temperature about 800--1200℃, a pressure about 0.9--1.68 GPa and differential stress of 0.2--0.35 GPa in relatively dry conditions, forming ultrabasie mylonite with porphyroclastic and mylonitic textures, Primary crystallized silicate melt inclusions and melt-fluid inclusions are discovered in porphyroclastic minerals and ore-forming chrome spinel. These rocks are formed under relatively stable physico-chemical conditions through liquid immiscibility of silicate melts, at 1200°-- 1300° and 1.1--1.38 GPa, equivalent to a depth of 40--50 km. No inclusion has been found in recrystallized secondary olivine and pyroxene, indicating that the plastic deformation happened after the formation of the rocks.     

Expansivity and compressibility of strontium fluorapatite and barium fluorapatite determined by in situ X-ray diffraction at high-T/P conditions: significance of the M-site cations

Strontium fluorapatite (SrF-Ap) and barium fluorapatite (BaF-Ap) were synthesized by using a piston-cylinder apparatus at 1.0 GPa and 800 °C. Their thermal expansivity and compressibility were subsequently investigated by using in situ high-T powder X-ray diffraction method (up to 1,000 °C at ambient P) and by using a diamond-anvil cell coupled with synchrotron X-ray radiation (up to about 5 GPa at room T), respectively. The derived thermal expansion coefficients and bulk moduli were combined with the literature data for calcium fluorapatite (CaF-Ap) and lead fluorapatite (PbF-Ap) to constrain the influence of the M-site cations on the elasticity of the fluorapatites (MF-Ap). The results show that both the size of the M cations and their polarizability affect the thermal expansion coefficients of the MF-Ap. For the axial and volumetric bulk moduli, the size of the M cations plays a dominant role, with some crystallographic features of the MF-Ap being potentially important as well.     

Transformation of garnet megacrysts captured by alkali mafic magma

The results of research of symplectites from the Shavaryn-Tsaram (Hangaj plateau, Mongolia) and Bartoj (Dzhida basaltic field, Russia) alkali basaltic rocks are presented. The symplectite compositions and structures were studied, and the physical and chemical parameters at which primary megacrysts were transformed into secondary mineral assemblages were defined. It is established that both garnet megacrysts and garnet-clinopyroxene aggregates were formed at pressures of 10–13 kbar and temperatures over 1300°C. The transformation of garnet into minerals of the secondary assemblage is considered as solid state water assisted resorption of garnet at a depth corresponding to pressures of 4–8 kbar and temperatures ranging from 1000 to 1300°C. The kelyphitic rims on the garnet megacrysts resulted from melting of the megacrysts at the contact with the hosting alkali basaltic rock.     

The pyrope-coesite rocks and their country rocks at Parigi,Dora Maira Massif,Western Alps: detailed petrography,mineral chemistry and PT-path

Both the coarse- and fine-grained varieties of the partly coesite-bearing pyrope-quartzites, their interlayered jadeite-kyanite rocks, and the biotite-phengite gneiss country rock common to all of them were subjected to detailed petrographic and textural studies in order to determine the sequence of crystallisation of their mineral constituents, which were also studied analytically by microprobe. Prior to pyrope and coesite growth, the Mg-rich metapelites were talc-kyanite-chlorite-rutile-ellenbergerite schists which — upon continued prograde metamorphism — developed first pyrope megacrysts in silica-deficient local environments at the expense of chlorite + talc + kyanite, and subsequently the smaller pyrope crystals with coesite inclusions from reacting talc + kyanite. Based on geobarometrically useful mineral inclusions as well as on experimentally determined phase relations, a prograde PT-path — simplified for water activity = 1 — is constructed which passes through the approximate PT-conditions 16 kbar and 560° C, 29 kbar and 720° C, and finally up to 37 kbar at about 800° C, where the Mg-rich metapelite was a pyrope-coesite rock with phengite, kyanite, and talc still present. During the retrograde path, pyrope was altered metasomatically either into phlogopite + kyanite + quartz or, at a later stage, to chlorite + muscovite + quartz. Both assemblages yield PT-constraints, the latter about 7–9 kbar, 500–600° C. The country rock gneisses have also endured high-pressures of at least 15 kbar, but they provide mostly constraints on the lowest portion of the uplift conditions within the greenschist facies (about 5 kbar, 450° C). Microprobe data are presented for the following minerals: pyrope, ellenbergerite, dumortierite (unusually MgTi-rich), jadeite, vermiculite (formed after Na-phlogopite?), paragonite, and for several generations of phengite, chlorite, talc, phlogopite, dravite, and glaucophane in the high-pressure rocks, as well as for biotite, chlorite, phengites, epidote, garnet, albite, and K-feldspar in the country rock gneisses. An outstanding open problem identified in this study is the preservation of minerals as inclusions within kyanite and pyrope beyond their PT-stability limits.