High temperature heat contents and heat capacities of liquids and glasses in the system NaAlSi3O8-CaAl2Si2O8

Enthalpies and heat capacities of glasses and of stable liquids in the system NaAlSi₃O₈-CaAl₂Si₂O₈ have been measured by drop and differential scanning calorimetry. Within experimental error, values of C _p and of H _{T 300} of three intermediate compositions fall on straight line interpolations between the end members for both liquids and glasses, indicating that excesses in true and in mean heat capacities [(H _T –H ₃₀₀)/(T–300)] are small or absent. A value for the heat capacity of the An₁₀₀ liquid component can therefore be derived, and is probably a better estimate than that based on measurements on the pure substance alone. On the assumption of zero excess heat capacity in this system, heats of mixing in the stable liquids are equal to those measured in the glasses by solution calorimetry, and can be as negative as -2 kcal mol^–1.Heat capacities of solids and glasses in the Ab-An system are similar and do not vary greatly with composition. The C _P's of the liquids, however, increase strongly with An content, suggesting major structural changes take place across the binary.     

Das System NaAlSi3O8-BaAl2Si2O8-H2O bei 1 Kbar

The system albite-celsian-water was investigated at isothermal sections of 670, 760, 800, 900, 1000 and 1100° C at 1 Kbar. At temperatures above about 950° C the existence of a solid solution series could be shown. In the condensed part of the 930° C/1 Kbar section the partition of barium between melt and coexisting crystals was measured using an electron probe microanalyzer. The barium content of crystals grown in equilibrium with a melt is always higher than the barium content of the starting composition, so albite-celsian shows an ascending type solid solution series at low total water pressures. In the subsolidus region two types of solvi are existent, which show different ways of phase unmixing. The relatively low barium contents of natural albites are interpreted as being due to geochemical reasons rather than crystalchemical reasons.

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Meinem hochverehrten Lehrer, Herrn Prof. Dr. K. Jasmund, danke ich für sein lebhaftes Interesse während der Durchführung dieser Arbeit und für die kritische Durchsicht des Manuskripts. Mein Dank gilt ferner Herrn Dr. H. A. Seck für die Einarbeitung in die experimentellen Methoden der Hydrothermalsynthese und für kritische Anmerkungen zum Manuskript. Fräulein Dr. M. Corlett danke ich für wertvolle Informationen zur Messung mit der Elektronenstrahl-Mikrosonde.

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Die Untersuchung wurde mit Hilfe von Personal- und Sachmitteln durchgeführt, die Herrn Professor Dr. K. Jasmund von der Deutschen Forschungsgemeinschaft zur Verfügung gestellt worden waren.     

CaAl2Si2O8 polymorphs: Sensitive geothermometers and geospeedometers

Plagioclase is the major rock-forming mineral constituting the Earth’s crust, whereas anorthite (CaAl₂Si₂O₈) is a common minerals in lunar highlands crust, meteorites, possibly in some comets and on Mercury. Besides anorthite, two high-temperature polymorphs of CaAl₂Si₂O₈ are known: dmisteinbergite and svyatoslavite, which are found in burnt coal dumps, meteorites and pseudotachylytes. Here we present the results of detailed studies (quenching experiments, elemental analysis, Raman spectroscopy and in situ high temperature single crystal X-ray diffraction (up to 1000 °C)) on naturally co-occurring CaAl₂Si₂O₈ polymorphs (anorthite, dmisteinbergite and svyatoslavite) from a burnt coal dump in Kopeisk, Russia. New polymorphs were found in all natural samples and obtained upon heating of dmisteinbergite (unquenchable β-dmisteinbergite and quenchable γ-dmisteinbergite). It was shown that Ca coordination differs significantly in CaAl₂Si₂O₈ polymorphs, resulting in a different capacity to host Ba and possibly other large ion lithophile elements. Combining our data on natural samples with the previously published data on natural and synthetic compounds, we propose a new scheme of CaAl₂Si₂O₈ polymorphs stability. Our results indicate that CaAl₂Si₂O₈ polymorphs could be used for temperature estimations for both Earth and planetary sciences.     

Nucleation,growth and stability of CaAl2Si2O8 polymorphs

By means of in situ observation, the nucleation and growth of triclinic, pseudo-orthorhombic and pseudo-hexagonal CaAl₂Si₂O₈ were investigated and their relative stabilities established. Pseudo-hexagonal and pseudo-orthorhombic CaAl₂Si₂O₈ nucleate prior to anorthite and grow in a supercooled anorthite melt before the latter appears. They either dissolve or transform to anorthite once the latter nucleates and starts to grow. Corundum and mullite also nucleate metastably prior to anorthite in this melt. The liquidus temperatures of the four metastably nucleated phases were determined precisely by in situ measurements of the transformation temperatures from a polyhedral to a rounded morphology. On the basis of the supercooling thus determined, the growth rate versus supercooling relations were measured and analysed for the respective phases. The growth rate of the stable phase is one order of magnitude higher than those of any metastable phases. However, the growth rates of the three CaAl₂Si₂O₈ polymorphs normalized by the viscosities are nearly the same.     

Phase relations in the system NaAlSi3O8-KAlSi3O8-CaAl2Si2O8-SiO2 at 1 kilobar water vapour pressure

Crystal-melt relations at a water vapour pressure of 1 kilobar have been determined for planes at 3, 5, 7.5, and 10 weight per cent anorthite in the system NaAlSi₃O₈KAlSi₃O₈-CaAl₂Si₂O₈-SiO₂. The ratio of the silicate components in the liquids which are in univariant equilibrium with plagioclase, alkali feldspar, quartz and gas are Ab₃₁Or₂₈Q₃₈An₃ (weight per cent) at 730°±5–10° C, Ab₂₁Or₃₄Q₄₀An₅ at 745°±5–10° C and Ab₁₀Or₃₉ Q_43.5An_7.5 at 780°±10° C. The univariant curve on which the above compositions lieoriginates on the H₂O-saturated Or-An-Q plane at a composition containing less than 10 weight per cent An and terminates within 1.5 weight per cent An of the H₂O-saturated Or-Ab-Q plane. Experimental data for the synthetic system have been used to illustrate a discussion on the partial melting of metasediments and the possible significance of such a process with respect to the genesis of granitic rocks. Data taken from the literature (Winkler and v. Platen, 1960, 1961a) have been used to illustrate that the normative salic composition of a sediment has a strong influence on the composition of any melt which form when such a rock is subjected to high temperatures and pressures.     

High pressure transitions in the system KAlSi3O8-NaAlSi3O8

Phase relations in the system KAlSi₃O₈-NaAlSi ₃O₈ have been examined at pressures of 5–23 GPa and temperatures of 700–1200° C. KAlSi₃O₈ sanidine first dissociates into a mixture of wadeite-type K₂Si₄O₉, kyanite and coesite at 6–7 GPa, which further recombines into KAlSi₃O₈ hollandite at 9–10 GPa. In contrast, NaAlSi₃O₈ hollandite is not stable at 800–1200° C near 23 GPa, where the mixture of jadeite plus stishovite directly changes into the assemblage of calcium ferrite-type NaAlSiO₄ plus stishovite. Phase relations in the system KAlSi₃O₈-NaAlSi₃O₈ at 1000° C show that NaAlSi₃O₈ component gradually dissolves into hollandite with increasing pressure. The maximum solubility of NaAlSi₃O₈ in hollandite at 1000° C was about 40 mol% at 22.5 GPa, above which it decreases with pressure. Unit cell volume of the hollandite solid solution decreases with increasing NaAlSi₃O₈ component. The hollandite solid solution in this system may be an important candidate as a host mineral of K and Na in the uppermost lower mantle     

Heat capacity of liquid silicates: new measurements on NaAlSi3O8 and K2Si4O9

Drop calorimetric measurements of H_T-H₂₇₃ are reported for glassy and liquid albite and potassium tetrasilicate for the temperature interval 600–1500 K. Analysis of these observations as well as data for 13 other stable and supercooled silicate liquids suggests strongly that the isobaric heat capacities of stable and supercooled liquids are equal and thus temperature independent. Available evidence indicates that the isochoric heat capacities of liquid alkali silicates are also temperature independent within present experimental uncertainties.     

Liquidas phase relationships in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 atP(H2O)=5 kb

Liquidus phase equilibria have been determined in the system CaAl₂Si₂O₈-NaAlSi₃O₈-KAlSi₃O₈-NaAlSiO₄-KAlSiO₄ (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An₄, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An₆. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation.     

Iī-I2/c phase transition in alkaline-earth feldspars along the CaAl2Si2O8-SrAl2Si2O8 join: Thermodynamic behaviour

Feldspars crystallized in the range SrF₈₀An₂₀-SrF₆₀An₄₀ of the join CaAl₂Si₂O₈-SrAl-₂Si₂O₈ from gels at T = 1350–1500° C for short time show cell parameters significantly different from those obtained from longer heating. This difference has been interpreted as due to higher metastable Al/Si disorder in short heated samples and to more ordered configurations with longer heat treatments. HT powder spectra show that the T _c of the Iī-I2/c phase transition of feldspars changes with composition and with the degree of order at constant composition; the evolution of the spontaneous strain (～cosα^*) versus T for the samples examined shows a variation in the order of the transition from continuous (II order) in more ordered and Sr-rich samples to a discontinuous behaviour (presumably I order) for more disordered and Sr-poor samples. A biquadratic coupling between displacive and OD parameters is therefore suggested.     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.     

Der Einfluß des Drucks auf die Zusammensetzung koexistierender Alkalifeldspäte und Plagioklase im System NaAlSi3O8-KAlSi3O8-CaAl2Si2O8-H2O

Pairs of alkali feldspars and plagioclases were synthesized at pressures of 1, 5, and 10 kbar and a temperature of 650° C, to study the composition of coexisting feldspars in relation to pressure. Data were obtained mainly from pairs of feldspars crystallized from dehydrated gels in the presence of an aqueous vapor phase. Data obtained were confirmed by exchange reactions in mixtures of synthetic alkali feldspars and plagioclases. The effects of temperature and pressure on the distribution of albite molecule in coexisting feldspars are opposed to each other. An increase in pressure of 10 kbar equals to a decrease in temperature of about 125–150° C, thus posing severe restrictions to the application of the feldspar geothermometer of Barth. Pairs of coexisting feldspars are discussed in terms of their temperature and pressure of formation.

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Dem Direktor des Mineralogisch-Petrographischen Instituts der Universität zu Köln, Herrn Prof. Dr. K. Jasmund, danke ich für sein förderndes Interesse an dieser Arbeit sowie die kritische Durchsicht des Manuskripts. Herrn Prof. Dr. M. Okrusch und Herrn Dr. V. Rudert sei ebenfalls für kritische Anmerkungen zum Manuskript gedankt.

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Die Untersuchung wurde mit Hilfe von Personal- und Sachmitteln durchgeführt, die Herrn Professor Dr. K. Jasmund von der Deutschen Forschungsgemeinschaft zur Verfügung gestellt worden waren.     

P--T Stabilities of Laumontite, Wairakite, Lawsonite, and Related Minerals in the System CaAl2Si2O8-SiO2-H2O

Hydrothermal investigation of the bulk composition CaO.Al₂O₃.4SiO₂+excessH₂O has been conducted using conventional techniques over thetemperature ranges 200–450 °C and 500–6000 barsP_fluid. A number of reactions have been studied by employingmineral mixtures consisting of reactants and products in about9: 1 and 1: 9 ratios. The phase relations were deduced fromrelatively long experiments by observing which seeded assemblagedisappeared or decreased markedly in one of the paired run charges. Laumontite was synthesized in the laboratory, probably for thefirst time. Laumontite was grown from seeded wairakite to over99 per cent using a weak NaCl solution. The refractive indicesof the synthetic material are about = 1.504 and = 1.514. Theaverage unit cell dimensions are a₀ = 14.761±0.005 Å;b₀ = 13.077±0.005 Å; c₀ = 7.561±0.003 Å;and ß = 112.02°±0.04°. Within the errorof measurement, the optical properties and cell parameters arein good agreement with those of natural laumontite. The equilibriumdehydration of laumontite involves two reactions: (1) laumontite= wairakite+2H₂O, passing through about 230 °C at 0.5 kb,255±5 °C at 1 kb, 282±5 °C at 2 kb, 297±5°C at 3 kb and 325±5 °C at 6 kb; and (2) laumontite= lawsonite+2 quartz+2H₂O, taking place at about 210 °Cat 3 kb and 275 °C at 3.2 kb. Above 300 °C, the equilibriumcurve for the solid-solid reaction (3) lawsonite+2 quartz =wairakite passes through 305 °C, 3.4 kb and 390 °C,4.4 kb. Equilibrium has been demonstrated unambiguously forthe above three reactions. The hydrothermal decomposition ofnatural laumontite above its own stability limit appears tobe a very slow process. Combined with previously published equilibria determined hydrothermallyfor wairakite, the phase relations are further investigatedby chemographic analysis interrelating the phases, laumontite,wairakite, lawsonite, anorthite, prehnite+kaolinite, and 2 pumpellyite+kaolinitein the system CaAl₂Si₂O₈-SiO₂-H₂O. This synthesis allowed theconstruction of a semiquantitative petrogenetic grid applicableto natural parageneses and the delineation of the physical conditionsfor the various low-grade metamorphic facies in low µCO₂environments. The similar stratigraphic zonations, consistentlyfound in a variety of environments, are recognized to be a functionof burial depth, geothermal gradient, and mineralogical andchemical composition of the parental rocks. Departures fromthe normal sequences are believed to be due to the combinationsof mineralogical variations, availability of H₂O, differencesin the ratio µCO₂/µH₂O, and the rate of reaction.The possible P-T boundaries for diagenesis, the zeolite facies,the lawsonite-albite facies, the prehnite-pumpellyite facies,and the adjacent metamorphic facies are illustrated diagrammatically.     

钙长石成分熔体粘滞度和自扩散系数压力效应的分子动力学研究

用分子动力学方法,研究了1999 K下,压力由23 MPa上升到15183 MPa的过程中,CaAl_2Si_2O_8成分熔体的微观结构、剪切粘滞度和粒子自扩散系数的压力效应。在此基础上,探讨压力对剪切粘滞度与粒子自扩散系数之间关系的影响,并将它同微观结构的变化联系起来。结果表明,粒子自扩散系数的压力效应与熔体结构有很强的相关性;压力的挤压效应阻碍了粒子的扩散,而Si-O和Al-O 5次配位体的形成又加速了扩散过程,两种相反的作用相互抵消,造成的结果是在0～5 GPa范围内,Si~(4 ),O~(2-)和Al~(3 )等网架形成粒子的自扩散系数随压力变化不明显;当压力继续增大时,挤压效应占了主导,导致自扩散系数值快速减小。Ca~(2 )作为网架修饰粒子,自扩散系数随压力升高单调下降。压力小于5 GPa时,粒子自扩散系数的大小关系是:D_(Ca)>D_(Al)>D_O>D_(Si)。系统粘滞度随压力的变化与熔体中BO的含量密切相关:BO含量小于域值时,一定范围内BO含量的变化不会对粘滞度产生很大的影响,超过域值,BO含量的微小增加会导致粘滞度值迅速增大。有效应用Eyring方程的关键是方程中粒子跳跃距离的确定,本研究发现,Si~(4 )和O~(2-)的跳跃距离可以通过系统中非桥氧的百分含量来获得。这一发现使得我们能够利用系统中NBO的含量,结合Eyring方程有效进行不同压     

High temperature solvent growth of anorthite on the join CaAl2Si2O8-SiO2

Stoichiometric anorthite, CaAl₂Si₂O₈, Pˉ1, with sharp a, b, c, and d diffractions was grown, using a CaV₂O₆ solvent, by cooling at 2 ° C per hour from 1450 to 750 ° C in air. Euhedral crystals up to 5 × 3× 0.5 mm, with prominent {010} and well-developed {110} and {001}, were obtained by spontaneous nucleation. Nonstoichiometric anorthite with excess SiO₂ (CaAl₂Si₂O₈+Si₂Si₂O₈) was grown on the join CaAl₂Si₂O₈-SiO₂. Chemical analysis of the synthetic anorthite, having the highest SiO₂ content, with maximum vacancies on M-site gave □_0.110 Na_0.006Ca_0.884Al_1.80Si_2.20O₈, and X-ray diffraction showed a trend from stoichiometric Pˉ1 through diffuse Pˉ1 to body-centered Iˉ1 probably reflecting increasing disorder caused by a higher Si/Al ratio in the T-sites and the positional disorder accompanied by M-site vancancies. Annealing of the nonstoichiometric diffuse Iˉ1 anorthite in air at 1050 ° C for 14 days resulted in exsolution of minute SiO₂ inclusions due to probable ordering in the T-sites and filling of M-sites by Ca. Stoichiometric Pˉ1 anorthite was not obtained by annealing at 1050 ° due to appreciable solubility of SiO₂ in CaAl₂Si₂O₈. Metastable hexagonal CaAl₂Si₂O₈ was found to be a twinned monoclinic crystal with cell dimensions: a = 10.24 (2), b = 17.74 (3), c= 14.99 (5) ?, β = 92.05 (5) °, space group C2.     

Heat capacities of Fe2O3-bearing silicate liquids

Direct measurements of liquid heat capacity, using a Setaram HT1500 calorimeter in step-scanning mode, have been made in air on six compositions in the Na₂O-FeO-Fe₂O₃-SiO₂ system, two in the CaO-FeO-Fe₂O₃-SiO₂ system and four of natural composition (basanite, andesite, dacite, and peralkaline rhyolite). The fitted standard deviations on our heat capacity measurements range from 0.6 to 3.6%. Step-scanning calorimetry is particularly useful when applied to iron-bearing silicate liquids because: (1) measurements are made over a small temperature interval (10K) through which the ferric-ferrous ratio of the liquid remains essentially constant during a single measurement; (2) the sample is held in equilibrium with an atmosphere that can be controlled; (3) heat capacity is measured directly and not derived from the slope of enthalpy measurements with temperature. Liquid compositions in the sodic and calcic systems were chosen because they contain large concentrations of Fe₂O₃ (up to 19 mol%), and their equilibrium ferric-ferrous ratios were known at every temperature of measurement. These measurement have been combined with heat capacity (Cp) data in the literature on iron-free silicate liquids to fit Cp as a function of composition. A model assuming no excess heat capacity (linear combination of partial molar heat capacities of oxide components) reproduces the liquid data within error (±2.2% on average). The derived partial molar heat capacity of the Fe₂O₃ component is 240.9 ±7.9 J/g.f.w.-K, with a standard error reduced by more than a factor of two from that in earlier studies. The model equation, based primarily on simple, synthetic compositions, predicts the heat capacity of the four magmatic liquids within 1.8% on average.     

Das System KFeSi3O8−KAlSi3O8−H2O mit Untersuchungen über die Mikroklin-Sanidin-Beziehungen

Zusammenfassung Im System KFeSi₃O₈–KAlSi₃O₈ wird eine Mischungslücke gefunden, welche den Bereich von 10–60 Mol. % K-Fe-Feldspat umfaßt. Die Mischkristalle links und rechts der Mischungslücke verhalten sich ähnlich wie ihre benachbarten Endglieder. Das Fehlen von intermediären Phasen auf der Eisenseite und die Mischungslücke machen es wahrscheinlich, daß das Verhalten des K-Fe-Feldspates nicht auf das Verhalten des K-Al-Feldspates extrapoliert werden darf.

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Summary In the system KFeSi₃O₈–KAlSi₃O₈ a miscibility-gap is found from 10 to 60 Mol.% K-Fe-felspar. The mixed crystals on the right and left side of the miscibility-gap show a behaviour similar to the corresponding end-members. The lack of intermediate phases on the iron-side and the miscibility-gap make probable that one cannot extrapolate the behaviour of the K-Fe-felspar to the behaviour of the K-Al-felspar.

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Mit 3 Textabbildungen

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.     

A dynamical model for the P1 — I1 phase transition in anorthite,CaAl2Si2O8

Electron diffraction and electron microscopic evidence is presented for a dynamical and reversible phase transition in anorthite at T _c=516 K. Antiphase boundaries with a displacement vector, R=1/2[111] become unstable at T _c, while other antiphase boundary loops with the same displacement vector are formed. These interfaces are very mobile and vibrate with a frequency which increases strongly with temperature. At temperatures considerably above T _c, a shimmering effect is observed on imaging in dark field using diffuse c reflections. These observations are in agreement with the interpretation of the high temperature body-centered phase as a statistical dynamical average of very small c type antiphase domains of primitive anorthite. We propose that the c type antiphase domains in primitive anorthite originate from ordered and anti-ordered configurations around Ca²⁺ ions at (ooo) and (oio) [likewise (zoo) and (zio)] positions. The dynamical model for the transition involves a two-stage mechanism: a softmode mechanism causing the aluminosilicate framework to approach body-centered symmetry, followed by an orderdisorder of the Ca²⁺ ion configurations. Close to T _c, statistical fluctuations set in and breathing motion type lattice vibrations of the aluminosilicate framework cause the configurations around Ca (ooo) and Ca(oio) [likewise Ca(zoo) and Ca(zio)] in the configuration to dynamically interchange through an intermediate configuration. The dynamical nature of the phase transition in anorthite is comparable to the — phase transition in quartz.     

Analysis of the displacement vectors of antiphase domain boundaries in anorthites (CaAl2Si2O8)

As part of an electron microscopic study of plagioclase, displacement vectors for b- and c-domains have been determined from contrast experiments and calculations. In lunar anorthite from breccia 15459 (An 94.9), b-domains could be imaged in dark field with b-reflections and c-domains with c-reflections. The vector corresponding to these contrast conditions is 1/2[110] for b-domains and 1/2[111] for c-domains. The face centering vector 1/2 [110] relates two domains with a reverse Al/Si arrangement. The body-centering vector 1/2[111] relates domains of identical Al/Si distribution but different atomic coordinates. Fringe patterns for c-domains have been obtained for Pasmeda anorthite. Calculated intensity profiles applying multi-beam dynamic theory and a 1/2[111] displacement vector are in agreement with the observations.     

Glass transitions and thermodynamic properties of amorphous SiO2, NaAlSinO2n+2 and KAlSi3O8

A drop calorimetric study, between 900 and 1800 K, of amorphous SiO₂, NaAlSi₃O₈, NaAlSi₂O₆, NaAlSiO₄ and KAlSi₃O₈ shows the increase in heat capacity which results from glass transitions. For these glasses, the fictive temperature has a negligible effect on the heat capacity above room temperature, but it has an important influence on the enthalpy of formation as obtained from solution calorimetry. From these results and published Cp and enthalpy of solution data, several properties have been calculated: the enthalpies of fusion of high albite, nepheline, Jadeite and high sanidine, the thermodynamic functions of amorphous NaAlSi₃O₈ and KAlSi₃O₈ between 0 and 2000 K, and some mixing properties of liquids along the join SiO₂-NaAlSi₃O₈. The latter data suggest that these liquids behave more closely as athermal solutions than as regular solutions.     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.