Thermochemistry of A2M3O12 negative thermal expansion materials

2007 ◽  
Vol 22 (9) ◽  
pp. 2512-2521 ◽  
Author(s):  
Tamas Varga ◽  
Julianna L. Moats ◽  
Sergey V. Ushakov ◽  
Alexandra Navrotsky
Keyword(s):  
Low Temperatures ◽  
Monoclinic Phase ◽  
Negative Thermal Expansion ◽  
Orthorhombic Phase ◽  
Solution Calorimetry ◽  
Enthalpies Of Formation ◽  
Ambient Conditions ◽  
Scanning Calorimetry ◽  
Binary Oxides ◽  
Negative Thermal Expansion Materials

The enthalpies of the monoclinic to orthorhombic transition for a series of A2M3O12 (A = Al, Cr, Fe, In, and Sc; M = Mo or W) compounds were measured by differential scanning calorimetry, and entropies of transition were estimated. The enthalpies of formation from the binary oxides at 25 °C for several A2M3O12 samples were obtained from drop solution calorimetry in molten 3Na2O·4MoO3 at 702 °C. The monoclinic and orthorhombic phases of Sc2Mo3O12 and Sc2W3O12 are the only phases that are enthalpically stable under ambient conditions. The enthalpies of formation from the oxides (ΔHf,ox) for orthorhombic Sc2Mo3O12 and Sc2W3O12 are −47.2 ± 2.1 kJ/mol and −8.5 ± 2.7 kJ/mol, respectively. For Fe2Mo3O12, In2Mo3O12, and In2W3O12, ΔHf,ox values are 51.5 ± 4.5, 7.4 ± 2.9, and 44.5 ± 2.3 kJ/mol, respectively. These phases are entropically stabilized and/or metastable. Enthalpies of formation for phases that could not be measured by calorimetry have been estimated from the enthalpies of transition or trends in the enthalpies of formation. In general, the monoclinic phase is slightly enthalpically stabilized over the orthorhombic phase, while transition to the orthorhombic phase is entropically favored. This confirms that the orthorhombic phase is stable at high temperatures, the monoclinic is stable at low temperatures, and the monoclinic to orthorhombic transition is reversible.

Enthalpy of Formation of Rare-earth Silicates Y2SiO5 and Yb2SiO5 and N-containing Silicate Y10(SiO4)6N2

1999 ◽  
Vol 14 (4) ◽  
pp. 1181-1185 ◽  
Author(s):  
Jian-Jie Liang ◽  
Alexandra Navrotsky ◽  
Thomas Ludwig ◽  
Hans J. Seifert ◽  
Fritz Aldinger
Keyword(s):  
Rare Earth ◽  
High Temperature ◽  
Enthalpy Of Formation ◽  
Temperature Drop ◽  
Solution Calorimetry ◽  
Enthalpies Of Formation ◽  
Binary Oxides ◽  
Standard Enthalpies Of Formation ◽  
Oxygen Gas ◽  
The Enthalpy Of Formation

The enthalpies of formation of two rare-earth silicates (Y2SiO5 and Yb2SiO5) and a N-containing rare-earth silicate Y10(SiO4)6N2 have been determined using high-temperature drop solution calorimetry. Alkali borate (52 wt% LiBO2·48 wt% NaBO2) solvent was used at 800 °C, and oxygen gas was bubbled through the melt. The nitrogen-containing silicate was oxidized during dissolution. The standard enthalpies of formation are for Y2SiO5, Yb2SiO5, and Y10(SiO4)6N2, respectively, –22868.54 ± 5.34, –22774.75 ± 8.21, and –14145.20 ± 16.48 kJ/mol from elements, and –52.53 ± 4.83, –49.45 6 ± 8.35, and –94.53 ± 11.66 kJ/mol from oxides (Y2O3 or Yb2O3, SiO2) and nitride (Si3N4). The silicates and N-containing silicate are energetically stable with respect to binary oxides and Si3N4, but the N-containing silicate may be metastable with respect to assemblages containing Y2SiO5, Si3N4, and SiO2. A linear relationship was found between the enthalpy of formation of a series of M2SiO5 silicates from binary oxides and the ionic potential (z/r) of the metal cation.

Microdomains in BaFeO3-y (0.35 < y < 0.50)

1990 ◽  
Vol 48 (4) ◽  
pp. 780-781
Author(s):  
M. Vallet-Regí ◽  
M. Parras ◽  
J.M. González-Calbet ◽  
J.C. Grenier
Keyword(s):  
Electron Diffraction ◽  
Chemical Analysis ◽  
Monoclinic Phase ◽  
Orthorhombic Phase ◽  
Total Iron ◽  
Zone Axis ◽  
Electron Micrograph ◽  
X Ray Diffraction ◽  
X Ray ◽  
Compositional Variations

BaFeO3-y compositions (0.35<y<0.50) have been investigated by means of electron diffraction and microscopy to resolve contradictory results from powder X-ray diffraction data.The samples were obtained by annealing BaFeO2.56 for 48 h. in the temperature range from 980°C to 1050°C . Total iron and barium in the samples were determined using chemical analysis and gravimetric methods, respectively.In the BaFeO3-y system, according to the electron diffraction and microscopy results, the nonstoichiometry is accommodated in different ways as a function of the composition (y):In the domain between BaFeO2.5+δBaFeO2.54, compositional variations are accommodated through the formation of microdomains. Fig. la shows the ED pattern of the BaFeO2.52 material along thezone axis. The corresponding electron micrograph is seen in Fig. 1b. Several domains corresponding to the monoclinic BaFeO2.50 phase, intergrow with domains of the orthorhombic phase. According to that, the ED pattern of Fig. 1a, can be interpreted as formed by the superposition of three types of diffraction maxima : Very strong spots corresponding to a cubic perovskite, a set of maxima due to the superposition of three domains of the monoclinic phase along [100]m and a series of maxima corresponding to three domains corresponding to the orthorhombic phase along the [100]o.

scholarly journals Phase Transition and Coefficients of Thermal Expansion in Al2−xInxW3O12 (0.2 ≤ x ≤ 1)

Materials ◽  
2021 ◽  
Vol 14 (14) ◽  
pp. 4021
Author(s):  
Andrés Esteban Cerón Cerón Cortés ◽  
Anja Dosen ◽  
Victoria L. Blair ◽  
Michel B. Johnson ◽  
Mary Anne White ◽  
...  
Keyword(s):  
Phase Transition ◽  
Thermal Expansion ◽  
Thermal Shock ◽  
Monoclinic Phase ◽  
Ceramic Materials ◽  
Precipitation Method ◽  
Scanning Calorimetry ◽  
Orthorhombic Crystal ◽  
Co Precipitation

Materials from theA2M3O12 family are known for their extensive chemical versatility while preserving the polyhedral-corner-shared orthorhombic crystal system, as well as for their consequent unusual thermal expansion, varying from negative and near-zero to slightly positive. The rarest are near-zero thermal expansion materials, which are of paramount importance in thermal shock resistance applications. Ceramic materials with chemistry Al2−xInxW3O12 (x = 0.2–1.0) were synthesized using a modified reverse-strike co-precipitation method and prepared into solid specimens using traditional ceramic sintering. The resulting materials were characterized by X-ray powder diffraction (ambient and in situ high temperatures), differential scanning calorimetry and dilatometry to delineate thermal expansion, phase transitions and crystal structures. It was found that the x = 0.2 composition had the lowest thermal expansion, 1.88 × 10−6 K−1, which was still higher than the end member Al2W3O12 for the chemical series. Furthermore, the AlInW3O12 was monoclinic phase at room temperature and transformed to the orthorhombic form at ca. 200 °C, in contrast with previous reports. Interestingly, the x = 0.2, x = 0.4 and x = 0.7 materials did not exhibit the expected orthorhombic-to-monoclinic phase transition as observed for the other compositions, and hence did not follow the expected Vegard-like relationship associated with the electronegativity rule. Overall, compositions within the Al2−xInxW3O12 family should not be considered candidates for high thermal shock applications that would require near-zero thermal expansion properties.

scholarly journals Ultra-low thermal expansion realized in giant negative thermal expansion materials through self-compensation

APL Materials ◽  
2017 ◽  
Vol 5 (10) ◽  
pp. 106102 ◽  
Author(s):  
Fei-Ran Shen ◽  
Hao Kuang ◽  
Feng-Xia Hu ◽  
Hui Wu ◽  
Qing-Zhen Huang ◽  
...  
Keyword(s):  
Thermal Expansion ◽  
Negative Thermal Expansion ◽  
Low Thermal Expansion ◽  
Negative Thermal Expansion Materials

Monoclinic-to-orthorhombic phase transition in Cu2(AsO4)(OH) olivenite at high temperature: strain and mode decomposition analyses

2018 ◽  
Vol 82 (2) ◽  
pp. 347-365 ◽  
Author(s):  
Serena C. Tarantino ◽  
Michele Zema ◽  
Athos M. Callegari ◽  
Massimo Boiocchi ◽  
Michael A. Carpenter
Keyword(s):  
Phase Transition ◽  
High Temperature ◽  
Single Crystal ◽  
Volume Expansion ◽  
Monoclinic Phase ◽  
Orthorhombic Phase ◽  
Unit Cell ◽  
The Other ◽  
Unit Cell Parameters ◽  
Cell Parameters

ABSTRACTA natural olivenite single crystal was submitted to in situ high-temperature single-crystal X-ray diffraction from room temperature (RT) to 500°C. Unit-cell parameters were measured at regular intervals of 25°C, and complete datasets collected at T = 25, 50, 100, 150, 200, 250, 300, 400 and 500°C. Evolution of unit-cell parameters and structure refinements indicates that olivenite undergoes a structural phase transition from P21/n to Pnnm at ~200°C, and eventually becomes isostructural with the other members of the olivenite-mineral group. Volume expansion with temperature is larger in the monoclinic phase – where it follows a non-linear trend – than in the orthorhombic one. Axial and volume expansion coefficients of the orthorhombic olivenite phase are positive and linear and similar to those of the other Cu-bearing member of the mineral family, namely libethenite, but rather different from those of the Zn-analogue arsenate adamite.Distortion of Cu polyhedra is quite high in the olivenite monoclinic phase at RT and goes towards a relative regularization with increasing T until the phase transition occurs. In the orthorhombic phase, no significant variation of the polyhedral distortion parameters is observed with increasing temperature, and maximum expansion is along the b direction and governed by corner-sharing. Landau potential provides a good representation of the macroscopic changes associated with the phase transition, coupling between the strains and the order parameter is responsible for the nearly tricritical character of the transition.

scholarly journals Формирование и трансформация моноклинной и орторомбической фаз в реакторных порошках сверхвысокомолекулярного полиэтилена

2018 ◽  
Vol 60 (9) ◽  
pp. 1847
Author(s):  
М.В. Байдакова ◽  
П.В. Дороватовский ◽  
Я.В. Зубавичус ◽  
Е.М. Иванькова ◽  
С.С. Иванчев ◽  
...  
Keyword(s):  
Mechanical Stress ◽  
Room Temperature ◽  
Monoclinic Phase ◽  
Orthorhombic Phase ◽  
Ultrahigh Molecular Weight Polyethylene ◽  
Polymer Synthesis ◽  
X Ray Diffraction ◽  
Reactor Powder ◽  
X Ray ◽  
The One

AbstractUsing powerful synchrotron X-ray radiation of the beamline “Belok” operated by the National Research Center “Kurchatov Institute,” we perform X-ray diffraction (XRD) study of an intact, virgin (not subjected to any external mechanical loads) particle isolated from reactor powder of ultrahigh molecular weight polyethylene. Along with the peaks originating from the orthorhombic phase, we detect the peaks characteristic of the monoclinic phase that is stable only under mechanical stress, suggesting that the mechanical stress that leads to the formation of the monoclinic phase and persists at room temperature develops during the polymer synthesis. The monoclinic phase gradually disappears when the particle is heated stepwise in increments of 5 K, and its peaks become undetectable when the temperature reaches 340 K. We contrast the results obtained for the phase composition of the virgin particle to those for a tablet prepared by compaction of the same reactor powder at room temperature. XRD analyses of the tablet were performed on D2 Phaser (Bruker) instrument. The monoclinic phase that originates during the polymer synthesis and the one that forms in the tablet during compaction have different parameters. We discuss the mechanisms by which these two different monoclinic phases originate during the processes involved.

scholarly journals Thermodynamics of Molybdenum Trioxide (MoO3) Encapsulated in Zeolite Y

2021 ◽  
Author(s):  
Xianghui Zhang ◽  
Andrew Strzelecki ◽  
Cody Cockreham ◽  
Vitaliy Goncharov ◽  
Houqian Li ◽  
...  
Keyword(s):  
Molybdenum Trioxide ◽  
Zeolite Y ◽  
Formation Enthalpy ◽  
Solution Calorimetry ◽  
Metal Species ◽  
Enthalpies Of Formation ◽  
Host Interactions ◽  
Oxide Melt ◽  
High Temperature Oxide ◽  
Temperature Oxide

Zeolites with encapsulated transition metal species are extensively applied in the chemical industry as heterogenous catalysts for favorable kinetic pathways. To elucidate the energetic insights into formation of subnano-sized molybdenum trioxide (MoO) encapsulated/confined in zeolite Y (FAU) from constituent oxides, we performed a systematic experimental thermodynamic study using high temperature oxide melt solution calorimetry as the major tool. Specifically, the formation enthalpy of each MoO/FAU is less endothermic than corresponding zeolite Y, suggesting enhanced thermodynamic stability. As Si/Al ratio increases, the enthalpies of formation of MoO/FAU with identical loading (5 Mo-wt%) tend to be less endothermic, ranging from 61.1 ± 1.8 (Si/Al = 2.9) to 32.8 ± 1.4 kJ/mol TO (Si/Al = 45.6). Coupled with spectroscopic, structural and morphological characterizations, we revealed intricate energetics of MoO – zeolite Y guest – host interactions likely determined by the subtle redox and/or phase evolutions of encapsulated MoO.

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