The Peter A. Rock Thermochemistry Laboratory at UC Davis provides knowledge and equipment to determine thermochemical properties of inorganic substances. Traditionally, the emphasis has been on hightemperature chemistry of refractory ceramics and materials of geological interest. Projects have included work
on spinels, oxide superconductors, and rock-forming minerals. Material properties that can be investigated in
our laboratory include heat effects associated with chemical reactions, particularly formation reactions, phase
transitions, order-disorder processes and mixing processes in the solid or liquid state. Heat capacities can be
determined from liquid nitrogen temperature up to about 1400° C. Over the years, the laboratory has contributed to a sound experimental basis for thermochemical properties of materials.
In more recent years, the research interests were extended to explore materials that have less well-defined
structures, stability fields and thermochemical properties. The goal is to provide a solid basis from a thermodynamic point of view for small-particle-size, high-surface-area, metastable, or environmentally relevant
materials that previously could only be treated empirically. Nanomaterials and surface energies are major emphases.
Headed by Dr. Alexandra Navrotsky (http://navrotsky.engr.ucdavis.edu/), the research group averages between twenty and thirty people at any given time. Strong emphasis is placed on international collaboration - at any given time, about seven postdoctorate scholars and an equal number of graduate students are
working on a variety of projects. Graduate and undergraduate courses are provided in the university. Projects
http://thermo.ucdavis.edu • Phone: (530) 752-9289 • Fax: (530) 752-9307
Professor Alexandra Navrotsky
Alexandra Navrotsky’s research
interests lie at the intersection of
solid state chemistry, geochemistry,
and materials science. The fundamental question that gives unity to
a diverse set of studies (over five
hundred papers) on materials ranging from oxide superconductors to
silicates deep in the Earth’s mantle
is “Why does a given structure form
for a specific composition, pressure
and temperature?” The “why” involves relating thermodynamic properties, structural parameters, and chemical
bonding in a systematic fashion. At Arizona State University in the 1970s and 80s, at Princeton from 1985 to 1997,
and at UC Davis since 1997, Navrotsky has built a unique
high temperature calorimetry facility, designed and improved the instrumentation, and developed and applied
methods for measuring the energetics of crystalline oxides,
of glasses, amorphous, nanophase, and porous materials,
of hydrous phases and carbonates, and of nitrides, oxynitrides, and sulfides. The thermochemical data obtained
are essential to understanding materials compatibility and
reactivity in both technological and geological application,
but, more fundamentally, the energetics offer insight
into chemical bonding, order-disorder reactions, and
phase transitions.
Notable Honors for Professor Navrotsky
* Member, National Academy of Sciences (1993)
* American Ceramic Society Fellow (2001)
* American Ceramic Society, Best Paper Award of the
Nuclear and Environmental Technology Division
(2001)
* Benjamin Franklin Medal in Earth Science (2002)
* Highly Cited Researchers Award, ISI Thomson Scien
tific (2002)
* Fellow, The Mineralogical Society (Great Britain)
(2004)
* Urey Medal, European Association of Geochemistry
(EAG) (2005)
* Spriggs Phase Equilibria Award, American Ceramic
Society(ACerS) (2005)
* Rossini Award, International Association of Chemical Thermodynamics (IACT) (2006)
* Harry H. Hess Medalist, American Geophysical
Union (AGU) (2006)
* UC Davis College of Engineering Outstanding Engi
neering Senior Career Research Award (2007 - 08)
The Laboratory in Detail
The Thermochemistry Facility, supervised by A. Navrotsky, is a unique
laboratory for the determination of thermodynamic properties by calorimetric
techniques. It occupies over 5000 square feet of space on the fourth floor of the
Chemistry Annex building. Though used primarily by Navrotsky’s group, it is
open to collaborative research and is a major resource for NEAT-ORU (Nanomaterials in the Environment, Agriculture, and Technology-Organized Research
Unit) and the growing UC Davis initiatives for the future.
Calorimeters:
The heart of the Thermochemistry Facility is the collection of both custom built
Calvet micro-calorimeters for solution calorimetry using molten oxide solvents
and commercial calorimeters. The following are available:
* 4 Calvet-type, high temperature, custom-built calorimeters for solution and reaction calorimetry at 700 to 800° C.
* 1 Setaram HT-1500 calorimeter for transposed-temperature-drop, direct melting, and scanning experiments at
600 to1500° C.
* 1 Setaram 9600 calorimeter system for heat capacities, heats of reaction, and
large mass thermogravimetry (TGA) at 700 to 1600° C.
* 1 Setaram Setsys 2400 calorimeter system for heats of reaction and thermal
mechanical analysis (TMA) at 25 to 2400° C.
* 1 Setaram C-80 and 1 Setaram BT2.15 Calvet-type calorimeter for work at –150 to
300° C and 2 TSC 4400 Isothermal Microcalorimeters for work at –40 to 100° C.
These very sensitive instruments are used for heat of solution experiments in
aqueous and organic solvents, for gas adsorption studies, and for in situ synthesis
calorimetry.
* 2 Setaram DSC 111 TG and Sensys systems for differential scanning calorimetry
and thermogravimetry (TGA) at 50 to 700° C. The DSC 111 has been successfully
combined with the Micromeritics ASAP2020 gas sorption analyzer so that heat of
gas adsorption and surface area can be determined simultaneously.
* 1 Netzsch 404 System with a low temperature cell (-50 to 250° C) and a high
High Temperature Oxide Melt Solution Calorimetry
temperature cell (40 to 1500° C) for
differential scanning calorimetry
High Temperature Reaction Calorimeter Schematic
(DSC).
Quartz Dropping Tube
* 1 Netzsch 409 DSC/DTA and 1 Netzsch
Protection Tube
Platinum Bubbling Tube
449 DSC/DTA thermal analysis sys
Main Heater
Quartz Liner
Top Heater
tems for thermogravimetry (TGA), dif
Alumina Plug
Exit Lead
ferential scanning calorimetry (DSC),
Iconel Block
and evolved gas analysis (EGA). Quali
Thermopile
tative gas analysis is by mass spectrom
Sample Chamber
Pt Crucibles With Solvent
etry (MS) and quantitative gas analysis
Quartz Crucible
Bottom Heater
is by Fourier transform infrared (FTIR)
Insulation
spectroscopy.
Platinum Crucible
Block Support
* A comprehensive collection of thermody
namic data compilations and software
Sodium Molybdate
(ACerS, FACTSage, and HSC Chemistry) for calculating
thermodynamic parameters.
Characterization:
For thermodynamic data to be of use, the samples used to generate the data must be well characterized both compositionally and structurally. These instruments are used primarily by members of the Thermochemistry Group for
specialized studies and are not available for routine sample characterization that can be done elsewhere on campus.
* High temperature furnaces, a hydrothermal synthesis bench, balances, gas flow systems, and other ancillary
equipment.
* 2 glove boxes for air and moisture sensitive samples.
* An INEL diffractometer, operated jointly with S.M. Kauzlarich (Professor of Chemistry), has a position-sensitive
detector (PSD) covering 120°. A variety of sample holders (flat plate, capillary, rotating for both reflective and
transmission modes, and a holder for air sensitive samples) are available. A heating stage (30 to 1200° C) is also
available. Complete diffraction patterns can be obtained in 1 to 10 minutes. A Bruker D8 Advance X-ray diffractometer recently has been recently has been installed. It has parafocusing and parallel geometries, a very
fast linear detector, a point detector, and a diffracted beam monochromator. It also can be configured for small
angle X-ray scattering (SAXS) analysis for size analysis of nanoparticles (1 to 50 nm).
* A wide range of software for processing and analyzing diffraction data (JADE, WINDIF, GSAS, NANOFIT, EVA,
TOPAS3 and others) and major crystallographic databases (PDF, ICSD, and CCDC) are available. There is also
software to simulate diffraction patterns and to visualize crystal models (jPWD and CrystalMaker) and to optimize crystal structures (Material Studio and Cerius 2 molecular modeling packages).
* A Bruker Equinox 55 FTIR spectrometer for mid- and near-IR range analysis. Transmission and reflective
sample holders are available as well as a gas cell.
* A Balzers MSC 200 quadrapole mass spectrometer for identifying gaseous decomposition products.
* Two Micromeritics ASAP2020 gas sorption analyzers for determining surface area, porosity, pore size and pore
distributions of zeolites and nanomaterials. Each analyzer can be paired with a Setaram DSC III for combined
surface area analysis and heat of absoption measurements.
* Charles Bennett, Senior Engineer, designs, constructs and monitors the equipment. John Neil, a staff member in
Navrotsky’s group, has extensive diffraction experience and is in charge of these instruments. He also oversees
the DSCs and chemical operations. George Wayrynen helps in laboratory maintenance and operations.
Recent Publications
“High-temperature Calorimetry of Zirconia: Heat Capacity and Thermodynamics of Monoclinic-tetragonal Phase
Transition”, Y. Moriya and A. Navrotsky, Journal of Chemical Thermodynamics, 38, 211-223 (2006).
“Surface Energy and Thermodynamic Stability of γ-alumina: Effect of Dopants and Water”, R. Castro, S.
Ushakov, L. Gengembre, D. Gouvêa, and A. Navrotsky, Chemistry of Materials, 18(7), 1867-1872 (2006).
“Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates”, K.A. Kubatko, K.
Helean, A. Navrotsky, American Mineralogist, 91, 658-666 (2006).
“Calorimetric Determination of the Enthalpies of Formation of Hydrotalcite-like Solids and Their Use in
Geochemical Modeling of Metals in Natural Waters”, R.K. Allada, E. Peltier, A. Navrotsky, W.H. Casey, A. Johnson,
H.T. Berbeco, D.L. Sparks, Clays and Clay Minerals, 54, 409-417 (2006).
“TiO2 Stability Landscape: Polymorphism, Surface Energy and Bound Water Energetics”, A.A. Levchenko, G. Li,
J. Boerio-Goates, B.F. Woodfield, and A. Navrotsky, Chemistry of Materials, 18, 6324-6332 (2006).
“A Clathrate Reservoir Hypothesis for Enceladus’ South Polar Plume”, S.W. Kieffer, X. Lu, C.M. Bethke, J.R.
Spencer, S. Marshak, A. Navrotsky, Science, 314, 1764-1766 (2006).
“Calorimetry of Nanoparticles, Surfaces, Interfaces, Thin Films, and Multilayers”, A. Navrotsky, Journal of
Chemical Thermodynamics, 39, 2-9 (2007).
“Enthalpy of Water Adsorption and Surface Enthalpy of Goethite (α-FeOOH) and Hematite (α-Fe2O3)”, L.
Mazeina and A. Navrotsky, Chemistry of Materials, 19(4), 825-833 (2007).
“Thermodynamic Properties of Soddyite from Solubility and Calorimetry Measurements”, D. Gorman-Lewis, L.
Mazeina, J. Fein, J. Szymanowski, P. Burns, and A. Navrotsky, Journal of Chemical Thermodynamics, 39, 568-575
(2007).
“Application of Calorimetry on a Chip to High Pressure Materials”, A. Navrotsky, M. Dorogova, F. Hellman,
D.W. Cooke, B.L. Zink, C.E. Lesher, J. Boerio-Goates, B.F. Woodfield, and B. Lang, Proceedings of the National
Academy of Sciences, 104(22), 9187-9191 (2007).
“Systematics of Phase Transition and Mixing Energetics in Rare Earth, Yttrium and Scandium Stabilized
Zirconia and Hafnia”, P. Simoncic and A. Navrotsky, Journal of the American Ceramic Society, 90(7), 2143-2150
(2007).
“Thermochemistry of A2M4O12 Negative Termal Expansion Materials”, T. Varga, J.L. Moats, S.V. Ushakov, and A.
Navrotsky, Journal of Materials Research, 22(9), 2512-2521 (2007).
“Kinetic and Thermodynamic Studies of Silica Nanoparticle Solution”, J.D. Rimer, O. Trofymluk, A. Navrotsky,
R.F. Lobo, and D.G. Vlachos, Chemistry of Materials, 19, 4189-4197 (2007).
“Energetics of CdSxSe1-x Quantum Dots in Borosilicate Glasses”, R.M. Morcos, C. Mitterbauer, N. Browning, S.
Risbud, and A. Navrotsky, Journal of Non-Crystalline Solids, 353, 2785-2795 (2007).
“Thermodynamically Stable SixOyCz Polymer-Like Amorphous Ceramics”, T. Varga, A. Navrotsky, J.L. Moats,
R.M. Morcos, F. Poli, K. Müller, A. Saha, and R. Raj, Journal of the American Ceramic Society, 90(10), 3213-3219
(2007).
“Inorganic Nanoparticles - Unique Properties and Novel Applications”, M. Asta, S.M. Kauzlarich, K. Liu, A.
Navrotsky, and F.E. Osterloh, Material Matters, 2(1), 3-6 (2007).
“Chemical Thermodynamics of Solid Solutions of Interest in Nuclear Waste Management”, J. Bruno, D. Bosbach,
D. Kulik, and A. Navrotsky, Organisation for Economic Co-operation and Development, Paris (2007).
“Surface Enthalpies of Nanophase ZnO with Different Morphologies”, P. Zhang, F. Xu, A. Navrotsky, J.S. Lee, S.
Kim, and J. Liu, Chemistry of Materials, 19, 5687-5693 (2007).
http://thermo.ucdavis.edu • Phone: (530) 752-9289 • Fax: (530) 752-9307