Overview

The Peter A. Rock Thermochemistry Laboratory, 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 (Nanomaterials in the Environment, Agriculture, and Technology).

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The Laboratory Detailed

Calorimeters:
The heart of the Peter A. Rock Thermochemistry Laboratory is the collection of both custom built Calvet micro-calorimeters for solution calorimetry using molten oxide solvents and commercial calorimeters. The following is 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 1500° C.

  • 1 Setaram Setsys 2400 calorimeter system for heats of reaction, thermogravimetry (TGA), and thermal mechanical analysis (TMA) at 25° to 2400° C.

  • 1 C-80 and 1 Setaram BT2.15 Calvet-type calorimeter for analysis between –150° to 300° C and 2 CSC 4400 Isothermal Microcalorimeters for analysis between –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.

  • 3 Setaram DSC 111 TG systems for differential scanning calorimetry and thermogravimetry (TGA) at 50° to 700° C. Two of the DSC 111s can be combined with the Micromeritics ASAP2020 gas sorption analyzers so that heat of gas absorption and surface area can be determined simultaneously.

  • 1 Netzsch 404 System with a low temperature cell (-50° to 250° C) and a high temperature cell (40° - 1500° C) for differential scanning calorimetry (DSC).

  • 1 Netzsch 409 DSC/DTA and 1 Netzsch 449 DSC/DTA thermal analysis systems for thermogravimetry (TGA), differential scanning calorimetry (DSC), and evolved gas analysis (EGA) from 40° and 1500° C . Qualitative gas analysis is done by mass spectrometry (MS) and quantitative gas analysis by Fourier transform infrared (FTIR) spectroscopy.

  • A comprehensive collection of thermodynamic data compilations and software (Phase Equilibria Database, FACTSage, and HSC Chemistry) for calculating thermodynamic parameters.

Sample Synthesis and Preparation:
When high quality samples are not available through collaboration with other research groups, the following equipment is available for synthesis by group members.

  • High temperature furnaces, a hydrothermal synthesis bench, balances, gas flow systems, and other ancillary equipment.

  • 2 glove boxes for air and moisture sensitive samples.

  • We are currently constructing a laser ablation synthesis system for nanoparticle synthesis under conditions that exclude water, wiht sample handling capabilities to maintain such dry samples all the way into the drop solution calorimetric experiments.

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 routine sample characterization that can be done elsewhere on campus.

  • An INEL x-ray 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 with a variety of interchangable components. The instrument;s capabilities include rapid analysis for qualitative phase identification includeing samples that fluoresce in copper radiation, high resolution data for lattice parameter and Riedtveld analysis and small angle scattering data for particle size analysis. The parallel geometry configuration allows irregular sample surfaces to be analyzed.

  • A wide range of software for processing and analyzing diffraction data, (JADE, TOPAS3, EVA, WINDIF, GSAS, 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).

  • John Neil, a staff member in Navrotsky's group, has extensive diffraction experience and is in charge of these instruments.

  • 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 Belzers 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.

Other Facilities:
Because of the complexities of modern instrumentation and the details needed to describe a sample, it is not feasible for one group to have and maintain all the instruments needed. The following lists the outside facilities routinely used to further our studies.

  • Access to low-temperature, adiabatic, calorimeters is available through our collaboration with Brian Woodfield’s group at Brigham Young University.

  • Access to 2 piston-cylinder high-pressure apparatus for synthesis between 25° and 1400° C and between 5 and 25 kbars at the UC Davis Geology Department.

  • Access to synchrotron and neutron diffractometers can be arranged at several national facilities.

  • The FEI XL30-SFEG, high resolution, Scanning Electron Microscope (SEM) at the Materials Science Central Facilities, UC Davis.

  • A JEOL JEM-2500SE, High Resolution Transmission Electron Microscope (HRTEM), a Philips CM-12 Trans-mission Electron Microscope (TEM) and the Electron Microscopy Specimen Prep Lab at the Materials Science Central Facilities, UC Davis.

  • Access to the National Center for Electron Microscopy (NCM) at the Lawerence Berkeley National Laboratory.

  • 400 and 500 MHz solid state Nuclear Magnetic Resonance (NMR) spectrometers at UC Davis.

  • Cameca SXC-100 electron microprobe with staff support at the UC Davis Geology Department’s Electron Microprobe Lab.

  • UC Davis Glass Shop, Machine Shops, Electronics Shops and Computer Support Group