University of California at Berkeley

1
Application of Calorimetry-on-a-Chip Technology
to Heat Capacities of Quenched High Pressure
Samples
David W. Cooke, Frances Hellman Department of
Physics, University of California, Berkeley
Alexandra Navrotsky, Maria Dorogova, Charles E.
Lesher Thermochemistry Facility and Dept. of
Geology, University of California, Davis
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
2
The Earths Mantle

• Seismic barrier _at_ 670km
• Chemical change barrier _at_ 1000km
• D boundary _at_ 1800km

Wikipedia image based on elements of an
illustration by USGS.
Gu, et al. J. geophys. Res., 106, 11,169-11,199
(2001).
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
3
Constituents of Mantle

• Primarily silicates
• Fe,Mg majority of composites
• Al,Ni,Ca,Cd,Co minority dopants
• High pressure and high temperatureyields
  complicated phase diagramof novel crystal
  structures
• Spinel (?)
• Modified Spinel (ß)
• Perovskite
• Post-perovskite

Navrotsky. Prog. Solid St. Chem. 17, 53-86 (1987).
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
4
Constituents of Mantle

• (Mg,Fe)2SiO4 Spinel

(Mg,Fe)SiO3 Perovskite
Illustrations courtesy of Dr. Helmut Föll at
University of Kiel - http//www.tf.uni-kiel.de/mat
wis/amat/def_en/index.html
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
5
Synthesizing in the Lab

• Multi-anvil cell (lt 27 GPa)
• Diamond anvil cell (lt 200 GPa)
• X-ray/IR spectroscopy, conductivity,
  compressibility
• P-V-T, K, µ, more

The first diamond-anvil cell, fabricated by
Charles Weir and Alvin Van Valkenburg NIST -
http//nvl.nist.gov/pub/nistpubs/sp958-lide/100-10
3.pdf
Navrotsky. Prog. Solid St. Chem. 17, 53-86 (1987).
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
6
Fe v. Mg Silicates
Hazen, R. Science 259, 206-9 (1993).
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
7
Calorimeter on a Chip

• Specific heat of thin films
• 100nm 5µg
• 2K - 500K
• 0T - 8T
• Information gained
• Thermodynamics
• Decomposition
• Magnetic transitions
• Electrical changes

2006 APS KeithleyInstrumentation Award
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
8
Device Simulation
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
9
Device Simulation
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
10
Proof of Principle
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
11
Proof of Principle
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
12
COMPRES Proposal

• Multi-anvil and/or diamond-anvil cell experiments
• Thermal contact
• Sample size
• Crystal shape
• Magnetic transitions in high pressure minerals
• Test case Fe2SiO4 spinel
• Data across an Mg-Fe substituted series
• (Fe,Mg)2SiO4 olivine and/or spinel phases
• (Mg,Fe)O magnesiowustites

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
13
COMPRES Proposal

• Multi-anvil and/or diamond-anvil cell experiments
• Thermal contact
• Sample size
• Crystal shape

• Used indium in past
• Low melting point, but not good for metastable
  materials
• Silver paint
• Reproducibility?

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
14
COMPRES Proposal

• Multi-anvil and/or diamond-anvil cell experiments
• Thermal contact
• Sample size
• Crystal shape

• Sample Size
• Data on large devices (CoO)
• Addenda (Cu/LSN) 50 µJ
• Ag Addenda 100 µJ
• Sample 200 µJ

• Sample Size
• Data on regular devices
• Addenda (LSN) 3 µJ
• Copper Addenda 2 µJ
• Sample 2 µJ

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
15
COMPRES Proposal

• Multi-anvil and/or diamond-anvil cell experiments
• Thermal contact
• Sample size
• Crystal shape
• Magnetic transitions in high pressure minerals
• Test case Fe2SiO4 spinel
• Data across an Mg-Fe substituted series
• (Fe,Mg)2SiO4 olivine and/or spinel phases
• (Mg,Fe)O magnesiowustites

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
16
Fe2SiO4 Spinel

• Why Fe2SiO4 Spinel?
• Relatively low pressure of formation (8GPa)
• Larger quantity of sample
• Multi-anvil apparatus (Charles Leshers lab)
• Relevant to mantle physics
• Potential Mg/Fe substitutional analysis
• Iron silicate we expect a magnetic transition
• Fe2 v. Fe3 potential electronic interactions?

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
17
Fe2SiO4 Spinel
K. Suito et al. Proc. 9th AIRAPT Intl. High P.
Conference. 295-8 (1983).
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
18
Fe2SiO4 Spinel
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
19
Fe2SiO4 Spinel
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
20
COMPRES Proposal

• Multi-anvil and/or diamond-anvil cell experiments
• Thermal contact
• Sample size
• Crystal shape
• Magnetic transitions in high pressure minerals
• Test case Fe2SiO4 spinel
• Data across an Mg-Fe substituted series
• (Fe,Mg)2SiO4 olivine and/or spinel phases
• (Mg,Fe)O magnesiowustites

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
21
Future Work

• Diamond Anvil Cell Sample Capability
• Develop reliable method for 10µg sample
• Consistency of silver paint?
• Fe2SiO4 Spinel
• Can we factor out the magnetic entropy
• Why is the magnetic transition so much more
  broad?
• Substitutional (Fe,Mg)2SiO4 series
• Decomposition enthalpy
• Other materials of geophysical applications
• (Mg,Fe)O magnesiowustites
• (Mg,Fe)SiO3 perovskites
• High pressure phases in zirconia and titania

University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007
22
Thanks to
Frances Hellman Alex Navrostsky Masha
Dorogova Charles Lesher
Ray Jeanloz Daniel Queen Erik Helgren
Department of Energy Lawrence Berkeley National
Lab University of California Berkeley University
of California Davis Oak Ridge National
Laboratory
University of California at Berkeley Physics
Department Hellman Lab
COMPRES Calorimetry on a Chip Workshop March
15, 2007