Pressure Calibration in DAC --

Challenges for Increasing Accuracy and Precision

Ho-kwang Mao Carnegie Institution of Washington

Pressure Calibration Workshop January 26-28, 2007

• 1- 100 GPa

• 10 MPa – 1 GPa

• 100- 300 GPa

• High temperatures

Different Challenges in Different P-T Ranges

2

Topics

• Primary calibration (accuracy)

• Secondary calibration (precision)

• Hydrostaticity

• X-ray diffraction (axial and radial)

• Optical spectroscopy (Brillouin, Raman, fluorescence)

• Inelastic x-ray scattering spectroscopy

3

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

4

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

4

Primary calibration requires measurements of two independent functions related to pressure.

Examples:

• F and A – free rotation piston-cylinder

• US and UP – shock Hugoniot

• V and – DACV

2 = K/ K = dP/d P = V

2d.

5

Primary calibration requires measurements of two independent functions related to pressure.

Examples:

• F and A – free rotation piston-cylinder

• US and UP – shock Hugoniot

• V and – DACV

2 = K/ K = dP/d P = V

2d.

5

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

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Pressure calibration, P/P ±1%

from x-ray diffractionVfrom Brillouin scatteringP- EOS by integration (Primary)

Ruby fluorescence shiftCalibrated by MgO P- EOS(Secondary)

Zha, Mao, Hemley, PNAS (2000)

6

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

10

Secondary Calibration of Six Metals

XRD, ±0.2%,P/P ±1%

Ruby fluorescence shiftCalibrated by MgO P- EOS(Secondary)

Dewaele, Loubeyre, Mezouar, PRB (2004)

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

12

High T Primary Calibration Using V and

Problem: KS = (1 + T) KT

Difference ~10% at 3000 K introduces >1% error

A practical alternative is to combine 300 K primary calibration and high resolution high P-T XRD

13

121

122

123

124

125

126

127

106 110 114 118 122 126 130 134

0

0.006

0.012

0.018

0.024

0.03

300 900 1500 2100

Pressure (GPa)

Vol

ume

(Å3 )

300 K

1400 K

2000 K

Fs20 ppv

Temperature (K)

(VT –

V30

0)/

V30

0

14

Post-perovskite P-V-TW. Mao et al, submitted (2007)

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

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- BIOCHEMICAL REACTIONS IN HYDROTHERMA FLUIDS

- LIFE IN EXTREME ENVIRONMENTS (>1600 MPa)

[Sharma et al., Science 295, 1514 (2002)]- PRESSURE EFFECTS ON STRUCTURE-FUNCTION RELATIONS

Single-Crystal Diffraction of Cow Pea Mosaic Virus

[Lin et al., Acta Crystal. D61, 737 (2005)]

Biomaterials -- bacteria and virus16

350 MPa

Hydrogen storage in clathrate

Energy, keV

d-spacing, Å

Intensity

25 35 45 55 65

311

5 2.56 4 35.5 4.5 3.5

533

220

222

400

331 42

2

440

531

620

511

333

H2-2H2O S-II clathrate-- A clean and efficient material for hydrogen storage

0.2 GPa

10 kPa77 K 110 140 240

HH-sII

280

H2+H2O

17

W Mao et al, Science (2002)--Synthesis S-II at HP and quenched to low PT;

Lokshin et al, PRL (2004)--Identification of H2 in S-II cages with neutron;

Florusse et al, Science (2004)-- Stabilized to 280K at 1 bar

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

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High Pressure Experiments Challenge Existing Understanding of Seismic Waves in Deep Earth

The crushing pressures in the lower mantle squeeze atoms and electrons so closely together that they interact differently from under normal conditions, even forcing spinning electrons to pair up in orbits. In theory, seismic-wave behavior at those depths may result from the vice-gripping pressure effect on the electron spin-state of iron in lower-mantle materials. Carnegie’s team performed ultra high-pressure experiments on the most abundant oxide material there, magnesiowüstite (Mg,Fe)O, and found that the changing electron spin states of iron in that mineral drastically affect the elastic properties of magnesiowüstite. The research may explain the complex seismic wave anomalies observed in the lowermost mantle.

Normalized volume of magnesiowüstite, (Mg0.83,Fe0.17)O, as a function of pressure at 300 K.

Jung-Fu Lin, Viktor V. Struzhkin, Steven D. Jacobsen, Michael Y. Hu, Paul Chow, Jennifer Kung, Haozhe Liu, Ho-kwang Mao and Russell J. Hemley; "Spin transition of iron in magnesiowüstite in the Earth's lower mantle" Nature 436, 377-380 (21 July 2005)

Spin transition of iron in magnesiowüstite19

Goals

Primary calibration (accuracy)• 1- 100 GPa P/P = ±1%

• 100- 300 GPa P/P = ±1%

• High temperatures -- at 100 GPa-2500 K P/P = ±1%

Secondary calibration (precision)• 10 MPa – 1 GPa P = ±5 MPa

• 1- 100 GPa P/P = ±0.2%

• 100- 300 GPa P/P = ±0.2%

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Topics

• Primary calibration (accuracy)

• Secondary calibration (precision)

• Hydrostaticity

• X-ray diffraction (axial and radial)

• Optical spectroscopy (Brillouin, Raman, fluorescence)

• Inelastic x-ray scattering spectroscopy

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0

1

2

3

0 20 40 60

Argon

t(G

Pa)

P(GPa)

Shear strength of argon

Mao, et al, J. Phys.: Cond. Mat. (2006)

Primary calibration needs to use He medium

Topics

• Primary calibration (accuracy)

• Secondary calibration (precision)

• Hydrostaticity

• X-ray diffraction (axial and radial)

• Optical spectroscopy (Brillouin, Raman, fluorescence)

• Inelastic x-ray scattering spectroscopy

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Attaining V /V± 1%

• Ultrasonic measurements

• Nuclear resonant inelastic x-ray scattering

• Brillouin Spectroscopy

• Inelastic x-ray scattering spectroscopy

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Attaining V /V± 1%

• Ultrasonic measurements to 50-300 GPa?

• Nuclear resonant inelastic x-ray scattering

• Brillouin Spectroscopy

• Inelastic x-ray scattering spectroscopy

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Nuclear resonant inelastic x-ray spectroscopy (NRIXS)

APD

APD HRM M

KBmirrors

x-rays

DAC150nsec

NRIXS signal

SMS signal

nonmagnetic

magnetic

time

Energy

Inte

nsi

ty

Anti-stokes Stokes

Elastic line

XOR, Sector 3, APS, ANLXOR, Sector 3, APS, ANL

g(

) de

nsity

of s

tate

s

Debye Model

“Real” Crystal

2322

)(

Vg

333

213

SpD

222

3

4

)(

SP

KV

PVK

Attaining V /V± 1%

• Ultrasonic measurements

• Nuclear resonant inelastic x-ray scattering

• Brillouin Spectroscopy

• Inelastic x-ray scattering spectroscopy

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Brillouin Spectroscopy

• Single crystalV accuracy ±1%

• PolycrystallineV accuracy 3-10%

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Fiquet et al., Science 2001

Antonangeli et al., EPSL 2004

Antonangeli et al, PRL 2005

Single-xtal Co at 39 GPa

Inelastic x-ray scattering spectroscopy (IXSS)Poly-xtal hcp-Fe to over 100 GPa

Determines phonon dispersion

Inelastic x-ray scattering spectroscopy (IXSS)

7.6

7.8

8

8.2

8.4

0 10 20 30 40 50 60 70 80 90

angle between q and DAC compression axis

VP

(km

/sec

)

high resolution

medium resolution

Improve energy resolution from 6 meV to 1 meVto get to V /V± 1%

35XU, SPring-8

30

hcp-Fe at 52 GPa

W. Mao et al, in prep.

High Res. XRD with panoramic DAC

CCD

CCD

ctn Going from 2 = 10º to 2 = 90º, / improves 10x !

UNICAT, 34-ID, APS, ANL

Summary: Achievable Goals

Primary calibration (accuracy)• Hydrostaticity of He? P/P = 0.2-1%?

• Single-xtl Brillouin scattering or single-xtl ixss to 100- 300 GPa V/ V = ±1%

• Polycrystalline XRD to 100- 300 GPa and 100 GPa-2500 K / = ±0.2% P/P = ±1%

Secondary calibration (precision)• High resolution XRD at 10 MPa- 300 GPa

/ = ±0.02% P/P = ±0.2%

• Optical calibration P/P = ±0.2%

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