High Pressure X-ray Diffraction

Goal

Measure the response of unhydrous and hydrated phases of cement under high pressure.

Why?

!!To obtain elastic properties of the small crystals

!!To validate atomistic models

How far have we progressed?

!!Not too bad. !!As the list of references indicates we have developed a large data basis.

!!References (1) Clark, S.M., B. Colas, M. Kunz, S. Speziale, and P.J M. Monteiro, "Effect of pressure on the crystal structure of ettringite," Cement and Concrete Research 38(1), 19-26 (2008). (doi:10.1016/j.cemconres.2007.08.029) Hargis, C.W., J. Moon, B. Lothenbach, F. Winnefeld, H. Wenk, and P.J.M. Monteiro, "Calcium Sulfoaluminate Sodalite (Ca 4Al 6O 12SO 4) Crystal Structure Evaluation and Bulk Modulus Determination," Journal of the American Ceramic Society 97(3), 892-898 (2014). (doi:10.1111/jace.12700) Jackson, M.D., J. Moon, E. Gotti, R. Taylor, S.R. Chae, M. Kunz, A.H. Emwas, C. Meral, P. Guttmann, P. Levitz, H. Wenk, and P.JM. Monteiro, "Material and Elastic Properties of Al-Tobermorite in Ancient Roman Seawater Concrete," Journal of the American Ceramic Society 96(8), 2598-2606 (2013). (doi:10.1111/jace.12407) Jackson, M.D., S.R. Chae, S.R. Mulcahy, C. Meral, R. Taylor, P. LI, J. Moon, S. Yoon, A.H. Emwas, G. Vola, H. Wenk, and P. Monteiro, "Unlocking the secrets of Al-tobermorite in Roman seawater concrete," American Mineralogist 98(10), 1669-1687 (2013). (doi:10.2138/am.2013.4484)

!!References (2) Moon, J., S. Speziale, C. Meral, B. Kalkan, S.M. Clark, and P.J.M. Monteiro, "Determination of the elastic properties of amorphous materials\u58# Case study of alkali silica reaction gel," Cement and Concrete Research 54, 55-60 (2013). (doi:10.1016/j.cemconres.2013.08.012 Moon, J., J.E. Oh, B. Balonis, F.P. Glasser, S.M. Clark, and P.J.M. Monteiro, "High pressure study of low compressibility tetracalcium aluminum carbonate hydrates 3CaO.Al2O3.CaCO3.11H2O," Cement and Concrete Research 42(1), 105-110 (2012). (doi:10.1016/j.cemconres.2011.08.004) Moon, J., S. Yoon, R.M. Wentzcovitch, S.M. Clark, and P.J.M. Monteiro, "Elastic Properties of Tricalcium Aluminate from High-Pressure Experiments and First-Principles Calculations," Journal of the American Ceramic Society 95(9), 2972-2978 (2012). (doi:10.1111/j.1551-2916.2012.05301.x) Moon, J., J. Oh, M. Balonis, F. Glasser, S.M. Clark, and P. Monteiro, "Pressure induced reactions amongst calcium aluminate hydrate phases," Cement and Concrete Research 41(6), 571-578 (2011). (doi:10.1016/j.cemconres.2011.02.004)

!!References (3) Oh, J.E., S.M. Clark, and P.J. Monteiro, "Does the Al substitution in C-S-H(I) change its mechanical property? ," Cement and Concrete Research 41(1), 102-106 (2011). (doi:10.1016/j.cemconres.2010.09.010) Moon, J., S. Yoon, and P.J.M. Monteiro, "Mechanical properties of jennite: A theoretical and experimental study," Cement and Concrete Research 71, 106-114 (May 2015). (doi:10.1016/j.cemconres.2015.02.005) Oh, J.E., S.M. Clark, H. Wenk, A.R. Kampf, and P.JM. Monteiro, "Experimental Determination of Bulk Modulus of 14\u8491# Tobermorite Using High Pressure Synchrotron X-ray Diffraction," Cement and Concrete Research 42(2), 397-403 (2012). (doi:10.1016/j.cemconres.2011.11.004)

Diamond Anvil Cell

400!m

Sample in the metal gasket

X-ray Detector

180!m

63!m

X-ray

Gasket

Experimental Procedures of XRD

= !TdPK VdV

!!As the pressure increases, the unit cell shrinks.

!!Unit cell dimensions (a, b, c, ", #, $) at a certain pressure can be calculated from X-ray diffraction pattern

!!P(V/Vo) can be obtained

!!Bulk modulus =

!"#$%&'()*%+,(-"..%+/0"12(3+00&%2("2(4&+56"2&(78'8'8(9014&%51%"0&:(

;0(61<(=%&>>$%&( ;0(?"#?(=%&>>$%&(

Birch Murnaghan Equation of State

!! Equation of State (EOS): V = f (P,T) !! EOS of condensed material !! Volume vs. Hydrostatic Pressure !! Isothermal Equation

!! 3rd order Birch Murnaghan EOS

where, 1. Ko=bulk modulus at zero pressure 2. Ko’=the derivative of bulk modulus at zero pressure

7 5 23 3 33 3( / ) ( / ) 1 ( 4) ( / ) 1

2 4o o o o oP K V V V V K V V! ! !" #" # $ %

&= ! + ! !' () *' (' (+ , - .+ ,

Experimental results

Tobermorite 14A

Ca in CaO-layerSi

O

Interlayer Water

InterlayerSpace

Interlayer Ca

Simulation Study Structure Model Bulk Modulus

(GPa) Simulation Tool and Conditions

Manzano et al. (2007)

Tobermorite 14Å (Ca/Si= 0.8) 46

Potential Minimization (GULP code: General Utility Lattice Program)

Pellenq et al. (2008)

Tobermorite-like 14Å structure with Ca/Si= 0.83 starting from Hamid's 11Å tobermorite structure

35.4 (Voigt)

20.7 (Reuss)

Potential Minimization (GULP code: General Utility Lattice Program)

Shahsavari et al. (2009)

Tobermorite 14Å (Ca/Si= 0.83) using Bonaccorsi et al.'s structure [Error! Reference source not found.]

35.91 (Reuss-Voigt

-Hill Average)

First Principles Study using DFT (Density Functional Theory) and GGA exchange correlation functional, implemented by PWSCF package of Quantum Espresso

Al-Ostaz et al. (2010)

14Å tobermorite (Ca/Si= 0.83) using Bonaccorsi et al.'s structure [Error! Reference source not found.]

33.4

1!single unit cell size with MD tools and force fields = F-U

The same MD method by Manzano et al (2009). and Pellenq et al.(2008); MD simulation (F=Forcite, D=discover, U=UFF, C=Compass force field), implemented by Materials Studio software

45.68

1!single unit cell size with MD tools and force fields = D-C

49.79

2!single unit cell size with MD tools and force fields = D-C

52.89

3!single unit cell size with MD tools and force fields = D-C

!

Results

0.0

1.0

2.0

3.0

4.0

5.0

6.0

0.885 0.910 0.935 0.960 0.985 1.010

P(GPa)

V/Vo

14A tobermorite-CELREF

B-M (Ko'=4.00)-CELREF

14A tobermorite-Rietveld

B-M (Ko'=4.00)-Rietveld

From CELREF:Ko = 47 ± 3 GPa(Ko'=4.0, assumed), R2 = 0.995

From Rietveld Method:Ko = 47 ± 4 GPa(Ko'=4.0, assumed), R2 = 0.991

J.E. Oh, Simon M. Clark , H.-R. Wenk and P.J.M. Monteiro, Experimental Determination of Bulk Modulus of 14Å Tobermorite Using High Pressure Synchrotron X-ray Diffraction, CCR, Volume 42, Issue 2, February 2012, Pages 397-403.

How does it compare to CSH(I)?

0.0

1.0

2.0

3.0

4.0

5.0

0.900 0.920 0.940 0.960 0.980 1.000

a/ao, b/bo or c/co

P(GPa)

SYN C-S-H(I) a/ao

AAS C-S-H(I) a/ao

SYN C-S-H(I) b/bo

AAS C-S-H(I) b/bo

SYN C-S-H(I) c/co

AAS C-S-H(I) c/co

14A-TOB a/ao (CELREF)

14A-TOB a/ao (Rietveld)

14A-TOB b/bo (CELREF)

14A-TOB b/bo (Rietveld)

14A-TOB c/co (CELREF)

14A-TOB c/co (Rietveld)b/bo

a/ao

c/co

a/ao , b/bo ofC-S-H(I)and 14Åtobermorite

c/co of 14Åtobermorite

c/co of C-S-H(I)

J.E. Oh, J. Moon, S.M. Clark, P.J.M. Monteiro, Does the Al substitution in CSH (I) Change Its Mechanical Property? Cement and Concrete Research 41 (2011) 102–106.

AFM Phases!

!!Strätlingite!

!!Hemicarboaluminate !!Monocarboaluminate!

Monocarboaluminate Calcium Hydroxide

Strätlingite !! Ca2Al2SiO7%8H2O !! slag-containing Portland cements or blended cements

and in commercial high alumina cement !! trigonal, R3 or R3 !!Principal layer: [Ca2Al(OH)6]+

!! Interlayer: [AlSi(OH)8%H2O]-

Results – AFm phases!

!!Strätlingite, C2ASH8!

!! Irreversibly transform to an amorphous phase at 3.4GPa.!

Big jump!!

Results – AFm phases!

!!Strätlingite, C2ASH8!

!! Irreversibly transform to an amorphous phase at 3.4GPa.!

J. Moon, J. E. Oh, M. Balonis, F. P. Glasser, S.M. Clark and Paulo J.M. Monteiro, Pressure induced reactions amongst calcium aluminate hydrate phases, Cement and Concrete Research 41 (2011) 571–578.

Hemicarboaluminate (Ca4Al2(CO3)0.5(OH)13!5.5H2O)

•! It occurs in ordinary Portland cement with very low carbonate contents. •! trigonal, Rc or R3c system.

Monocarboaluminate !! With rising carbonate activity, hydroxyl-AFm is replaced

first by hemicarboaluminate and then by monocarboaluminate.

Projection along [100] of the monocarboaluminate; (a) general view, and (b) detail of interlayer region. Blue and green polyhedral are, respectively, sevenfold Ca polyhedra and sixfold Al polyhedral. White, grey, red, blue, green, and black spheres represent, respectively, O atoms in principal layers, O atoms in interlayers, C, Ca, Al, and H atoms.

Results – AFm phases!

!!Monocarboaluminate , C4ACH11!

Results – AFm phases!

"!Monocarboaluminate (54 GPa) !! low compressibility

"!Hemicarboaluminate (15-32 GPa) !! pressure-induced dehydration!

First-principles elasticity of monocarboaluminate hydrates: density functional theory

LDA: local-density approximation

GGA: Generalized gradient approximation

Moon et al. American Mineralogist, 2014.