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Phase Evolution of Oil Well Cements with

Nanoadditive at Elevated Temperature and Pressure

Siwei Ma, PhD student


Shiho Kawashima, Assistant Professor
Civil Engineering and Engineering Mechanics
Columbia University School of Engineering and Applied Science

Nanoscale Fiber-Reinforced Concrete Session


ACI Spring Convention 2016 – Milwaukee, Wisconsin
April 18, 2016
Collaborators

• Tony Yu
– Research Beamline Scientist, Center for Advanced Radiation Sources, GSECARS

• Yanbin Wang
– Senior Scientist, University of Chicago, GSECARS

2
Purified Attapulgite Clay

Chemically exfoliated from bulk attapulgite (Mg,Al)2Si4O10(OH)4(H2O)


Rod-like (1.75 μm in length, 3 nm in diameter)
High aspect ratio
Highly hydrophilic
Readily dispersible

Agglomerated Dispersed

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Thixotropy

Flocculation behavior
De-flocculation Re-flocculation
Floc

Time…

Cement particle

Flow behavior
Viscosity

Time
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Breakdown and recovery kinetics

Experimental method: “Breakdown-recovery” shear rheological protocol

Protocol γ
γ/τ τ

1
1 Shear rate control

2 Shear stress control


Recovery kinetics

Breakdown kinetics 2

τapp< τy

time
Breakdown and recovery kinetics

Experimental method: “Breakdown-recovery” shear rheological protocol

Recovery kinetics
Nanoclays accelerate thixotropic recovery
Protocol γ  Factor of 10 (vs 2 for bentonite clay*)
γ/τ τ
Kawashima et al., Cem Concr Res, 2015

1 f (t) = A*[exp(-t / a )r ]
α, characteristic time
r, fitting parameter
Recovery kinetics

Shear rate [1/s]


Breakdown kinetics 2
Neat paste
α = 0.306 s
τapp< τy r = 1.02

Paste w/nanoclay
α = 0.0341 s
r = 2.52

time
Time [s]

*Kaci et al., Cem Conc Res, 2011


Static yield stress

Experimental method: Creep


creep recovery

Shear stress/Pa

Time/s

Creep Recovery
Strain

Strain

Time [s] Time [s]


Static yield stress

Experimental method: Creep


creep recovery

Shear stress/Pa

Qian and Kawashima, In Prep, 2016


Cohesive strength

Experimental method: Tack test

Adhesive strength

Adhesive strength [N]

Cohesion

Plate velocity [μm/s]


Comparing results of creep and tack

Sample height << diameter – determine adhesive force from static yield stress using lubrication
approach:

•Assuming Herschel Bulkley fluid [Meeten, Rheol Acta, 2002 through Kaci et al. CCC 2013]
n
2p R3t 0 2p k æ 2n +1 ö R3 æ RV ö
n

Fmax = + ç ÷ ç ÷
3hm n + 3 è n ø hm è hm2 ø

•Setting velocity to zero, to obtain cohesion force:


2p R3t 0
Fmax =
3hm
Bentonite vs attapulgite

Kaci, A., M. Chaouche et al. (unpublished)

Kawashima et al., Cem Concr Com, 2014


Critical strain

Experimental method: Small amplitude oscillatory shear (SAOS)

Applied strain and stress response:


g = g 0 sin wt t (t) = g 0 (G'sinwt +G"coswt)

G’ = storage modulus; G” = loss modulus

Shultz and Struble, Cem Concr Res, 1993.

Linear viscoelastic regime (LVR)

Roussel et al. CCR 2012


Qian and Kawashima, In Prep, 2016
Applications for thixotropic concrete

Slipform paving
Conventional SF mix “Semi” flowable SCC mix
SCC formwork pressure

Height

Thixotropic material

Yield stress material

Shotcrete
Hydrostatic

Lateral Pressure

Nationwide Shotcrete, Inc.


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Other potential applications?

Oil well cementing

•Structural support for production pipe


•Zonal isolation
– Lower risk of gas penetration from formations
– Gas penetration can result in permanent fluid channels in
cement sheath
Geological Formations

•Role of clays …
– High flowability during cementing
– Rapid stiffening to resist gas penetration

Pipe

Cement

Image source: http://www.theoildrum.com/


Seeding effect

at 25C at 60C
0.3% clay 0.3% clay
0% clay 0% clay

Ma, Kawashima et al., Under review by ACI Mat J 15


Use of attapulgite clays for oil well cementing

• Shear rheological characterization


– Rotational rheometer – high pressure cell
• 30 MPa [300 bar]
• 200C [392F]

• Corresponding phase evolution


– Synchrotron x-ray diffraction (XRD)
• ~15 GPa
• 400C [800C]
Shear rheology – High pressure cell

Pressure cell

Upper rotor

Temp sensor

Hand pump Pressure sensor

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Phase evolution

Synchrotron x-ray diffraction A deformation-DIA (D-DIA)

Wang et al. Review of Scientific Instruments 74, 3002-3011


XRD patterns collected over 8 hours.

 Consumption/conversion/formation of crystalline phases – alite, ferrite, gypsum,


ettringite, monosulfate, portlandite, jaffeite
 High temperature, High pressure
 In-situ, Real-time

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Materials

 Class A oil well cement (OWC)

 Water/cement = 0.43

 0 and 0.5% nanoclay addition slurry

 Nanoclay blended with the mixing water in a Waring blender and added to the
cement as a suspension.

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Phase evolution

 Monochromatic synchrotron XRD tests

 Advanced Photon Source (APS) in


Argonne National Laboratory (ANL)

 Bending magnet beamline 13-BM-D


(GeoSoilEnvironCARS)

 Temperature range: 150ºC


 Pressure level: approx. 100 MPa.

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Experimental Setup

Wang et al. . Review of Scientific Instruments 74, 3002-3011


Heater

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Pressure marker
Sample assembly

 The fresh cement slurry cast in cylindrical capsule

Cylindrical Capsule

Cell assembly

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Sources of Uncertainty

1. The beamline is used to study geological material – designed pressure range of


D-DIA is up to 15 GPa.

2. Pressure variable with temperature


 Pressure can increase with increasing temperature as the sample undergoes
thermal expansion
 Pressure can decrease with increasing temperature as the material
surrounding the sample, i.e. cylindrical capsule, softens and relaxes.

3. The errors in NaCl pressure marker method generally correspond to around 20


MPa level of uncertainty in pressure.

 A constant load of 11 tons was maintained for all samples. Average marker
readings indicated that the pressure of the sample was within 100 MPa for all
tests

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Effect of Temperature – 60, 85C

C3S, ferrite, and gypsum

 Evolution of phases C3S, ferrite, and


gypsum at 60C – each decrease over
time due to the progression of
hydration.

 Very similar results at 85C

Ma, Kawashima et al., Under review by ACI Mat J 24


Effect of Temperature – 60, 85C

Plain OWC – Ettringite, monosulfate

at 60C at 85C

Ma, Kawashima et al., Under review by ACI Mat J 25


Effect of Temperature – 60, 85C

Plain OWC – Ettringite, monosulfate

at 60C at 85C

Ma, Kawashima et al., Under review by ACI Mat J 26


Effect of Temperature – 150C

Before and after heating to 150C Plain OWC paste at 150C

1. Ettringite, 2. Gypsum, 3. Katoite.

Ma, Kawashima et al., Under review by ACI Mat J 27


Effect of nanoclay

Formation of Portlandite at 150C

 No measurable effect by nanoclay


was observed at 60C & 85C

 Potential seeding effect of nanoclay


captured through acceleration in
Portlandite formation

Ma, Kawashima et al., Under review by ACI Mat J 28


Effect of nanoclay

Formation of Jaffeite at 150C

 Potential seeding effect of nanoclay


captured through acceleration in
Jaffeite formation.

 Jaffeite – crystalline form of CSH –


compared to amorphous:
 Lower mechanical strength
 Higher permeability

 Formation of Jaffeite not desirable –


the addition of silica may mitigate its
formation

Ma, Kawashima et al., Under review by ACI Mat J 29


Conclusions and ongoing work

• Increase in temperature lead to acceleration in ettringite-monosulfate conversion.


• Etringite-monosulfate conversion in the XRD results agreed well with the
appearance of the second peak in heat of hydration curves

• At 150C, the formation of jaffeite occurs.


• Potential seeding effect of nanoclay was captured through acceleration in
portlandite and jaffeite formation.

• Ongoing work:
– Development of the experimental setup to achieve precise pressure control
within range of interest.
– Silica systems (e.g. replacement of cement with silica flour and fly ash) will be
explored to mitigate jaffeite formation.

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Thank you! Questions

• Siwei Ma, PhD student

• Ye Qian, PhD student; Jumari Robinson, Undergraduate; Akiva Goldstein,


Undergraduate; Wendy Jo, H.S. student; Augusta Uwamanzu, H.S. student

• Funding support from NSF (EEC-1342377)

• Lab support from Columbia University’s Carleton Strength of Materials


Laboratory

• Materials from Lafarge, Active Minerals, GRACE

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Table 1 – Chemical composition of Class A oil well cement

SiO2 , % 20.1
Al2O3 , % 4.5
Fe2O3 , % 4.9
SO3 , % 2.3
CaO , % 63
MgO , % 2.5
Na2O , % /
K2O , % /
Loss of Ignition , % 0.51
Total , % 97.3
C3S, % 60
C2A, % 4
C4AF + 2C3A, % 22

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Shear rheological protocol

Step 1: Static yield stress


– Stress growth protocol – 3.3 Pa/s

Step 2: Steady-state viscosity


– Constant shear rate – 300 1/s
τ
.
γ

2
Preshear
1

Rest

time

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Results

Effect of clay Effect of pressure


80 90

70 Plain 80 0 bar
0.3% nanoclay 70 300 bar
60
60
Yield stress (Pa)

Yield stress (Pa)


50
50
40
40
30
30
20 20
10 10
0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time (min) Time (min)

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Results
Plain (0 bar) Plain (300 bar)
0.3% nanoclay (0 bar) 0.3% nanoclay (300 bar)

Static yield stress Steady-state viscosity


300 1.4

250 1.2

Plastic viscosity (Pa-s)


1
200
Yield stress (Pa)

0.8
150
0.6
100
0.4

50 0.2

0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time (min) Time (min)

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