Multifunctional Corrosion-resistant Foamed Well Cement Composites

1 | US DOE Geothermal Office eere.energy.gov

Public Service of Colorado Ponnequin Wind Farm

Geothermal Technologies Office 2013 Peer Review

Multifunctional Corrosion-resistant Foamed Well Cement Composites Project Officer: Dan King/Greg Stillman Total budget: $300 K April 24 , 2013

Principal Investigator: Dr. Toshifumi Sugama Co-PI; Dr. Tatiana Pyatina Presenter Name: Dr. Toshifumi Sugama

This presentation does not contain any proprietary

confidential, or otherwise restricted information.

Microstructure developed in conventional foamed (left) and corrosion-

resistant foamed cements (right)


Relevance/Impact of Research

Objectives: The thrust of this project is to develop cost-effective multifunctional

corrosion-resistant foamed cement composites for carbon steel-based

casings in EGS wells, to characterize their properties, and to transfer

developed technology to cost-sharing industrial partners.

Impact: When a field-applicable corrosion-resistant foamed well cement

possessing all required properties is formulated, it will provide the following

five bottom-line benefits for EGS wellbore integrities:

1. Extension of the carbon steel-based casing’s lifecycle;

2. Reduction of capital investment instead of using very expensive corrosion-

resistant titanium and zirconium alloys, stainless steel or clad materials;

3. Decrease in well operation and maintenance (O&M) costs;

4. Reduction of substantial expenditures for abandoning, re-drilling, re-

cementing, reconstructing or repairing wells brought about by the failure of

well cement;

5. Cost-effective cements will reduce some capital investment.


Scientific/Technical Approach

The field applicable multifunctional cements will be formulated to meet

the following thirteen material criteria:

1) Slurry density of foamed cement, < 1.3 g/cm3;

2) Maintenance of pumpability for at least 3 hours;

3) Thermal and hydrothermal stability >300C

4) Corrosion rate of carbon steel casing < 70 milli-inch/year;

5) Compressive strength, > 1000 psi after five superheating-cooling

cycles (one cycle: 500C heat for 24 hrs and 25C water-quenching for

4 hrs) as thermal shock resistance test;

6) Water permeability, < 1 x 10 -4 Darcy;

7) Bond strength to steel casing and granite rock, > 30 psi;

8) Resistance to CO2-induced mild acid (pH ~ 5.0) at 300C, < 5 wt%

loss after 30 days exposure;

9) Fracture toughness, > 0.006 MN/m3/2 at 300C, 24 hour-curing time;

10) No shrinkage;

12) Thermal conductivity < 0.5 W/m.K;

13) Total raw material cost < $0.20/lb.


Accomplishments, Results and Progress

Original Planned Milestone/ Technical

Accomplishment

Actual Milestone/Technical Accomplishment

Date Completed

Task 1. Develop thermal shock-resistant

cements

Completed.

S. Gill, T. Pyatina, and T. Sugama “Thermal

shock-resistant cement,” GRC Transactions,

36 (2012) 445-451.

2012 GRC Best Presentation Award

March 2012

Task 2. Develop formulation of air-foamed

light weight cements

Completed.

Jun 2012

Task 3. Develop corrosion inhibitors for

foamed cement

Completed.

T. Sugama, S. Gill, T. Pyatina, R. Keese, A.

Khan, and D. Bour “Corrosion-resistant

foamed cements for carbon steel,” BNL

informal report, January (2013).

December 2012

Task 4. Deliver interim report to DOE Completed. Two reports December 2012

Task 5. Complete technology transfer to

cost-sharing industrial partners

Completed. Schlumberger, Baker Hughes, and

Geodynamics

December 2012



Synthesis of Thermal Shock-resistant Cement (TSRC)

Hydrothermal synthesis of new cement consists of three cementitious

phases, hydro-garnet, hydro-ceramic, and hydro-Al oxide, from starting

materials including refractory calcium aluminate cement (RC), Class F

fly ash, and sodium silicate

CaO.Al2O3

CaO.2Al2O3

3Al2O3.2SiO2

SiO2H2O

H2O

Na2O.SiO2

C

Ca5Al2(OH)12

Ca3Al2Si2O8(OH)4

++

+

hydrothermal reaction at 200 C

Na4Al3Si3O12(OH)

gamma-AlOOH

Hydro-garnet

Hydro-ceramic

Hydro-garnet

RC

Class F fly ash

Hydrogrossular

Katoite

Hydroxysodalite

hydrothermal reaction at 200°

°

Hydro-Al oxide

boehmite

1/1 NaO2/SiO2 ratio



Thermal shock-resistance test (one cycle: 500C annealing for

24 hrs + 25C water-quenching for 5 hr)

Heat-water quenching cycles

0 1 2 3 4 5

Co

mp

ress

ive

stre

ng

th,

psi

1000

2000

3000

4000

5000

6000

7000

100/0 Class G/additive

65/35 Class G/Quartz fluor

100/0 RC/Fly ash F

80/20 RC/Fly ash F

60/40 RC/Fly ash F



Phase compositions formed in TSRC after 5 cycle testing

Ca3Al2Si2O8(OH)4 Ca5Al2(OH)12

CaCO3

+ Na4Al3Si3O12(OH) gamma-AlOOH

Hydro-garnet Hydro-ceramicHydro-garnet

+ +

Hydrogrossular Katoite Hydroxysodalite

500°C, CO2

Na8Al6Si6O24CO3

Carbonated sodalite

as nano-scale crystal

gamma-Al2O3>>+ + +

Boehmite

Hydro-Al oxide

1 µm



Phase compositions formed in Class G/quartz flour system after 1 cycle testing

CaO

Ca(OH)2

Ca5(OH)2Si6O16.4H2O

CaCO3 Ca(OH)2

CaO

CaO.SiO2.H2O

CaCO3

Ca5(OH)2Si6O16.4H2O

Ca(OH)2

Ca(OH)2

CaO.SiO2.H2O

1.1 nm tobermorite

+ +

Portlandite

500°C, CO2

Lime

+

Portlandite

+ >> + +

1.1 nm tobermorite

+

Calcite

500°C, CO2 + water

in-situ volumetric expansion of cement

by reformation of portlandite

Phase transformation of portlandite in hydrated

Class G cement under dry and wet conditions



Cool water-thermal stress cycle test for cement sheaths (One cycle: 350C

heated-25C cool water passing in tube)

~25C water

Class G/quartz flour

cement sheath after

1 cycle

New cement sheath

after 5 cycles

Shear bonding strength at interfaces between

cement and casing before

and after 5 cycle testing

Class G

/quartz

flour

60/40 R

C/Cla

ss F fl

y ash

40/60 R

C/Cla

ss F fl

y ash

Sh

ea

r b

on

din

g s

tre

ng

th,

ps

i

0

20

40

60

80

100

Before test

After 5-cycle test



Corrosion-resistant foamed TSRC for carbon steel

CH3

Ca2+

+ 2 OH-

COOH or COOR

CH3

COO-

Ca2+ -

OOC

CH3

-[-CH2-C-]-n2 +

-[-CH2-C-]-n -[-C-CH2-]-n

R: C2H5 or C4H9

+ 2H2O + ROH

(in cement) >150oC

High-temperature Corrosion Inhibitor: Acrylic polymer (AP)

Thermal stability of Ca-complex AP formed in cement

60

70

80

90

100

Weig

ht (%

)

0 200 400 600 800

Temperature (°C) Universal V4.7A TA Instruments

333.9C

359.7C

150C-autoclaved cement

200C-autoclaved cement



FA content, wt%

0.0 0.5 1.0 1.5 2.0 2.5

Den

sit

y o

f cem

en

t slu

rry,

g/c

m3

0.0

0.5

1.0

1.5

2.0

Slurry density of foamed cements and compressive strength of AP-

modified and non-modified foamed cements after autoclaving at 200C

Foaming Agent (FA): Cocamidopropyl dimethylamine oxide

AP content, wt%

0 2 4 6 8 10 12 14

Co

mp

res

siv

e s

tren

gth

, M

Pa

0

2

4

6

8

10

12

14

16

18

20

0%FA

1%FA

2%FA

Criterion



-0.050

-0.150

-0.250

-0.350

-0.450

-0.550

-0.650

-0.750-0.700 -0.600 -0.500 -0.400 -0.300 -0.200-0.800 -0.100

Po

ten

tia

l vo

lts

vs.

SC

E

Current Density (A/cm2)

5%AP-1%FA

10AP-1%FA

0%AP-1%FA

15%AP-1%FA2%AP-1%FA

Metal

Cement

Good coverage of cement

Metal

Cemet

Poor coverage of cement

H2O + 1/2O2 + 2e- 2OH- (Cathodic reaction)

Fe0 – 2e- Fe2+ + O2 + 2OH- Fe2O3 .H2O Rust (Anodic reaction)

DC polarization diagrams for carbon steel

panels coated with unmodified and AP-

modified foamed cements after autoclaving

at 200C

Corrosion mitigation of carbon

steel by AP-modified foamed

cements

AP content, wt%

0 2 4 6 8 10 12 14

Co

rro

sio

n r

ate

, m

illi

-in

ch

per y

ear (

mp

y)

0

50

100

150

200

0 % FA

1 % FA

2 % FA

start


Future Directions

Milestone or Go/No-Go Status & Expected

Completion Date

Task 1. Complete thermal stress resistant test for 300C-cured

foamed TSRC

Apri.2013

Task 2. Develop high temperature-stable corrosion inhibitors

300C

Jun. 2013

Task 3. Develop toughness enhancing additives Aug.2013

Task 4. Develop setting control additives

Nov.2013

Go/no-go decision

Task 5. Deliver interim report covering all information

obtained in FY2013 to DOE and prepare peer-reviewed

journal article

Dec.2013

Task.6 Complete technology transfer to geothermal industry Dec.2013


Mandatory Summary Slide

Thermal shock-resistant cement (TSRC) and 200C-withstanding corrosion

inhibitor suitable for foamed TSRC were developed in FY 2012.

FY2012 (Dec. 2011-

May 2012)

FY2012 (Jun. 2012- Jan.

2013)

Target/Milestone Complete annealing-

water quenching test.

•Complete density and

electrochemical corrosion tests.

•Meeting with industrial partners

to evaluate its technical

feasibility and to address future

R&D direction.

Results Formulated thermal

shock-resistant

cement.

•Developed two specific

additives, foaming agent and

corrosion inhibitor suitable for

TSRC.

•Report covering all data was

prepared and set to DOE and

industrial partners for review.


Timeline:

Budget:

Project Management

Federal Share Cost Share Planned

Expenses to

Date

Actual

Expenses to

Date

Value of

Work Completed

to Date

Funding

needed to

Complete Work

$300 K 0 $300 K $250 K $300 K 0

Planned

Start Date

Planned

End Date

Actual

Start Date

Current

End Date

December 2011 December 2012 December 2011 December 2012*

* Some work ongoing with carry forward funds

Documents

Multifunctional Corrosion-resistant Foamed Well Cement Composites