Engineering Fly Ash-based Geopolymer Concrete

E. Ivan Diaz-Loya Ph.D. Candidate Erez N. Allouche Ph.D., P.E.

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

OUTLINE
Geopolymers
Structure Reactions Properties

Sustainability Engineering fly ash-based GPC Results

Conclusions

Fly ash analysis Mechanical characterization of GPC Data analysis y

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

Geopolymers
Geopolymers are cementitious materials that do not require the presence of OPC to harden g g or gain strength. Geopolymers are formed by a 3d network of Si & Al mineral molecules linked through covalent bonds with oxygen molecules. A positive ion must be provided to allow aluminum to become t t b tetravalent. l t

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

Geopolymers
The source of Si & Al for geopolymers can be any mineral (e.g. metakaolin) or by-product ( g y (e.g. fly ash) ) The positive ion is usually provided by a hydroxide solution of Na or K, etc. Water glass provides the monomers from which the polymeric chains grow. In most cases a slightly elevated temperature i required to ki k is i d kick start the geopolymerization reaction
2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

Geopolymerization
Geopolymeric reaction occurs can be divided into three steps: 1. 1 Dissolution of species - Si and Al dissolve in the alkaline media providing monomers. 2. Transportation/Initial gelation- Orientation of the th precursors t k place. takes l 3. Condensation/setting- Hydrolyzed aluminate and silicate species policondensate and p p harden.

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

MIXING
Geopolymer paste can be mixed with the same aggregates used for Portland cement, cement for its use as mortar or concrete.
ACTIVATOR SOLUTION FLY ASH FINE & COARSE AGGREGATES

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

PROPERTIES
COMPRESSIVE STRENGTH
80 Compressive strength (MPa) e 70 60 50 40
Geopolymer

30 20 10 0 0 20 40 60 80 100 Ag e (d ays )
OPC

Typical compressive strength curve of Geopolymer vs. Portland cement. Ob Observe the hi h early strength of geopolymer ( to 12,000 h high l h f l (up psi after 3 day of curing).

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

PROPERTIES
CHEMICAL RESISTANCE
Geopolymer made from class C fly ash

REMAINING COMPRESSIVE STRENGTH after sulfuric acid immersion test (pH = 0.6)
120

COMPRESSIVE STRE ENGTH (%)

100

Geopolymer made from class F fly ash

80

60

40

Class F fly ashbased geopolymer Class C fly ash-based geopolymer OPC

20

Ordinary Portland Cement

0 0 1 2 4 6 8

WEEK

Geopolymers corrosion resistance to the attack of sulfuric acids is significantly greater than that of Portland cement. It is practically inert to sulfate salts attack.

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

Sustainability y
POLLUTION AND ECOLLOGICAL FOOTPRINT Actual production of Portland cement p contributes 13.5 billion tons of CO2 per year. Approximately 5% of the total global emission of CO2 to the atmosphere.

Geopolymer made out of waste materials like fly ash not only have a smaller footprint but help reduce the footprint of other industries namely, p plants. coal-fired power p

2010 International Concrete Sustainability Conference, Dubai, UAE

Engineering fly ash-based geopolymer concrete

Sustainability
ENERGY CONSUMPTION

Portland cement production requires heating raw materials over 2550 F Fly ash based-geopolymers are a much less energy consuming alternative.

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Engineering fly ash-based geopolymer concrete

Sustainability

480 Million Tons of fly ash produced in 2001 World wide utilization ranges 20 to 80%
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Engineering fly ash-based geopolymer concrete

Sustainability
Energy production sources in the U.S. Coal reserves in the U.S.

72 million tons of fly ash produced in 2008 Only 30 million tons were used sending around 42 million tons to the landfills
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Engineering fly ash-based geopolymer concrete

Sustainability y
Monthly Fuel Cost to U.S. Electric Utilities 1995 2009, In 2009 cents per kilowatt-hour

Source: Ventyx Velocity Suite Updated: 5/10

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Engineering fly ash-based geopolymer concrete

Sustainability
POTENTIAL RISKS OF FLY ASH STORAGE LAGOONS

In December 2008 a TVAs fly ash storage lagoon ruptured in Kingston, TN 1.1 billion gal. of fly ash slurry were spilled into the Emory and Clinch Rivers 300 acres of the surrounding land were contaminated Estimated clean-up costs: 675 to 975 million

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Engineering fly ash-based geopolymer concrete

New Opportunities in the US

Increasing Cost Of Fly Ash Disposal
New regulations proposed by the EPA are expected to tighten fly ash disposal requirements increasing its cost.

Fly Ash Only For Encapsulated Applications

EPAs new regulations may only allow fly ash to be recycled in encapsulated applications. LEED Certification is aimed at improving p g performance across all the metrics that matter most: energy savings, water efficiency, CO2 emissions reduction, improved indoor environmental quality, and stewardship of resources and sensitivity to their impacts.

Green Construction Boom

Carbon Trading
Geopolymer offers the possibility to offset carbon emissions.

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Engineering fly ash-based geopolymer concrete

Challenges of fly ash-based geopolymer concrete

Fly ash Variability

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Engineering fly ash-based geopolymer concrete

Challenges of fly ash-based geopolymer concrete

Raw Materials Limestone Sand Clay Shale Iron ore
Calcination reactions

Cement C3S C2S C3A C4AF

Hydration reactions

Add aggregates

Cement paste C-S-H C-A-H AFt AFm

Ordinary concrete fc fr Ec

Fly ash

Geopolymerization reactions

Add aggregates

Geopolymer paste Poly-sialate Poly-sialate siloxo Poly-sialate disiloxo

Geopolymer concrete fc fr Ec

Mostly amorphous

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Engineering fly ash-based geopolymer concrete

Challenges of fly ash-based geopolymer concrete

Raw Materials Limestone Sand Clay Shale Iron ore
Calcinations reactions

Cement C3S C2S C3A C4AF

Hydration reactions

Add aggregates

Cement paste C-S-H C-A-H AFt AFm

Ordinary concrete fc fr Ec

Fly ash

Regression Model
Mostly amorphous

Geopolymer concrete

fc fr Ec

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Engineering fly ash-based geopolymer concrete

Engineering fly ash-based geopolymer concrete

1. Identify the fly ash characteristics that significantly impact GPC
Collect fly ash samples Keep mix design constant Full mechanical characterization of GPC samples Compressive vs. t C i tensile strength il t th Compressive vs. elastic modulus Density vs. fly ash fineness

2. Evaluate the mechanical behavior of GPC made from each of the fly ash samples

3 3. Determine the feasibility of establishing a y g regression model to predict GPCs mechanical properties using the characteristics fly ash
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Engineering fly ash-based geopolymer concrete

COLLECTION OF FLY ASH SAMPLES

SAMPLE 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 FLY ASH ORIGINS RODEMACHER PP RODEMACHER PP 2ND BATCH MONTICELLO PP DOLET HILLS PP DOLET HILLS PP 2/09/09 DOLET HILLS PP 3/16/09 DOLET HILLS PP 07/01/09 DOLET HILLS PP 08/10/09 MARTIN LAKE PP AVON LAKE PP SAN JUAN PP (LANDFILL) SAN JUAN PP UNIT 1 SAN JUAN PP UNIT 2 SAN JUAN PP UNIT 3 SAN JUAN PP UNIT 4 COUTLAND PAPER MILL TENNESSE TENNESSE REBURNED MERRIMACK STATION UNIT 1 MERRIMACK STATION UNIT 2 SAN MIGUEL ELECTRIC COOP. GIBBON'S CREEK PP COLETO CREEK PP PIRKEY PP LOCATION BOYCE, LA BOYCE, LA MOUNT PLEASANT, TX MANSFIELD, MANSFIELD LA MANSFIELD, LA MANSFIELD, LA MANSFIELD, LA MANSFIELD, LA TATUM, TX AVON L., OHIO FARMINGTON, FARMINGTON NM FARMINGTON, NM FARMINGTON, NM FARMINGTON, NM FARMINGTON, NM COURTLAND, AL TENNESSEE TENNESSEE BOW, NH BOW, NH TILDEN, TX BRYAN, TX FANIN, TX HALLSVILLE, TX HALLSVILLE, TX GENTRY, AR THOMPSON, TX ID CODE BY BY2 MO DH DH 2 DH 3 DH 4 DH 5 ML OH SJLF SJ1 SJ2 SJ3 SJ4 CL TN TNRB NH1 NH2 SM GC CC PK SE FC NE WA 459 390 454 600 721 1,674 528 946 3,565 1,097,920 227,760 265,136 350,400 421,064 977,616 308,352 552,464 1,040,980 1,800 1,051,200 2,250 745 1,314,000 435,080 750 438,000 CAPACITY (MW) 963 1871 1,880 FLY ASH PRODUCTION PER YEAR (TONS) 438,000 1,092,664 1,097,920

WELSH PP FLINT CREEK PP NORTHEASTERN STATION U 3&4 OOLOGAH, OK W.A. PARISH PP TOTAL

11,108,556

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Engineering fly ash-based geopolymer concrete

Elemental analysis of fly ash via XRF

ID Code BY Oxide SiO2 Al2O3 SiO2/Al2O3 SiO2+Al2O3 CaO Fe2O3 MgO SO3 Na2O K2O TiO2 MnO2 P2O5 SrO BaO Moisture content Loss On Ignition 0.12 0.17 37.77 32.41 55.61 58.52 61.01 61.23 62.12 59.32 48.70 55.07 56.60 56.22 56.39 57.11 57.35 37.99 23.48 44.56 40.75 36.18 66.50 39.25 33.02 59.25 19.13 18.40 19.87 20.61 20.06 19.20 19.59 19.72 16.60 28.61 25.68 27.15 27.36 28.18 27.78 17.37 13.15 24.79 22.79 17.70 18.80 21.09 19.82 18.43 1.97 1.76 2.80 2.84 3.04 3.19 3.17 3.01 2.93 1.92 2.20 2.07 2.06 2.03 2.06 2.19 1.79 1.80 1.79 2.04 3.54 1.86 1.67 3.21 BY2 MO DH DH 2 DH 3 DH4 DH5 ML OH SJLF SJ1 SJ2 SJ3 SJ4 CL TN TNRB NH1 NH2 SM GC CC PK

56.90 57.90 75.48 79.13 81.07 80.43 81.71 79.04 65.30 83.68 82.28 83.37 83.75 85.29 85.13 55.36 36.63 69.35 63.54 53.88 85.30 60.34 52.84 77.68 22.45 28.07 12.93 7.33 4.81 1.56 1.80 7.17 4.52 5.11 2.49 2.04 0.49 2.28 0.67 0.41 0.86 1.45 0.03 1.22 0.35 0.68 0 68 0.07 0.03 0.38 0.23 0.14 0.05 5.00 9.43 1.86 0.49 0.52 5.48 7.00 2.26 0.28 0.82 1.27 1.09 0.14 0.08 0.21 0.23 0 23 0.05 0.08 5.64 7.27 2.23 0.29 1.13 1.28 0.97 0.16 0.09 0.24 0.22 0 22 0.04 0.06 5.01 6.88 2.18 0.21 0.88 1.37 1.01 0.16 0.09 0.20 0.20 0 20 0.17 0.10 6.90 18.72 7.22 2.23 0.36 1.11 1.27 1.00 0.18 0.10 0.23 0.22 0 22 0.08 0.15 6.93 3.91 0.85 0.71 1.22 0.97 0.21 0.10 0.31 0.30 0 30 0.12 0.49 1.97 6.22 1.08 0.19 0.38 2.63 1.56 0.02 0.16 0.08 0.21 0 21 0.12 1.82 5.73 3.92 0.73 0.34 1.30 1.00 0.80 0.05 0.13 0.06 0.10 0 10 0.09 3.50 5.43 3.73 0.77 0.22 1.47 1.00 0.93 0.04 0.18 0.07 0.10 0 10 0.04 2.69 4.69 3.34 0.75 0.26 1.50 0.95 0.96 0.03 0.18 0.07 0.11 0 11 0.00 3.41 5.18 4.00 0.82 0.28 1.53 1.05 1.00 0.03 0.21 0.07 0.11 0 11 0.00 0.44 5.57 18.46 3.65 0.82 0.18 1.42 1.01 1.01 0.03 0.19 0.06 0.09 0 09 0.01 3.09 1.44 2.77 0.22 3.46 0.91 0.54 0.50 0.17 0.24 0 24 0.12 2.30 4.72 0.74 0.26 0.31 0.93 0.90 0.02 1.01 0.08 0.08 0 08 0.72 4.39 4.64 2.26 4.91 23.53 26.19 1.95 0.63 0.22 2.90 2.63 0.89 0.09 0.01 0.14 0.12 0 12 0.02 0.26 4.99 4.45 0.85 1.47 0.57 1.50 0.02 1.18 0.36 0.62 0 62 0.03 0.11 6.75 6.34 1.36 1.92 0.35 1.50 0.03 1.52 0.33 0.72 0 72 0.01 0.16 9.23 5.61 3.23 0.35 0.50 1.63 1.21 0.06 0.05 0.21 0.21 0 21 0.03 0.04

8.46 17.76 10.59 1.35 0.16 0.63 1.73 1.67 0.04 1.80 0.14 0.13 0 13 0.05 1.23 1.29 1.33 2.19 1.28 0.03 0.62 0.25 0.19 0 19 0.14 1.20 0.20 0.73 1.59 1.03 0.03 0.43 0.14 0.08 0 08 0.16

0.83 12.83 52.01 10.14

5.72 27.84

Parameter Min
SiO2+Al2O3 SiO2/Al2O3 CaO 36.63 36 63 1.79 2.26

Max
85.30 85 30 3.19 28.07

Avg
71.15 71 15 2.35 9.78

Sta Div
13.93 13 93 .59 8.24

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Engineering fly ash-based geopolymer concrete

Crystallographic characteristics of fly ash

Amorphous Other Mullite Quartz

100.00 75.00 50.00 25.00 0.00

Sample
Parameter Min
Amorphous FA Amorphous GP 27.9 55.3

Max
75.1 86.8

Avg
62.41 74.44

Std Dev
12.46 8.3

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Engineering fly ash-based geopolymer concrete

Particle size distribution of fly ash

100
OPC BY

90

MO DH

80

DH2 DH3 DH4

70

DH5 ML OH

60

SJ1 SJ2

% Passing

50

SJ3 SJ4 NH1

40

NH2 GC PK

30

CC SM

20

SE FC NE

10

BY2 WA

0 0.1 1 10 100 1000

TN TNRB

Size (m)

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Engineering fly ash-based geopolymer concrete

Particle M h l P i l Morphology
Fly Ash Before Activation Fly Ash After Activation (Geopolymer)

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Engineering fly ash-based geopolymer concrete

Correlations Within the Mechanical Properties

Flexural vs. Compressive Strength

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Engineering fly ash-based geopolymer concrete

Correlations Within the Mechanical Properties

Elastic Modulus vs. Compressive Strength

The ACI equation: was design for normal weight concrete (2300 kg/m3)while the GPC samples ranged from 1890 to 2371 kg/m3 Therefore the density was included in the regression model: Compared to ACI equation:

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Engineering fly ash-based geopolymer concrete

Correlations Within the Mechanical Properties

Elastic Modulus vs. Compressive Strength & Density

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Engineering fly ash-based geopolymer concrete

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Engineering fly ash-based geopolymer concrete

Development of a Prediction Model

FLY ASH VARIABLES: Reactive Silica Reactive Alumina Reactive Calcium Loss on Ignition Fineness Specific Surface Area GPC RESPONSE: Compressive Strength

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Engineering fly ash-based geopolymer concrete

Development of a Prediction p Model

Elemental Analysis
BY

Introduction of Silica, Alumina and Calcium Content to the Model

SiO2 Al2O3 SiO2/Al2O3 SiO2+Al2O3 CaO

37.77 19.13 1.97 56.90 22.45

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Engineering fly ash-based geopolymer concrete

Development of a Prediction Model

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Engineering fly ash-based geopolymer concrete

Development of a Prediction Model

Model with all possible variables

Stepwise regression

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Engineering fly ash-based geopolymer concrete

Development of a Prediction Model

2nd model (Al not included)

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Engineering fly ash-based geopolymer concrete

Model Adequacy

Sample

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Engineering fly ash-based geopolymer concrete

Conclusions
Geopolymer concrete possesses a very similar mechanical behavior to that of ordinary Portland cement concrete. Si il or i some cases the same equations given Similar in h i i in the ACI building code can be used for the design of GPC structures. A model t predict th mechanical properties of d l to di t the h i l ti f GPC based on characteristics inherent to the fly ash is put forward. The model is based on the fly ash variables: SiO2, CaO, Loss on ignition, fineness & SSA
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