Fly Ash in Concrete

PCA R&D Serial No.
2989
The Durability of Concrete Containing

High Levels of Fly Ash
by Donald Burden
Donald Burden Thesis, Masters of Science in Engineering 2006

All rights reserved
The Durability of Concrete Containing High Levels of

Fly Ash
by
Donald Burden
B.Sc. E., University of New Brunswick, 2003.
A Thesis Submitted in Partial Fulfillment of
the Requirements for the Degree of
Masters of Science in Engineering

In the Graduate Academic Unit of Civil Engineering
Supervisor:
Dr. Michael Thomas, Civil Engineering
Examining Board:
Dr. Lloyd M. Waugh, Civil Engineering

Dr. Theodore W. Bremner, Civil Engineering
External Examiner:
Dr. Guida Bendrich, Chemical Engineering
This thesis is accepted by the

Dean of Graduate Studies
THE UNIVERSITY OF NEW BRUNSWICK

January 2006
Donald Burden, 2006
Abstract
This thesis presents data from a laboratory study on the effect of curing on the
carbonation and permeability of high-volume fly ash concrete (HVFAC). Concrete
mixtures were produced at a range of water-to-cementing-materials ratios (W/CM = 0.34,
0.40 and 0.50) and fly ash replacement levels (0%, 30%, 40% and 50%) using fly ashes
of different compositions (Type F, CI and CH). Concrete specimens were moist-cured for
various periods (1 to 28 days) prior to exposure to one of the following conditions: (i)
accelerated carbonation (approximately 1% CO2 by volume), (ii) indoor (23oC and 50%
RH), or (iii) outdoors (sheltered from direct precipitation). A limited number of
specimens were treated with different curing compounds after stripping the moulds at 1
day and these specimens were subjected to the same exposure conditions. In addition to
monitoring changes in compressive strength, the depth of carbonation was determined
periodically by spraying freshly fractured surfaces with phenolphthalein indicator, and
the permeability was measured indirectly by determining electrical conductivity (as per
ASTM C 1202).
The data indicate that HVFAC carbonates at a significantly faster rate than plain Portland
cement concrete at the same W/CM. The rate of carbonation increases with the level of
fly ash and differences become particularly marked as the degree of moist curing is
reduced or the W/CM is increased. The increased sensitivity of HVFAC can be offset by
(i) specifying lower W/CM, (ii) extending the period of moist curing, or (iii) increasing
the depth of cover when such concretes are used. The results are discussed in the context
of code requirements for reinforced concrete structures.
ii
Acknowledgements
I would like to take this opportunity to acknowledge the persons that aided in the
completion of this project. I would like to thank Dr. Michael Thomas for his guidance
and support throughout the duration of the project. I would also like to thank the
undergraduate and graduate students in the Materials Group for their help during the
project but especially Andrew Ross and David Smith. My appreciation and thanks also go
out to the Civil Engineering Technical Staff and Faculty Shop for their support,
knowledge, and suggestions during the laboratory study. Finally, I would like to thank the
Portland Cement Association (PCA), EcoSmartTM, and the National Science Engineering
Research Council (NSERC) for their financial contributions to the project.
iii
Table of Contents
Abstract ......................................................................................................................ii
Acknowledgement .....................................................................................................iii
Table of Contents.......................................................................................................iv
List of Tables .............................................................................................................vi
List of Figures ............................................................................................................vii
1.0 Introduction..........................................................................................................1
1.1 Background Information..........................................................................1
1.2 Problem Statement ...................................................................................2
1.3 Significance of Problem...........................................................................3
1.4 Goal and Objectives.................................................................................4
2.0 Literature Review.................................................................................................5
2.1 Trend To Higher Fly Ash Replacement Levels .......................................5
2.1.1 Incentives ...............................................................................5
2.1.2 Examples................................................................................7
2.1.3 Definition of High Volume Fly Ash Concrete (HVFA) ........8
2.2 Effect of HVFA on Concrete Properties / Potential Problems ................9
2.2.1 Scaling....................................................................................9
2.2.2 Plastic Shrinkage....................................................................10
2.2.3 Heat of Hydration ..................................................................11
2.2.4 Strength ..................................................................................12
2.2.5 Permeability ...........................................................................14
2.2.5.1 Relationship Between Electrical Conductivity
and Permeability .......................................................15
2.2.6 Carbonation............................................................................16
2.2.6.1 Mechanisms of Carbonation ......................................16
2.2.6.2 Factors Influencing the Rate of Carbonation .............17
2.2.6.3 Conditions that Promote Carbonation Induced
Corrosion of Steel ......................................................18
3.0 Laboratory Research ............................................................................................20
3.1 Methodology ............................................................................................20
3.2 Materials & Mixture Proportions.............................................................20
3.2.1 Cement ...................................................................................20
3.2.2 Fly Ash...................................................................................21
3.2.3 Aggregate...............................................................................22
3.2.4 Admixture ..............................................................................23
3.2.5 Curing Compounds ................................................................23
3.2.6 Mixture Proportions ...............................................................23
3.3 Preparation, Casting, Curing, & Testing of Specimens ...........................23
iv
3.3.1
3.3.2
3.3.3
3.3.4
Preparation .............................................................................23
Casting ...................................................................................25
Curing ....................................................................................26
Testing....................................................................................30
4.0 Summary of Results.............................................................................................34

4.1 Compressive Strength ..............................................................................34
4.2 Rapid Chloride Permeability....................................................................40
4.3 Electrical Resistivity ................................................................................51
4.4 Carbonation..............................................................................................53
4.4.1 Accelerated ............................................................................53
4.4.2 Indoor.....................................................................................59
4.4.3 Outdoor ..................................................................................64
5.0 Discussion of Results...........................................................................................69
5.1 Relationship between Compressive Strength, Rapid Chloride
Permeability, and Carbonation.................................................................69
5.2 Impact of Curing on High Volume Fly Ash Concrete.............................74
5.3 Master Builders Rapid Chloride Permeability Prediction
Software ...................................................................................................75
5.4 Performance of Different Fly Ashes ........................................................78
5.5 Carbonation Rate Predictive Model.........................................................79
5.6 Relationship between Accelerated and Natural
(Indoor & Outdoor) Carbonation Rates ...................................................84
5.7 Interpretation of Carbonation Rates (Comparison Between
CSA A23.1-00 and CSA A23.1-04) ........................................................86
5.8 Guidelines for Use of High Volume Fly Ash Concrete...........................88
6.0 Conclusions..........................................................................................................93
7.0 Recommendations................................................................................................95
8.0 References............................................................................................................97
Curriculum Vitae .......................................................................................................101
List of Tables
Table 3.1 Chemical Analysis & Physical Properties of Portland Cement...............21
Table 3.2 Chemical Analysis & Physical Properties of Fly Ashes..........................22
Table 3.3 Mixture Proportions.................................................................................24
Table 3.4 Phase 1 Curing Regimes ..........................................................................26
Table 4.1 Compressive Strength Data .....................................................................35
Table 4.2 Rapid Chloride Permeability Data...........................................................41
Table 4.3 Chloride Ion Penetrability Based on Charge Passed ...............................42
Table 4.4 Electrical Resistivity Data .......................................................................52
Table 4.5 Accelerated Carbonation Data .................................................................54
Table 4.6 Accelerated Carbonation Rates, k (mm/y^0.5)........................................59
Table 4.7 Indoor Carbonation Data .........................................................................60
Table 4.8 Indoor Carbonation Rates, k (mm/y^0.5) ................................................63
Table 4.9 Outdoor Carbonation Data.......................................................................65
Table 4.10 Outdoor Carbonation Rates, k (mm/y^0.5)..............................................68
Table 5.1 Carbonation Rate Predictive Model Data ................................................80
Table 5.2 Carbonation Rate Data from Dr. Michael Thomas..................................83
Table 5.3 k-Values for Various Values of Design Life and Cover..........................88
Table 5.4 Concrete Qualities and Nominal Cover to Steel for 100 Year
Service Life..............................................................................................92
vi
List of Figures
Figure 2.1 Relationships between Results of Hydraulic Permeability Tests
and Rapid Chloride Penetration Tests (RCPT).......................................16
Figure 3.1 Sketch of Accelerated Carbonation Setup..............................................28
Figure 3.2 Accelerated Carbonation Chamber.........................................................29
Figure 3.3 Outdoor Exposure Condition..................................................................30
Figure 3.4 Equipment Used to Obtain Freshly Fractured Concrete.........................31
Figure 3.5 Freshly Fractured Concrete Sprayed with Phenolphthalein
Indicator Solution....................................................................................32
Figure 4.1 Curing vs. 28 Day Compressive Strength (W/CM=0.50) ......................36
Figure 4.4 Compressive Strength of Different Fly Ashes Continuously
Moist Cured for 28 Days.........................................................................37
Figure 4.5 Curing vs. 1 Year Compressive Strength (W/CM=0.50) .......................38
Figure 4.8 Curing vs. 28 Day Rapid Chloride Permeability (W/CM=0.50)............42
Figure 4.14 Curing vs. 1 Year Rapid Chloride Permeability (W/CM=0.50).............47
Figure 4.17 Curing vs. Rapid Chloride Permeability of Different Fly Ashes ...........50
Figure 4.18 Relationships between Resistivity and Rapid Chloride
Permeability Testing ...............................................................................53
Figure 4.19 Curing vs. 90 Day Accelerated Carbonation (W/CM=0.50)..................57
Figure 4.22 Curing vs. 90 Day Accelerated Carbonation of Different
Fly Ashes ................................................................................................58
Figure 4.23 Curing vs. 1 Year Indoor Carbonation (W/CM=0.50) ...........................61
Figure 4.26 Curing vs. 1 Year Outdoor Carbonation (W/CM=0.50) ........................66
Figure 4.29 Curing vs. 1 Year Outdoor Carbonation of Different Fly Ashes ...........67
Figure 5.1 Strength vs. Rapid Chloride Permeability at 28 Days of Age................69
Figure 5.2 Strength vs. Rapid Chloride Permeability at 1 Year of Age ..................70
Figure 5.3 Rapid Chloride Permeability vs. Carbonation at 90 Days of Age..........71
Figure 5.4 Rapid Chloride Permeability vs. Carbonation at 1 Year of Age ............71
vii
Figure 5.5 Rapid Chloride Permeability vs. Carbonation for Different

Levels of Fly Ash at 90 Days..................................................................72
Figure 5.6 Rapid Chloride Permeability vs. Carbonation for Different
Levels of Fly Ash at 1 Year ....................................................................73
Figure 5.7 Strength vs. Carbonation at 1 Year of Age.............................................74
Figure 5.8 Screenshot from Master Builder's RCPT Prediction Model ..................76
Figure 5.9 Laboratory Tested vs. Master Builder's Prediction of
RCPT at 28 Days ....................................................................................77
RCPT at 90 Days ....................................................................................77
RCPT at 1 Year.......................................................................................78
Figure 5.12 Predicted Carbonation Rates vs. Measured Carbonation Rates .............82
Figure 5.13 Predicted Carbonation Rates vs. Measured Carbonation Rates
(Dr. Michael Thomas).............................................................................84
Figure 5.14 Relationship between Accelerated & Natural Indoor
Carbonation Rates...................................................................................85
Figure 5.15 Relationship between Accelerated & Natural Outdoor
Carbonation Rates...................................................................................85
Figure 5.16 Guidelines for Concrete with k = 3.0 mm/year0.5 ...................................89
Figure 5.19 Guidelines for Concrete with k = 10.0 mm/year0.5 .................................90
viii
1.0 Introduction
1.1 Background Information
Fly ash is an inorganic, non-combustible by-product of coal - burning power plants. As
coal is burnt at high temperatures, carbon is burnt off and most of the mineral impurities
are carried away by the flue gas in the form of ash. The molten ash is cooled rapidly and
solidifies as spherical, glassy particles (Malhotra and Mehta, 2002). Fly ash particles
range in diameter from <1 microns up to 150 microns (Malhotra and Ramezanianpour,
1994). Fly ash is removed from the flue gas by means of a series of mechanical
separators followed by electrostatic precipitators or bag filters (Malhotra and Mehta,
2002). Not all fly ashes are suitable for use in concrete. As many power companies are
installing scrubber systems to remove sulfur dioxide from stack gasses, many fly ashes
are being mixed with scrubber products, resulting in fly ash containing free lime and
calcium sulfates or sulfites. These materials cannot be used in concrete (Mindess et al.,
2003).
ASTM C618 classifies fly ash as Class C or F. It is true that the specification states that
Class F ashes are mainly produced from bituminous or anthracite coals and that Class C
ashes are mainly produced from sub-bituminous or lignite coals, but the main criterion
for classification are its chemical requirements: SiO2 + Al2O3 + Fe2O3 > 70% for Class F
and SiO2 + Al2O3 + Fe2O3 > 50% for Class C. However, many sub-bituminous and lignite
coal ashes meet the chemical requirements of Class F. This has caused some confusion so
Canada has removed reference to coal types and CSA A3000-03 classifies fly ash on the
basis of calcium content as follows: Type F < 8% CaO, Type CI 8-20% CaO, and CH >
20% CaO.
Fly ash is a pozzolanic material. A pozzolan is defined by the American Society for
Testing and Materials (ASTM) as a siliceous or siliceous and aluminous material which
in itself possesses little or no cementitious value but which will, in finely divided form
and in the presence of moisture, chemically react with calcium hydroxide at ordinary
temperature to form compounds possessing cementitious properties. (ASTM, 1975). In
the presence of moisture, alumino-silicates within the fly ash react with calcium ions to
2
form calcium silicate hydrates (Malhotra and Ramezanianpour, 1994). Many ready-mix
companies use fly ash to partially replace Portland cement in concrete. Although the
addition of fly ash to concrete has economic benefits to the ready-mix producer (fly ash is
typically cheaper than Portland cement), fly ash also provides enhanced fresh and
hardened concrete properties (Mindess et al., 2003). Fly ash influences the rheological
properties of the fresh concrete and the strength, finish, porosity, and durability of
hardened concrete (Malhotra and Ramezanianpour, 1994).
Today, there is a general trend to replace higher levels of Portland cement with fly ash in
concrete. The increased pressure to use higher levels of fly ash in concrete stems from
three main aspects. The first aspect is economics. In most markets fly ash is less
expensive than Portland cement. Therefore, as the replacement level of fly ash increases,
the cost to produce concrete decreases. The second aspect and arguably the most
important is the environment. Fly ash is an industrial by-product, much of which is
deposited in landfills if not used in concrete. As of 1999, 4 mega-tonnes of fly ash per
year was being deposited in Canadian landfills. Also from an environmental perspective,
the more fly ash being utilized in concrete, the less the demand for Portland cement, the
less Portland cement production, and therefore the lower CO2 emissions. The third and
final aspect influencing the use of higher replacement levels is the technical benefits of
high volume fly ash concrete (HVFAC). HVFAC has improved performance over
ordinary Portland cement concrete, especially in terms of durability when appropriately
used. HVFAC is defined as concrete containing greater then 30% fly ash by mass of total
cement material. To date, the construction industry in Canada is only comfortable with
concrete containing 15 to 30% fly ash, but as more technical information and proven field
performance becomes available, this percentage should rise.
1.2 Problem Statement

Although there are clearly economic and environmental benefits associated with the use
of high levels of fly ash in concrete, there is relatively little information on the behavior
of such concrete and almost no guidance on its production or use. Studies have
demonstrated that well-cured high-volume fly ash concrete with very low water-to-
3
cementitious-material ratios (e.g., W/CM <0.35) has excellent properties when mature,
but there have been relatively few studies on the performance of concrete at higher
W/CM when produced and cured under normal conditions. The data that does exist
indicates that improperly proportioned and cured concrete with high levels of fly ash may
be of inferior quality, especially in terms of carbonation and resistance to deicer salt
scaling resistance. There are also indications that low quality concrete may be more
sensitive to the quality of fly ash being used. Further investigations are required to
determine the factors that influence the properties of concrete with high levels of fly ash
and to produce guidelines to ensure that the best practices are upheld.
1.3 Significance of Problem

The use of materials such as fly ash as a supplementary cementing material in concrete
has become commonplace in North America. Properly used, fly ash can significantly
enhance the properties of concrete. There is increasing pressure to replace higher levels
of Portland cement with fly ash to help reduce the CO2 emissions associated with the
manufacturing of Portland cement. Essentially, for every tonne of Portland cement
manufactured, one tonne of CO2 is released into the atmosphere. The total worldwide
environmental release of CO2 in 1998 was estimated at 23 billion tonnes, with Portland
cement production accounting for approximately 7% of the total carbon dioxide
emissions (Mehta, 1999). Therefore, replacing Portland cement with fly ash could reduce
cement production and hence reduce CO2 emissions. The current annual worldwide
production of fly ash is approximately 500 million tonnes, but only approximately 20% is
being used by the cement and concrete industry (Mehta, 1999). The demand and
consumption of Portland cement is increasing, therefore it is important for the cement and
concrete industry to start utilizing more fly ash to meet these demands rather then
increase Portland cement production (Malhotra and Mehta, 2002). In Western Canada,
EcoSmartTM (an industry-government partnership) is aggressively promoting the use of
high-volume fly ash in concrete construction. Also, reducing CO2 emissions through the
increased use of fly ash is part of the Canadian federal governments Action Plan 2000 on
Climate Change. Many architects are embracing Green Building strategies, part of
which involves maximizing the use of recycled materials in construction.
1.4 Goal and Objectives

The goal of the project was to determine the factors that influence the properties of
concrete with high levels of fly ash and to produce guidelines to ensure the safe and
appropriate use of high-volume fly ash concrete.
The objectives of the project were as follows:
1. To determine the effect of the water-to-cementitious-material ratio on
compressive strength, permeability, and carbonation.
2. To determine the effect of fly ash replacement level on compressive strength,
permeability, and carbonation.
3. To determine the effect of curing on compressive strength, permeability, and
carbonation.
4. To determine the effect of fly ash composition on compressive strength,
5. To determine the effect of curing compounds on carbonation.
6. To develop guidelines for the use of high-volume fly ash concrete with respect
to W/CM, fly ash replacement level, curing, and depth of cover.
2.0 Literature Review

2.1 Trend to Higher Fly Ash Replacement Levels
2.1.1 Incentives
The origin, properties, and use of low levels of fly ash in concrete are now generally well
established and accepted in the construction industry. However sustainability is the
driving force behind the trend to higher fly ash replacement levels. For example in
Canada, the Canadian Green Building Council has introduced a program that promotes
the development and implementation of green building practices. This program is
referred to as LEED (Leadership in Energy and Environmental Design). LEED is based
on a point system such that points are earned for environmentally friendly actions taken
during the building process. Projects are then LEED certified according to the following
LEED Green Building Certification Levels:
LEED Certified
LEED Silver
LEED Gold
LEED Platinum
26-32 points
33-38 points
39-51 points
52-70 points
The LEED program is broken down into six point categories with a maximum number of
points being 70:
Sustainable Sites
Water Efficiency
Energy and Atmosphere
Materials and Resources
Indoor Environmental Quality
Innovation and Design Process Points
14 points
5 points
17 points
14 points
15 points
5 points
Concrete as a building material is very effective in earning LEED points. The maximum
number of LEED points a project can receive through use of concrete is 23 points; 5
points through Sustainable Sites, up to 10 points through Energy and Atmosphere, 7
points through Materials and Resources, and 1 point through Innovative and Design
Process. However, although 23 points are available through concrete, 6 of these points
would be very difficult if not impossible to earn unless concrete contained low to high
levels of supplementary cementing materials. For example, Materials and Resources
Credits 4.1 and 4.2 (Recycled Content) are only achieved with concrete if the concrete
6
building is built with 25 and 40% of the Portland cement replaced with fly ash (or ground
granulated blast furnace slag), respectively. Other examples where higher levels of fly
ash replacement may be necessary to obtain maximum LEED points with concrete are:
Credit 5.1 (Regional Materials, 10% Extracted and Manufactured Regionally), Credit 5.2
(Regional Materials, 20% Extracted and Manufactured Regionally), Credit 8 (Durable
Building), and Credit 2 (LEED Accredited Professional, Innovation and Design).
Although LEED certification for private buildings is still not mandatory and probably
wont be in the near future, support for green buildings has increased over the last
number of years in order to achieve a more environmentally friendly image. For example,
Mountain Equipment Coop (MEC), a Canadian company that specializes in outdoor
adventure products has recently built stores in Ottawa and Montreal that are LEED
certified and insist all new MEC stores will be LEED certified. This is just one
companys attempt to promote sustainability and environmentalism. Many cities and
government agencies require LEED certification for new public buildings. For example,
City of Vancouver, Alberta Infrastructure, City of Calgary, Manitoba Hydro, Public
Works and Government Services Canada, and BC Buildings Corporation all require new
public buildings to be LEED certified (Cement Association of Canada, 2005).
Sustainability, durability, and economy are the paramount reasons for the use of high
volume fly ash concrete instead of conventional Portland cement concrete. As can be
seen from the comparison below, HFVA concrete is more environmentally friendly and
has more desirable technical properties then conventional concrete (Green Resource
Center, 2004)
High Volume Fly Ash Concrete
Less energy intensive manufacture
Higher ultimate strength
More durable
Requires less water
Uses a waste by-product
Creates fewer global warming gases
Conventional
Energy intensive manufacture
Lower ultimate strength
Less durable
Requires more water
Uses virgin materials only
Creates more global warming gases
2.1.2 Examples
EcoSmart is a government industry partnership aimed at reducing CO2 emissions by
encouraging the use of high volume supplementary cementing materials in concrete to the
greatest extent possible within the parameters of performance, constructability, and
profitability (de Spot, 2003). EcoSmart has coined the term EcoSmart concrete and
defines it as concrete produced by replacing roughly half of the Portland cement used in
conventional concrete with a supplementary cementing material such as fly ash.
EcoSmarts mission is to explore the potential of EcoSmart concrete as a cost effective
and practical solution to an environmental challenge and to increase awareness of the
benefits and challenges of EcoSmart concrete. The technology to create HFVA concrete
was first introduced in Canada by CANMET (Canada Center for Mineral and Energy
Technology) in 1985. CANMET (which is a part of Natural Resources Canada) has
demonstrated that under both laboratory and field conditions (for example, indoor
parking garage for Park Lane Hotel / Office Complex and drilled caisson piles for 22
storey office tower in Purdys Wharf, both projects in Halifax) the performance of HVFA
concrete is on par or better then conventional concrete. EcoSmart is operating under the
premise that high volume fly ash in concrete is beneficial from two perspectives: the first
being economic and performance based (fly ash is a waste product that is typically
cheaper than Portland cement, reducing the overall cost of concrete while maintaining
desirable concrete properties) and the second being environmental / sustainable
(replacing Portland cement with fly ash reduces Portland cement production and
therefore reduces greenhouse gas emissions).
As with any new technology, until the technology is proven successful in field conditions
there is reluctance from the public to use such a technology. Understandably, the
construction industry is no different. Until high volume fly ash concrete is used and
proven in field conditions, there will be resistance to the adoption of such a material.
EcoSmart is an organization that examines and, if possible, resolves the major obstacles
that are limiting the use of HVFA concrete. EcoSmart through the use of case studies
hopes to help the construction industry with a smooth transition into the use of HVFA
concrete. Below are projects that have used EcoSmart concrete and have been tracked by
8
EcoSmart to determine the effects of fly ash on concrete properties, appearance and cost
implications:
Ardencraig Townhouse Renovation

University of British Columbia Lui Center
Brentwood Skytrain Station
Gilmore Skytrain Station
York University Computer Science Building
British Columbia Gas Coastal Facilities Operations Center
Results from the aforementioned case studies will be further discussed in later sections of
the literature review (Gillies, 2001; de Spot, 2003).
2.1.3 Definition of High Volume Fly Ash Concrete (HVFA)

In recent years economic and environmental considerations have increased the incentive
to use fly ash at higher replacement levels than those traditionally used. In some cases,
fly ash has replaced more than 50% of the Portland cement in concrete mixtures
(Thomas, 2003). The term high volume fly ash (HVFA) was coined in 1985 by Malhotra
at CANMET. This concrete has very low water content and at least 50% of the Portland
cement by mass is replaced with fly ash. The HVFA concrete has excellent workability,
low heat of hydration, adequate early-age strength and very high later-age strength, low
drying shrinkage, and excellent durability (Malhotra and Mehta, 2002). HFVA concrete
has generally been found to be an economical and durable concrete system for structural
concrete and many other concreting projects. HVFA concrete can be mixed, transported,
placed, and finished by conventional means (Langley and Leaman, 1998). However, in
order to achieve the full benefits of HVFA concrete particular attention has to be paid to
certain design and placement issues when using high levels of fly ash. The two most
important factors that have to be addressed in order to ensure HVFA concrete be durable
is a low water to cementitious materials ratio and an extended period of moist curing. It is
perhaps for this reason that specifications have been reluctant to permit higher levels of
fly ash to be used for general concreting purposes (Thomas, 2003). The Canadian
Standards Association (CSA) has developed a standard, CSA A23.1-04 Clause 8.8, which
is entitled Concrete Made with a High-Volume of Supplementary Cementing Material
(HVSCM). This standard is an industry guide which details such information as:
9
maximum water to cementing materials ratio for different exposure classes, maximum
water to cementing materials ratio for reinforced concrete, curing requirements, etc. This
standard defines high volume supplementary cementing material concrete with two
definitions depending on the proportions of fly ash (FA) and slag (S):
HVSCM-1: FA/40 + S/45 >1.00
HVSCM-2: FA/30 + S/35 > 1.00
However, further research and information is needed to supplement and strengthen this
standard. To date, there are two outstanding durability issues associated with HVFA
concrete, carbonation and deicer salt scaling resistance. These concerns will be discussed
further in this literature review.
2.2 Effect of HVFA on Concrete Properties / Potential Problems

2.2.1 Scaling
Scaling of concrete exposed to deicing chemicals occurs when immature or non-air
entrained concrete is exposed to large quantities of deicing chemicals in a freezing and
thawing environment (ACI Committee 232, 2003). The destructive forces associated with
cyclic freezing and thawing of concrete is exacerbated in the presence of deicing salts
(Bremner and Thomas, 2004). Concrete containing fly ash should only be exposed to
deicing chemicals if the concrete is air entrained and has reached a specified strength (1
year maturity is recommended by ACI Committee 232, 2003). A number of laboratory
studies have indicated inferior scaling resistance of concrete containing levels of fly ash
in excess of 25 to 30% when subjected to cycles of freezing and thawing in the presence
of deicing chemicals. However, accelerated salt scaling tests in the laboratory do not
provide a reliable indication of field performance, and concrete with HVFA has been
used in various applications exposed to deicer salts and freezing and thawing conditions
with satisfactory performance (Langley and Leaman, 1998). There are three important
guidelines that must be adhered to if fly ash concrete is to be exposed to deicing salts:
low W/CM, adequately air entrained, and proper finishing and curing (Bremner and
Thomas, 2004). The type and the amount of fly ash used and the W/CM of the concrete
affect considerably the deicing salt scaling resistance of concrete. In general, the
resistance to the deicing salt scaling decreases with increasing amounts of fly ash and
10
increasing W/CM. When cured with liquid curing compounds, concrete containing fly
ash showed substantially less scaling than concrete cured in a moist room (Zhang et al.,
1998). CANMET has performed deicing salt scaling tests on HVFA concrete, in
accordance with ASTM C672, and have reported that its performance is less than
satisfactory. The HVFA specimens, when compared to normal Portland cement concrete
with the same W/CM and the same cementitious materials content, showed severe
surface scaling both visually and by weight loss. However, field performance contradicts
the laboratory findings. For example, a HVFA concrete sidewalk was placed in Halifax,
Nova Scotia, Canada, in 1996. This sidewalk is exposed to approximately 100 freezing
and thawing cycles and numerous applications of deicing chemical each year. To date,
this HVFA sidewalk has demonstrated good performance (Malhotra and Mehta, 2002;
Langley and Leaman, 1998). The contradictions on the scaling resistance of fly ash
concrete results from variations in the materials used, and differences in the conditions of
testing, exposure, finishing, and curing regime (Bilodeau et al., 1998). It is believed by
many researchers that the HVFA concrete salt scaling problem is more of a result of the
test method (ASTM C672) rather then the actual performance of the concrete (Malhotra
and Mehta, 2002).
2.2.2 Plastic Shrinkage

Plastic shrinkage occurs on the surface of freshly mixed concrete soon after it has been
placed, while it is being finished or shortly thereafter. Plastic shrinkage occurs when
environmental conditions produce rapid evaporation of moisture from the concrete
surface. These cracks occur when water evaporates from the surface faster than it can rise
to the surface during the bleeding process. This creates rapid drying shrinkage and tensile
stresses in the surface that often result in short, irregular cracks (Cement Association of
Canada, 2003). Plastic shrinkage is a potential problem of HFVA concrete. The amount
of bleed water available for evaporation of HVFA concrete is very low because of its low
unit water content, and therefore it is recommended that moist curing of HVFA concrete
be started as soon as the concrete is poured to limit the amount of evaporable water and
reduce plastic shrinkage. (Malhotra and Mehta, 2002; Langley and Leaman, 1998).
11
2.2.3 Heat of Hydration

Replacing Portland cement with fly ash can reduce the exothermic reaction between
cement and water (Bremner and Thomas, 2004). Because of the slower pozzolanic
reaction, partial replacement of Portland cement with fly ash results in a release of heat
over a longer period of time. Therefore, the concrete temperature remains lower because
heat is dissipated as it is produced (Joshi and Lohtia, 1997). It has been estimated that the
contribution of fly ash to early age heat generation ranges from 15-30% of that of an
equivalent mass of Portland cement (Berry and Malhotra, 1986). Although most low
calcium fly ashes (Class F) will reduce the rate of temperature rise when used as Portland
cement replacement, high calcium fly ashes (Class C) do not always cause reduced heat
evolution because of their self cementitious properties (Joshi and Lohtia, 1997). In
general, the rate of heat evolution parallels the rate of strength development. Some high
calcium ashes react very rapidly with water, generating excessive heat rather then
reducing the heat of hydration (Berry and Malhotra, 1986). Temperature rise in concrete
depends upon the following factors: rate of heat generated by hydration and pozzolanic
reactions, rate of heat loss and the thermal properties of the concrete and surrounding
environment, and the size of the concrete member (Joshi and Lohtia, 1997).
When HVFA concrete is used, a substantial reduction in maximum temperature results,
allowing large sections to be cast without exceeding a maximum temperature differential
of 40o C (Bremner and Thomas, 2004). For example, in a large concrete block made with
HVFA, the maximum temperature reached in the middle of the block was 54o C. In this
case the concrete placement temperature was 19o C, resulting in only a 35o C differential
between the interior and exterior of the concrete block. The same size block was also cast
using only ASTM Type I Portland cement. The maximum temperature reached in the
middle of this block was 83o C. In this particular case the concrete placement temperature
was 18o C, resulting in a temperature differential of 65o C between the interior and
exterior of the concrete block. In this example, the total amount of cementitious material
by weight was the same for the two blocks (Malhotra and Mehta, 2002).
12
2.2.4 Strength
Both the strength at a given age and the rate of strength gain of fly ash concrete are
affected by the characteristics of the fly ash (properties, chemical composition, particle
size, reactivity), the cement with which it is used, the proportions of each used in the
concrete, the temperature and other curing conditions, as well as the presence of other
additives (Hobbs, 1983; Berry and Malhotra, 1986; ACI Committee 232, 2003).
Although concrete mixtures containing fly ash tend to gain strength at a slower rate than
concrete without fly ash, the long-term strength is usually higher (Bremner and Thomas,
2004). After the rate of strength gain of hydraulic cement slows, the continued pozzolanic
activity of fly ash provides strength gain at later ages if the concrete is kept moist;
therefore, concrete containing fly ash with equivalent or lower strength at early ages may
have equivalent or higher strength at later ages than concrete without fly ash as long as
the concrete is moist cured or exposed to sufficient quantities of moisture during service.
The strength gain will continue with time and results in higher later-age strength than can
be achieved by using additional cement (Berry and Malhotra, 1986; ACI Committee 232,
2003). However, by using accelerators, activators, water reducers, or by changing the
mixture proportions, equivalent 3 or 7-day strength may be achieved (ACI Committee
232, 2003). High calcium fly ashes (Class C) will show a more rapid strength gain at
early ages than concrete made with a lower calcium fly ash (Class F) because Class C
ashes often exhibit a higher rate of reaction at early ages than Class F ashes (Bremner and
Thomas, 2004; Smith et al., 1982; ACI Committee 232, 2003). However, Class F ashes
will contribute to greater long-term strength gain of concrete than Class C ashes in spite
of its slower rate of strength development at early age. Because of its fineness and
pozzolanic activity, fly ash in concrete improves the quality of cement paste and the
microstructure of the transition zone between the binder matrix and the aggregate. As a
result of the continual process of pore refinement, due to the inclusion of fly ash
hydration products in concrete, a gain in strength development with curing is achieved
(Joshi and Lohtia, 1997). It should be noted that elevated temperature curing is very
beneficial to early strength and subsequent future strength gain of fly ash concrete
because of the higher activation energy required for pozzolanic reactions (ACI
Committee 232, 2003).
13
With respect to HVFA concrete, there is concern within the industry that the low early
strength is a potential problem. However, many studies have been conducted regarding
this issue and the findings are positive. Siddique (2003) reports that replacement of
cement with 40%, 45%, and 50% fly ash content reduces the compressive strength of
concrete at 28 days, but there is a continuous and significant improvement of strength
beyond 28 days when compared to conventional Portland cement concrete. He also states
that the strength of concrete with 40%, 45%, and 50% fly ash content, even at 28 days is
sufficient for use in reinforced concrete construction (Siddique, 2003).
CANMET has performed studies to investigate the typical strength development of high
volume fly ash concrete and have shown one-day strengths of approximately 8 MPa, 28day strength of approximately 35 MPa, and 91-day strengths of approximately 45 MPa.
However, it must be noted that strength values will differ depending on the materials and
proportions used. CANMET also reports that HVFA concrete can be used for high
strength concrete applications since field studies have been conducted on HVFA concrete
and strengths ranged from 35 to 50 MPa at 28 days, and from 50 to 70 MPa at 90 days
(Bilodeau et al., 2001; Langley and Leaman, 1998).
EcoSmarts various case studies have also resulted in positive information regarding
early age strength of HVFA concrete. In general, they report experience from field
mixtures that HVFA concrete demonstrates enough strength development to produce
adequate strength at one day. They report one day strength of 10 MPa, which is
consistent with the findings of CANMET. EcoSmart also found that some concrete mixes
containing fly ash developed lower strengths at 3 and 7 days of age, but achieved higher
ultimate strengths when properly cured (Gillies, 2001). It is well accepted amongst
researchers that in order for HVFA concrete to achieve equivalent or higher ultimate
strengths than conventional Portland cement concrete, adequate extended moist curing is
necessary.
14
2.2.5 Permeability
Permeability is the most important aspect of concrete durability. To be durable, concrete
must be relatively impervious (Berry and Malhotra, 1986). In general, lower permeability
means greater durability (Joshi and Lohtia, 1997). Permeability of concrete is governed
by many factors such as the amount of cementitious material, water content, aggregate
grading, consolidation, and curing. Through its pozzolanic properties, fly ash chemically
reacts with Ca(OH)2 and water to produce C-S-H gel (ACI Committee 232, 2003). The
Ca(OH)2 is consumed in the pozzolanic reaction and is converted into a water-insoluble
hydration product (Joshi and Lohtia, 1997). This reaction reduces the risk of leaching
Ca(OH)2 (Ca(OH)2 is water soluble and may leach out of hardened concrete) (ACI
Committee 232, 2003). The incorporation of fly ash can result in considerable pore
refinement (Joshi and Lohtia, 1997). The transformation of large pores to fine pores, as a
result of the pozzolanic reaction between Portland cement paste and fly ash, substantially
reduces permeability in cementitious systems (Manmohan and Mehta, 1981). The
reduced permeability of fly ash concrete can decrease the rate of ingress of water,
corrosive chemicals, and oxygen (ACI Committee 232, 2003). This leads to enhanced
durability because aggressive agents cannot attack the concrete nor the reinforcing steel
embedded in it (Bremner and Thomas, 2004). The permeability of concrete is directly
related to the quantity of hydrated cementitious material. After 28 days of curing, at
which time little pozzolanic activity would have occurred, fly ash concretes are more
permeable than ordinary Portland cement concretes. However, after 6 months of curing,
fly ash concretes are much less permeable than ordinary Portland cement concretes due to
the slow pozzolanic reaction of fly ash (Davis, 1954; Berry and Malhotra, 1986; Joshi
and Lohtia, 1997).
The permeability of HFVA concrete is very low. The estimated permeability (hydraulic
conductivity) of HVFA concrete is less than 10-13 m/s. As a comparison, normal Portland
cement concrete with a W/C of 0.40, would have an estimated permeability of 10-12 m/s
(Malhotra and Mehta, 2002). In general, the resistance of a reinforced concrete structure
to corrosion, alkali aggregate expansion, sulfate and other forms of chemical attack
depends on the water tightness of the concrete. HVFA concrete when properly cured is
15
able to provide excellent water-tightness and durability (Mehta, 2004). The use of fly ash
in concrete decreases the required water and this combined with the production of
additional cementitious compounds leads to a low porosity and discontinuous pore
structure which reduces the permeability of the concrete (Estakhri and Saylak, 2004;
Malhotra and Mehta, 2002). It is worth re-emphasizing that the permeability of HVFA
concrete is greatly influenced by curing.
2.2.5.1 Relationship between Electrical Conductivity and Permeability

One test that indirectly measures permeability involves the movement of electrical charge
through concrete. The rapid chloride permeability test or RCPT (ASTM C1202
Standard Test Method for Electrical Indication of Concretes Ability to Resist Chloride
Ion Penetration) involves the application of a voltage between two sides of a 100-mm
diameter x 50-mm thick slice of concrete with solutions of sodium hydroxide and sodium
chloride on opposite sides. The total charge passed during a six-hour period provides an
indirect measure of permeability. For concrete with W/CM between 0.4 and 0.75, results
from the RCPT correlate well with permeability and total porosity as can be seen from
the figure below.
RCPT actually measures the electrical charge passing through a specimen. Low
permeability concretes exhibit a nearly constant current during the six hour test, whereas
high permeability concrete can exhibit increasing current, due to heating, which results in
increased conductivity (Mindess et al., 2003).
16
Hydraulic Permeability (u Darcys)
10
0.1
0.01
2000
4000
6000
8000
Rapid Chloride Permeability (Coulombs)
Figure 2.1 Relationship between Results of Hydraulic Permeability Tests and Rapid
Chloride Penetration Tests (RCPT) [From D. Whiting in Permeability of Concrete,
SP-108, American Concrete Institute, Detroit, MI, pp. 195-222 (1988).]
2.2.6Carbonation
2.2.6.1 Mechanisms of Carbonation
Carbonation or neutralization is the process whereby calcium hydroxide in hydrated
Portland cement paste reacts in moist conditions with carbon dioxide from the
atmosphere to form calcium carbonate (Berry and Malhotra, 1986). As carbonation
proceeds, the remaining cement hydration products consisting of hydrated calcium
silicates, aluminates and ferrities, or related complex hydrated salts, are attacked and
decomposed with the ultimate formation of calcium carbonate and hydrated silica,
alumina and ferric oxide, and hydrates calcium sulfate (Roberts, 1981). Carbonation in
concrete may result in the following deleterious consequences: increased permeability
(under some circumstances), increased shrinkage and cracking, and the reduction of the
passive layer which protects reinforcing steel from corrosion (Berry and Malhotra, 1986).
It is fairly well known and accepted amongst researchers that carbonation depth increases
as: compaction decreases, permeability increases, strength decreases, W/CM increases,
17
cement content decreases, and fly ash content increases (Gebauer, 1982; Berry and
Malhotra, 1986; Roberts, 1981).
2.2.6.2 Factors Influencing the Rate of Carbonation

The rate at which concrete carbonates is a function of the following factors: level of
compaction, carbon dioxide concentration/level, period of moist curing, permeability,
ambient temperature and humidity conditions, mix proportions, degree of saturation
(moisture content), and the mass of calcium hydroxide available for reaction (Berry and
Malhotra, 1986; Joshi and Lohtia, 1997; Parrott, 1987; Roberts, 1981). The main factor
that can be used to limit the rate of carbonation is W/CM. In general a reduction in
W/CM greatly reduces the measured depth of carbonation (Parrott, 1987). Slow reacting
systems such as those with fly ash benefit more from prolonged moist curing because the
cement in the surface layers of drying concrete will virtually stop hydrating if the internal
relative humidity drops to about 80%. This results in a high porosity and a high
permeability in the surface layers and increases the rate of carbon dioxide diffusion
(Parrott, 1987). It has been suggested by some researchers however that little or no
further reduction in carbonation is achieved by increasing the curing period beyond 7
days (Thomas and Matthews, 1992; Ho, 1987; Nagataki, 1986). Concretes containing fly
ash, carbonate to a similar or slightly higher degree compared with ordinary Portland
cement concrete of the same strength grade, even when the concretes are poorly cured
(Roberts, 1981; Thomas and Matthews, 1992; Matthews, 1984; Hobbs, 1988;
Lewandowski, 1983; Tsukayama, 1980; Dhir, 1989). In lower grade concretes or when
concretes are subjected to high levels of carbon dioxide, there is evidence that
carbonation of fly ash concrete is greater than carbonation of ordinary Portland cement
concrete (Thomas and Matthews, 1992; Gebauer, 1982; Ho, 1987). Concrete containing
50% fly ash, carbonates at a significantly higher rate than ordinary Portland cement
concrete of equal strength grade, however the rate of carbonation decreases by extending
the initial period of moist curing or by increasing the design strength (Thomas and
Matthews, 1992). With relative humidity in the region of 25% there is a lack of free water
available for the carbonation reaction. However, the presence of a large amount of water
will also hinder the reaction of carbon dioxide with hydrated cement compounds by
18
reducing or preventing entry of the carbon dioxide into the concrete, and as a result no
carbonation is generally found in concrete kept completely saturated or exposed to 100%
relative humidity. There is general agreement that the depth of carbonation reaches a
maximum at a relative humidity between 50 and 75%. (Parrott, 1987; Roberts, 1981). An
increase in temperature increases the rate of reaction of carbon dioxide and hydrated
cement compounds but it also promotes drying, therefore depending on the degree of
drying, elevated temperatures could increase or decrease the rate of carbonation (Parrott,
1987; Roberts, 1981). Protective coatings should limit carbonation by limiting water and
carbon dioxide diffusion, however the performance of coatings tends to be variable
(Parrott, 1987). The rate of carbonation decreases with increasing time of exposure to air,
and for concrete kept continuously dry at normal relative humiditys it appears that the
depth of carbonation is approximately proportional to the square root of the time of
exposure (Roberts, 1981).
2.2.6.3 Conditions that Promote Carbonation Induced Corrosion of

Steel
Although corrosion of reinforcing steel due to carbonation does not appear to be a
problem in North America today, if high levels of fly ash are used in general concreting
work without using a lower W/CM and extending the initial moist curing period,
problems due to carbonation induced corrosion will eventually become a reality (Thomas,
2003).
The high pH of concrete is due to the presence of alkali hydroxides in the pore solution,
which typically produces a pH of 13.0, and an abundance of solid calcium hydroxide
Ca(OH)2, which acts as a buffer to maintain a high pH even in the absence of the alkalis;
saturated calcium hydroxide solution has a pH of 12.45. Carbon dioxide from the
atmosphere can penetrate into concrete and react chemically with the alkali and calcium
hydroxides to produce carbonates. This process, carbonation, results in a significant
reduction in the pH of the concrete because carbonated concrete has a pH less then 9.0. If
the process of carbonation, which begins at the surface of concrete exposed to the
atmosphere, penetrates through the concrete cover to the steel, the pH in the vicinity of
19
the steel will drop enough to destroy the passive layer, at which point corrosion of the
metal will commence (Thomas, 2004; Parrott, 1987). The reduction of pore fluid
alkalinity that accompanies carbonation can lead to corrosion of reinforcing steel,
cracking of concrete cover and eventual spalling; resulting in the need for difficult and
expensive repairs (Parrott, 1987; Roberts, 1981). There are several conditions that
promote carbonation induced corrosion of steel:
Exposure Carbonation induced corrosion is most prevalent in environments

where there is not enough moisture to prevent carbon dioxide diffusion but there
is sufficient moisture to sustain corrosion. This condition most commonly occurs
on the underside of balconies and bridge decks, or locations where the concrete is
exposed to the environmental relative humidity, however is protected from direct
precipitation.
High W/CM The permeability of concrete will be increased and hence its
propensity for greater depth of carbonation (Roberts, 1981).
Poor curing Permeability will also be increased by inadequate curing because
inadequate curing results in the incomplete hydration of cement (Roberts, 1981).
Low cover Protection of reinforcement from carbonation induced corrosion can
be achieved by selecting an adequate concrete cover so that carbonation will not
reach the bar surface within the expected lifetime of the structure (Papadakis et
al., 1991).
Pozzolans - As the permeability of the concrete is reduced by the addition of fly
ash, you would expect it to become harder for CO2 to penetrate the concrete.
However, fly ash reduces permeability by reacting with Ca(OH)2. This reaction
reduces the amount of material available for reaction with CO2. Thus less CO2 has
to penetrate to neutralize the concrete.
20
3.0 Laboratory Research

3.1 Methodology
Concrete samples were produced at a range of different supplementary cementing
materials (SCM) contents using fly ashes from various sources across North America.
For this project, specimens were produced such that the Portland cement was replaced
with 30, 40, 50% fly ash. Fly ash samples were selected to represent the very broad range
of compositions that exist. Concrete was produced to represent the wide range of W/CM
used in practice, but emphasis was placed on concrete of low to moderate W/CM (e.g. 0.3
to 0.5) typical of that used in commercial, industrial, and transportation structures. The
variables used for curing included: duration of moist curing, ambient temperature and
relative humidity after termination of moist curing, and type and application rate of the
curing membrane system.
Although a range of fresh and hardened concrete properties were evaluated, the focus of
this study was the effect of curing on: strength development, chloride resistance, and
carbonation. With exception of carbonation, these properties were determined using
standard tests. Three different environments were used for carbonation testing; these
were: accelerated carbonation using a carbon dioxide enriched environment
(approximately 1% CO2 by volume) and optimum moisture conditions (65% RH), indoor
carbonation at 23oC and 55% relative humidity, and outdoor carbonation protected from
direct precipitation. The depth of carbonation was determined at specific times using
phenolphthalein indicator sprayed onto freshly fractured surfaces.
3.2 Materials & Mixture Proportions

3.2.1 Cement
The Portland cement used met the requirements of CSA A3001-03 Type GU and ASTM
C150 Type I. Its chemical and physical properties are given in Table 3.1.
21
Table 3.1 Chemical Analysis & Physical Properties of Portland Cement
Portland Cement
Chemical Analysis, %
Silicon dioxide (SiO2)
Aluminum oxide (Al2O3)
Ferric oxide (Fe2O3)
Calcium oxide (CaO)
Magnesium oxide (MgO)
Sodium oxide (Na2O)
Potassium oxide (K2O)
Phosphorous oxide (P2O5)
Titanium oxide (TiO2)
Sulphur trioxide (SO3)
Loss on ignition (LOI)
Equivalent alkali (Na2Oe
20.56
4.34
3.05
63.92
2.37
0.23
0.82
0.13
0.21
3.35
1.32
0.77
Bogue Potential Compound Composition, %

Tricalcium silicate (C3S)
Dicalcium silicate (C2S)
Tricalcium aluminate (C3A)
Tetracalcium aluminoferrite (C4AF)
60.8
13.2
6.3
9.3
Physical Properties
Fineness
325 Passing, %
specific surface, Blaine, m2/kg
97
363
3.2.2 Fly Ash

For the project five different fly ashes were used: SD, TB, BR, CM, and RP. As can be
seen in Table 3.2, fly ashes were chosen to represent the wide range of fly ash
compositions available.
22
Table 3.2 Chemical Analysis & Physical Properties of Fly Ashes

Chemical Analysis, %
Silicon dioxide (SiO2)
Aluminum oxide (Al2O3)
Ferric oxide (Fe2O3)
Calcium oxide (CaO)
Magnesium oxide (MgO)
Sodium oxide (Na2O)
Potassium oxide (K2O)
Phosphorous oxide (P2O5)
Titanium oxide (TiO2)
Sulphur trioxide (SO3)
Manganese oxide (Mn2O3)
Strontium oxide (SrO)
Loss on ignition (LOI)
SiO2+Al2O3+Fe2O3
Physical Properties
Fineness
Passing 45 um
(wet), %
SD
TB
BR
CM
RP
54.36
24.13
3.82
10.87
1.10
3.15
0.71
0.10
0.66
0.19
0.06
0.11
0.48
82.31
46.00
19.65
4.99
13.51
3.04
7.08
1.17
0.30
0.74
1.62
0.03
0.41
0.67
70.64
36.94
20.09
6.21
16.69
4.15
7.56
0.85
0.62
1.29
2.96
0.04
0.77
0.40
63.24
33.45
17.97
5.28
29.09
5.34
1.67
0.31
1.17
1.59
2.47
0.05
0.45
0.41
56.70
40.69
21.72
6.08
19.12
4.73
1.55
1.11
1.05
1.50
1.02
0.03
0.30
0.67
68.49
84.37
84.71
90.27
94.03
76.72
According to ASTM C618, SD and TB fly ashes are Class F (SiO2 + Al2O3 + Fe2O3 >
70%), whereas BR, CM, and RP are Class C (SiO2 + Al2O3 + Fe2O3 > 50%). The
Canadian standard CSA A3001 recognizes, SD, TB, BR, and RP as Type CI ashes (CaO
between 8-20%), whereas CM is a Type CH (CaO > 20%). TB and BR fly ashes are
characterized by high alkali contents. All fly ashes meet the requirements of CSA A300103 and ASTM C618.
3.2.3 Aggregate
The coarse aggregate used was a crushed coarse aggregate from McGundy Quarry with a
maximum nominal size of 19 mm. The fine aggregate used was Zeeland sand. Both the
coarse and fine aggregate was from local sources in the Fredericton region. The coarse
aggregate had a specific gravity of 2.68 and a water absorption value of 0.81%. The fine
aggregate had a specific gravity of 2.60 and a water absorption value of 1.32%. Both
aggregates meet the requirements of CSA A23.1-04.
23
3.2.4 Admixtures
A normal-range and high-range water reducing admixture were used in varying
proportions to achieve a target slump in the range of 100mm. The water reducing
admixture used was a normal-range water reducer that meets ASTM C-494 requirements
for a Type A water reducer. The superplasticizer that was used for this project meets the
requirements of ASTM C494 for a Type F, high-range water reducer.
3.2.5 Curing Compounds

For this project, the effect of three different curing compounds on concrete carbonation
was investigated. The three curing compounds selected were: CC1 (ASTM C309, Type
1, Class B); CC2 (ASTM C309, Type 2, Class B) and CC3 (ASTM C309, Type 1, Class
B). ASTM C309 characterizes the type of liquid membrane forming compound as: Type
1 is clear or translucent without dye, whereas Type 2 has a white pigment. The solids
dissolved in the vehicle indicates a curing compounds class. Class B indicates the solids
dissolved must be a resin.
3.2.6 Mixture Proportions

The proportions of the concrete mixtures are outlined in Table 3.3. All aggregates are
listed in a saturated surface dry condition (SSD).
3.3 Preparation, Casting, Curing, & Testing of Specimens

3.3.1 Preparation
The concrete was mixed in a laboratory counter-current mixer for a total of five minutes.
The coarse aggregate, Portland cement, fly ash, and fine aggregate were added to the
mixer, in that order, and the mixer was switched on. After one minute of dry mixing, the
water was added to the mixer over a period of another minute. Once the water was added,
the contents in the mixer were allowed to mix for another minute. The mixer was then
switched off for one minute. After this rest period, the mixer was again switched on
and superplasticizer was added if needed. Once the superplasticizer was added the mixer
was allowed to mix for another minute and then the concrete was discharged.
Table 3.3 Mixture Proportions

Mix
No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
CC
FA Type
FA Content,
% by wt. of
CM
0
30
SD
40
50
CM
BR
TB
RP
SD
50
50
50
50
50
W/
(C+FA)
Water
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.50
0.50
0.50
0.50
170
160
158
170
160
153
170
160
153
170
160
153
170
170
170
170
170
Quantities, kg/m3
SSD
Cement
FA
Fine
340
0
758
400
0
716
465
0
692
238
102
709
280
120
658
315
135
629
204
136
680
240
160
639
270
180
612
170
170
710
200
200
621
225
225
589
170
170
659
170
170
659
170
170
659
170
170
659
170
170
666
SSD
Coarse
1111
1109
1106
1110
1108
1109
1110
1110
1108
1080
1108
1108
1108
1108
1111
1111
1109
Water Reducer,
mL/m3
Super-P
mL/m3
Date Cast
850
1200
1755
648
1000
1755
0
0
1755
0
0
1755
0
0
0
0
0
850
1429
5714
0
0
762
0
952
762
0
500
476
0
0
0
0
0
Feb. 3/04
Feb. 24/04
May 18/04
Feb. 10/04
May 5/04
May 20/04
Feb. 12/04
May 6/04
May 25/04
Feb. 19/04
May 11/04
May 27/04
Oct. 19/04
Oct. 19/04
Oct. 21/04
Oct. 21/04
Dec. 9/04
Note: All measured slumps were 100-150 mm.
24
25
The only fresh property of the concrete that was determined was the slump. The slump
test was performed according to ASTM C143 and the target slump for all mixes was
approximately 100 mm. Water reducer and superplasticizer were added to the concrete
mixture in order to achieve the desired slump.
3.3.2 Casting
Specimens for the project were cast in three phases:
Phase 1 Twelve mixtures were produced which included three 0% fly ash mixes, three
30% fly ash mixes, three 40% fly ash mixes, and three 50% fly ash mixes. All mixes in
Phase 1 used SD fly ash. For each of the mixes in Phase 1, thirty-nine 100 mm x 200 mm
concrete cylinders were produced. Twenty-two of the cylinders were used for
compressive strength determination and the other seventeen cylinders were used for rapid
chloride permeability testing. Five 50 mm x 50 mm x 300 mm prisms (small prisms)
were cast for accelerated carbonation determination. Also, ten 75 mm x 75 mm x 300 mm
prisms (large prisms) were cast, five for indoor carbonation and five for outdoor
carbonation determination. All cylinders and prisms were cast according to ASTM C 192
/ C 192M-98.
Phase 2 Four mixtures were produced, each mixture using a different fly ash, CM, BR,
TB, or RP. All mixes in Phase 2 had a W/CM of 0.50 and a fly ash replacement level of
50%. For each of the mixes in Phase 2, five 100 mm x 200 mm cylinders were produced.
Two cylinders were used to determine compressive strength and the other three were
used for rapid chloride permeability testing. Five 50 mm x 50 mm x 300 mm prisms
(small prisms) were cast for accelerated carbonation determination. Also, five 75 mm x
75 mm x 300 mm prisms were cast for outdoor carbonation determination. Again, all
cylinders and prisms were cast according to ASTM C 192 / C 192M-98.
Phase 3 One mix was produced having a W/CM of 0.50 and SD fly ash with a
replacement level of 50%. The specimens from Phase 3 were used to determine the
effects of different curing compounds on concrete carbonation. Eight 50 mm x 50 mm x
300 mm prisms (small prisms) were produced for accelerated carbonation testing and
26
eight 75 mm x 75 mm x 300 mm prisms (large prisms) were produced for outdoor
carbonation determination. All cylinders and prisms were produced according to ASTM
C 192 / C 192M-98.
3.3.3 Curing
Curing of concrete specimens was different for each of the Phases, as described below.
Table 3.4 Phase 1 Curing Regimes

Property
Strength & RCPT
Accelerated
Carbonation
Normal Carbonation
Subsequent
Exposure
Continuously moist-cured until test
Laboratory air
drying until test at
28 days
1,3,7,14 or 28 days
Laboratory air
curing
drying until 35 days
and then placed in
outdoor exposure
until tested
Laboratory air dry
until 35 days and
1,3,7,14 or 28 days
then placed in
curing
chamber at 23oC,
65% RH with 1%
CO2 until tested
Laboratory air
drying until 35 days.
Indoor carbonation:
specimens remain in
laboratory air until
1,3,7,14 or 28 days
test. Outdoor
curing
carbonation:
specimens stored
outdoors under
cover from direct
precipitation
Curing
Testing
Test at 28 days, 90
days (RCPT only),
and 1 year
Test after
7,14,28,56, and 90
days in CO2
chamber
Test at 90 days and

1 year
Phase 2 Concrete prisms for carbonation testing were cured for 1, 3, 7, 14, and 28 days.
After each curing duration, one small prism (50mm x 50mm x 300mm) and one large
prism (75mm x 75mm x 300mm) was removed from the water tank and placed in the
27
laboratory to air dry. At 35 days of age, the large concrete prisms (75mm x 75mm x
300mm) were placed in an outdoor exposure condition, covered from direct precipitation
and the smaller prisms (50mm x 50mm x 300mm) were placed in the accelerated
carbonation chamber. In Phase 2, the concrete cylinders for compressive strength and
rapid chloride permeability testing were continuously moist cured until testing.
Phase 3 Concrete was only moist cured for 1 day, under wet burlap and plastic. After
this time, the concrete prisms were treated with curing compounds as follows:
2 small prisms (50mm x 50mm x 300mm) and 2 large prisms (75mm x 75mm x
300mm) were left untreated for controls.
1 small prism (50mm x 50mm x 300mm) and 1 large prism (75mm x 75mm x
300mm) were given 1 application of each of the three curing compounds.
1 small prism (50mm x 50mm x 300mm) and 1 large prism (75mm x 75mm x
300mm) were given 2 applications of each of the three curing compounds.
Each application of curing compound consisted of spraying the concrete specimen with
the curing compound and then brushing the sprayed curing compound until the surface of
the specimen was completely covered. After the application of the curing compounds, all
prisms were placed in the laboratory for 35 days to air dry. After this time, the large
prisms (75mm x 75mm x 300mm) were placed in the outdoor exposure site, covered
from direct precipitation, and the small prisms (50mm x 50mm x 300mm) were placed in
the accelerated carbonation chamber.
The following is a description of the curing conditions and exposure conditions
mentioned above:
Moist Curing: All specimens were cured for 1 day in the moulds under wet burlap and
sacking. After stripping at 24 hours specimens were either provided with no further
curing or were stored in lime water for an additional period of 2, 6, 13, or 27 days. This
provided total moist curing periods of 1, 3, 7, 14, and 28 days. A limited number of
specimens remained in water storage until test (i.e. continuous curing).
Air-Storage: After curing specimens were allowed to air dry in the laboratory.
Accelerated Carbonation: Accelerated carbonation chamber, where the concentration of
CO2 was maintained at approximately 1% by volume using flow meters and tanks of
28
compressed gas and CO2. The chamber was located within a temperature-controlled
laboratory where the temperature of the laboratory and chamber was 23oC. Relative
humidity within the chamber was maintained at 65% with a saturated sodium bromide
salt. Accelerated carbonation set-up is demonstrated in Figures 3.1 and 3.2.
Figure 3.1 Sketch of Accelerated Carbonation Setup
29
Figure 3.2 Accelerated Carbonation Chamber

Indoor Carbonation: Stored in laboratory air.
Outdoor Carbonation: Specimens were stored on a shelving unit that was covered with
plastic sheeting. Specimens were protected from direct precipitation but were exposed to
typical temperatures and relative humiditys in the Fredericton region (see Figure 3.3).
The outdoor carbonation conditions were chosen because it represents conditions most
likely to lead to carbonation-induced corrosion. CO2 penetrates very slowly when the
concrete pores are filled with water and therefore the rate of penetration increases as the
relative humidity decreases. However, the chemical reaction of CO2 with Ca(OH)2
requires that the CO2 first dissolve in water to form carbonic acid, which cannot occur if
there is insufficient water in the pores. Thus, the worst-case condition for the process of
carbonation is generally considered to be at a relative humidity in the range of 55 to 65%.
However, under these conditions, there is insufficient moisture available to sustain the
corrosion process when the carbonation front reaches the steel.
30
Figure 3.3 Outdoor Exposure Condition

Thomas and Matthews (2000) have argued that the worst case for carbonation induced
corrosion is in concrete that is externally exposed but protected from direct precipitation.
For externally exposed but protected specimens, there is not enough moisture in the pores
to completely block CO2 but there is enough moisture to support corrosion of steel once
initiated. These conditions exist on the underside of balconies, ledges, bridge decks, and
leeward sides of buildings that dont receive frequent direct exposure to rain.
3.3.4 Testing
For this project, essentially four tests were conducted, compressive strength, rapid
chloride permeability, electrical resistivity, and carbonation. Compressive strength testing
was conducted according to ASTM C39, with the exception that the cylinders were tested
dry rather then saturated as stated in the standard. It is widely reported that testing
concrete cylinders dry will yield a compressive strength approximately 10 to 15% higher
compared with the same concrete tested saturated. All rapid chloride permeability testing
was conducted according to ASTM C1202. In some cases the test had to be terminated
early due to excessive charge passing and subsequent temperature increase. The 6-hour
charge was then estimated by extrapolating the data at termination. Since there is no
31
standard for determining carbonation penetration in concrete, the method employed for
this project was described by Roberts (1981). This method involves spraying
phenolphthalein indicator solution (colorless to purple red in highly alkaline solution)
onto a freshly fractured concrete surface and measuring the depth of carbonation (see
Figures 3.4 and 3.5). A purple red coloration is obtained almost immediately in the
unaffected interior of the sample where the concrete is still highly alkaline owing to the
presence of calcium hydroxide and alkali hydroxides, and no coloration is observed in the
outermost surface layer where the alkalinity of the concrete has become reduced by
penetration of atmospheric carbon dioxide (Roberts, 1981). The depth of the uncolored
zone is measured in several locations and averaged to obtain an approximate depth of
carbonation.
Figure 3.4 Equipment Used to Obtain Freshly Fractured Concrete
32
Figure 3.5 Freshly Fractured Concrete Sprayed with Phenolphthalein Indicator

Solution
There is also no standard for determining electrical resistivity of concrete. The electrical
resistivity of the concrete was determined using the same test apparatus as described in
ASTM C1202 but using a power source that provided a constant alternating current of
100 A. With 100 A passing through the sample, the voltage (V) was measured. By
using Ohms Law (V=IR), the resistance (R) of the concrete was calculated. Knowing the
resistance of the concrete (R), the cross sectional area (A), and the length of the specimen
being tested (L), resistivity () was calculated using the equation = RA/L.
Phase 1 Compressive strength testing of the differently cured concrete cylinders
occurred at 28 and 365 days of age. Rapid chloride permeability testing and electrical
resistivity of the differently cured concrete cylinders occurred at 28, 90, and 365 days of
age. Carbonation testing of the differently cured concrete prisms, both indoor and outdoor
occurred at 90 and 365 days of age. Carbonation testing of the small prisms in the
accelerated carbonation chamber occurred at 7, 14, 28, 56, and 90 days after the prisms
were placed in the accelerated chamber.
33
Phase 2 - Compressive strength testing of the continuously moist cured concrete cylinders
occurred at 28 days of age. Rapid chloride permeability testing and electrical resistivity
of the continuously cured concrete cylinders occurred at 28 and 90 days of age.
Carbonation testing of the differently cured concrete prisms in the outdoor exposure site
occurred at 90 days and 1 year of age. Carbonation testing of the small prisms in the
accelerated carbonation chamber occurred at 7, 14, 28, 56, and 90 days after the prisms
were placed in the accelerated chamber.
Phase 3 - Carbonation testing of the concrete prisms containing different applications of
curing compounds in the outdoor exposure site occurred at 90 days of age. Carbonation
testing of the small prisms in the accelerated carbonation chamber occurred at 7, 14, 28,
56, and 90 days after the prisms were placed in the accelerated chamber.
Phase 4 - Testing will continue beyond this thesis. Long term carbonation measurements,
for indoor and outdoor exposure conditions will be tested at 2, 5, and 10 years.
34
4.0 Summary of Results

4.1 Compressive Strength
Compressive strength results are summarized below in Table 4.1.
Compressive strength is the most widely tested property of hardened concrete. As can be
seen from Figures 4.1, 4.2, and 4.3, at 28 days of age for all three W/CM, concrete
containing no fly ash yielded higher strengths then the concrete containing fly ash. Also,
as the fly ash replacement level increased the compressive strength of the concrete
decreased. The reason the fly ash concrete has a lower compressive strength then the
concrete containing no fly ash is because of the slow pozzolanic reaction that fly ash
experiences. As expected with any concrete, as the W/CM decreases the compressive
strength of the concrete increases. This statement is also true for concrete containing
various levels of fly ash. From Figures 4.1, 4.2, and 4.3, it appears as though moist
curing concrete for 14 days would yield the highest compressive strength and that moist
curing for 28 days actually decreases the compressive strength from the 14-day value. For
this project concrete cylinders that were moist cured for 1, 3, 7, and 14 days were tested
for compressive strength at 28 days in a dry state and the 28-day moist cured samples
were tested saturated according to the procedure outlined in ASTM C39. It is well known
that concrete cylinders tested dry will yield a compressive strength 10-15% higher then
concrete tested saturated. Therefore, if the 28-day moist cure specimens were tested dry,
as were the other moist cured duration specimens, the 28-day moist cured sample would
have yielded the highest compressive strength. Figure 4.4 shows 28-day compressive
strengths for concrete made with each of the five different fly ashes. These specimens
were cast with a W/CM = 0.50, fly ash level of 50%, were continuously moist cured, and
tested saturated according to ASTM C39. BR fly ash yielded the highest compressive
strength of 26.0 MPa, whereas RP yielded the lowest compressive strength of 19.0 MPa.
Table 4.1 Compressive Strength Data

Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
FA Content, % by wt. of CM
W / (C+FA)
50
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
1
40.3
44.3
55.5
26.6
31.4
37.0
19.1
29.4
30.4
14.6
26.6
22.0
-
50
50
50
0.50
0.50
0.50
30
40
50
28 Day Strength, MPa

Curing, days
3
7
14
33.7
44.3
46.0
49.1
53.3
54.0
61.8
67.0
67.7
28.0
34.4
35.1
42.1
47.1
40.4
49.3
50.9
53.4
27.2
29.5
30.8
37.3
40.3
42.6
44.8
48.5
53.6
21.2
23.4
27.3
30.5
34.3
38.4
38.1
44.6
46.1
-
28
38.8
48.0
60.5
29.5
36.8
47.1
26.3
39.2
48.5
21.7
36.3
45.9
22.0
1
39.3
47.2
55.8
14.3
32.7
40.2
24.2
34.8
32.9
16.9
28.0
34.1
-
26.0
23.7
19.0
1 Year Strength, MPa

Curing, days
3
7
14
28
46.2
43.0
48.6
52.0
49.8
54.0
54.0
54.3
61.7
68.3
69.3
67.7
30.8
36.7
36.5
38.0
35.6
43.9
46.1
48.5
41.3
45.4
41.8
57.1
30.8
32.1
34.9
35.9
40.9
42.5
43.0
48.8
43.7
49.9
52.0
55.1
23.0
24.7
28.5
33.3
30.5
35.9
37.6
43.4
47.8
51.6
43.9
54.2
-
365
49.2
58.1
68.5
49.0
61.8
62.8
51.8
50.3
69.1
50.1
54.2
63.8
-
35
36
70.0
28 Day Compressive Strength (MPa)
60.0
50.0
40.0
fly ash 0%
30.0
fly ash 30%

fly ash 40%
fly ash 50%
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.1 Curing vs. 28 Day Compressive Strength (W/CM=0.50)

70.0
60.0
50.0
40.0
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
30.0
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
Curing (days)
37
70.0
60.0
50.0
40.0
fly ash 0%
30.0
fly ash 30%

fly ash 40%
fly ash 50%
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
Curing (days)
30.0
Compressive Strength (MPa)
25.0
20.0
15.0
10.0
5.0
0.0
CM
BR
TB
RP
SD
28 Day Continuous Moist Cure
Figure 4.4 Compressive Strength of Different Fly Ashes Continuously Moist Cured
for 28 Days
38
When tested at 1 year of age, compressive strength followed much of the same trends as
it did when it was tested at 28 days of age, however for the most part compressive
strengths at 1 year were higher than at 28 days. Again as the W/CM decreased, the
compressive strength of the concrete increased. Also, concrete containing no fly ash still
had higher compressive strengths then concrete containing fly ash. However, when tested
at 28 days of age, concrete containing fly ash demonstrated clearly that higher levels of
fly ash would yield lower compressive strengths. At 1 year this trend was not as clear.
Although concrete containing 50% fly ash generally yielded the lowest compressive
strength, the concrete containing 30 and 40% fly ash demonstrated similar compressive
strengths. As can be seen from Figures 4.5, 4.6 and 4.7, the longer the duration of moist
curing the higher the compressive strength. Although this trend was not observed at 28
days because of a testing error, the trend is clearly illustrated at 1 year of age. At 1 year
of age all cylinders tested for compressive strength were tested dry.
70.0
1 Year Compressive Strength (MPa)
60.0
50.0
40.0
fly ash 0%
30.0
fly ash 30%

fly ash 40%
fly ash 50%
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
1-year
Curing
Figure 4.5 Curing vs. 1 Year Compressive Strength (W/CM=0.50)
39
70.0
60.0
50.0
40.0
fly ash 0%
30.0
fly ash 30%

fly ash 40%
fly ash 50%
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
1-year
Curing

70.0
60.0
50.0
40.0
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
30.0
20.0
10.0
0.0
1-day
3-day
7-day
14-day
28-day
1-year
Curing
40
Fly ash concretes only achieve comparable strength at 1 year if it is continuously cured.
The long-term strength of HVFA concrete is only realized if the concrete is exposed to
sufficient moisture during service to promote continued hydration and pozzolanic
reaction. In exposed elements protected from direct precipitation, it may take much
longer to achieve strength parity and in interior elements such benefits may never be
realized.
4.2 Rapid Chloride Permeability

Rapid chloride permeability (RCPT) results are summarized below in Table 4.2.
Rapid chloride permeability testing as outlined in ASTM C1202 is a test that measures
electrical conductivity not chloride permeability but there is a reasonable relationship
between these two parameters. Table 4.3 is taken from ASTM C1202 and relates charged
passed in coulombs to chloride ion penetrability.
As can be seen in Figures 4.8, 4.9, and 4.10, all concrete tested at 28 days had a chloride
ion penetrability classified as high by the criteria in ASTM C1202. Although the charge
passed decreased with W/CM, there were no apparent trends with respect to the effect of
moist curing or the effect of fly ash levels on the amount of charge passed. There are
several reasons why clear trends may not have been established. These include: slow /
delayed pozzolanic reaction, and the variable nature of concrete.
Table 4.2 Rapid Chloride Permeability Data
Mix
No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
FA
Content,
% by
wt. of
CM
30
40
50
50
50
50
50
W/
(C+FA)
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.5
0.5
0.5
28 Day RCPT, Coulombs

Curing, days
1
9192
6330
4694
9815
7454
4578
9758
5163
5114
7785
4378
6526
-
3
8752
6005
5425
5974
6056
4409
6699
5787
3939
6272
4829
5089
-
7
6823
6175
4109
6599
6478
4238
5724
4323
3997
6271
4630
5415
-
14
6070
7173
4357
6619
6759
4163
6697
4883
4512
6858
4511
4932
-
28
6967
6158
4930
5887
5487
4695
7871
4557
5326
5535
5376
4995
10314
3405
5011
7478

Curing, days
1
5689
5583
4153
5610
4667
4343
6694
4961
3973
6552
5342
4832
-
3
6493
4907
3112
6599
4386
3764
5254
3738
2427
5879
4526
3228
-
7
6582
5685
4147
6031
3476
3046
5737
3613
2073
6438
4334
3218
-
14
5693
5613
3491
6232
3669
2947
5834
3204
2181
5881
3338
2373
-
28
6300
5387
3625
6468
2982
2216
5415
2098
1754
7318
2225
1605
-

Curing, days
90
6155
5472
4392
4676
2250
1523
4003
1352
1249
4440
1625
1348
6637
1551
1601
4051
1
3327
4977
2545
5692
3029
2026
4498
2799
2510
5510
2555
2962
-
3
3591
3535
2461
4613
2906
1857
3282
3161
1782
6294
2303
672
-
7
3727
3798
2355
3904
2729
1904
5190
2624
1747
6333
2803
2050
-
14
3287
4600
2256
3808
2712
1392
4477
2229
1725
4001
3253
947
-
28
3281
3697
1975
3657
2345
1310
4769
1566
1143
2890
1872
1505
-
365
4387
3293
1955
1165
766
451
620
473
439
284
479
546
-
41
42
Table 4.3 Chloride Ion Penetrability Based on Charge Passed

Charge Passed (coulombs) Chloride Ion Penetrability
>4000
High
2000 - 4000
Moderate
1000 - 2000
Low
100 - 1000
Very Low
<100
Negligible
28 Day Rapid Chloride Permeability (coulombs)
10000
9000
8000
7000
6000
fly ash 0%
fly ash 30%
5000
fly ash 40%

fly ash 50%
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.8 Curing vs. 28 Day Rapid Chloride Permeability (W/CM=0.50)
43
10000
9000
8000
7000
6000
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
5000
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
10000
9000
8000
7000
6000
fly ash 0%
fly ash 30%
5000
fly ash 40%

fly ash 50%
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
44
When tested at 90 days, the effect of moist curing and fly ash replacement levels on the
amount of charge passed became evident. Again, as expected the amount of charge
passed decreased as the W/CM decreased. At W/CM = 0.50, the chloride ion
penetrability was High for all fly ash levels and moist curing durations. There was also
no apparent relationship between moist cure duration and charge passed or fly ash level
and charged passed at this particular W/CM.
8000
7000
6000
5000
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)

At W/CM = 0.40, extended moist curing of the concrete containing no fly ash appeared to
have little effect on the amount of charge passed. The chloride ion penetrability for the
0% fly ash concrete was High. Although there was no apparent relationship between
fly ash replacement level and the amount of charge passed, there was a clear trend that
extended moist curing of fly ash concrete drastically reduces that amount of charge
passing through it. Concrete containing all levels of fly ash (30, 40, 50%) at 1-day moist
45
cure yielded a chloride ion penetrability of High, however, after 90 days of moist curing
yielded a chloride ion penetrability of Low.
8000
7000
6000
5000
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)

0% fly ash concrete was Moderate to High. Again there was no clear relationship
between fly ash replacement level and the amount of charge passed, but there was a trend
demonstrating that extended moist curing of fly ash concrete reduces the amount of
charge passing through it. Concrete containing all levels of fly ash (30, 40, 50%) at 1-day
moist cure yielded a chloride ion penetrability of High, however after 90 days of moist
curing the same concrete yielded a chloride ion penetrability of Low.
46
8000
7000
6000
5000
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
4000
3000
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)

When tested at 1 year, many of the findings reported are similar to those found at 90
days, with the exception that the amount of charge passed at 1 year for all concrete is
lower then at 90 days. Again, as expected the amount of charge passed decreased as the
W/CM decreased. At W/CM = 0.50, the chloride ion penetrability for the concrete
containing no fly ash was Moderate and it appeared as though moist curing had little
effect on the amount of charge passed. The chloride ion penetrability for the concrete
containing fly ash was High for all fly ash levels at 1-day moist cure but Very Low after
1-year moist cure. There was no apparent relationship between fly ash level and charged
passed at this particular W/CM, however moist curing had the greatest effect on the 50%
fly ash concrete. This particular concrete when moist cured for 7 days had a charge
passed of over 6000 coulombs, however, at 1 year moist cured had a charge passed of just
a few hundred coulombs.
47
1 Year Rapid Chloride Permeability (coulombs)
7000
6000
5000
4000
fly ash 0%
3000
fly ash 30%

fly ash 40%
fly ash 50%
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)
Figure 4.14 Curing vs. 1 Year Rapid Chloride Permeability (W/CM=0.50)

0% fly ash concrete was Moderate to High. Although there was no apparent relationship
between fly ash replacement level and the amount of charge passed, there was a clear
trend that extended moist curing of fly ash containing concrete drastically reduces that
amount of charge passing through it. Concrete containing all levels of fly ash (30, 40,
50%) at 1-day moist cure yielded a chloride ion penetrability of Moderate, however after
1 year of moist curing yielded a chloride ion penetrability of Very Low.
48
7000
6000
5000
4000
fly ash 0%
3000
fly ash 30%

fly ash 40%
fly ash 50%
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)

0% fly ash concrete was Low to Moderate. Again there was no clear relationship between
fly ash replacement level and the amount of charge passed, but there was a trend
demonstrating that extended moist curing of fly ash containing concrete reduces the
amount of charge passing through it. Concrete containing all levels of fly ash (30, 40,
50%) at 1-day moist cure yielded a chloride ion penetrability of Moderate, however after
1 year of moist curing yielded a chloride ion penetrability of Very Low.
49
7000
6000
5000
4000
fly ash 0%
3000
fly ash 30%

fly ash 40%
fly ash 50%
2000
1000
0
1-day
3-day
7-day
14-day
28-day
Continous
Curing (days)

The bar chart below shows the rapid chloride permeability performance of different fly
ashes tested at 28 and 90 days. These specimens were cast with a W/CM = 0.50 and fly
ash level of 50%. As expected the amount of charge passed decreases at the later age
because of the slower pozzolanic reaction. Of the fly ashes tested, BR performed the best
with chloride ion penetrability at 90 days of Low, whereas CM had the least desirable
chloride ion penetrability at 90 days of High.
50
Rapid Chloride Permeability (coulombs)
12000
10000
8000
6000
4000
2000
CM
BR
TB
28 Day
RP
CM
SD
BR
TB
90 Day
RP
SD
Curing (days)
Figure 4.17 Curing vs. Rapid Chloride Permeability of Different Fly Ashes
The following is a list of trends that are apparent from the RCPT data:
At 28 days RCPT is high for all concretes regardless of curing, fly ash level or
W/CM.
With two exceptions, the RCPT is moderate to high (i.e. >2000 coulombs) for all
control concrete regardless of curing, age of test, or W/CM. The exceptions are
the mix with W/CM = 0.34 which just achieved a low rating of <2000 coulombs
when tested at 1 year after either 28 day curing or continuous curing. These
values were 1975 and 1955 coulombs, respectively, for concrete moist cured for
28 days and 365 days prior to test at 1 year.
The influence of moist curing on RCPT of fly ash appears to be minimal at early
age for all W/CM or at any age for concrete with W/CM = 0.50.
The influence of curing on the RCPT of fly ash concrete becomes more pronounced
at later ages (i.e. 90 and 365 days) and with lower W/CM (i.e. 0.40 and 0.34).
With one exception, all fly ash concretes (containing SD ash) achieve a low or very
51
low RCPT rating when they are continuously cured for 1 year. The exception is
the mix with W/CM = 0.50 and 30% fly ash which recorded a value of 1175
coulombs.
The composition of fly ash clearly has an impact on the electrical conductivity of
the concrete.
Concretes with W/CM = 0.50 and 50% fly ash had RCPT values ranging from 1601
to 6037 coulombs when continuously cured before testing at 90 days. The Type
CI fly ash with the highest CaO content (RP) gave the highest reading and the fly
ashes with the highest alkali contents gave the lowest reading.
4.3 Electrical Resistivity

Electrical resistivity (AC) results are summarized in Table 4.4.
The purpose of conducting electrical resistivity testing was to compare the results
obtained using this method with results obtained using ASTM C1202, rapid chloride
permeability test (RCPT). Conducting the non-standard resistivity test was to provide
further information to support changing the RCPT from a 6-hour test to an
instantaneous measurement. Since resistivity = 1/conductivity, one would expect a
good relationship between electrical resistivity and rapid chloride permeability testing
(RCPT actually measures conductivity). As can be seen in Figure 4.18, there is good
correlation between electrical resistivity testing and the traditional rapid chloride
permeability test as demonstrated by the R-squared values. At 28, 90, and 365 days of
age the R-squared values were 0.56, 0.78, and 0.86 respectively. The relationship
between resistivity and conductivity is reasonably good at later ages but the relationship
isnt strong at early ages. This is because resistivity was measured instantaneously (no
heating) whereas the conductivity was measured over 6 hours, resulting in significant
heating for low resistivity samples. The correlation appears stronger at later ages because
at later ages the concrete has become less permeable. Lower permeability concrete tested
according to ASTM C1202 results in less heat produced during the test and therefore a
more accurate reading of charge passed. Concrete containing fly ash is more permeable at
early ages than at later ages because of the slow pozzolanic reaction.
Table 4.4 Electrical Resistivity Data
Mix
No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
FA
Content,
% by
wt. of
CM
30
40
50
50
50
50
50
W/
(C+FA)
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.4
0.34
0.5
0.5
0.5
0.5
28 Day Resistivity, k cm
Curing, days
1
3.57
3.24
4.46
2.76
3.49
4.05
2.59
3.32
3.65
2.92
4.95
2.92
-
3
3.57
3.4
5.19
3.32
3.16
5.19
3.49
4.3
4.86
3.08
4.95
4.38
-
7
3.49
3.57
5.19
3.16
3.65
5.11
4.22
5.11
5.51
3.08
4.3
4.62
-
14
3.81
3.65
5.43
3.4
3.57
5.67
4.54
5.35
5.03
3.49
5.11
4.86
-
28
2.84
3.4
5.03
2.43
3.65
4.95
3.4
4.54
4.62
4.3
4.78
4.54
2.68
7.78
4.38
3.49
90 Day Resistivity, k cm
Curing, days
1
4.46
4.22
5.67
5.35
9.4
5.51
4.54
6.89
5.76
4.46
5.43
5.43
-
3
3.81
4.38
6.4
4.22
9
7.22
4.95
7.13
8.43
4.13
6.08
7.86
-
7
3.73
5.03
6.49
4.38
10.54
6.73
5.67
8.03
8.19
5.11
6.97
9.57
-
14
3.97
4.46
6.4
4.05
8.76
7.86
6.89
9.49
9.73
4.38
7.22
9.4
-
28
3.65
4.95
6.97
4.46
7.78
12.65
5.27
9.73
12.73
4.54
11.27
12.24
-
1 Year Resistivity, k cm
Curing, days
90
3.32
3.97
6.24
5.76
9.16
13.78
6.4
9.24
15.24
6.24
14.19
16.62
2.35
15.57
13.62
4.3
1
4.62
5.51
7.46
5.11
5.92
7.7
7.38
7.22
7.54
4.86
8.11
8.35
-
3
4.54
5.11
7.22
5.43
6.32
9.08
6.32
7.7
10.13
6.24
7.46
31.46
-
7
5.11
4.7
7.22
6.57
11.27
12.24
6.81
9.32
10.21
6.16
8.43
9.08
-
14
5.03
5.84
7.62
5.92
6.32
14.75
6.89
8.51
9.49
5.43
9.16
23.1
-
28
5.03
6.4
7.94
5.35
14.59
6.57
12.48
18.48
6.89
14.43
16.3
-
365
4.46
5.03
10.78
15.73
41.99
31.62
37.05
38.02
56.02
36
33.08
-
52
53
When highly permeable concrete is tested according to ASTM C1202 the concrete heats
up during the duration of the 6-hour test. This heating effect, results in the concrete being
less resistant and more conductive to the current passing through the 50 mm sample. It is
well known that conductivity increases with temperature. Therefore, concrete tested at
early ages using ASTM C1202 is susceptible to a heating effect.
Resistivity vs. Rapid Chloride
100000
2
28 Day R = 0.5609
2
Rapid Chloride (Coulombs)
90 Day R = 0.7817
2
1 Year R = 0.8647
10000
Day 28
Day 90
Year 1
Power 28 Day
Power 90 Day
Power 1 Year
1000
100
10
100
Resistivity (kohms cm)
Figure 4.18 Relationship between Resistivity and Rapid Chloride Permeability

Testing
4.4 Carbonation
4.4.1 Accelerated Carbonation
Accelerated carbonation data are summarized below in Table 4.5.
54
Table 4.5 Accelerated Carbonation Data

Mix No.
FA Type
FA Content, % by
wt. of CM
CM
W/
(C+FA)
0.50
CM2
CM3
0.40
0.34
SD
30F
30F2
0.50
30
0.40
30F3
0.34
40F
0.50
40F2
40
40F3
50F
0.40
0.34
50
0.50
Curing,
days
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
Accelerated Carbonation, mm
Time in Accelerated Carbonation
Exposure, days
7
14
28
56
90
1
2
2
4
5
0
0
1
3
3.5
0
0
1
1
2
0
0
1
1
2
0
0
0.5
1
1.5
6
6
4
5
6
5
5.5
4
5
5.5
1
1
0
0.5
1
0
0
1
0.5
1
0
0
0
0.5
0.5
0.5
0.5
1
1
1
0
0
0
0
0.5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
5
7
9
0
2
4
4
7
0
1
1.5
3
4.5
0
1
2
2
3.5
0
1
1.5
2
3
1
2
3.5
5
8
1
1
3
3
4
0.5
0.5
1
2
2
0
0.5
1
1
2
0
0
0.5
0.5
1
1
2
2
4
5
0.5
0.5
1
1
2
0.5
0.5
0.5
0.5
1
0.5
0
0.5
0.5
1
0
0
0
0
0.5
0
10
5
9
12
0
5
4
5
9
0
2
5
5
6
0
1
3
4
5.5
0
1
1
3
5
2
3
4
5
7
1
1
2
3
5
1
1
2
2
4
0.5
1
1
1.5
3
0
0
0.5
1
1.5
2
3
4
5
9
1
1
1.5
3
5
0.5
0.5
1
1.5
3
0
0.5
1
1
2
0
0
0.5
0.5
1
15
15
15
15
16
10
8
8
9
12
55
50F2
0.40
50F3
0.34
CM
50
0.50
BR
BR
50
0.50
TB
TB
50
0.50
RP
RP
50
0.50
50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
Control 1
Control 2
CC1 (X1)
CC1 (X2)
CC2 (X1)
CC2 (X2)
CC3 (X1)
CC3 (X2)
SD
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
1
1
1
1
1
1
1
Control 1 no curing compound

Control 2 no curing compound
CC1 (X1) one application of curing compound CC1
CC1 (X2) two applications of curing compound CC1
7
3
1
7
5
3
1
0.5
5
2
1
1
0.5
12
7
5
2.5
2
7
4
3
2.5
1
9
7
4.5
3
2
11
7
4
3
2
12
12
11
7.5
9
6
10
9
7
3
2
4
3
2
1
0.5
5
2
1
1
0.5
14
7
6
2.5
2
7
4.5
3.5
3
1.5
10
7
4.5
3
2
11
7
4
3
2
13
12
11.5
8
9
7
11
10
6
3.5
2
4
3
2
1
1
7
3
2
1
0.5
14
12.5
12
9
9
7.5
12
10
7
6
5
5
4
3
2
2
10
5
3
2
1
13
8
6
4
4
7.5
6
5
4.5
3
11
8.5
7
6
4.5
11
9
7
6
4
20
18
14
12
13
10
16
15
9
8
7
11
8
7
4
4
12
7
5
4
3
15
11
6
5
4.5
10
8
8
7
5.5
11
8.5
7
6
5
11
9
7.5
7
5
26
26
26
17
17
15
25
25
56
As can be seen Figures 4.19, 4.20, and 4.21, at 90 days of exposure in the accelerated
carbonation chamber, concrete containing no fly ash yielded lower amounts of
carbonation then concrete containing fly ash. Also, the following trends are clearly
displayed: increased fly ash levels, increased W/CM, and decreased moist curing duration
all increase carbonation depths. Figure 4.22 compares the accelerated carbonation
performance of five different fly ashes. As can be seen in the figure, SD fly ash has the
greatest depths and therefore the least desirable carbonation performance. CM fly ashes
carbonation performance is most affected by the duration of moist curing and BR, TB,
and RP have very similar carbonation performance. The carbonation rates of all the
concrete tested in the accelerated carbonation chamber are given in Table 4.6. The 90 day
accelerated carbonation rates were calculated using k = d/tm, where k = carbonation rate
(mm/y1/2), d = carbonation depth (mm), t = age (years), m = 0.5. To determine the
accelerated carbonation rate at 90-days, only the 90-day data was used; as opposed to
fitting a line to the d vs. t1/2 plot for all of the data for a particular concrete / curing
condition. With respect to the effect of curing compounds on the rate of carbonation, CC1
with two applications reduces the depth of carbonation from 26mm (control) to 17mm,
CC2 with one application reduces the depth of carbonation from 26mm to 17mm, and
CC2 with two applications reduces the depth of carbonation from 26mm to 15mm. All of
these reductions in carbonation depth are significant; however the curing compound CC2
appears the most effective.
57
18
16
90 Day Carbonation (mm)
14
12
fly ash 0%
10
fly ash 30%

fly ash 40%
fly ash 50%
8
6
4
2
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.19 Curing vs. 90 Day Accelerated Carbonation (W/CM=0.50)

18
16
14
12
10
fly ash 0%
fly ash 30%
fly ash 40%

fly ash 50%
6
4
2
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
58
18
16
14
12
fly ash 0%
10
fly ash 30%

fly ash 40%
fly ash 50%
8
6
4
2
0
1-day
3-day
7-day
14-day
28-day
Curing (days)

18
16
14
12
CM
BR
TB
RP
SD
10
8
6
4
2
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.22 Curing vs. 90 Day Accelerated Carbonation of Different Fly Ashes
59
Table 4.6 Accelerated Carbonation Rates, k (mm/y^0.5)
Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
Control 1
Control 2
CC1 (X1)
CC1 (X2)
CC2 (X1)
CC2 (X2)
CC3 (X1)
CC3 (X2)
FA Type
FA Content,
% by wt. of
CM
W/
(C+FA)
CM
BR
TB
RP
50
50
50
50
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.50
0.50
0.50
SD
50
0.50
30
SD
40
50
90 Day Accelerated Carbonation Rate, k

(mm/y0.5)
Curing, days
1
3
7
14
28
10.1
7.1
4.0
4.0
3.0
12.1
11.1
2.0
2.0
1.0
2.0
1.0
0.0
0.0
0.0
18.1
14.1
9.1
7.1
6.0
16.1
8.1
4.0
4.0
2.0
10.1
4.0
2.0
2.0
1.0
24.2
18.1
12.1
11.1
10.1
14.1
10.1
8.1
6.0
3.0
18.1
10.1
6.0
4.0
2.0
32.2
24.2
18.1
16.1
14.1
22.2
16.1
14.1
8.1
8.1
24.2
14.1
10.1
8.1
6.0
30.2
22.2
12.1
10.1
9.1
20.1
16.1
16.1
14.1
11.1
22.2
17.1
14.1
12.1
10.1
22.2
18.1
15.1
14.1
10.1
52.4
52.4
52.4
34.2
34.2
30.2
50.4
50.4
-
4.4.2 Indoor Carbonation

Indoor carbonation data are summarized below in Table 4.7.
As can be seen Figures 4.23, 4.24, and 4.25, at 1 year of age, concrete containing no fly
ash yielded lower depths of carbonation compared with concrete containing fly ash. Also,
the same general trends are clearly displayed that were observed in the accelerated
carbonation tests: increased fly ash levels, increased W/CM, and decreased moist curing
duration all increase carbonation depths.
Table 4.7 Indoor Carbonation Data

Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
FA Type
30
SD
40
50
90 Day Indoor Carbonation, mm
1 Year Indoor Carbonation, mm
Curing, days
3
7
14
1
1
0.5
4
0.5
0.5
0
0
0
3
2.5
2
1
1
1
1
0.5
0.5
4
4
3.5
1.5
1.5
1
1.5
1
1
7
6
4
3
2
1.5
3
1.5
1
Curing, days
3
7
14
6
4
3
5
1
0.5
1
1
0
9
6.5
6
5
4
3.5
4
2
1
10
8.5
8
6
5.5
4
6
4
3.5
10
8.5
7
11
8
7
8
5
4.5
W / (C+FA)
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
1
3
4
1
6
3
2
6
3
4
12
5
6
28
0.5
0.5
0
1
0.5
0
2
1
0.5
3
1
0.5
1
8
5
3
12
8
6
13
7.5
9
13
13
13
28
2
0.5
0
5
2
1
6
4
2.5
6.5
6
3
60
61
Indoor carbonation rates were calculated and are displayed in Table 4.8. Carbonation
rates were calculated based on both 90 day and 1-year carbonation depth measurements.
Since, the indoor conditions remained constant at 23oC and 50% relative humidity for the
entire year, it is expected that the carbonation rates at 90 days would be the same as the
carbonation rates at 1 year. Since the method used to measure carbonation was accurate
to plus/minus 1 mm, the carbonation rates calculated for 90 days and 1 year should be
within 2 mm of each other. As can be seen in Table 4.8, there is relatively good
correlation between the 90-day and 1 year carbonation rates, with few exceptions.
14
1 Year Carbonation (mm)
12
10
fly ash 0%
fly ash 30%

fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.23 Curing vs. 1 Year Indoor Carbonation (W/CM=0.50)
62
14
12
10
fly ash 0%
fly ash 30%

fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)

14
12
10
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Table 4.8 Indoor Carbonation Rates, k (mm/y^0.5)

Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
FA Type
FA Content, % by wt.
of CM
30
SD
40
50
90 Day Indoor Carbonation Rate, k (mm/y0.5)

W / (C+FA)
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
1
6.0
8.1
2.0
12.1
6.0
4.0
12.1
6.0
8.1
24.2
10.1
12.1
Curing, days
3
7
2.0
2.0
8.1
1.0
0.0
0.0
6.0
5.0
2.0
2.0
2.0
1.0
8.1
8.1
3.0
3.0
3.0
2.0
14.1
12.1
6.0
4.0
6.0
3.0
14
1.0
1.0
0.0
4.0
2.0
1.0
7.1
2.0
2.0
8.1
3.0
2.0
28
1.0
1.0
0.0
2.0
1.0
0.0
4.0
2.0
1.0
6.0
2.0
1.0
1 Year Indoor Carbonation Rate, k (mm/y0.5)

1
8.0
5.0
3.0
12.0
8.0
6.0
13.0
7.5
9.0
13.0
13.0
13.0
Curing, days
3
7
14
6.0
4.0
3.0
5.0
1.0
0.5
1.0
1.0
0.0
9.0
6.5
6.0
5.0
4.0
3.5
4.0
2.0
1.0
10.0
8.5
8.0
6.0
5.5
4.0
6.0
4.0
3.5
10.0
8.5
7.0
11.0
8.0
7.0
8.0
5.0
4.5
28
2.0
0.5
0.0
5.0
2.0
1.0
6.0
4.0
2.5
6.5
6.0
3.0
63
64
4.4.3 Outdoor Carbonation

Outdoor carbonation data are summarized below in Table 4.9.
As can be seen from Figures 4.26, 4.27, and 4.28 below, at 1 year of age, concrete
containing no fly ash yielded lower amounts of carbonation then concrete containing fly
ash. Also, the same general trends are clearly displayed that were observed in the
accelerated and indoor carbonation tests: increased fly ash levels, increased W/CM, and
decreased moist curing duration all increase carbonation depths. Outdoor carbonation
rates were calculated and are displayed in Table 4.10. Again, carbonation rates were
calculated based on both 90 day and 1-year carbonation depth measurements. However,
the outdoor conditions varied at 90 days and 1 year. Temperatures and relative humidity
would not have been constant throughout the concrete exposure, therefore it is expected
that the carbonation rates at 90 days would not be the same as the carbonation rates at 1
year. As can be seen in Table 4.10, the correlation between the 90-day and 1 year
carbonation rates is not as good as the indoor exposure.
Figure 4.29 illustrates the outdoor carbonation performance of the same five fly ashes
that were tested in the accelerated chamber. The findings for the outdoor exposure are
very similar when compared to the findings for the accelerated exposure. For the outdoor
exposure, CM fly ash has the least desirable carbonation performance and the other three
fly ashes, SD, TB, and RP have very similar carbonation performances. For the outdoor
exposure, BR fly ash exhibited the least amount of carbonation depth. With respect to the
effect of curing compounds at slowing the rate of carbonation, the outdoor exposure data
somewhat agrees with the accelerated carbonation data. However, the outdoor exposure
data suggests that the only curing compound tested that appears to significantly reduce
the carbonation rate is CC2 with two applications or coats.
Table 4.9 Outdoor Carbonation Data

Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
Control 1
Control 2
CC1 (X1)
CC1 (X2)
CC2 (X1)
CC2 (X2)
CC3 (X1)
CC3 (X2)
FA Type
W / (C+FA)
CM
BR
TB
RP
50
50
50
50
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.50
0.50
0.50
SD
50
0.50
30
SD
40
50
90 Day Outdoor Carbonation,

mm
Curing, days
1
3
7
14
28
2
1
1
0.5
0
5
5
0.5 0.5
0
1
0
0
0
0
7
6
4
3
2
4
2
1
1
1
2.5
1
0.5 0.5
0
11
6
5
3
2
4
3
2
1.5
1
5
1.5
1
1
0.5
13
7
5
5
3
4
3
3
2
1
7
4
2
1.5
1
5
4
3
2
1
5
4
3.5
2
1
6
5
4
3
2
6
5
3
2.5
2
10
12
9
8
8
3
12
11.5
-
1 Year Outdoor Carbonation,

mm
Curing, days
1
3
7
14
28
5
3
2
1
0.5
6
6
1
0.5
0
1
0.5
0
0
0
8
7
5
4.5 2.5
7
4
3
2
1
5
2
1
1
0.5
12
8
6.5
6
5
7
4.5
4
3.5 2.5
6
2.5 1.5
1
0.5
13
10
9.5
8
6
9
7
5
4
3.5
10
6
3.5
3
2
14
10
8
6.5
6
8
7
6.5
6
6
12.5 11
8.5
6
6
13
10
7
6.5 5.5
-
65
66
14
12
10
fly ash 0%
fly ash 30%

fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.26 Curing vs. 1 Year Outdoor Carbonation (W/CM=0.50)

14
12
10
fly ash 0%
fly ash 30%
fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
67
14
12
10
fly ash 0%
fly ash 30%

fly ash 40%
fly ash 50%
0
1-day
3-day
7-day
14-day
28-day
Curing (days)

16
14
12
10
CM
BR
TB
RP
SD
0
1-day
3-day
7-day
14-day
28-day
Curing (days)
Figure 4.29 Curing vs. 1 Year Outdoor Carbonation of Different Fly Ashes
Table 4.10 Outdoor Carbonation Rates, k (mm/y^0.5)

Mix No.
CM
CM2
CM3
30F
30F2
30F3
40F
40F2
40F3
50F
50F2
50F3
C
BR
TB
RP
Control 1
Control 2
CC1 (X1)
CC1 (X2)
CC2 (X1)
CC2 (X2)
CC3 (X1)
CC3 (X2)
FA Type
FA Content, %
by wt. of CM
W/
(C+FA)
CM
BR
TB
RP
50
50
50
50
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.40
0.34
0.50
0.50
0.50
0.50
SD
50
0.50
30
SD
40
50
90 Day Outdoor Carbonation Rate, k (mm/y0.5)
1
4.0
10.1
2.0
14.1
8.1
5.0
22.2
8.1
10.1
26.2
8.1
14.1
10.1
10.1
12.1
12.1
20.1
24.2
18.1
16.1
16.1
6.0
24.2
23.2
3
2.0
10.1
0.0
12.1
4.0
2.0
12.1
6.0
3.0
14.1
6.0
8.1
8.1
8.1
10.1
10.1
-
Curing, days
7
2.0
1.0
0.0
8.1
2.0
1.0
10.1
4.0
2.0
10.1
6.0
4.0
6.0
7.1
8.1
6.0
-
14
1.0
1.0
0.0
6.0
2.0
1.0
6.0
3.0
2.0
10.1
4.0
3.0
4.0
4.0
6.0
5.0
-
28
0.0
0.0
0.0
4.0
2.0
0.0
4.0
2.0
1.0
6.0
2.0
2.0
2.0
2.0
4.0
4.0
-
1 Year Outdoor Carbonation Rate, k

(mm/y0.5)
Curing, days
1
3
7
14
28
5.0
3.0
2.0
1.0
0.5
6.0
6.0
1.0
0.5
0.0
1.0
0.5
0.0
0.0
0.0
8.0
7.0
5.0
4.5
2.5
7.0
4.0
3.0
2.0
1.0
5.0
2.0
1.0
1.0
0.5
12.0
8.0
6.5
6.0
5.0
7.0
4.5
4.0
3.5
2.5
6.0
2.5
1.5
1.0
0.5
13.0
10.0
9.5
8.0
6.0
9.0
7.0
5.0
4.0
3.5
10.0
6.0
3.5
3.0
2.0
14.0
10.0
8.0
6.5
6.0
8.0
7.0
6.5
6.0
6.0
12.5
11.0
8.5
6.0
6.0
13.0
10.0
7.0
6.5
5.5
-
68
69
5.0 Discussion of Results

5.1 Relationship between Compressive Strength, Rapid Chloride
Permeability, and Carbonation
Figures 5.1 and 5.2 below show the relationship between compressive strength and rapid
chloride permeability at 28 days and 1 year. An exponential trend line was fitted to the
data and the R-squared was 0.20 and 0.38 at 28 days and 1 year respectively. Based on
these R-squared values there does not appear to be a strong correlation between
compressive strength and rapid chloride permeability data. This result is expected since
fly ash clearly has a greater impact on RCPT than strength, especially when it is
adequately cured. Strength is not a good prediction of permeability or durability.
12000
10000
8000
6000
R2 = 0.1982
4000
2000
0
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
Strength (MPa)
Figure 5.1 Strength vs. Rapid Chloride Permeability at 28 Days of Age
80.00
70
7000
6000
5000
4000
3000
2000
R2 = 0.3771
1000
0
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
80.00
Strength (MPa)
Figure 5.2 Strength vs. Rapid Chloride Permeability at 1 Year of Age

Figures 5.3 and 5.4 show the relationship between rapid chloride permeability and indoor
and outdoor carbonation at 90 days and 1 year. A linear trend line was fitted to the data
and at 90 days the R-square values for indoor carbonation was 0.25 and for outdoor
carbonation 0.25. At 1 year the R-square values for indoor was 0.19 and for outdoor 0.31.
Again there does not appear to be a strong relationship between rapid chloride
permeability and indoor and outdoor carbonation. Fly ash will tend to reduce
permeability (especially in well cured concrete) and increase carbonation (especially in
poorly cured concrete). For a given permeability the carbonation will be greatest in fly
ash concrete because there is less calcium hydroxide. Therefore, a good relationship is
not expected.
71
14
12
Outdoor R = 0.2469
2
Carbonation (mm)
Indoor R = 0.2548
10
Outdoor Carbonation
Indoor Carbonation
Linear Outdoor Carbonation
Linear Indoor Carbonation
0
2000
4000
6000
8000
Figure 5.3 Rapid Chloride Permeability vs. Carbonation at 90 Days of Age

14
Outdoor R = 0.3106
2
Indoor R = 0.1884
Carbonation (mm)
12
10
Outdoor Carbonation
Indoor Carbonation
0
0
1000
2000
3000
4000
5000
6000
7000
Figure 5.4 Rapid Chloride Permeability vs. Carbonation at 1 Year of Age
72
Figures 5.5 and 5.6 show the relationship between rapid chloride permeability and
carbonation at 90 days and 1 year, respectively. It is evident from both figures that for a
given permeability, concrete containing higher replacement levels of fly ash will yield
higher carbonation depths.
14
2
Control R = 0.0422
2
30% fly ash R = 0.5989
12
40% fly ash R = 0.6167

2
Carbonation (mm)
50% fly ash R = 0.4248

10
Control
fly ash 30%
fly ash 40%
fly ash 50%
Linear Control
Linear 30% fly ash
Linear 40% fly ash
Linear 50% fly ash
0
0
1000
2000
3000
4000
5000
6000
7000
8000
RCPT (coulombs)
Figure 5.5 Rapid Chloride Permeability vs. Carbonation for Different Levels of Fly
Ash at 90 Days
73
14
Control R = 0.2634
2
30% fly ash R = 0.6389

12
40% fly ash R = 0.5439

2
Carbonation (mm)
50% fly ash R = 0.5434

10
Control
fly ash 30%
fly ash 40%
fly ash 50%
Linear Control
Linear 30% fly ash
Linear 40% fly ash
Linear 50% fly ash
0
0
1000
2000
3000
4000
5000
6000
7000
RCPT (coulombs)
Figure 5.6 Rapid Chloride Permeability vs. Carbonation for Different Levels of Fly
Ash at 1 Year
One might expect a good relationship between permeability and carbonation. As the
permeability of the concrete is reduced by the addition of fly ash you would expect it to
become harder for CO2 to penetrate the concrete. However, fly ash reduces permeability
by reacting with Ca(OH)2. This reaction reduces the amount of material available for
reaction with CO2. Thus less CO2 has to penetrate to neutralize the concrete.
Figure 5.7 below shows the relationship between compressive strength and carbonation at
1 year. A linear trend line was fitted to the data and the R-squared values were 0.76 for
indoor carbonation and 0.74 for outdoor carbonation. Based on these relatively high Rsquared values it appears as though compressive strength is a better indicator of
carbonation depth than permeability.
74
14
Outdoor R = 0.7423
2
Indoor R = 0.7592
Carbonation (mm)
12
10
Outdoor Carbonation
Indoor Carbonation
0
0.00
20.00
40.00
60.00
80.00
Strength (MPa)
Figure 5.7 Strength vs. Carbonation at 1 Year of Age
5.2 Impact of Curing on High Volume Fly Ash Concrete

Curing of high volume fly ash concrete is essential in order to achieve the long-term
benefits of this material. There is a lot of literature that promotes HVFA concrete on the
basis of long-term strength and permeability, but the data presented in this thesis, show
that these benefits will only be achieved if the concrete is exposed to sufficient moisture
during service to promote continued hydration and pozzolanic reaction (i.e. continuously
moist cured). In exposed elements protected from direct precipitation, continued
hydration and pozzolanic reaction will be relatively slow resulting in concrete with less
than desirable strength and permeability. Data from this thesis suggest that unless HVFA
concrete is moist cured for an extended period of time its benefits over ordinary Portland
cement concrete are minimal. However, HVFA concrete that is continuously moist cured
does yield concrete with very desirable long-term strength and permeability. Extending
curing of concrete on a construction site is expensive and not of interest to contractors,
therefore it is the authors opinion that HVFA concrete is best suited for moist
75
environments such as bridge decks or marine structures where the extended exposure to
sufficient moisture during service would yield the desirable long-term properties of
HVFA concrete. Also, it should be noted that in relatively dry environments such as
underside of balconies, bridges, and soffits HVFA concrete would not achieve its longterm strength and permeability properties and would be more susceptible to carbonation
induced corrosion. In consistently dry indoor environments, HVFA concrete will not be
expected to achieve long-term strength and impermeability, but its failure to do so is
probably inconsequential as such environments do not pose a significant threat to
concrete. Even if carbonation reaches the steel during the service life of the concrete,
there is unlikely to be sufficient moisture available to sustain corrosion.
5.3 Master Builders Rapid Chloride Permeability Prediction Software

Master Builders has created a computer program that forecasts rapid chloride
permeability based on mixture design. The program consists of a large database of
different mixture designs and corresponding rapid chloride permeability values. The
programs user-defined inputs are: age of test (assuming continuous moist curing),
concrete curing temperature, mixture proportions of cement, silica fume, slag, Class C fly
ash, Class F fly ash, coarse aggregate, water, and percentage of air. The user can also
specify various admixture dosages. The program generates the fine aggregate portion of
the mixture based on a total volume calculation using default specific gravity values. The
output from the program is a rapid chloride permeability value, in coulombs, that would
be expected if the concrete mixture was subjected to ASTM C1202 Rapid Chloride
Permeability Test. The figure below (5.8) is a screenshot from the Master Builders
model.
76
Figure 5.8 Screenshot from Master Builder's RCPT Prediction Model

Below are three figures that compare rapid chloride permeability data obtained in this
project with predicted rapid chloride permeability results from Master Builders software,
continuously moist cured for 28, 90, and 365 days. It should be noted that Master
Builders software only provides coulomb values ranging from 0 to 4000. If a defined
concrete has a RCPT greater then 4000 coulombs, the program returns an output of
4000+. To make a graphic comparison between the actual (Laboratory Tested) and
theoretical (Master Builders Prediction) RCPT, any actual or theoretical data above 4000
coulombs or 4000+ respectively was plotted at 4000 coulombs.
77
4500
4000
3500
3000
2500
RCPT Laboratory Tested
2000
RCPT Master Builder's

Prediction
1500
1000
500
RP
TB
BR
CM
30
F
40
F
50
F
CM
2
30
F2
40
F2
50
F2
CM
3
30
F3
40
F3
50
F3
Mixture Identification
Figure 5.9 Laboratory Tested vs. Master Builder's Prediction of RCPT at 28 Days
4500
4000
3500
3000
2500
2000

Prediction
1500
1000
500
RP
TB
BR
CM
30
F
40
F
50
F
CM
2
30
F2
40
F2
50
F2
CM
3
30
F3
40
F3
50
F3
Figure 5.10 Laboratory Tested vs. Master Builder's Prediction of RCPT at 90 Days
78
4500
4000
3500
3000
2500
2000

Prediction
1500
1000
500
0
CM
30F
40F
50F CM2 30F2 40F2 50F2 CM3 30F3 40F3 50F3

Figure 5.11 Laboratory Tested vs. Master Builder's Prediction of RCPT at 1 Year
As can be seen from the above figures, Master Builders software program is somewhat
effective at predicting actual RCPT data, with exceptions. The most notable exception
being the control mixes (CM, CM2, CM3) containing no fly ash. At all three test ages,
the actual RCPT results produced in the laboratory are higher then that predicted by
Master Builders software. With respect to the concrete containing fly ash, it appears as
though Master Builders model is somewhat successful at predicting general trends in
rapid chloride permeability test results.
5.4 Performance of Different Fly Ashes

The data clearly demonstrate that the performance of the concrete varies with the fly ash
composition. Strength, permeability, and carbonation values were all affected by the
source of ash used. However, from the data it is not possible to discern any trends
between composition and performance. In fact, if the ashes were ranked in terms of their
impact on strength, permeability or carbonation, the rankings would be different for each
property measured. For example, ranking the different fly ashes from highest to lowest
79
compressive strength (28 day continuous moist cure) yields the following: BR, TB, CM,
SD, and finally RP. Ranking permeability (90 day continuous moist cure) from least to
most permeable yields: BR, TB, RP, SD, and finally CM. Although the compressive
strength rankings agree somewhat with the permeability rankings, there appears to be no
correlation with the carbonation rankings. Ranking the 90 day accelerated carbonation
depths from least to greatest penetrability for the 1 day cured samples reveals: BR,
RP/TB, CM, and finally SD. However, ranking the 90 day accelerated carbonation depths
from least to greatest penetrability for the 28 day cured samples reveals something
different: CM, RP/TB, BR, and SD. From this comparison it appears as though CMs
carbonation performance is the most sensitive to moist curing. Ranking the 1 year
outdoor carbonation depths from least to greatest penetrability for the 1 day cured
samples displays: BR, TB, RP/SD, and finally CM. However, the 1 year outdoor
carbonation depths for the 28 day cured samples are essentially equal. So again, the same
trend is observed as was observed in the accelerated carbonation exposure, CMs
carbonation performance is the most sensitive to moist curing. Since no correlation could
be concluded regarding fly ash composition and concrete performance, further research
should be conducted to determine the influence of fly ash composition on strength,
5.5 Carbonation Rate Predictive Model

A carbonation rate predictive model was developed based on curing duration, W/CM, and
percentage of fly ash replacement. An equation was developed by conducting an analysis
on the outdoor carbonation data at 1 year. The outdoor carbonation conditions were
chosen for this model because these conditions are most likely to result in carbonationinduced corrosion.
The equation is:
kpredicted = (a x W/CM) x (1 + FA/b) x (cure)c + d
a = 13.8
b = 45
c = -0.25
d = -2
80
The above equation was developed from the following observations:
For a given fly ash replacement level (FA) and cure, carbonation rate (k)
increases linearly with W/CM.
For a given W/CM and cure, carbonation rate (k) increases linearly with fly ash
replacement level (FA).
For a given W/CM and fly ash replacement level (FA), carbonation rate (k)
decreases with curing. This relationship is best represented with the power law.
The +d is necessary because for some mixes, k = 0. This is an artifact of the testing.
When tested at one year, some of the well-cured, low-W/CM mixes showed little
measurable carbonation. However, if these specimens were measured at later ages
(greater then two years) there would be some measurable carbonation, so k would not be
equal to zero.
When the above equation is verified using the data from Table 5.1, k values can be
predicted with confidence as can be seen from the Table 5.1[k (predicted)] and Figure
5.12. However a good relationship would be expected since the measured data were used
to produce the model.
Table 5.1 Carbonation Rate Predictive Model Data
Curing
(days)
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
W/CM
0.5
0.5
0.5
0.5
0.5
0.4
0.4
0.4
0.4
0.4
0.34
0.34
0.34
0.34
0.34
0.5
0.5
0.5
0.5
FA%
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
30
30
30
30
k
k
(measured) (predicted)
5.0
4.9
3.0
3.2
2.0
2.2
1.0
1.6
0.5
1.0
6.0
3.5
6.0
2.2
1.0
1.4
0.5
0.9
0.0
0.4
1.0
2.7
0.5
1.6
0.0
0.9
0.0
0.4
0.0
0.0
8.0
9.5
7.0
6.7
5.0
5.1
4.5
3.9
81
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
1
3
7
14
28
0.5
0.4
0.4
0.4
0.4
0.4
0.34
0.34
0.34
0.34
0.34
0.5
0.5
0.5
0.5
0.5
0.4
0.4
0.4
0.4
0.4
0.34
0.34
0.34
0.34
0.34
0.5
0.5
0.5
0.5
0.5
0.4
0.4
0.4
0.4
0.4
0.34
0.34
0.34
0.34
0.34
30
30
30
30
30
30
30
30
30
30
30
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
2.5
7.0
4.0
3.0
2.0
1.0
5.0
2.0
1.0
1.0
0.5
12.0
8.0
6.5
6.0
5.0
7.0
4.5
4.0
3.5
2.5
6.0
2.5
1.5
1.0
0.5
13.0
10.0
9.5
8.0
6.0
9.0
7.0
5.0
4.0
3.5
10.0
6.0
3.5
3.0
2.0
3.0
7.2
5.0
3.7
2.8
2.0
5.8
3.9
2.8
2.0
1.4
11.0
7.9
6.0
4.7
3.7
8.4
5.9
4.4
3.4
2.5
6.9
4.7
3.4
2.6
1.9
12.6
9.1
7.0
5.5
4.3
9.7
6.9
5.2
4.0
3.1
7.9
5.5
4.1
3.1
2.3
82
15
y = 0.9984x
2
R = 0.8576
k (measured)
10
0
0
10
15
k (predicted)
Figure 5.12 Predicted Carbonation Rate vs. Measured Carbonation Rate

The table and figure below demonstrate applying the aforementioned carbonation rate
predictive model to data obtained by Thomas (unpublished) in a previous study. As
expected, the equation predicts carbonation rates more accurately when applied to data
presented in this thesis rather then data presented in Dr. Thomass study. However, as
further carbonation data becomes available (for example, the 2 year carbonation
measurements) the model will be refined such that the predictive model will become
more reliable for predicting carbonation rates and depths.
83
Table 5.2 Carbonation Rate Data from Dr. Michael Thomas

FA%
W/CM
0
0
0
0
0
0
0
0
0
15
15
15
15
15
15
15
15
15
30
30
30
30
30
30
30
30
30
50
50
50
50
50
50
50
50
50
0.68
0.68
0.68
0.57
0.57
0.57
0.49
0.49
0.49
0.61
0.61
0.61
0.51
0.51
0.51
0.44
0.44
0.44
0.54
0.54
0.54
0.45
0.45
0.45
0.39
0.39
0.39
0.44
0.44
0.44
0.37
0.37
0.37
0.32
0.32
0.32
Curing
(days)
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
1
3
7
k
k
(measured) (predicted)
7.0
7.4
5.8
5.1
4.9
3.8
5.0
5.9
3.1
4.0
2.4
2.8
2.4
4.8
0.8
3.1
0.3
2.2
8.4
9.2
6.4
6.5
4.7
4.9
5.1
7.4
3.8
5.1
3.3
3.8
2.8
6.1
2.1
4.2
1.3
3.0
8.3
10.4
6.3
7.4
5.3
5.6
5.3
8.4
4.0
5.9
3.3
4.4
3.1
7.0
2.1
4.8
1.2
3.5
10.5
10.8
8.4
7.7
7.1
5.9
6.6
8.8
5.9
6.2
4.9
4.6
3.9
7.3
2.6
5.1
1.8
3.7
84
15
y = 0.797x
2
R = 0.6849
k (measured)
10
0
0
10
15
k (predicted)
Figure 5.13 Predicted Carbonation Rate vs. Measured Carbonation Rate (Dr.
Michael Thomas)
5.6 Relationship between Accelerated and Natural (Indoor & Outdoor)

Carbonation Rates
From Figures 5.14 and 5.15, there appears to be a good correlation between accelerated
and natural carbonation rates for both indoor and outdoor exposure conditions. Figure
5.14 demonstrates a strong correlation (R2 value of 0.88) between accelerated and indoor
carbonation rates. However, more importantly Figure 5.15 clearly shows that natural
carbonation rates in Fredericton, New Brunswick or any location that has similar
environmental conditions (temperature, relative humidity, CO2 concentrations) to
Fredericton can be predicted with confidence using an accelerated carbonation chamber
containing approximately 1% CO2 by volume , 65% relative humidity, and 23o C
temperature. An R2 value of 0.91 demonstrates there is a significant relationship between
the carbonation rates obtained from specimens exposed in the accelerated carbonation
chamber for 90 days with the specimens in the outdoor exposure condition protected
from direct precipitation for 1 year. Therefore it can be concluded that an accelerated
carbonation chamber is an effective tool for predicting natural carbonation rates.
85
18.0
y = 0.455x + 1.3545
R2 = 0.8837
16.0
k-Indoor (mm/year^0.5)
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0.0
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
k-Accelerated (mm/year^0.5)
Figure 5.14 Relationship between Accelerated & Natural Indoor Carbonation Rates
16.0
y = 0.4591x + 0.1479
R2 = 0.912
14.0
k-Outdoor (mm/year^0.5)
12.0
10.0
8.0
6.0
4.0
2.0
0.0
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
k-Accelerated (mm/year^0.5)
Figure 5.15 Relationship between Accelerated & Natural Outdoor Carbonation

Rates
86
5.7 Interpretation of Carbonation Rates (Comparison between CSA

A23.1-00 and CSA A23.1-04)
Carbonation rates or the rate at which CO2 is able to penetrate concrete and reach the
reinforcing steel is very important in terms of reinforced concrete durability. The
initiation period is defined as the length of time it takes for CO2 to reach the reinforcing
steel and initiate corrosion, whereas the propagation period is the length of time until
enough corrosion had occurred to crack the concrete. For carbonation induced corrosion
the assumed propagation period is generally 15 years. The initiation period in a given
environment is a function of the depth and quality of concrete cover. CSA A23.1-00 was
published in 2000 and does not account for high volume fly ash concrete and its risk of
carbonation induced corrosion. However attempts have been made in the most recent
CSA standard (A23.1-04) to address the carbonation issues of high volume fly ash
concrete. The following example compares the initiation periods of high volume fly ash
concrete produced under the guidelines of CSA A23.1-00 with the initiation periods of
the same concrete produced under the direction of CSA A23.1-04. As will be clear from
the example, the guidelines in the latest edition of CSA are a step in the right direction in
terms of extended service life for structures containing high levels of fly ash.
CSA A23.1 defines an F2 exposure as concrete in an unsaturated condition exposed to
freezing and thawing, but not to chlorides. Examples of F2 exposure include exterior
walls and columns. In CSA A23.1-00, concrete exposed to an F2 exposure must have
40mm of cover to reinforcing steel, 25 MPa strength at 28 days, a maximum W/CM of
0.55, and curing of 3 days or until the concrete has reached 40% of its design strength.
Using the formula d = kt1/2 or t = (d / k)2, the initiation period (t) can be calculated using
the depth of cover specified in CSA A23.1-00 and carbonation rates presented in Table
4.10, outdoor carbonation rates. For an ordinary Portland cement concrete, 3 day cure,
W/CM of 0.50, depth of cover of 40mm, and a carbonation rate of approximately 2.5
mm/year1/2 (2.0 mm/year1/2 at 90 days and 3.0 mm/year1/2 at 1 year) the initiation period
is calculated to be 256 years. However, for a 50% fly ash concrete, 3 day cure, W/CM of
0.50, depth of cover of 40mm, and a carbonation rate of approximately 12 mm/year1/2
87
(14.2 mm/year1/2 at 90 days and 10.0 mm/year1/2 at 1 year) the initiation period is
reduced to 11 years.
The newest addition of CSA A23.1-04 specifies two designations for high volume fly ash
concrete. Concrete containing greater then 40% fly ash is referred to as HVSCM 1 and
concrete containing less then 40% fly ash but greater then 30% is referred to as HVSCM
2. In CSA A23.1-04, concrete exposed to F2 exposure must have 50mm of cover to
reinforcing steel, 25 MPa strength at 28 days for HVSCM 2 or 25 MPa strength at 56
days for HVSCM 1, a maximum W/CM of 0.55 for HVSCM 2 or a maximum W/CM of
0.50 for HVSCM 1, and 7 days curing or until the concrete has reached 70% of its design
strength. If the cover to the reinforcing steel is less then 50mm, then the W/CM must be
reduced as follows: 0.45 for HVSCM 2 and 0.40 for HVSCM 1. For a 50% fly ash
concrete, depth of cover of 50mm, 7 day cure, W/CM of 0.50, and a carbonation rate of
9.75 mm/year1/2 (see Table 4.10), the initiation period is 26 years. If the 50% fly ash
concrete has only 40mm of cover depth, the W/CM must be reduced to 0.40. The
carbonation rate for this concrete assuming 7 days of curing is 5.5 mm/year1/2 (6.0
mm/year1/2 at 90 days and 5.0 mm/year1/2 at 1 year) yielding an initiation period of 53
years. It should be pointed out that reducing W/CM is more effective at extending the
initiation period than increasing concrete cover.
In summary, the initiation period for a Portland cement concrete that meets the minimum
requirement of CSA A23.1-00 and CSA A23.1-04 for an F2 exposure is 256 years. The
initiation period for a 50% fly ash concrete that meets the minimum requirement of CSA
A23.1-00 is 11 years. However, the initiation period of a 50% fly ash concrete that meets
the requirements of CSA A23.1-04 is 26 years with a concrete cover of 50mm and W/CM
of 0.50; and 53 years with a concrete cover of 40mm and W/CM of 0.40. Therefore,
producing high volume fly ash concrete in accordance with the requirements presented in
CSA A23.1-04 will result in greater initiation periods and service life then HVFA
concrete produced with CSA A23.1-00. Although the revised standard is a step in the
right direction, these initiation periods are still too short, therefore there is need for
improvement. The poor performance of HVFA in the laboratory with regards to
carbonation should be confirmed by field exposure of larger samples. For example, larger
88
specimens should be constructed and placed on an exposure site. These specimens could
include suspended slab specimens to investigate carbonation of the top (exposed) surface
versus the bottom surface, exposed wall specimens to investigate windward versus
leeward exposure, and column specimens both exposed and covered.
5.8 Guidelines for Use of High Volume Fly Ash Concrete

Based on the equation that was developed in Section 5.5, guidelines have been produced
for the use of high volume fly ash concrete. The table below illustrates k values required
for a specific design life, given the depth of concrete cover to the reinforcing steel. The k
values were calculated using the equation d = kt1/2 or k = d/t1/2. As can be seen from
Table 5.3, a k value of 3.0 mm/y0.5 is necessary to achieve a 100 year design life with
30mm of cover, a k value of 5.0 mm/y0.5 is necessary to achieve a design life of 50 years
with 30mm of cover or a 75 year design life with 40mm of cover, a k value of 7.0
mm/y0.5 is necessary to achieve a 50 year design life with 40mm of cover or a 100 year
design life with 60mm of cover, and finally a k value of 10.0 mm/y0.5 is necessary to
achieve a design life of 50 years with 60mm of cover.
Table 5.3 k-Values for Various Values of Design Life & Cover
Cover Depth (mm)
30
40
50
60
50
5.07
6.76
8.45
10.14
Design Life (years)

75
3.87
5.16
6.45
7.75
100
3.25
4.34
5.42
6.51
Figures 5.16, 5.17, 5.18, and 5.19 illustrate the relationship between W/CM and curing
for a given percentage of fly ash necessary to achieve k values of 3.0, 5.0, 7.0, and 10.0
mm/y0.5, respectively.
89
7
K = 3.0 mm/y0.5
Curing (days)
0%
30% Fly ash
40% Fly Ash
50% Fly Ash
0
0.10
0.20
0.30
0.40
0.50
0.60
W/CM
Figure 5.16 Guidelines for Concrete with k = 3.0 mm/y0.5
7
K = 5.0 mm/y0.5
Curing (days)
0%
30% Fly ash
40% Fly Ash
50% Fly Ash
0
0.20
0.30
0.40
0.50
0.60
0.70
W/CM
0.80
90
7
K = 7.0 mm/y0.5
Curing (days)
0%
30% Fly ash
40% Fly Ash
50% Fly Ash
0
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
W/CM
7
K = 10.0 mm/y0.5
Curing (days)
0%
30% Fly ash

40% Fly Ash
50% Fly Ash
0
0.40
0.50
0.60
0.70
0.80
0.90
W/CM
1.00
91
As can be seen from the above figures, as the necessary k values increase, the curing and
W/CM requirements decrease. Although these figures suggest a W/CM in excess of 0.55
for concrete without fly ash is acceptable, this guideline only considers carbonation, other
durability problems would be encountered at W/CM above 0.55. The requirements are
not very demanding for concrete without fly ash. To see carbonation induced corrosion in
the field, concrete without fly ash would have to have very low concrete cover depths to
the reinforcing steel or be present in even a very old structure. This may explain why
carbonation is not thought to be a big problem in North America. The requirements
become more demanding very quickly when fly ash is incorporated. It therefore may not
be practical to use more than a moderate amount of fly ash in buildings with an extended
service life requirements and normal amounts of cover. To avoid carbonation-induced
corrosion when using HVFAC in buildings with a plus 50 year design life it is necessary
to pay close attention to all three aspects: cover, W/CM, and curing.
The above guidelines can function in two ways. First, given a specific concrete design,
the guidelines can predict the design life of that concrete in terms of carbonation, or
alternatively, given a specified design life the guidelines can be used to develop an
appropriate concrete design in terms of cover, W/CM, fly ash replacement, and curing.
Table 5.4 is an example of how the guidelines work. For example, given a cover depth of
50mm, a W/CM of 0.34, and a percent fly ash replacement of 50%, how many days cure
is required to achieve a 100 year service life?
Table 5.4 Concrete Qualities and Nominal Cover to Steel for 100 Year Service Life
Exposure
Service
Life
(years)
Initiation
Period (years)
Propagation Period
(years)
Cover Depth
(mm)
W/CM
% Fly Ash
Replacement
Minimum
Curing
(days)
(from
Figure
5.17)
F2 Concrete in an
unsaturated
condition exposed to
freezing and thawing
but not to chlorides.
100
85
15
50
0.34
50
92
93
6.0 Conclusions
This project determined the factors that influence the properties of concrete with high
levels of fly ash and produced guidelines to ensure the safe and appropriate use of highvolume fly ash concrete.
The conclusions of the project are as follows:
1. Increasing the water to cementitious material ratio decreases compressive
strength, increases permeability and increases carbonation rates.
2. At early ages (28 days), concrete containing fly ash at replacement levels of
30, 40, and 50% has lower compressive strength, higher permeability, and
higher carbonation rates then concrete containing no fly ash. However, at later
ages (90 days & 1 year), concrete containing fly ash at replacement levels of
30, 40, and 50% has lower permeability, but still lower compressive strengths
(if not continuously cured for 1 year) and higher carbonation rates then
concrete containing no fly ash.
3. Increasing the duration of moist curing for high-volume fly ash concrete
results in higher compressive strength, lower permeability, and lower
carbonation rates.
4. Strength, permeability, and carbonation values were all affected by fly ash
composition. However, from the data it is not possible to discern trends
between composition and performance.
5. Only one curing compound of the three tested was effective at slowing the
rate of carbonation. The most effective curing compound at slowing the rate
of carbonation was the curing compound CC2 (Type 2, Class B) with 2
applications. However, this conclusion is based on limited data and further
investigation is required to determine the effect of curing compounds on
carbonation rates.
6. Electrical resistivity correlates very well with rapid chloride permeability
testing. There is a better correlation with low permeable concrete than with
highly permeable concrete because of the heating effect that occurs during the
rapid chloride permeability test with high permeable concrete.
94
7. Accelerated carbonation is an effective method for predicting natural
carbonation rates.
8. Guidelines for the use of high-volume fly ash concrete were developed with
respect to W/CM, curing, fly ash content, and depth of cover.
95
7.0 Recommendations
After completion of the project, the following recommendations for further research with
regards to high volume fly ash concrete are outlined below.
1. Annual testing of the indoor and outdoor exposed carbonation specimens produced
for this project should be continued for the next 10 years. Carbonation rates (k)
and the carbonation predictive model developed for this project should be updated
as annual data become available.
2. Methods of internal curing such as the incorporation of saturated lightweight
aggregate or water-absorbing polymers should be investigated.
3. The effects of curing on freeze-thaw resistance, deicer salt scaling resistance, and
drying shrinkage should be investigated.
4. Specimens made with HFVA concrete should be reinforced with steel and
measurements made to determine corrosion rates, once corrosion has initiated.
5. Micro structural studies should be conducted on paste and mortar samples to
provide the following information:
a. How curing affects the development of the pore structure using both
mercury intrusion porosimetry and image analysis of polished samples by
scanning electron microscopy.
b. How micro structural changes influence carbonation using microhardness,
scanning electron microscopy, and X-ray diffraction analysis.
c. How curing and carbonation influence water, vapor, and chloride transport
using magnetic resonance imaging measurements.
6. Field studies should be conducted on concrete structures built with relatively high
volumes of fly ash (greater than 40%) to determine strength, permeability, and
carbonation depths of HVFA concrete in the field.
7. Research should be conducted to determine if concrete consisting of high volume
supplementary cementing materials (HVSCM) made with slag are equally as
vulnerable as HVSCM made with fly ash.
8. Research should be conducted to determine the influence of fly ash composition on
strength, permeability, and carbonation. A study that included more ashes and
more detailed characterization of the ashes may address this.
96
9. The poor performance of HVFA in the laboratory with regards to carbonation
should be confirmed by field exposure of larger samples. For example, larger
specimens should be constructed and placed on an exposure site. These specimens
could include suspended slab specimens to investigate carbonation of the top
(exposed) surface versus the bottom surface, exposed wall specimens to
investigate windward versus leeward exposure, and column specimens both
exposed and covered.
10. A field survey of existing HVFAC structures should be conducted to determine
the extent of corrosion and influence of microenvironment.
11. Effect of curing compounds on the rate of carbonation warrants further
investigation.
97
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101
CURRICULUM VITAE
Candidate's full name:
Donald Burden
Universities attended:
Memorial University 1997 1999.

University of New Brunswick, 1999-2003, B.Sc. E. (Civil).
Publications:
N/A
Conference Presentations:
N/A
Awards:
Bremner Scholarship in Concrete Materials 2004/2005

Natural Sciences and Engineering Research Council (NSERC) Industrial
Postgraduate Scholarship 2004/2005
Portland Cement Association Research Fellowship 2003/2005
Board of Governors Merit Award for Graduate Studies 2003/2004
Natural Sciences and Engineering Research Council (NSERC) Summer Research
Award 2003
D. Malcolm Jeffrey Memorial Prize 2002/2003
J. Nairn McCaffrey Memorial Scholarship 2002/2003, 2001/2002, 2000/2001
Dr. Theodore Weiner Memorial Scholarship 2002/2003
Allan K. Grimmer Prize 1999/2000
Barney Goodland Memorial Scholarship 1997/1998
University of New Brunswick Deans List 1999/2000, 2000/2001, 2001/2002,
2002/2003
Principle Honor List Memorial University 1997/1998, 1998/1999

Fly Ash in Concrete

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Fly Ash in Concrete

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PCA R&D Serial No.

The Durability of Concrete Containing

Donald Burden Thesis, Masters of Science in Engineering 2006

The Durability of Concrete Containing High Levels of

Masters of Science in Engineering

Dr. Michael Thomas, Civil Engineering

Dr. Lloyd M. Waugh, Civil Engineering

Dr. Guida Bendrich, Chemical Engineering

This thesis is accepted by the

THE UNIVERSITY OF NEW BRUNSWICK

4.0 Summary of Results.............................................................................................34

Figure 5.5 Rapid Chloride Permeability vs. Carbonation for Different

1.2 Problem Statement

1.3 Significance of Problem

1.4 Goal and Objectives

2.0 Literature Review

Ardencraig Townhouse Renovation

2.1.3 Definition of High Volume Fly Ash Concrete (HVFA)

2.2 Effect of HVFA on Concrete Properties / Potential Problems

2.2.2 Plastic Shrinkage

2.2.3 Heat of Hydration

2.2.5.1 Relationship between Electrical Conductivity and Permeability

Hydraulic Permeability (u Darcys)

Rapid Chloride Permeability (Coulombs)

2.2.6.2 Factors Influencing the Rate of Carbonation

2.2.6.3 Conditions that Promote Carbonation Induced Corrosion of

Exposure Carbonation induced corrosion is most prevalent in environments

3.0 Laboratory Research

3.2 Materials & Mixture Proportions

Bogue Potential Compound Composition, %

3.2.2 Fly Ash

Table 3.2 Chemical Analysis & Physical Properties of Fly Ashes

3.2.5 Curing Compounds

3.2.6 Mixture Proportions

3.3 Preparation, Casting, Curing, & Testing of Specimens

Table 3.3 Mixture Proportions

Note: All measured slumps were 100-150 mm.

Table 3.4 Phase 1 Curing Regimes

Strength & RCPT

Test at 90 days and

Figure 3.1 Sketch of Accelerated Carbonation Setup

Figure 3.2 Accelerated Carbonation Chamber

Figure 3.3 Outdoor Exposure Condition

Figure 3.4 Equipment Used to Obtain Freshly Fractured Concrete

Figure 3.5 Freshly Fractured Concrete Sprayed with Phenolphthalein Indicator

4.0 Summary of Results

Table 4.1 Compressive Strength Data

28 Day Strength, MPa

1 Year Strength, MPa

28 Day Compressive Strength (MPa)

fly ash 30%

Figure 4.1 Curing vs. 28 Day Compressive Strength (W/CM=0.50)

28 Day Compressive Strength (MPa)

Figure 4.2 Curing vs. 28 Day Compressive Strength (W/CM=0.40)

28 Day Compressive Strength (MPa)

fly ash 30%

Figure 4.3 Curing vs. 28 Day Compressive Strength (W/CM=0.34)

Compressive Strength (MPa)