Effect of Early Carbonation Curing on Alkali-Silica Reaction in Concrete

by
Naweed Mohammad

Department of Civil Engineering and Applied Mechanics

McGill University, Montréal, Québec, Canada
Dec. 2017

A thesis submitted to McGill University in partial fulfillment of the requirements for the degree of
Master of Civil Engineering

© Naweed Mohammad, 2017

This page is intentionally left blank
 ABSTRACT

Alkali-silica reaction (ASR) is one of the principal causes of maintenance and rehabilitation in concrete
structures. ASR is a reaction between alkali from cement and reactive silica from aggregates. The
primary aim of this thesis was to investigate the possibility of ASR reduction or elimination in concrete
by early carbonation curing. The secondary goal was to determine the optimum early carbonation
exposure time that leads the highest strength and carbon dioxide gas sequestration in concrete. The
effect of early carbonation curing on ASR expansion was assessed via length increase standard tests
such as accelerated mortar bar test (AMBT) and modified accelerated mortar bar test (MAMBT). Spratt
aggregates were used as alkali-reactive aggregates in mortar bar tests. Four batches were tested
including moist hydration reference, air dry hydration reference, 2-hour carbonation and 18-hour
carbonation. It was found that both 2-h and 18-h carbonation reduce significantly the ASR expansion.
At 14 days, the expansion in carbonated mortar bar was 0.01-0.02%, considerably lower than the
threshold value of 0.1% while the two hydration references experienced an expansion in a range of
0.32-0.35%, confirming that Spratt aggregates were reactive. ASR reduction by early carbonation is
attributed to the facts that early carbonation converts calcium hydroxide, an essential compound in
ASR reaction, to calcium carbonate, and the surface densification of mortar decreases water flow
which is essential for ASR reaction. Moreover, the 112 days’ compressive strength of mortar cubes is
higher in carbonated samples (63.3, and 59.3 MPa) than that in hydrated references (46.3 and
41.9MPa), leading to more resistance to expansion induced cracking. The carbon dioxide uptake by 2h
and 18h carbonation cured mortar bars were 15.8 and 22.8 %. It was indicative that early carbonation
is effective in carbon utilization and sequestration. The carbonation duration has an effect on carbon
uptake, but not on strength gain and the degree of ASR reduction.

I
 RÉSUMÉ

La réaction alcali-silice (ASR) est l'une des principales causes de maintenance et de réhabilitation des
structures en béton. ASR est une réaction entre l'alcali du ciment et la silice réactive des agrégats. Le
but principal de cette thèse était d'étudier la possibilité de réduction ou d'élimination de l'ASR dans le
béton par un durcissement précoce par carbonatation. L'objectif secondaire était de déterminer le
temps d'exposition optimal à la carbonatation précoce qui conduit à la plus forte concentration et à la
séquestration de gaz carbonique dans le béton. L'effet de la maturation rapide de la carbonatation sur
l'expansion de l'ASR a été évalué au moyen d'essais normalisés d'augmentation de la longueur tels que
l'essai accéléré au mortier (AMBT) et l'essai au mortier accéléré modifié (MAMBT). Les agrégats de
Spratt ont été utilisés comme agrégats réactifs aux alcalis dans les essais de barres de mortier. Quatre
lots ont été testés, y compris la référence d'hydratation humide, la référence d'hydratation sèche à
l'air, la carbonatation à 2 heures et la carbonatation à 18 heures. Il a été constaté que la carbonatation
de 2 h et de 18 h réduit significativement l'expansion de l'ASR. Après 14 jours, l'expansion dans la barre
de mortier carbonatée était de 0,01-0,02%, considérablement inférieure à la valeur seuil de 0,1%,
tandis que les deux références d'hydratation présentaient une expansion dans une plage de 0,32-
0,35%, confirmant que les agrégats de Spratt étaient réactifs. La réduction de l'ASR par carbonatation
précoce est attribuée au fait que la carbonatation précoce convertit l'hydroxyde de calcium, un
composé essentiel dans la réaction ASR, en carbonate de calcium et que la densification du mortier
diminue le débit d'eau essentiel à la réaction ASR. De plus, la résistance à la compression de 112 jours
des cubes de mortier est plus élevée dans les échantillons carbonés (63,3 et 59,3 MPa) que dans les
références hydratées (46,3 et 41,9 MPa), ce qui augmente la résistance aux fissures induites par
dilatation. L'absorption de dioxyde de carbone par les barres de mortier durcies par carbonatation 2h
et 18h était de 15,8 et 22,8%. Il était indicatif que la carbonatation précoce est efficace dans
l'utilisation et la séquestration du carbone. La durée de la carbonatation a un effet sur l'absorption du
carbone, mais pas sur le gain de force et le degré de réduction de l'ASR.

II
 ACKNOWLEDGEMENTS

I am immensely thankful to my supervisor, Prof. Yixin Shao, without whom this work would not
have been possible. His exceptional technical knowledge, patience, and guidance helped me overcome
many challenges throughout my research.
I would like to thank Mr. John Bartczak, Dr. Bill Cook, Dr. Andrew Komar, Ms. Galyna Shul, Mr.
Michel Preda, Dr. Mehrdad Mahoutian, Damon Kiperchuk, and Mr. Shipeng Zhang for their technical
knowledge and their help with the laboratory work. Moreover, I am grateful for being part of Professor
Shao’s fantastic research group. I would like to also thank Mr. Muhammad Shoaib Ashraf for continuing
the laboratory experiments.
I would like to extend my gratification to Ontario’s Ministry of Transport, and Bauval CMM for
supplying of Spratt and Granite aggregates, respectively. I am thankful to Mr. Richard Sideritz and Mr.
Serge Baril for their help and kindness.
I appreciate the financial assistance of Natural Sciences and Engineering Research Council of
Canada (NSERC), and McGill’s Financial Aid and Bursary Office.

III
 DEDICATIONS

I would like to dedicate this dissertation to my family and Ms. Noor Hassanaly for their
continuous support, patience and unconditional love.

IV
 TABLE OF CONTENTS
ABSTRACT ............................................................................................................................................ I

RÉSUMÉ .............................................................................................................................................. II

ACKNOWLEDGEMENTS ...................................................................................................................... III

DEDICATIONS .....................................................................................................................................IV

LIST OF TABLES .................................................................................................................................VIII

LIST OF FIGURES ................................................................................................................................. IX

LIST OF ACRONYMS ............................................................................................................................ XI

I. GENERAL ............................................................................................................................................ XI
II. STANDARDS ........................................................................................................................................ XI
III. TESTS .................................................................................................................................................. XI
IV. CEMENT CHEMISTRY NOTATIONS ....................................................................................................... XI
V. CURING CONDITIONS ......................................................................................................................... XII

1 Chapter 1 - INTRODUCTION ..................................................................................................... - 1 -

1.1 OVERVIEW ................................................................................................................................... - 1 -
1.2 RESEARCH OBJECTIVES ................................................................................................................ - 3 -
1.3 THESIS STRUCTURE ...................................................................................................................... - 3 -

2 Chapter 2 - LITERATURE REVIEW.............................................................................................. - 5 -

2.1 OVERVIEW ................................................................................................................................... - 5 -
2.2 SUMMARY OF ALKALI-SILICA REACTION (ASR) ............................................................................. - 5 -
2.2.1 ASR CHEMISTRY ............................................................................................................................. - 11 -
2.2.2 CURRENT ASR MITIGATION TECHNIQUES ..................................................................................... - 16 -
2.2.3 CURRENT ASR PREVENTING TECHNIQUES ..................................................................................... - 19 -
2.3 PROPOSED MITIGATION ALTERNATIVE ...................................................................................... - 20 -
2.4 CARBONATION .......................................................................................................................... - 21 -
2.4.1 WEATHERING CARBONATION ....................................................................................................... - 21 -
2.4.2 EARLY CARBONATION CURING MECHANISMS .............................................................................. - 22 -
2.4.3 CARBON UPTAKE QUANTIFICATION METHODS ............................................................................ - 24 -

V
 2.5 EXPANSION TESTS METHODS FOR ASR EVALUATION ................................................................. - 27 -
2.5.1 ACCELERATED MORTAR BAR TEST (AMBT or ASTM C1260) .......................................................... - 27 -
2.5.2 CONCRETE PRISM TEST (CPT or ASTM C1293)............................................................................... - 28 -
2.5.3 COMPETING ASR ASSESSMENT TESTS ........................................................................................... - 29 -
2.6 ASR ASSESSMENT BY NON-DESTRUCTIVE TECHNIQUES .............................................................. - 30 -
2.6.1 CRACK QUANTIFICATION TEST ...................................................................................................... - 30 -
2.6.2 SURFACE RESISTIVITY TEST ............................................................................................................ - 32 -
2.7 CHEMICAL ANALYSIS .................................................................................................................. - 34 -
2.7.1 X-RAY DIFFRACTION (XRD) ............................................................................................................. - 34 -
2.8 COMPRESSIVE TEST ................................................................................................................... - 34 -

3 Chapter 3 - EXPERIMENTAL PROGRAM .................................................................................. - 37 -

3.1 OVERVIEW ................................................................................................................................. - 37 -
3.2 ASTM STANDARD MATERIAL PROPERTY TESTS .......................................................................... - 38 -
3.3 MORTAR BARS (MB) .................................................................................................................. - 38 -
3.3.1 MIX PROPORTIONS FOR MORTAR BARS ........................................................................................ - 38 -
3.3.2 SPRATT AGGREGATES’ PREPARATION FOR MORTAR BARS ........................................................... - 39 -
3.3.3 CASTING OF MORTAR BARS ........................................................................................................... - 40 -
3.3.4 CURING PROCEDURE FOR MORTAR BARS OF AMBT ..................................................................... - 41 -
3.3.5 CURING PROCEDURE FOR MORTAR BARS OF MAMBT ................................................................. - 43 -
3.3.6 CO2 UPTAKE MEASUREMENT METHODS USED FOR MB ............................................................... - 43 -
3.3.7 ASR EXPANSION TEST METHODS FOR MORTAR BARS .................................................................. - 46 -
3.3.8 ASR ASSESSMENT OF MB BY NON-DESTRUCTIVE TECHNIQUES .................................................... - 48 -
3.3.9 MORTAR BARS’ X-RAY DIFFRACTION (XRD) ................................................................................... - 51 -
3.3.10 MORTAR BARS’ COMPRESSIVE TEST AFTER AMBT ................................................................... - 52 -
3.3.11 pH tests...................................................................................................................................... - 53 -

4 CHAPTER 4 - RESULTS AND DISCUSSION ................................................................................ - 55 -

4.1 MORTAR BARS (MB) TEST FOR AMBT ........................................................................................ - 55 -
4.1.1 ACCELERATED MORTAR BAR TEST (AMBT /ASTM 1260) ............................................................... - 55 -
4.1.2 OPTIMAL WATER REMOVAL FOR CARBON UPTAKE IN MB ........................................................... - 58 -
4.1.3 CARBON UPTAKE OF MB ACCORDING TO DIFFERENT METHODS ................................................. - 59 -
4.1.4 CRACK QUANTIFICATION METHOD AFTER AMBT ......................................................................... - 70 -

VI
 4.1.5 SURFACE RESISTIVITY AFTER AMBT ............................................................................................... - 74 -
4.1.6 COMPRESSIVE TEST AFTER AMBT .................................................................................................. - 75 -
4.2 XRD OF MORTAR BARS .............................................................................................................. - 76 -
4.3 pH TESTS OF MORTAR BARS ...................................................................................................... - 78 -
4.4 MORTAR BARS (MB) FOR MAMBT ............................................................................................. - 81 -
4.4.1 CARBON UPTAKE OF MORTAR BARS ............................................................................................. - 81 -
4.4.2 MODIFIED ACCELERATED MORTAR BAR TEST (MAMBT) .............................................................. - 82 -
4.4.3 CRACK QUANTIFICATION AFTER MAMBT ...................................................................................... - 84 -

5 CHAPTER 5 - CONCLUSIONS AND RECOMMENDATIONS ........................................................ - 87 -

5.1 CONCLUSIONS ........................................................................................................................... - 87 -
5.2 RECOMMENDATIONS FOR FUTURE WORK ................................................................................. - 89 -

6 REFERENCES .......................................................................................................................... - 90 -

VII
 LIST OF TABLES
Table 2-1: Aggregates types vulnerable to ASR ...................................................................................... - 6 -
Table 3-1: Mixture proportions of MB .................................................................................................. - 38 -
Table 3-2: Fine Spratt aggregates grading requirements of MB .......................................................... - 39 -
Table 3-3: Fine Spratt aggregates properties ....................................................................................... - 39 -
Table 3-4: Details of curing procedure for MB ..................................................................................... - 42 -
Table 3-5: MB water loss due to curing ................................................................................................ - 42 -
Table 3-6: Curing procedure for MB ..................................................................................................... - 43 -
Table 3-7: MB water loss due to curing ................................................................................................ - 43 -
Table 4-1: Summary of AMBT ............................................................................................................... - 56 -
Table 4-2: Summary of MB CO2 content according to different methods ........................................... - 60 -
Table 4-3: CO2 content of MB used for TGA according to mass gain method ..................................... - 61 -
Table 4-4: CO2 content of MB used for AMBT according to mass gain method .................................. - 61 -
Table 4-5: TGA summary of crushed MB .............................................................................................. - 62 -
Table 4-6: Calcium carbonate and calcium hydroxide dissociation temperature from MS of MB ...... - 62 -
Table 4-7: Chemical analysis of cement and aggregates ...................................................................... - 68 -
Table 4-8: Chemical analysis of crushed MB by XRF ............................................................................. - 69 -
Table 4-9: Corrected average TGA-MS CO2 content of crushed MB by XRF ........................................ - 69 -
Table 4-10: MB CO2 content according to TGA-MS and TGA-MS-XRF ................................................. - 70 -
Table 4-11: MB pH after initial curing and subsequent hydration ....................................................... - 80 -
Table 4-12: CO2 content of MB according to mass gain method ......................................................... - 82 -
Table 4-13: Evaluation criteria for AMBT and MAMBT ........................................................................ - 82 -
Table 4-14: Summary of MAMBT.......................................................................................................... - 83 -

VIII
 LIST OF FIGURES
Figure 2-1: Conditions for ASR damage .................................................................................................. - 6 -
Figure 2-2: A typical curve of the Pessimum reactive aggregates in concrete....................................... - 7 -
Figure 2-3: The effect of aggregate type on the Pessimum ratio in AMBT ............................................ - 8 -
Figure 2-4: The aggregate grain size effect on expansions..................................................................... - 9 -
Figure 2-5: Cracking of concrete by ASR ............................................................................................... - 10 -
Figure 2-6: Map cracking of concrete by ASR ....................................................................................... - 10 -
Figure 2-7: Pop-outs caused by ASR ..................................................................................................... - 11 -
Figure 2-8: Crystalline structure of silica network ................................................................................ - 12 -
Figure 2-9: Amorphous structure of silica network .............................................................................. - 12 -
Figure 2-10: Dissolution of silica (siloxane) network ............................................................................ - 13 -
Figure 2-11: Typical crack pattern of concrete due to ASR .................................................................. - 15 -
Figure 2-12: Topical application of lithium solution for ASR ................................................................ - 17 -
Figure 2-13: Topical application of Silane solution ............................................................................... - 18 -
Figure 2-14: Benefits of Silane solution for highway barriers .............................................................. - 19 -
Figure 2-15: Cement composition changes during hydration and carbonation curing........................ - 24 -
Figure 2-16: A typical original image of moist reference ..................................................................... - 31 -
Figure 2-17: Matlab processed image with TH = 0.62 .......................................................................... - 32 -
Figure 2-18: Matlab processed image with TH = 0.40 .......................................................................... - 32 -
Figure 2-19: Correction factor K for surface resistivity......................................................................... - 33 -
Figure 2-20: Surface resistivity setup for mortar bars .......................................................................... - 34 -
Figure 2-21: Hydration vs. carbonation curing for the strength of concrete ....................................... - 35 -
Figure 2-22: Steam vs. carbonation curing for the strength of concrete ............................................. - 36 -
Figure 3-1: Map of major tests ............................................................................................................. - 37 -
Figure 3-2: Spratt aggregates’ preparation overview ........................................................................... - 40 -
Figure 3-3: Carbonation curing setup ................................................................................................... - 42 -
Figure 3-4: Length comparator apparatus for AMBT and MAMBT ...................................................... - 47 -
Figure 3-5: Image acquisition and analysis setup ................................................................................. - 49 -
Figure 3-6: Specimen locations used for image analysis ...................................................................... - 49 -

IX
Figure 3-7: Surface resistivity measurement ........................................................................................ - 51 -
Figure 3-8: XRD sample preparation ..................................................................................................... - 51 -
Figure 3-9: XRD apparatus .................................................................................................................... - 52 -
Figure 3-10: Compressive test 25 mm MB samples ............................................................................. - 53 -
Figure 3-11: Compressive strength test setup ...................................................................................... - 53 -
Figure 4-1: Effect of early carbonation curing on expansion of Spratt MB according to AMBT .......... - 56 -
Figure 4-2: Effect of carbonation on weight increase of MB during AMBT ......................................... - 57 -
Figure 4-3: Optimal initial water removal for max carbon uptake in MB ............................................ - 59 -
Figure 4-4: Dissociation of moist reference sample of crushed MB during a TGA-MS test ................. - 64 -
Figure 4-5: Dissociation of dry reference sample of crushed MB during a TGA-MS test ..................... - 65 -
Figure 4-6: Dissociation of 2h carbonation sample of crushed MB during a TGA-MS test .................. - 65 -
Figure 4-7: Dissociation of 18h carbonation sample of crushed MB during a TGA-MS test ................ - 66 -
Figure 4-8: TG and MS (ion currents) of moist reference sample of crushed MB................................ - 66 -
Figure 4-9: TG and MS (ion currents) of dry reference sample of crushed MB ................................... - 67 -
Figure 4-10: TG and MS (ion currents) of 2h carbonation sample of crushed MB............................... - 67 -
Figure 4-11: TG and MS (ion currents) of 18h carbonation sample of crushed MB............................. - 68 -
Figure 4-12: Visual crack inspection of MB after AMBT ....................................................................... - 71 -
Figure 4-13: Microscopic crack inspection samples of MB after AMBT ............................................... - 72 -
Figure 4-14: Effect of carbonation on crack width of MB after AMBT ................................................. - 73 -
Figure 4-15: Effect of carbonation on crack area of MB after AMBT ................................................... - 74 -
Figure 4-16: Effect of early carbonation on surface resistivity of 112 days old MB ............................. - 75 -
Figure 4-17: Effect of early carbonation on compressive strength of MB cubes ................................. - 76 -
Figure 4-18: XRD patterns of crushed MB samples .............................................................................. - 77 -
Figure 4-19: Effect of early carbonation on MB carbonation depth .................................................... - 79 -
Figure 4-20: MB pH after initial curing and subsequent hydration ...................................................... - 81 -
Figure 4-21: Expansion of MB (Spratt fines) according to MAMBT ...................................................... - 83 -
Figure 4-22: Visual crack inspection of MB after MAMBT .................................................................... - 84 -
Figure 4-23: Effect of carbonation on crack width of MMB after MAMBT .......................................... - 85 -
Figure 4-24: Microscopic crack inspection samples of MMB after MAMBT ........................................ - 86 -

X
 LIST OF ACRONYMS

I. GENERAL

OD: Oven dry

SSD: Surface saturated dry
MB: Mortar bars

II. STANDARDS

ASTM: American Society for Testing and Materials

CSA: Canadian Standards Association

III. TESTS

ASTM C1260-14 or AMBT: Standard test method for
potential alkali reactivity of aggregates
Accelerated mortar bar test
MAMBT: Modified test method for
potential alkali reactivity of aggregates
TGA-MS: Thermogravimetric analysis – mass spectrometry
XRD: X-ray diffraction
XRF: X-ray fluorescence

IV. CEMENT CHEMISTRY NOTATIONS

C CaO - Calcium oxide or lime

C CO2 - Carbon dioxide

H H2O – Water
S SiO2 - Silicon dioxide or silica
A Al2O3 - Aluminum oxide
F Fe2O3 - Iron oxide
C3S 3 CaO ⋅ SiO2 - Tricalcium silicate

C2S 2 CaO ⋅ SiO2 - Dicalcium silicate

C3A 3 CaO ⋅ Al2O3 - Tricalcium aluminate

XI
 CSH Calcium silicate hydrates of various C/S ratio

V. CURING CONDITIONS

AMBT
Reference moist sample: tested for 16 days at 80 C according to ASTM C1260
Reference dry sample: tested for 16 days at 80 C according to ASTM C1260
2h carbonation sample: tested for 16 days at 80 C according to ASTM C1260
18h carbonation sample: tested for 16 days at 80 C according to ASTM C1260
AMBT modified
Reference moist sample: tested for 30 days at 100 C according to modified ASTM C1260
18h carbonation sample: tested for 30 days at 100 C according to modified ASTM C1260

XII
 1 Chapter 1 - INTRODUCTION

1.1 OVERVIEW

Concrete is the most used construction material in structures worldwide (Chen et al.
2016, Portland Cement Association 2017). It is composed primarily of three components:
cement, aggregates, and water. If the aggregates have enough reactive silica and a sufficient
alkali supply is available either from cement or an external source, then alkali-silica reaction
(ASR), a detrimental reaction may occur in concrete. Spratt aggregate has been shown to have
sufficient reactive silica (9 % SiO2) to cause ASR (Rogers et al. 2012). Alkali-silica reaction (ASR)
is one of the principal reasons of maintenance and rehabilitation in concrete structures
worldwide (Rajabipour et al. 2015). ASR requires the right amount of alkali, reactive silica and
moisture to cause damage. The reaction between unstable silica and alkalis leads to a
hydrophilic silica gel formation (Stark 1991, Liu et al. 2002, Grinys et al. 2014, Lucerno 2016). In
the presence of moisture, the gel absorbs moisture and expands causing tensile stress in
concrete (Stark 1991). If enough moisture is supplied, the pressure posed by the gel will surpass
the tensile stress of concrete and generate micro-cracks. The formation of micro-cracks allows a
higher flow of moisture inside concrete that is absorbed by silica gel and accelerates the ASR-
induced damage. At later stages of ASR, a crack pattern is visible on the surface of concrete
structures (Kosmatka et al. 2011).
ASR cannot occur if any of the three conditions is not met (Stark 1991). In existing
structures affected by ASR, a mitigation that completely stops ASR damage is not in place
(Johnson 2011). Three improvements are available to suppress ASR damage in new structures
possibly: using low-alkali cement, supplementary cementing materials (SCM), avoiding reactive
aggregates or adding lithium ions (Golmakani 2013). The most efficient way to prevent ASR
would be to avoid reactive aggregates altogether. However, these options may not always be
available.
This work attempts to find an effective alternative to mitigate or prevent ASR in new
structures. An early carbonation curing is the proposed alternative. The early carbonation

-1-
curing could alleviate ASR via at least two mechanisms. First, the early carbonation converts
calcium hydroxide (CH) to calcium carbonate a stable and denser compound (Rostami et al.
2012). CH is an essential reactant in ASR. Therefore, a decrease in CH content should reduce
ASR. Second, surface densification by early carbonation curing reduces the permeability of
mortar and concrete (Rostami et al. 2012). Thus, less water is penetrated in carbonation cured
mortar and concrete. Since, water is an essential component of ASR, a decrease in water
ingress should consequently mitigate ASR in carbonated cured mortar and concrete. The early
carbonation curing as compared to steam or moist room curing has been reported to have
many other benefits such as higher early strength, better durability and capacity of storing
carbon dioxide (Shao et al. 2011, Zhang 2016).
Carbon dioxide gas is a greenhouse gas that impacts global warming. Greenhouse gases
absorb energy in the form of light. Once, the gases become energized and unstable, they
release their energy in the form of heat in the atmosphere (Creamer et al. 2015). Consequently,
the capturing and sequestration of carbon dioxide is thought to be potentially beneficial in
coping with global warming.
Early carbonation curing is a carbon sequestration process. Gaseous CO2 is converted
into solid calcium carbonates, making concrete stronger and more durable. It is hoped that
early carbonation can also reduce or eliminate the ASR in concrete with reactive aggregates
because of the reduction in calcium hydroxide and the improved resistance to moisture
permeation.

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1.2 RESEARCH OBJECTIVES

The primary aim of this research was to investigate the possibility of ASR reduction or
elimination in mortar made with ASR reactive aggregates by an early carbonation curing
process. The secondary goal was to determine the optimum early carbonation exposure time
that leads to the highest strength and maximum carbon dioxide gas sequestration in mortar.
One of the ASR standard test methods is the accelerated mortar bar test (AMBT or
ASTM C1260) (Pac 2008). AMBT is preferred over the other test methods since it predicts the
reactivity of aggregates within only 16 days (ASTM C1260-14 2014). Thus, AMBT was used to
assess the effectiveness of the early carbonation curing on ASR. Moreover, a modified
accelerated mortar bar test (MAMBT) was also tested to demonstrate the effectiveness of early
carbonation curing at excessively severe conditions.
To accomplish the two principal goals, the research objectives were:

1. To develop carbonation curing protocol to maximize carbon uptake and

compressive strength, and minimize ASR in mortar bars.
2. To assess the effectiveness of the early carbonation curing on alkali-silica
reactive mortar bars via accelerated mortar bar test (AMBT) and modified
accelerated mortar bar test (MAMBT).
3. To evaluate the efficiency of the early carbonation curing on alkali-silica reactive
mortar bars via non-destructive tests such as crack quantifications and surface
resistivity.

1.3 THESIS STRUCTURE

This dissertation is divided into five chapters. Chapter 1 introduces the context,
importance, and objectives of the research. Chapter 2 presents the relevant literature review
needed to understand the reactions, processes, and tests. It also explains the rationale behind
the experimental program. Chapter 3 demonstrates the details of the experimental program.
Mortar bars are split into two parts: mortar bar tests (MB) and modified mortar bar test

-3-
(MMB). MB and MMB followed ASTM C1260-14 for the materials preparation, apparatus, mix
proportions and procedures (2014). Chapter 4 presents the results and discussions. Finally,
Chapter 5 summarizes the conclusions and recommends improvements for future research.

-4-
 2 Chapter 2 - LITERATURE REVIEW

2.1 OVERVIEW

First, ASR’s general expansion mechanism, chemical reactions and the current mitigation
options are explained. Then, an ASR alleviation methods including early carbonation curing is
described. The laboratory test methods used to evaluate the effectiveness of the proposed
mitigation method are also reviewed. The tests were crack quantification, surface resistivity, X-
ray fluorescence (XRF), X-ray diffraction (XRD), phenolphthalein investigation, and compressive
test.

2.2 SUMMARY OF ALKALI-SILICA REACTION (ASR)

Alkali-silica reaction (ASR) is one of the leading causes of maintenance and rehabilitation
in concrete structures worldwide (Rajabipour et al. 2015). ASR is a reaction between alkali pore
solution from cement and reactive silica from aggregates. For ASR to occur the right amount of
alkali, reactive silica and moisture must be present as shown in Figure 2-1. ASR is a kinetic
reaction, so it accelerates as the temperature is increased (Lucerno 2016). ASR is a multiple step
process. First, the hydroxyl ions from alkalis such as calcium hydroxide (Portlandite), sodium
hydroxide, and potassium hydroxide react with unstable (amorphous) silica from reactive
aggregates (Stark 1991, Xu et al. 1995, Liu et al. 2002, Grinys et al. 2014). All aggregates do not
have reactive silica. The list of most popular reactive aggregates is presented in Table 2-1
(Lucerno 2016). The reaction between unstable silica and alkalis leads to a hydrophilic silica gel
formation (Stark 1991, Liu et al. 2002, Grinys et al. 2014, Lucerno 2016). In the presence of
sufficient moisture (above 80 %), the gel absorbs moisture and expands causing tensile stress in
concrete (Stark 1991, Pedneault 1996). Moisture or water should be continuously supplied
from an outside source for the stress resulting from the gel to surpass the tensile stress of
concrete and generate micro-cracks. The formation of micro-cracks allows a higher flow of
moisture inside concrete that is absorbed by silica gel and thus, accelerates the ASR-induced
damage.

-5-
 Figure 2-1: Conditions for ASR damage
(Lucerno 2016)

reactive
physical property rock type occurrence
component
common as a minor
Opaline limestone (Spratt
Opal constituent in
limestone), cherts, shale, flint
sedimentary rocks
amorphous Regions of volcanic
volcanic glasses (rhyolite, andesite, origin; river gravels
Silicate glass
dacite) and tuffs; synthetic glasses originating in volcanic
areas; container glass
microcrystalline Silicious limestones and
Chalcedony Widespread
Quartz sandstones, cherts, and flints
Cristobalite crystalline
Opaline rocks, fired ceramics Uncommon
(Tridymite) metastable
Metaquartzite, sands, gravel,
disordered due to sandstones, many metamorphic
Strained Quartz
strain effects rocks (e.g., granite gneiss and Common
schists)
Table 2-1: Aggregates types vulnerable to ASR
(Lucerno 2016)

-6-
 Other factors that affect ASR are the type, the Pessimum ratio of aggregates containing
reactive (amorphous) silica, and size. The Pessimum ratio is defined as the percentage of
reactive aggregate that causes the maximum expansion in ASR (Binal 2015). Two of the most
common types of aggregates known for causing ASR in Canada are Spratt and Sudbury. These
aggregates have been extensively studied in several laboratories over many years. In this work,
Spratt, the most famous alkali-silica reactive aggregate, has been used. Spratt aggregate is a
limestone with a small amount of visible black Chert and Chalcedony. It comes from a quarry in
Stittsville, Ontario and is slightly siliceous (9 % SiO2) (Rogers et al. 2012). Another literature
classifies the Spratt aggregates as Opal as demonstrated in Table 2-1 (Lucerno 2016). In any
case, the most convenient and economical way of obtaining Spratt aggregate for research
purposes is through the Ontario Ministry of Transport.
The reactive aggregate’s Pessimum ratio is believed to be 25 % in concrete as shown in
Figure 2-2 (French 1980). In mortar bars made according to AMBT, the Pessimum ratio is
dependent on the type of reactive aggregate used as demonstrated in Figure 2-3. The
Pessimum ratio for Opal, Chert, and Chalcedony are about 20, 40, and 50 %, respectively (Binal
2015).

Figure 2-2: A typical curve of the Pessimum reactive aggregates in concrete

(French 1980)

-7-
Figure 2-3: The effect of aggregate type on the Pessimum ratio in AMBT
(Binal 2015)

-8-
 Figure 2-4: The aggregate grain size effect on expansions
(Binal 2015)

Based on fundamentals of chemical reactions, the reactivity of the aggregates is

expected to intensify with decreasing size of the aggregates since the surface area of reactants
are increased (Rajabipour et al. 2015). However, the experimental data does not support this
theory. In fact, the aggregate size range that causes maximum expansion in AMBT for Opal,
Chert and Chalcedony is 0.15-0.3 mm as demonstrated in Figure 2-4 (Binal 2015).

-9-
 At later stages of untreated ASR, a cracking pattern is usually visible on the surface of
structures. ASR can cause serviceability problems and can worsen other deleterious
mechanisms such as freeze-thaw, sulfate attack and damage resulting from deicing salts
(Kosmatka et al. 2011). Figure 2-5, Figure 2-6, and Figure 2-7 demonstrates the types of
cracking caused by ASR.

Figure 2-5: Cracking of concrete by ASR

(Kosmatka et al. 2011)

Figure 2-6: Map cracking of concrete by ASR

(Kosmatka et al. 2011)

- 10 -
 Figure 2-7: Pop-outs caused by ASR
(Kosmatka et al. 2011)

2.2.1 ASR CHEMISTRY

The alkali-silica reaction (ASR) is divided into a few significant steps for explanation
purposes: the dissolution of the reactive silica by hydroxyl ions present in pore solution, the
ASR gel formation, and the ASR gel expansion. However, in reality, these steps coincide
(Golmakani 2013, Rajabipour et al. 2015). In general, most researchers agree about the overall
mechanism of ASR. There has been some disagreement on some steps of the reaction over the
years (Chatterji 2005, Ichikawa et al. 2007, Federal Highway Administration 2012, Pan et al.
2012, Golmakani 2013).

2.2.1.1 DISSOLUTION OF THE REACTIVE SILICA

The aggregates coming from rocks are primarily made from a 3D network of tetrahedral
silica with a silica atom at the center bonded to four oxygen atoms at 109 ° (≡Si–O–Si≡). A 2D
representation of the tetrahedral (crystalline) network is shown in Figure 2-8 for simplicity. The
crystalline network is dense and well-formed. The aggregates sometimes contain impure silica
that is bonded to other atoms such as hydrogen, calcium (Ca), sodium (Na), and potassium (K)

- 11 -
(Rajabipour et al. 2015). The impure silica network is considered amorphous (reactive) since it is
an open and not perfectly crystalline structure (Chatterji 2005). That is, it has imperfections
within the 3D network of silica. A 2D representation of amorphous silica network is shown in
Figure 2-9. In an alkaline solution (pH > 13.2 – 14.0), the hydroxyl (OH-) ions continuously attack
the siloxane (Si-O-Si) bridges in the aggregates (Rajabipour et al. 2015).
The attack on a well-crystalline form of silica occurs principally at the surface. Thus, it is
a slow and superficial process. On the other hand, the attack on the amorphous form of silica
can penetrate inside the silica network and break Si-O-Si bonds to form Silanol (Si-OH) bridges
(Dent Glasser et al. 1981, Federal Highway Administration 2012, Golmakani 2013). This
breakdown of silica network phenomenon is demonstrated in Figure 2-10.

Figure 2-8: Crystalline structure of silica network

(Rajabipour et al. 2015)

Figure 2-9: Amorphous structure of silica network

(Rajabipour et al. 2015)

- 12 -
 Figure 2-10: Dissolution of silica (siloxane) network
(Rajabipour et al. 2015)
The breakdown of reactive aggregate siloxane networks by hydroxyl ions (OH-) and alkalies (R+)
such as calcium (Ca+), sodium (Na+) and potassium (K+) ions produces alkali silicate gel and silicic
acid. The latter reaction is presented in equation (2-1) (Ichikawa et al. 2007, Pan et al. 2012).

≡ Si– O– Si ≡ +R+ + OH− → ≡ Si– O– R + H − O − Si ≡

(2-1)

2.2.1.2 ALKALI-SILICA GEL FORMATION

The dissolution of siloxane network by hydroxyl ions and alkali produces both alkali
silicate gel and a weak acid (silicic acid). The weak acid immediately reacts with more hydroxyl
and alkali ions to generate more of the alkali-silica gel. The acid to gel formation process is
represented by equation (2-2) (Ichikawa et al. 2007, Pan et al. 2012).

≡ Si– O– H + R+ + OH− → ≡ Si– O– R + H2 O

(2-2)

- 13 -
2.2.1.3 ALKALI-SILICA GEL EXPANSION
The alkali-silicate gel is believed to be hygroscopic. That is, it absorbs free water from
the pore structure of concrete and expands (Ichikawa et al. 2007, Pan et al. 2012). It is believed
that the gel does not cause damage unless sufficient calcium hydroxide is present in the form of
portlandite (Wang et al. 1991, Rajabipour et al. 2015). The role of calcium hydroxide is explored
in section 2.2.1.4. The expansion reaction is shown in equation (2-3) where n is the hydration
number.

≡ Si– O– R + 𝑛H2 O → ≡ Si– O− – (H2 O)𝑛 + R+

(2-3)

There have been multiple attempts to explain the mechanism behind cracking of
cement and aggregate by the aqueous alkali-silica gel. Hansen proposed the cement around
reactive aggregates is a semi-permeable membrane which allows water ingress but not larger
complex silicate ions. The water is drawn into the reacting aggregate by diffusion. An osmotic
pressure cell is built, and growing hydrostatic pressure is applied to the cement past until cracks
are formed (1944). This theory was criticized by McGowan and Vivian on the basis that cracking
of the membrane due to osmotic pressure would release the pressure and impede further
expansion (McGowan et al. 1952).
Other researchers have proposed that the ASR cracks form due to the accumulation of
pressure in the interface zone between the aggregates and cement paste. The expansive
pressure caused by the hygroscopic gel is believed to penetrate into the open micropores
around the aggregate. Once no more micropores are available to release the pressure, the gel
begins to exert tensile pressure on the cement paste. As the gel expands by absorbing more
and more water, the gel pressure becomes higher than the tensile strength of cement paste
and causes cracks in the cement paste (Baz̆ant et al. 2000). This theory explains the cracks in
the cement paste. However, it does not provide an explanation for cracks in the aggregates.
According to this theory, the expansive gel would exert a compressive stress onto the
aggregates in which case no cracks would form. Yet, that is not the case in reality. There are

- 14 -
cracks present in both aggregates and cement as shown in a cross-sectional image of a field
concrete affected by ASR as demonstrated in Figure 2-11. Thus, some researchers have
concluded that the pressure builds and accumulates in the aggregates first and then,
propagates into cement (Goltermann 1995, Idorn 2001). Another literature suggests that the
gel is formed within and/or around the aggregates (Federal Highway Administration 2012).
Regardless of the specific details, the fundamental of ASR mechanism is agreed upon by most
studies.

Figure 2-11: Typical crack pattern of concrete due to ASR

(Ichikawa et al. 2007)

2.2.1.4 CALCIUM HYDROXIDE ROLE IN ASR

The role of calcium hydroxide (Ca(OH)2 aka CH) is considered crucial in ASR by many
studies. CH is made up of a calcium ion (Ca+) and two hydroxyls (OH-) group. These elements
can react with other ions or groups when in the aqueous state (in solution). Some literature has
proposed that consumption of Ca(OH)2 decrease the expansion due to ASR in concrete via many
mechanisms (Wang et al. 1991, Chatterji 2005, Federal Highway Administration 2012,
Rajabipour et al. 2015).

- 15 -
 Primarily, the calcium from portlandite (CH) affects the properties of ASR gel and its
expansion. First, environments with a high concentration of alkali hydroxides and reactive silica,
but an inadequate amount of calcium hydroxide (portlandite), silica is believed to dissolve and
remain in solution without causing a significant damage (Diamond 1989, Federal Highway
Administration 2012, Rajabipour et al. 2015). The precise reason for this behavior is not
apparent. Nevertheless, researchers have proposed a series of mechanisms (Rajabipour et al.
2015):

1- The diffusion of silica from reactive aggregates is prevented when increased amounts of
calcium are present in the pore solution (Chatterji 1979, Chatterji et al. 1984).
2- Calcium reacts with silicate gel to form a semi-permeable membrane around the
reactive aggregate that is needed to cause expansion (Bleszynski et al. 1998, Thomas
1998).
3- Calcium is necessary to increase the viscosity and yield strength of the silicate gel,
yielding in higher stress during gel expansion (Bleszynski et al. 1998, Thomas 1998).

Another research drew a similar conclusion about the role of CH in ASR. It concluded
that CH exacerbates ASR by two significant ways. Firstly, it acts as a buffer to maintain a high
concentration of hydroxyl ions in the pore solutions which is detrimental to siloxane network of
reactive aggregates as explained in section 2.2.1.1. Essentially, the hydroxyl ions attack and
breakdown reactive aggregates (siloxane network). Secondly, the calcium ion concentration in
the pore solution governs the rate of silica diffusion out of the grains. The Ca+ concentration is
inversely proportional to the diffusion rate of silica. Expansion occurs when the alkalis and
hydroxyl ions entering an aggregate is higher than the dispersion of silica out of the grain
(Wang et al. 1991).

2.2.2 CURRENT ASR MITIGATION TECHNIQUES

In existing structures affected by ASR, a mitigation method that completely stops ASR
damage is not well documented. Lithium compounds have shown some positive results in

- 16 -
reducing ASR in a laboratory setting and real structures (Diamond 1975, Stark et al. 1993,
Stokes et al. 2000, Barborak et al. 2004). Some researchers proposed that lithium compounds
decrease ASR by entering into the expansive silica gel and either change its nature or inhibit the
ASR reaction (Diamond 1975, Fournier et al. 2010). Similarly, another literature suggested that
lithium may reduce the dissolution rate of silica and impede the formation of an alkali-silica gel.
It was also reported that lithium might decrease repulsive forces between gel particles,
reducing expansion (Rajabipour et al. 2015).

Figure 2-12: Topical application of lithium solution for ASR

(Fournier et al. 2010)

ASR damage is considerably reduced when relative humidity (RH) is below 80 % (Stark
1991, Pedneault 1996). Therefore, in existing structures, diverging drainages from ASR-induced
zone could be beneficial since water plays a crucial role in ASR. Adding exterior cladding is
another option to reduce moisture and ASR in existing structures. However, exterior cladding
only decreases ingress of external moisture and does not affect the moisture inside concrete.
When RH is above 80 %, ASR may remain active regardless of exterior cladding. An alternative
that could resist water ingress while allowing internal moisture to evaporate would be a better

- 17 -
solution. Siloxanes and Silanes sealers serve precisely that purpose. Therefore, the latter
alternatives are preferred and widely implemented. Nonetheless, these solutions are not
suitable for application where the ASR-affected structure is entirely or partially submerged in
water. Moreover, Siloxanes and Silanes are not beneficial for concrete with large crack width
and for structures that do not allow topical application on all exposed surfaces (Fournier et al.
2010). Figure 2-12, Figure 2-13 and Figure 2-14 demonstrate the application and benefits of
these methods, respectively.

Figure 2-13: Topical application of Silane solution

(Fournier et al. 2010)

- 18 -
 Figure 2-14: Benefits of Silane solution for highway barriers
(Bérubé et al. 2002a)

2.2.3 CURRENT ASR PREVENTING TECHNIQUES

In new structures, three improvements are available to prevent or suppress ASR

damage possibly: using low-alkali cement, supplementary cementing materials (SCM), or
avoiding reactive aggregates (Golmakani 2013). The most efficient way to prevent ASR would
be to avoid reactive aggregates altogether. However, sometimes non-reactive aggregates are
not available, or they are expensive (Johnson 2011). Three conditions are needed for ASR to
occur: sufficient alkalis (calcium hydroxide, sodium hydroxide, and potassium hydroxide),
reactive silica and continuous supply of water. If any of them is eliminated, ASR cannot occur
(Stark 1991).
When building new structures, SCM could be used in the mix design to mitigate ASR by
multiple mechanisms (Xu et al. 1995, Moser et al. 2010, Johnson 2011):
1. The microstructure is densified by SCM hydration products, yielding to a less permeable
paste.
2. SCM hydration products are bound to alkali ions, hindering alkali-silica reaction (ASR).
3. Alkali concentration in Portland cement (PC) is diluted by SCM with a low level of alkali
content, reducing ASR.

- 19 -
 4. Calcium hydroxide (Portlandite) is consumed by reacting with SCM, decreasing free Ca2+
and OH- to react with unstable silica.
Typically used SCM for ASR alleviation purpose are silica fume (SF), fly ash (FA) and
ground granulated blast furnace slag (GGBFS or slag) (Johnson 2011). SF alone only delays ASR,
so it is not an effective to reduce ASR (Duchesne et al. 1994). Effectiveness of FA depends on its
composition. FA with low calcium oxide (CaO) and minimal alkali content is very useful in
reducing ASR. However, FA with high CaO has little effect on ASR (Duchesne et al. 2001, Moser
et al. 2010). Slag has similar shortcoming as FA with high CaO (Moser et al. 2010, Johnson
2011). Remarkably, a mixture of different SCM is shown to create a synergetic effect and be
used for reduction of ASR (Bleszynski et al. 2002, Thomas 2011). Nonetheless, mix designs with
an excessive overall alkali content are usually not mitigated by SCM (Duchesne et al. 1994).

2.3 PROPOSED MITIGATION ALTERNATIVE

Early carbonation curing may be a useful alternative to mitigate or prevent ASR in new
mortar and concrete. Early carbonation curing could alleviate ASR via at least three
mechanisms. First, early carbonation converts calcium hydroxide (CH) — a reactive compound
in ASR, to calcium carbonate — a stable and denser compound. Given CH is an essential
reactant in ASR, a decrease in CH content should reduce ASR. A similar attempt has shown
positive results in the literature (Thomas 1998). Second, surface densification by early
carbonation curing decreases the permeability of mortar and concrete (Wang et al. 1991,
Rostami et al. 2012, Rajabipour et al. 2015). Thus, a lower amount of water is penetrated in
carbonation cured mortar and concrete. Since water is also an essential component of ASR, a
decrease in water ingress should consequently mitigate ASR in carbonated cured mortar and
concrete. Lastly, calcium ions released from the dissolution of calcium silicates that play a vital
role in ASR, are also transformed into calcium carbonate, a nonreactive compound (Kashef-
Haghighi et al. 2015). The importance of calcium hydroxide in ASR is explained in detail in
section 2.2.1.4. The early carbonation reactions are explained in section 2.4.2. Early

- 20 -
carbonation curing as compared to steam or moist room curing has many other benefits such
as higher early strength, better durability and is an innovative way of storing carbon dioxide
(Shao et al. 2011, Zhang 2016).

2.4 CARBONATION

Early carbonation curing must not be confused with weathering carbonation.

Weathering carbonation is a detrimental reaction, occurring in mature concrete. Whereas,
early carbonation curing is a beneficial process applied to freshly cast concrete.

2.4.1 WEATHERING CARBONATION

Weathering carbonation is a slow detrimental reaction mainly between carbon dioxide

(CO2) in the ambient air and cement hydration products such as calcium hydroxide (CH) and
calcium-silica-hydrate (C-S-H). The reaction consumes CH and reduces pH of the pore structure
below nine as compared to regular concrete that has a pH of 13 (Chang et al. 2006). Equation
(2-4) demonstrates this reaction. The reduction in pH below 9 deteriorates the protective film
around the steel reinforcement inside concrete. Once, the film is disintegrated, the rebars
corrode (Zhang 2016).
Ca(OH)2 + CO2 → CaCO3 + H2O
(2-4)

C-S-H is also believed to be decomposed by weathering carbonation as shown in

equation (2-5) (Groves et al. 1991, Morandeau et al. 2014). Weathering carbonation has been
reported to densify cementing matrix, lower porosity, and decrease the permeability of
concrete. Therefore, the ingress of harmful material is reduced in carbonated concrete (Zhang
et al. 2014). Weathering carbonation has been reported to induce shrinkage (Persson 1998,
Chang et al. 2006).

CSH + 2 CO2 → SiO2 + 2 CaCO3 + H2O

(2-5)

- 21 -
2.4.2 EARLY CARBONATION CURING MECHANISMS

Unlike weathering carbonation, early carbonation curing is a beneficial process for

concrete. The curing is commonly applied in the form of pure CO2 gas to fresh concrete within
24 hours after cast. Presence of water in pores of concrete is essential for the curing to work as
shown by equations (2-10), (2-12), (2-13), (2-14) and (2-17). However, the literature suggests
that about 40 % initial mix water must be evaporated from the pores to maximize reaction
surface area and carbon uptake. Additionally, a subsequent hydration is usually recommended
after the curing to increase the strength and performance of concrete (Zhang et al. 2016).
Before exploring the carbonation curing mechanisms, hydration reactions of cement
must be investigated since the products of hydration process are the reactants of carbonation
reactions. The hydration reactions are with 3CaO.SiO2 (C3S), 2CaO.SiO2 (C2S), 3CaO.Al2O3 (C3AS),
and 4CaO.Al2O3.Fe2O3 (C4FS) as demonstrated in equations (2-6) to (2-9), respectively (Kashef-
Haghighi et al. 2015).

3(3CaO.2SiO2) + 6H2O → 3CaCO3.2SiO2.3H2O + 3Ca(OH)2

(2-6)

2(2CaO.2SiO2) + 4H2O → 3CaCO3.2SiO2.3H2O + Ca(OH)2

(2-7)

3CaO.Al2O3 + 3CaSO4.2H2O(s) + 26H2O → 3CaO. Al2O3.3CaSO4.32H2O

(2-8)

4CaO.Al2O3.Fe2O3 + +2Ca(OH)2+ 2(CaSO4.2H2O) + 18H2O → 6CaO. Al2O3. Fe2O3.2CaSO4.24H2O

(2-9)

- 22 -
 Essentially, the CO2 gas dissolves in pore water of concrete and reacts with either water
or hydroxyl ions (OH-) to form bicarbonate (CO32-) as outlined in equations (2-10) and (2-11).
Then, the calcium ions released from the dissolution of calcium silicates such as 3CaO.SiO2 (C3S)
and 2CaO.SiO2(C3S) instantaneously react with carbonate ions from equations (2-10) and (2-11)
to form solid calcium carbonate. The overall carbonation reactions of hydrated cement are
outlined in equations (2-12) to (2-17). However, the reactions with highest carbonation rate are
C3S and Ca(OH)2 shown in equations (2-12) and (2-16) (Kashef-Haghighi et al. 2015). The
hydrated cement is densified by the production of calcium carbonate where the calcium ions
are in a stable form as compared to 3CaO.SiO2 (C3S), 2CaO.SiO2 (C2S), Ca(OH)2 (CH) and
3CaO.2SiO2.3H2O (CSH) (Zhang 2016).

CO2(aq) + H2O → H2CO3 → H+ + HCO3- →2H++ CO32-

(2-10)

CO2(aq) + OH- → HCO3- →H++ CO32-

(2-11)

3CaO.SiO2 (s) + 3CO2(aq) + n H2O → SiO2.nH2O + 3CaCO3

(2-12)

2CaO.SiO2 (s) + 2CO2(aq) + n H2O → SiO2.nH2O + 2CaCO3

(2-13)

3CaO.2SiO2.3H2O (s) + 3CO2(aq) + n H2O → 3CaCO3.2SiO2.3H2O

(2-14)

Ca(OH)2(s) → Ca(OH)2(aq)
(2-15)

- 23 -
 Ca(OH)2(aq) + CO2(aq) → CaCO3 + H2O
(2-16)

3CaO.Al2O3.3CaSO4.32H2O(s) + 3CO2(aq) → 3CaCO3+3CaSO4.2H2O + 2Al(OH)3(s) + 9H2O

(2-17)

Figure 2-15: Cement composition changes during hydration and carbonation curing
(Kashef-Haghighi et al. 2015)

Cement composition changes during hydration and carbonation curing are shown in
Figure 2-15. Calcium hydroxide (CH) and calcium silicates (C3S) contents are decreased, while
calcium carbonate (CC) content is increased after carbonation curing (Kashef-Haghighi et al.
2015).

2.4.3 CARBON UPTAKE QUANTIFICATION METHODS

Two carbon sequestration measurement methods were used in this work: mass gain
method, and thermogravimetric analysis coupled with mass spectrometry and X-ray
fluorescence (TGA-MS-XRF).

- 24 -
2.4.3.1 MASS GAIN METHOD
The mass gain method measures merely the mass increase by the early carbonation
curing and divides it by the initial mass of cement in the design mix. Calcium carbonate
formation during the curing accounts for the most of the mass increase (Monkman et al. 2006).
A small portion of the sample water is lost due to vaporization during the curing as shown in
the equations of the EARLY CARBONATION CURING MECHANISMS section. The mass gain
method uses the following formula (Zhang 2016) :

(𝑀 𝑎𝑓𝑡𝑒𝑟 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑖𝑜𝑛 + 𝑀𝑤𝑎𝑡𝑒𝑟 𝑙𝑜𝑠𝑡 ) − 𝑀𝑏𝑒𝑓𝑜𝑟𝑒 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑖𝑜𝑛

𝐶𝑎𝑟𝑏𝑜𝑛 𝑢𝑝𝑡𝑎𝑘𝑒 (%) = × 100 %
𝑀𝑐𝑒𝑚𝑒𝑛𝑡
(2-18)

Mafter carbonation represents the mass of the sample after carbonation curing, Mwater lost is
the water collected from the chamber surfaces, Mbefore carbonation is the mass of the sample before
the carbonation and Mcement is the calculated mass of cement used in the samples according to
the mix design.

2.4.3.2 TGA-MS-XRF
TGA-MS-XRF is the acronym for thermogravimetric analysis- mass spectrometry- X-ray
fluorescence. Thermogravimetric analysis (TGA) is one of the easiest and most common ways to
quantify carbon uptake in hydrated cement paste. Carbon uptake is measured by
decomposition of calcium carbonate (CC) in a sample of hydrated cement paste. TGA can also
measure calcium hydroxide (portlandite) ensuing from carbonation (Villain et al. 2007). The
mass loss between 105-450, 450-550, and 550-850 °C are associated with the decomposition
temperature of hydration products, calcium hydroxide (CH), and calcium carbonate (CC),
respectively (Mahoutian et al. 2015). However, researchers do not agree upon an exact
decomposition temperature of calcium hydroxide and calcium carbonate. Experimentally,
decomposition temperature range of compounds is shown by the edges of the characteristic

- 25 -
peaks of the differential thermogravimetric curves (DTG) (Villain et al. 2007). Thermal
decomposition equations of calcium hydroxide and calcium carbonate are as follows:

𝐶𝑎(𝑂𝐻)2(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐻2 𝑂(𝑔)

(2-19)

𝐶𝑎(𝐶𝑂)3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)

(2-20)

Mass spectrometry (MS) helps with identification of the decomposed compounds during
the TGA. MS provides the molecular weight of the compounds that decompose at a specific
temperature between 0 and 1000 °C. Usually, a decomposition of a compound is identified by a
peak ion current in the ion current versus temperature chart. MS charts are demonstrated in
Figure 4-8 to Figure 4-11.
TGA coupled with MS (TGA-MS) is a precise and convenient method of measuring
carbon uptake in hydrated cement paste. However, the samples used in this work are mortar, a
mix of hydrated cement paste and fine aggregates. Thus, TGA-MS alone does not give correct
carbon uptake results since it considers the total sample mass as cement when in reality a
significant portion of the sample is fine aggregates (sand). Consequently, a chemical analysis is
needed to determine the cement proportion in mortar samples to correct TGA-MS results
(Villain et al. 2007).
The chemical composition of pure cement and fine aggregates data sheets are provided
by the suppliers. However, the proportions of these elements are to be determined in the
mortar samples. Therefore, a chemical analysis, using tracers that are found in cement and fine
aggregates, is needed to determine the proportion of cement and fine aggregates in mortar
samples. Many tracers such as aluminum oxide (Al2O3), iron oxide (Fe2O3), calcium oxide (CaO),
and silicon oxide (SiO2) are used in this work. However, aluminum oxide (Al2O3) was trusted
and thus selected over other tracers to correct TGA-MS data. Aluminum oxide is more precise
than iron oxide (Fe2O3), is not disturbed by calcareous aggregates like calcium oxide (CaO), and
its solubility is not distorted by hydrate carbonation similar to SiO2 (Villain et al. 2007). X-ray

- 26 -
fluorescence is a rapid, inexpensive and accurate test as compared to wet-chemical or atomic
absorption (La Tour 1987). Therefore, it was selected to determine the chemical composition of
mortar bar samples used for TGA-MS.

2.5 EXPANSION TESTS METHODS FOR ASR EVALUATION

Many test procedures are available for alkali-silica reaction (ASR) evaluation. However,
there are two commonly used expansion tests for evaluating an aggregate’s reactivity in alkali-
silica reaction (ASR): accelerated mortar bar test (AMBT) or ASTM 1260 and concrete prism test
(CPT) or ASTM 1293 (Portland Cement Association 2017).

2.5.1 ACCELERATED MORTAR BAR TEST (AMBT or ASTM C1260)

The standard test method for potential alkali reactivity of aggregates (AMBT or ASTM
C1260) uses the gradation shown in Table 3-2 for making 25 mm x 25 mm x 285 mm mortar
bars that are preconditioned for two days, and then stored in a 1 M NaOH solution at 80 °C for
14 days. At least, three intermediate readings are required for the duration of the test (ASTM
C1260-14 2014, ASTM C490 / C490M-17 2017). AMBT was selected for this work thanks to its
many advantages. First of all, this test method detects the potential for the harmful alkali-silica
reaction of aggregates in mortar bars within only 16 days. It should be noted that the mortar
bars are preconditioned for two days. So, the length expansion measurements last only 14
days. Additionally, AMBT is relatively simple to conduct, and its results are easy to interpret.
Essentially, mortar bars are designed, mixed, cured, and its’ length measurements are recorded
according to ASTM C1260. Length measurements at 16 days after casting can be interpreted as
the following (ASTM C1260-14 2014):

1- Expansions of less than 0.10 % are suggestive of harmless behavior in most cases.
2- Expansions of more than 0.20 % are indicative of potentially harmful expansion.
3- Expansions between 0.10 % and 0.20 % are known to be innocuous and deleterious in
field performance. For this case, supplementary information must be developed such as
continuing the AMBT test until 28 days and/or conducting a petrographic test (ASTM

- 27 -
 C295) and/or examining the specimens after test according to ASTM C856 (ASTM C295 /
C295M-12 2012, ASTM C1260-14 2014, ASTM C856-17 2017).

AMBT’s short duration, ease of manipulation and interpretation of results makes this
method popular (Portland Cement Association 2017). Moreover, many literatures have used
AMBT and are available for reference (Liu et al. 2002, Owsiak 2007, Lenke et al. 2009, Johnson
2011, Golmakani 2013). Therefore, the 16-day AMBT was one of the chosen tests among many
tests to evaluate the effectiveness of early carbonation curing on ASR.
AMBT is not a perfect test. That is, it yields 36 % false negative results according to a
study which compared field performance of pavement slabs to AMBT results. The study
suggested lowering the limit of alkali-silica reactivity from 0.10 % to 0.06 % to minimize false
negatives (Lenke et al. 2009).

2.5.1.1 WEIGHT GAIN IN AMBT

Water source is an essential part of ASR reaction as demonstrated in section 2.2. The
early carbonation is believed to densify the surface of mortar bars and thus lower permeability.
Consequently, the mortar bars must be monitored for weight gain during AMBT to validate this
theory. Provided this theory be correct, carbonated samples should have lower weight gains
than moist and dry references.

2.5.2 CONCRETE PRISM TEST (CPT or ASTM C1293)

Concrete prism test also known as CPT or ASTM C1293 is one of the standard test
methods for determination of length change of concrete due to alkali-silica reaction. It detects
reactive aggregates within one year when no supplementary cement materials (SCM) are used
and within two years when SCM is used. At least three concrete prisms samples with the
dimensions 75 x 75 x 285 mm are stored over tap water inside sealed containers with 100 %
relative humidity (RH) at 38 °C (ASTM C157 / C157M-08(2014)e1 2014). After initial and zero
length measurements, intermediate length measurements are required at 7, 28 and 56 days as
well as 3, 9, and 12 months. Expansion of 0.04 % or more at one year is considered potentially

- 28 -
deleterious (ASTM C1293-08b 2015). This method’s long duration makes it inconvenient for
practical purposes. The Portland Cement Association recommends the CPT to evaluate ASR
since it provides the highest correlation between the laboratory and field data (2011).
However, another literature rejects CPT entirely for evaluating ASR due to numerous false
negatives and false positives associated with this test when compared to the field performance
of concrete slabs (Lenke et al. 2009). Essentially, relying solely on the CPT results is not
recommended since the literature is not clear about the correlation of laboratory test to the
field performance. Consequently, the CPT was not used in this dissertation due to its long
testing time and possible false negatives and false positives.

2.5.3 COMPETING ASR ASSESSMENT TESTS

Petrographic examination of aggregates for concrete is a possible test to identify

reactive silica. However, this test requires professional qualification with at least five years of
experience in the petrographic examination of concrete or concrete-making materials (ASTM
C295 / C295M-12 2012). Additionally, it is challenging to conduct this test (Owsiak 2007).
Another petrographic method (AAR-1) is suggested by RILEM for detection of potential alkali-
reactivity of aggregates (Sims et al. 2003). AAR-1 is based on similar concepts as ASTM C295,
and it has similar disadvantages. This procedure is believed to be relatively uncertain and
inappropriate for examining unknown or complex aggregates (Owsiak 2007). Hence, the
petrographic method was not preferred for this work.
Standard test method for potential alkali reactivity of cement-aggregate combinations
also known as ASTM C227 is another possible test for ASR (ASTM C227-10 2010). Literature
shows two principal disadvantages of this method. First, this method could take up to one year
(Liu et al. 2002). Second, it cannot detect reactive aggregates as well as the AMBT (Golmakani
2013). Therefore, ASTM C227 method was not selected for this research.

- 29 -
2.6 ASR ASSESSMENT BY NON-DESTRUCTIVE TECHNIQUES

Non-destructive techniques have been used by many researchers to evaluate mortar’s

and concrete’s performance (Rostami et al. 2011, Zhang et al. 2016, Zhang 2016). In this study,
three principal techniques have been used to evaluate the effect of the early carbonation
curing on ASR: crack quantification, surface resistivity, and pulse velocity.

2.6.1 CRACK QUANTIFICATION TEST

There have been attempts to employ image analysis to quantify cracks in rock and
concrete or efflorescence in concrete pavements. These automatic image analysis techniques
are believed to accelerate the quantification process as opposed to the traditional manual
counting of damages (Arena et al. 2014, Andreassen et al. 2016, Zhang 2016). Nonetheless,
false positive and false negative results are expected. Moreover, the designing process of a
sophisticated computer-aided algorithm is a repetitive and complex task (Arena et al. 2014).
Furthermore, the literature suggests that a fluorescent epoxy must be impregnated on the
surface of a concrete sample to differentiate the surrounding from the cracks while the image is
photographed under a UV light (Andreassen et al. 2016). In general, most studies use similar
steps to quantify damages. A high-resolution image is photographed, converted to greyscale,
processed with one or multiple Matlab algorithms to filter and quantify the cracks (Arena et al.
2014, Andreassen et al. 2016). So far, there is no standard method of assessing ASR in concrete
or mortar.
A Matlab algorithm similar to the literature was developed to quantify the cracks. The
algorithm compares each pixel of the original image to a user-defined threshold color value
(TH) to either classify as crack or non-crack area. Two TH were selected: 0.40 and 0.62. Neither
fluorescent epoxy nor UV light were used as the application of fluorescent epoxy at a few
micrometers is exceptionally challenging and requires special tools. Moreover, there were a
few issues with using the algorithm to quantify the cracks. First, it was difficult for the software
to differentiate among aggregates, pores, and cracks. That is, the algorithm was based on the
intensity of the color (or brightness in the case of greyscale images) and was not able to
distinguish among different types of dark spot such as cracks, aggregates or pores. Additionally,
the micro-crack caused by ASR in mortar bars (MB) during accelerated mortar bar test (AMBT)

- 30 -
had widths two orders of magnitude smaller as compared to surface pores and aggregates. For
instance, the average cracks widths were about 2-3 µm whereas, the pore diameters were
about 200 µm. Thus, the software detected mainly the dark spots other than the cracks. This
original image captured by the Olympus Soft Imaging Solutions GMBLT is demonstrated in
Figure 2-16, and the processed image by the Matlab algorithm is shown in Figure 2-17 and
Figure 2-18 with varying TH. Evidently, the algorithm was not able to detect the cracks
accurately even with different TH values. One may think to zoom on the cracks to solve this
issue. However, zooming on cracks would only create more problems. The zoomed crack area
would not be representative of the sample, and the dark spots would still be present. More
details about crack widths can be found in CHAPTER 4 - RESULTS AND DISCUSSION. Considering
the poor results of computer-aided image analysis (Matlab) and the small number of samples, it
was logical to use manual measurement tools on the Olympus Soft Imaging Solutions GMBLT to
quantify crack area rather than spending the time to develop a sophisticated algorithm.
Consequently, the manual crack measurement techniques were used in this work to evaluate
the effect of the early carbonation curing on ASR in MB. As additional data, images of entire
mortar bars were captured with a camera.

Figure 2-16: A typical original image of moist reference

- 31 -
 Figure 2-17: Matlab processed image with TH = 0.62
(35.5% crack area)

Figure 2-18: Matlab processed image with TH = 0.40

(4.5 % crack area)

2.6.2 SURFACE RESISTIVITY TEST

Surface resistivity test (SRT) is a well-known technique to evaluate concrete’s quality

and performance. The SRT is an indicator of concrete’s permeability property (Morris et al.
1996). A better hydration of cement typically yields a higher SR result (Rostami et al. 2012).
Concrete and mortar have high resistivity to an electrical current, whereas water present in
pores conducts well electrical current. Therefore, a porous concrete or mortar is saturated with
water results in a low surface resistivity value and a highly dense concrete or mortar yields a
high surface resistivity result.

- 32 -
 SR test has four principal benefits. It is non-destructive, fast, and inexpensive compared to
other methods and simple to conduct (Morris et al. 1996, AASHTO TP 95-11 2011). AASHTO
uses surface saturated standard concrete cylindrical 4-in x 8-in or 6-in x 12-in samples to relate
SR to chloride ion penetration. (AASHTO TP 95-11 2011). If the specimen is different from
standard sample size, the literature suggests correcting the result by a “K” factor to compare
results to literature. The surface resistivity formula (ρ) is presented in equation
(2-21). The Wenner probe gives a value for the entire equation, except the correction factor K.
The factor “K” can be obtained from equation
(2-21) (Morris et al. 1996). In the formula, “ρ” represents the surface resistivity; “a,” “d,”
“h” are dimensions of the sample, P’ is the potential while I’ is the current induced.

2 𝜋 𝑎 𝑃′
ρ= [𝑘𝛺𝑐𝑚]
𝐼′ 𝐾
(2-21)

Figure 2-19: Correction factor K for surface resistivity

(Morris et al. 1996)
No standard test relates SR to a specific density. The SR method used in this study
followed AASHTO TP 95-11 to compare the density of mortar bars with varying curing
conditions. Therefore, no correction factor is needed since the surface resistivity results are to
be compared to mortar bars themselves rather than to reference values in the literature. The
setup of SR test is shown in Figure 2-20.

- 33 -
 A current is induced by two outer probes of the Wenner Probe while the resistivity is
measured by two internal probes (Rostami et al. 2012). The samples must be in a saturated
surface dry condition for SR to work properly (AASHTO TP 95-11 2011).

Figure 2-20: Surface resistivity setup for mortar bars

(AASHTO TP 95-11 2011)

2.7 CHEMICAL ANALYSIS

2.7.1 X-RAY DIFFRACTION (XRD)

X-ray diffraction (XRD) patterns are typically used to analyze the microstructure of
concrete or mortar. As explained in section SUMMARY OF ALKALI-SILICA REACTION (ASR), the
early carbonation curing is believed to significantly decrease calcium hydroxide content and
increase calcium carbonate in concrete (Shao et al. 2015). The XRD analysis serves as a
validation technique for this theory when comparing different curing conditions.

2.8 COMPRESSIVE TEST

A compressive test demonstrates the performance of concrete or mortar. Research has

shown that the early carbonation curing has a superior early strength as compared to
traditional moist (hydration) curing. However, the ultimate strength of concrete cured by the
early carbonation curing and traditional hydration or steam curing method is thought to be
similar (Rostami et al. 2011, Zhang et al. 2017). The latter phenomenon is demonstrated in

- 34 -
Figure 2-21 where traditional hydration curing is compared to early carbonation curing.
Similarly, in Figure 2-22, conventional steam curing is compared to early carbonation curing.
The effect early carbonation on concrete’s strength in alkali-silica reaction prone conditions is
still unknown. That is, it is yet unclear if the ultimate strength of carbonation cured samples
will remain comparable to moist cured samples after exposing them to ASR susceptible
environment. Therefore, the mortar bars are to be tested for compressive strength after AMBT
to demonstrate the relative performance of carbonation cured samples over traditional moist
cured (hydration) samples.

Figure 2-21: Hydration vs. carbonation curing for the strength of concrete
(Zhang 2016)

- 35 -
Figure 2-22: Steam vs. carbonation curing for the strength of concrete
(Rostami et al. 2011)

- 36 -
 3 Chapter 3 - EXPERIMENTAL PROGRAM

3.1 OVERVIEW

The experiments were divided into two parts: mortar bar (MB) tests and modified
mortar bar (MMB) test. Generally, both MB and MMB followed ASTM C1260-14 for the
materials preparation, apparatus, mix proportions and procedures (2014). Figure 3-1 shows an
overview of the major tests completed in this work.
AMBT
(ASTM C1260)

image analysis

weight
increase

surface
resistivity

compressive
MB
test

carbonation
depth

TGA-MS

tests mortar bars

XRF

XRD

MAMBT
MMB
image analysis

Figure 3-1: Map of major tests

- 37 -
3.2 ASTM STANDARD MATERIAL PROPERTY TESTS

The following standard test methods were followed to determine the material properties
needed for this study:
 ASTM C29-16 Standard test method for bulk density and voids in aggregate.
 ASTM C33-16 Standard specifications for concrete aggregates.
 ASTM C127-16 Standard test method for relative density (specific gravity) and
absorption of coarse aggregates.
 ASTM C128-16 Standard test method for relative density (specific gravity) and
absorption of fine aggregates.

3.3 MORTAR BARS (MB)

3.3.1 MIX PROPORTIONS FOR MORTAR BARS

Ordinary Portland cement (OPC) Type GU by Ciment Quebec, reactive Spratt aggregates
by Ministry of Transport, Ontario, non-reactive Granite aggregates by Bauval CMM were
utilized in MB. MB’s mixture proportions, Spratt aggregates’ properties, gradation, and
properties are shown in Table 3-1, Table 3-2, and Table 3-3, respectively.

Table 3-1: Mixture proportions of MB

material type quantity source
fine aggregates (OD) Spratt 990 g/ 3 bars Stittsville, Ontario
cement Type I (GU) 440 g/ 3 bars Ciment Quebec
w/c tap water 0.47 —
cement alkali content sodium oxide equivalent 0.92 —
(Na2Oeq %)
storage solution sodium hydroxide 1 N 828 mL / bar —

- 38 -
 Table 3-2: Fine Spratt aggregates grading requirements of MB
sieve size mass (%)
passing retained on —
4.75 mm (No.4) 2.36 mm (No. 8) 10
2.36 mm (No. 8) 1.18 mm (No. 16) 25
1.18 mm (No. 16) 600 um (No. 30) 25
600 um (No. 30) 300 um (No. 50) 25
300 um (No. 50) 150 um (No. 100) 15

Table 3-3: Fine Spratt aggregates properties

property quantity* associated standard test

absorption 1.974 % ASTM ASTM C127-15 (2015)

relative density 2.643 ASTM ASTM C127-15 (2015)
*quantity values are an average of two samples.

3.3.2 SPRATT AGGREGATES’ PREPARATION FOR MORTAR BARS

Mortar bars in both AMBT and MAMBT followed the same aggregate preparation
procedure. Figure 3-2 shows an overview of Spratt aggregates preparation. About 300 g of
natural Spratt aggregates were pulverized for 45 seconds in Hengye IMZ-1000 to obtain the
gradation in Table 3-2. Then, the aggregates were sieved for 3 min in the RAINHART CAT. NO.
635 and were washed with tap water to remove impurities and were oven dried at 105 ° C until
constant mass was obtained (24 h). Then, the aggregates were cooled to room temperature for
two hours and were stored in Ziploc bags until casting time.

- 39 -
Natural Spratt  Fill and pulverize for 45 secs  Sieve for 3 min  Wash with water

Drain water and transfer to steel bowls  Oven dry at 105 °C  Cool to Tambient  Store
Figure 3-2: Spratt aggregates’ preparation overview

3.3.3 CASTING OF MORTAR BARS

AMBT and MAMBT were cast according to ASTM C1260 (2014). Molds were prepared
according to ASTM C490 (2017). Molds had dimensions of 25 mm x 25 mm x 285 mm. A thin
film of oil was applied to the molds as a release agent. The quantity of the aggregate, cement,
and water used for casting of three specimens are shown in Table 3-1. The water-to-cement
ratio (w/c) was 0.47. Cement was sieved through an 850 um to remove lumps. The various
aggregate sizes were proportioned as prescribed in Table 3-2. The mixing of mortar followed
ASTM C305 (2014). All mixing was added to the bowl. Cement was added to the water and
mixer was started at slow speed for 30 s. Then, sand was added to the bowl over 30 s while
mixing. The mixing speed was increased to medium while mixing for 30 s. Then, the mixer was
stopped for 90 s. During the first 15 s of this interval, any mortar collected on the sides of the
bowl was scraped down. For the remainder of the interval, the bowl was covered with a plastic
bag. The mixing was finalized with 60 s at medium speed (ASTM C1260-14 2014).

- 40 -
 The molds were filled with two equal layers of mortar; each layer was compacted with a
round steel tamper of ¾ inch. The mortar was worked into corners, around the gauge studs,
and along the surfaces of the mold with the tamper until a homogeneous specimen was
achieved. After the top layer had been compacted, the mortar flush was cut off with the top of
the mold, and the surface was made smooth with a few strokes of the trowel. The molding
should not last more than 2 min and 15 s. Three specimens were cast for each of the four curing
conditions, leading to twelve specimens in total (ASTM C305-14 2014).

3.3.4 CURING PROCEDURE FOR MORTAR BARS OF AMBT

The mortar bars (MB) of the accelerated mortar bar test (AMBT) was cured according to
Table 3-4. Essentially, the moist sample was transferred to a moist room immediately after
casting and kept there for 27 hours. However, the carbonated samples needed preconditioning
before carbonation curing to maximize carbon sequestration. The rationale for creating the dry
curing condition was to demonstrate that the reduction in ASR was thanks to carbonation
curing and not due to water removal process only. Therefore, the dry reference samples went
through the same preconditioning steps as the carbonated samples but were not carbonated.
The preconditioning required two steps: two hours of in-mold curing and five hours of off-mold
fan drying. The in-mold curing was necessary for the samples to withstand their weight. Off-
mold fan drying was needed to remove about 50 % of initial sample water to maximize carbon
uptake when pure CO2 (99.9 %) was introduced. Two fans, creating an average wind speed of
4.2 mph, were placed on either side of the samples at 1 foot to accelerate water evaporation.
Carbonation curing itself also had two steps. First, the carbonation chamber was vacuumed to
0.95 bar to create a negative pressure inside the chamber. Negative pressure helps maximize
carbon uptake in the samples. Then, the pure CO2 gas was introduced into the chamber to
obtain +1.0 bar. The carbonated samples were exposed to the sustained +1.0 bar pressure for
two and 18 hours depending on the curing conditions. While the carbonated samples were
exposed to CO2, the dry samples were air dried. The carbonation curing setup is shown in Figure
3-3.

- 41 -
 heater regulator regulator
vacuum pump
carbonation chamber (venture) compressed
air source

CO2 gas tank

Figure 3-3: Carbonation curing setup

Table 3-4: Details of curing procedure for MB

sample batch moist dry 2h 18h
reference reference carbonation carbonation
(moist room)
step 1: in-mold curing (hr) 26 2 2 2
step 2: off-mold fan drying (hr) 0 5 5 5
step 3: air drying (hr) 0 19 0 0
step 4: vacuum carbonation chamber to -0.95 bar (hr) 0 0 0.5 0.5
step 5: carbonation curing at 1 bar (hr) 0 0 2 18
step 6: air drying (hr) 0 0 16 0
all manipulations (hr) 1 1 1.5 1.5
total duration (hr) 27 27 27 27

Table 3-5: MB water loss due to curing

sample batch moist dry 2h 18h
reference reference carbonation carbonation
total initial water removed (%) — *target 50-55 % 0 54.1 52.5 49.9

The optimal initial water removal to maximize carbon uptake was between 50 to 55 %
according to Figure 4-3. Thus, the samples were preconditioned to match the target.

- 42 -
3.3.5 CURING PROCEDURE FOR MORTAR BARS OF MAMBT

MB for modified accelerated mortar bar test (MAMBT) followed a similar curing
procedure as the MB of AMBT. The first difference was that two curing conditions — namely
moist reference and 18 h carbonation, were evaluated instead of four curing conditions. The
second difference was that the carbonated samples were cured at 5 bars pressure instead 1
bar.

Table 3-6: Curing procedure for MB

sample batch moist 18h
reference carbonation
(moist room)
step 1: in-mold curing (hr) 26 2
step 2: off-mold fan drying (hr) 0 5
step 3: air drying (hr) 0 0
step 4: vacuum carbonation chamber to -0.95 bar (hr) 0 0.5
step 5: carbonation curing at 5 bar (hr) 0 18
step 6: air drying (hr) 0 0
all manipulations (hr) 1 1.5
total duration (hr) 27 27

Table 3-7: MB water loss due to curing

sample batch moist 18h
reference carbonation
total initial water removed (%) — *target 50-55 % 0 51.0

3.3.6 CO2 UPTAKE MEASUREMENT METHODS USED FOR MB

Two carbon uptake measurement methods were used for MB: the mass gain method and TGA-
MS-XRF.

- 43 -
3.3.6.1 MASS GAIN METHOD
The samples’ masses for two and 18 hours carbonation curing were measured before
and after carbonation. Additionally, the water accumulated on the walls and bottom of the
carbonation chamber after the curing was collected with a piece of an absorbent paper and
measured. Then, the carbon uptake was calculated according to equation (2-18).
3.3.6.2 TGA-MS-XRF
The TGA-MS-XRF was composed of three tests: thermogravimetric analysis (TGA), mass
spectrometry (MS) and X-ray fluorescence (XRF). Three mortar bars (MB) per curing condition
were mixed and cured according to section 3.3. The carbon uptake in 2 h and 18 h samples
were measured according to the mass gain method to compare to TGA-MS-XRF method.
TGA test was carried according to a test procedure developed by Villain et al. (2007).
Two specimens per curing condition were prepared for the TGA. MB was surface polished
(about 1 mm) with a diamond blade hand saw to avoid skin effects due to molds. Then, they
were dry sawn into 5 mm +/- 1 mm using a diamond blade hand saw to prevent leaching by
water. The slices were stored in sealed Ziploc bags until TGA test. Before TGA, the slices were
crushed in an agate mortar, and the sand grains were eliminated using a 150 µm sieve.
Apparently, there were a cross contamination phenomena between sand and cement grains.
That is, the crushing and sieving process may have removed some of the cement grains and left
behind some of the sand grains. Therefore, XRF was carried out to determine the exact
proportion of cement-to-sand grains in the samples. The powder obtained well mixed to obtain
a homogenous sample. Then, it was separated into three parts and stored in airtight glass vials.
One part was used for TGA-MS, and the other two parts were utilized for XRF and XRD. Two
samples of about 3 mg were needed for each TGA-MS test, and about 5 g were necessary for
each XRF and XRD tests. Thus, about 11 g of powder was obtained for each of the four curing
conditions.
The TGA-MS results such as thermogravimetric curve (TGA), the derived
thermogravimetric curve (DTG) and ion current curves were obtained using the TGA Q500 (0.1
µg sensitivity, 0.01 % precision) coupled with the mass spectrometer (MS Discovery) by TA
Instruments. Each powder sample of 3 +/- 0.2 mg was heated from 25 to 1000 with a 5 °C per

- 44 -
minute heating rate. The TGA and DTG curves are demonstrated in section 4.1.3.2. The TGA
data were analyzed with the Process Eye Professional software.
The cement and sand content of the powder sample obtained from the crushed mortar
bars was determined by a chemical analysis using X-ray fluorescence (XRF). To do so, an oxide
tracer that is present in both cement and sand, and takes part in neither hydration nor
carbonation reaction, was used to determine the cement and sand contents of the samples.
The Al2O3 tracer was preferred over the other oxide tracers such as SiO2, Fe2O3, and CaO thanks
to its accuracy as explained in section 2.4.3.2. The content of oxides in the cement (Ciment
Quebec) and sand (Spratt - MTO) was provided by the suppliers. 5 g well-mixed powder
samples were ground and sieved further to obtain a fraction around 40 microns to determine
the oxides’ content of the powder samples that were a mix of cement and sand. Then, they
were mixed with 10 % boric acid, pressed at 25t and were ran in the Bruker S-4 Pioneer XRF
apparatus. Then, the following system of two equations and two unknowns was developed and
solved to find the cement and sand content in the powder samples. The powder samples had
unknown portions of cement and sand:
𝑎𝑋 + 𝑏𝑌 =𝑐
𝑋 + 𝑌 =1
(3-1)

“X” represents the cement content in the sample (in decimal), and “Y” represents the
sand content in the sample (in decimal). “a” represents the Al2O3 content in the cement and has
a value of 4.8 %. “b” represents the Al2O3 content in the sand and has a value of 0.43 %. “c”
represents the Al2O3 content in the sample which is a mix of cement and sand. “c” is the
parameter that is determined by XRF test. In perfectly homogenized samples and ideal world
conditions, only one sample (only one “c” value) is needed to determine the cement and sand
content. However, in real-world sources of error exist, and thus four samples of well-mixed
powder collected from the crushed mortar bars were tested and used in equation (3-1).
The carbon uptake contents determined by TGA-MS test were associated with the total
sample. However, the carbon uptake content should be related to cement mass only.

- 45 -
Therefore, the carbon uptake values by TGA-MS were divided by the average cement content
(“X”) determined by XRF.

3.3.7 ASR EXPANSION TEST METHODS FOR MORTAR BARS

The alkali-silica reaction was evaluated in mortar bars (MB) via the standard accelerated
mortar bar test (AMBT or ASTM 1260) and modified accelerated mortar bar test (MAMBT).
3.3.7.1 ACCELERATED MORTAR BAR TEST (AMBT / ASTM 1260)
The mortar bars used for AMBT were cast and cured according to sections 3.3.3 and
3.3.4, respectively. A batch of three mortar bars was cast for each of the curing conditions such
as moist, dry, 2h carbonation and 18h carbonation. The mortar bars were placed in
polypropylene storage containers (Sistema Klip-it) filled with sufficient tap water to fully
submerge them. The containers were placed in the oven for 24 hours at 80 +/- 2 °C. Then, the
containers were removed from the oven one at a time. The other containers were only
removed after the first container had been measured and returned to the oven. The time
passed between removal and return of each container to the oven should not exceed 10 min.
Each bar was removed from the water and was dried with a towel. The mortar bars were
handled with attention not to damage the two metal gauge studs at their extremities. The
length measurements were made following ASTM C409/C490M (2017). The zero reading of
each bar was taken immediately after drying, and as soon as the bar was in position. The drying
and reading procedure of each bar were completed within 15 +/- 5 s after removing it from the
water. After the reading, the first bar was left on a towel until all of the bars of the same
container were read. Then, the bars were placed in the containers filled with 1 N NaOH
solution, and the container was stored in the oven at 80 +/- 2 °C until the next length
measurement. Approximately 740 ml of the NaOH solution was required for each mortar bar.
The reference metal bar was read before the readings of the mortar bars since the heat from
the mortar bars affects the length of the comparator.
The subsequent comparator readings of the samples were taken every two days at the
same time for 14 days after the zero reading. The procedure of the subsequent readings was
identical to that of the zero reading. The length change for each bar was calculated according to
the following formula:

- 46 -
 𝐿𝑥 − 𝐿𝑖
𝐿= × 100
𝐺
(3-2)

“L” was the change in length at “x” age (%). “Lx” was the comparator reading of
specimen at “x” age minus comparator reading of reference bar at x age (mm). “Li” was the
zero-comparator reading of specimen minus comparator reading of reference bar at that same
time (mm), and “G” was the nominal gauge length (250 mm). The average expansion of the
curing condition batch (three specimens) was reported to the nearest 0.01 % for a given period.
The reading and calculation processes were repeated for the remaining three containers. The
Humbolt H-3250D digital length comparator as shown in Figure 3-4 was used for length
measurements.

Comparator

Reference bar

Figure 3-4: Length comparator apparatus for AMBT and MAMBT

3.3.7.2 MODIFIED ACCELERATED MORTAR BAR TEST (MAMBT)

The MAMBT followed the same procedure as AMBT, except the mortar bars were stored
at 100 °C instead of 80 °C, and the MAMBT was continued until 30 days instead of 14 days as in
the case of THE AMBT.

- 47 -
3.3.8 ASR ASSESSMENT OF MB BY NON-DESTRUCTIVE TECHNIQUES

3.3.8.1 CRACK QUANTIFICATION METHOD

3.3.8.1.1 IMAGE ACQUISITION
First, one side-view image of each set of mortar bars tested according to ASTM C1260
and modified ASTM C1260 was captured using an iPhone 6 at 1 foot ± 1 in the distance from
samples. The images were taken under constant light and background to produce consistent
and comparable results. These pictures were used to roughly demonstrate the overall damage
done to the specimen due to ASR.
On the other hand, Olympus Soft Imaging Solutions Gmblt was used to determine
precisely the cracked areas in mortar bars. The images were taken under constant
magnification and light level to produce consistent and comparable results. Olympus Soft
Imaging Solutions Gmblt was composed of a light source (Olympus TH4-100), a microscope
(Olympus BX41), a camera (Olympus SC 100), and a computer with Stream Start 1.9 software.
Each specimen was placed under the microscope at 10 locations along its length spaced at 26
mm as shown in Figure 3-6. The light source was turned to camera mode, the microscope was
set to 10x magnification, and coarse/fine tuning knobs were used to get a clear picture, and
HDR option was used to acquire enhanced images. HDR option helps differentiate cracked area
from the normal concrete surface. Ten images were captured per specimen for a total of 30
images per curing condition (R, C, moist, dry, 2h carbonation, and 18h carbonation). Image
acquisition setup is shown in Figure 3-5.

- 48 -
 data acquisition/image analysis
(computer with Stream Start 1.9 software)

camera

light source (Olympus SC 100)

(Olympus TH4-100)

microscope
(Olympus BX41)

Figure 3-5: Image acquisition and analysis setup

10 spots @ 26 mm spacing
Figure 3-6: Specimen locations used for image analysis

3.3.8.1.2 IMAGE PROCESSING

No crack was found for all carbonated samples both with the naked eye and under
microscope up to 30x magnification. However, cracks were present in the non-carbonated
samples. Therefore, the image processing procedure was used for the moist and dry curing
conditions from AMBT as well as the moist curing condition from MAMBT. The test
temperatures for AMBT and MAMBT were 80 °C and 100 °C, respectively. Given that ASR is
amplified with rising temperature, MAMBT was expected to develop much larger cracks than
AMBT. Therefore, two different methods were developed to quantify cracks in mortar bars
from AMBT and MAMBT. Both methods used the Olympus Soft Imaging Solution software.
There were ten images per specimen and three specimens per curing condition, resulting in 30
images per curing condition.

- 49 -
 The following steps were followed to calculate the average crack width and the crack area
in moist and dry curing mortar bars due to AMBT:
1- The dimensioning tool was used to measure crack length and width in each image. Six
points along the crack were used to determine the average crack width in each picture.
2- The crack areas were found by multiplying the crack length by the average crack width.
3- The crack areas were divided by the total image area to determine the crack area
percentage for each image.
4- Finally, all 30 images of each curing condition were averaged to find the overall average
crack width and crack area.
Similarly, the following steps were used to calculate the average crack width and the
average area for moist mortar bars due to MAMBT:
1- The dimensioning tool was used to determine the average crack width from six points
along the crack in each image.
2- The area polyline tool was used to establish a crack area for each image.
3- The crack areas were divided by the total image area to determine the crack area
percentage for each image.

3.3.8.2 SURFACE RESISTIVITY

The mortar bars (MB) from AMBT were tested for surface resistivity (SR) following a
similar method as the AASHTO TP 95-11 (2011). The MB was left in saturated lime water for 24
hours before conducting the test to saturate the samples with water but avoid leaching. The
room temperature was 25.6 °C. The samples’ temperature varied between 22.0 °C to 23.9 °C.
The sample temperatures were measured with a laser thermometer gun and were necessary to
correct the measurements according to temperature. The Wenner probe used for this test was
RESIPOD PROCEQ 38 mm with an accuracy of ± 0.2 kilohm-cm or ±1 % of measurement. The
probe was calibrated before the test. Each specimen of the curing condition was measured time
times on all four faces for SR, resulting in 24 measurements per curing condition as shown in
Figure 3-7. Then, the measurements were corrected for temperature — 3 % decrease in surface
resistivity measurements for 1 °C increase from 20 °C calibrated temperature.

- 50 -
 Figure 3-7: Surface resistivity measurement

3.3.9 MORTAR BARS’ X-RAY DIFFRACTION (XRD)

First, the cement-aggregate powder was collected from the crushed mortar bars for
each of the curing conditions following the TGA sample preparation procedure as shown in
section 3.3.6.2. Each XRD sample holder had a diameter of 3.5 cm and a height of 0.5 cm. The
sample holders were slightly overfilled with the powder and were leveled with a glass scraper.
Then, the samples were loaded into the XRD apparatus — Bruker D8 Advance. The test was
controlled, and the results were analyzed by the XYZ Stage software.

Figure 3-8: XRD sample preparation

- 51 -
 Figure 3-9: XRD apparatus

3.3.10 MORTAR BARS’ COMPRESSIVE TEST AFTER AMBT

The mortar bars (MB) of AMBT were stored in sealed Ziploc plastic bags for 96 days after
AMBT. The internal water saturation degree of MB plays a crucial role in the compressive
strength of mortar. Thus, they were soaked in saturated lime water for 24 hours to saturate all
samples equally. Then, they were cut into 25 mm cubes using a diamond saw. Six cubes per
curing condition were compressed at a rate of 0.5 mm per sec using MTS Sintech 30/G. Each
max load was divided by the associated sectional area to calculate the compressive strength
(f’c). Finally, the average and standard deviations were also computed.

- 52 -
 Figure 3-10: Compressive test 25 mm MB samples

Figure 3-11: Compressive strength test setup

3.3.11 pH tests

The pH decrease due to the carbonation curing process was a concern since a pH below 9
promotes disintegration of the protective film around steel reinforcement in concrete and
mortar as discussed in section 2.4.1. Thus, the carbonated samples were tested with
phenolphthalein solution to validate that the carbonation curing did not decrease pH below
passivation film threshold.
The mortar bars were tested for pH with two methods. First, the phenolphthalein solution
was sprayed to the freshly fractured surface of mortar bars to demonstrate the carbonated
areas visually after the curing processes as well as 28 days after subsequent hydration. The

- 53 -
phenolphthalein yields colorless surface if the pH is below 9.5. In contrast, it turns the surface
to pink if the pH level is above approximately 9.5 (Dean 1985).
The second method to evaluate the pH of the mortar bars was via pH meter (Extech
pH150). For each measurement, the surface of interest was slightly scratched with a spatula,
and a drop of deionized water was added to the surface. The pH reading was taken after a
minute. Similar to the phenolphthalein test, the 25 mm mortar bars were tested after the initial
curing process and 28 days after subsequent hydration. The samples were tested on all four
surfaces - top, left side, right side, and bottom) and the core. The meter was calibrated before
the measurements according to the Extech pH150 instructions handbook.

- 54 -
 4 CHAPTER 4 - RESULTS AND DISCUSSION

4.1 MORTAR BARS (MB) TEST FOR AMBT

4.1.1 ACCELERATED MORTAR BAR TEST (AMBT /ASTM 1260)

Three mortar bars per curing condition were tested according to the accelerated mortar
bar test (AMBT aka ASTM 1260), and the average expansion results are shown in Figure 4-1 and
in Table 4-1. The MB was made with Spratt aggregates and GU cement. The ASTM 1260
standard test for alkali-silica reaction (ASR) categorizes the 16-days expansion below 0.10 %
non-reactive, between 0.10 and 0.20 % inconclusive, and greater than 0.20 % reactive (2014).
The actual duration of AMBT is 14 days with two days of preconditioning.
The moist and dry reference samples showed an average expansion of 0.35 and 0.32 %
at 16 days, respectively. These expansions are considered deleterious according to ASTM 1260.
However, the 2h carbonation and 18h carbonation samples yielded an average expansion of
0.02 and 0.01 % at 16 days, respectively. The 2h and 18h carbonated samples’ expansions
showed harmless expansions according to the ASTM 1260. The 2h carbonation was preferred
since it had a shorter carbonation time.
One could argue that the carbonated samples were deprived of water — an essential
element of ASR and that is why the carbonated samples showed non-reactive behavior as
compared to the moist (hydrated) reference samples. Therefore, another batch of mortar bars
— dry reference was cured in a similar fashion as the carbonated samples, however they were
not carbonated. The non-reactive behavior of the carbonated samples was thanks to the
carbonation curing and not due to the water removal process. This claim was proven by the
comparison between the dry reference and the carbonated expansion results. The dry
reference samples showed reactive expansions of 0.32 %, whereas the 2h and 18h carbonated
samples demonstrated harmless expansions of 0.02 and 0.01 %. Thus, the carbonation curing
rendered the alkali-silica reactive mortar bars harmless according to the AMBT.

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 0.40

average mortar bar expansion (%) 0.35

0.30

0.25
reactive above 0.20 %
0.20
inconclusive zone between 0.10
0.15

0.10

0.05 non-reactive up to 0.10 %

0.00
0 2 4 6 8 10 12 14 16
-0.05
age (d)
moist reference dry reference 2h carbonation at 1 bar
18h carbonation at 1 bar max innocuous limit (%) min deleterious limit (%)

Figure 4-1: Effect of early carbonation curing on expansion of Spratt MB according to AMBT

Table 4-1: Summary of AMBT

AMBT 14 days
curing condition expansion category
(%)
moist reference 0.35 reactive
dry reference 0.32 reactive
2h carbonation 0.02 non-reactive
18h carbonation 0.01 non-reactive
*The expansion values are the average of three samples.

- 56 -
 18.00

weight increase (% of initial sample water)

16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0 1 2 4 6 8 10 11 14
age (d)

moist reference dry reference

2h carbonation at 1 bar 18h carbonation at 1 bar

Figure 4-2: Effect of carbonation on weight increase of MB during AMBT

Provided that water be an essential element of ASR, the effect of carbonation curing on
weight increase of the mortar bars (MB) was monitored during AMBT. Essentially, a weight
increase of the MB during AMBT means that there is a water ingress inwards the MB. The
continuous ingress of water is needed for the ASR gel to swell and cause expansive stress in the
MB as explained in section 2.2.1.3. Therefore, a weight increase due to water ingress in samples
could yield to the gel expansion in an ASR prone environment. The carbonation curing densifies
the microstructure of the carbonated samples and decreases the water ingress during AMBT as
explained in section 2.4.2.
The weight increase due to water ingress during AMBT is shown in Figure 4-2 and is
based on the initial sample water. The moist reference, dry reference, 2h carbonation and 18h
carbonation samples showed 15.45, 16.81, 12.74, and 11.39 % weight increase, respectively.
Thus, the 2h and 18h carbonation curing was able to decrease the total ingress of water in
carbonated samples by 4.07 and 5.42 % as compared to the dry reference samples. The
carbonated samples were compared to the dry samples rather than to the moist samples since

- 57 -
the carbonated and dry samples followed a similar drying procedure. The reduced water ingress
is potentially indicative of surface densification in carbonated samples and a decrease in ASR.
As demonstrated in Figure 4-2, the 2h, 18h, and the dry samples absorbed more water
than the moist samples initially. This result was expected since the moist samples were kept in
a moist chamber to avoid water loss while the other samples were dried. Thus, the superficial
empty pores of the carbonated and dry samples were filled with water during the first two days
of submersion in 1N sodium hydroxide solution.
The 2h and 18h carbonated samples absorbed 2.05 and 0.66 % more water as compared
to the dry samples at the early age of two days. The carbonation curing could potentially
promote larger superficial pores in mortar bars which could explain the initial higher water
absorption as compared to the dry samples. However, the pores beyond surface are
significantly reduced in the carbonated samples as compared to the dry and moist references.
This claim is demonstrated by the lower ultimate weight increase in the carbonated samples.

4.1.2 OPTIMAL WATER REMOVAL FOR CARBON UPTAKE IN MB

The average optimal initial water removal for maximum carbon uptake in mortar bars
(MB) plot is shown Figure 4-3. Water plays an essential role in the carbonation reaction as
demonstrated in equations (2-10) to (2-17). However, some sample water must be removed to
facilitate carbon dioxide gas inflow. The optimal carbon dioxide is stored in mortar bar samples
when 52.5 % of the initial water is removed corresponding to 15.8 % carbon uptake. However,
achieving a precise water removal percentage is challenging in practice since the water
evaporation rate is variable and difficult to control. Hence, the initial water removal is
acceptable as long as it falls within the proximity of the 52.5 % target value.

- 58 -
 18

carbon uptake (% of cement mass)

16

14

12

10

8 vacuum: 0.95 bar

6 CO2 pressure: 1 bar
4
carbonation curing: 2 h
2
40 45 50 55 60 65
initial water removed (%)

Figure 4-3: Optimal initial water removal for max carbon uptake in MB

4.1.3 CARBON UPTAKE OF MB ACCORDING TO DIFFERENT METHODS

The averages of three carbon uptake measurement methods are shown in Table 4-2.
The mass gain method showed 14.7 and 17.4 % carbon uptake in the 2h and 18h carbonation
samples, respectively. On the other hand, the TGA-MS method resulted in 7.47 and 9.85 % for
the 2h and 18h carbonation specimens. However, once the TGA-MS results were corrected with
XRF, it yielded 14.6 and 19.2 % for the 2h and 18h carbonation specimens. The carbon uptake
increased by an average of 2.7 % between 2h and 18h carbonation exposure according to the
mass gain method. The carbon uptake improved by an average of 4.6 % according to the TGA-
MS-XRF.
The TGA-MS method without XRF assumes the powder samples to be composed entirely
of cement. In reality, the samples were 51 % cement and 49 % sand as measured by the XRF
test in section 4.1.3.3 and as explained section 2.4.3.2. Hence, the TGA-MS test was expected to
yield carbon contents that were 51 % of the carbon contents measured by the mass gain
method. For the two h carbonation samples, the expectation was met when TGA-MS yielded
7.47 % carbon content as compared to the 14.7 % measured by the mass gain method. The
ratio of the TGA-MS to the mass gain result was 50.8 % which was very close to the predicted
results of 51 %. However, the difference between the TGA-MS to the mass gain result was 56.7

- 59 -
% which was 4.7 % greater than the predicted result. This difference could be explained by the
high variability of microstructure in mortar bars. The mortar bars from which the powder
specimens are derived are carbonated inhomogeneously due to their non-uniform
microstructure. So, the three samples that were used for the TGA-MS were not representative
of the entire sample utilized for the mass gain method.
The mass gain method measured the carbon content by the mass increase due to the
carbonation curing, whereas the TGA-MS-XRF method measured the carbon content based on
the dissociation temperature range of calcium carbonate between 550 and 750 °C. A precise
dissociation temperature range is not agreed upon in the literature. Villain suggested the
temperature range to be between 530 and 950 °C (2007). However, Mahoutian suggested a
narrower range of 550 - 850 °C (2015). The carbon content of the samples will vary depending
on the temperature range selected for the TGA-MS and TGA-MS-XRF methods. For instance, a
broader temperature range may yield higher carbon content as opposed to a smaller range for
the same sample. Therefore, the carbon uptake differences between the mass gain and TGA-
MS-XRF could be associated with the dissociation temperature selected.

Table 4-2: Summary of MB CO2 content according to different methods

sample batch mass gain (%) TGA-MS (%) TGA-MS-XRF (%)
2h carbonation 14.7 7.47 14.6
18h carbonation 17.4 9.85 19.2
Values in the table are an average of three samples.

4.1.3.1 MASS GAIN METHOD

The carbon content of the mortar bars (MB) used for comparison with TGA method and
accelerated mortar bar test (AMBT) using the mass gain method is tabulated in Table 4-3 and
Table 4-4. These tables demonstrate that the carbon content of MB is dependent on the initial
water removal percentage. For the 2h carbonation curing, the carbon uptake was 14.7 % when

- 60 -
63.0 % of the original water was removed, and 15.8 % when 52.5 % of the original water was
removed. For the 18h carbonation curing, the carbon uptake was 17.4 % when 61.0 % of the
original water was removed, and 22.8 % when 49.9 % of the original water was removed. This
trend is demonstrated graphically in Figure 4-3.

Table 4-3: CO2 content of MB used for TGA according to mass gain method
sample batch mass gain (%) water removal (%)
2h carbonation 14.7 63.0
18h carbonation 17.4 61.0
Values in the table are an average of three samples.

Table 4-4: CO2 content of MB used for AMBT according to mass gain method
sample batch mass gain (%) water removal (%)
2h carbonation 15.8 52.5
18h carbonation 22.8 49.9
Values in the table are an average of three samples.

4.1.3.2 TGA-MS METHOD

The TGA-MS test was conducted at the age of two days to validate the carbon uptake
results obtained by the mass gain method in the cement portion of the samples. The secondary
purpose of the TGA-MS test was to confirm the transformation of calcium hydroxide to calcium
carbonate during the carbonation curing process.
The Spratt aggregates used as sand in the mortar bars are calcareous. Calcareous
aggregates dissociate in the similar temperature range as calcium carbonate that forms during
the carbonation curing process as demonstrated in Table 4-6. Therefore, the effect of
calcareous aggregates was removed from 2h and 18h carbonation batches based on the dry
reference batch as shown Table 4-5. In other words, the CO2 content from the calcareous
aggregates (%) in 2h and 18h carbonation samples are assumed to be the same as the dry
reference sample. Thus, the values of X and Y are assumed to be 18.71 %. The resulting carbon

- 61 -
uptakes are 7.47 and 9.85 % for the 2h and 18h carbonation batches. Cement used for the
mortar bars had 1.7 % CO2 coming from limestone addition according to Ciment Quebec’s
certificate. However, the CO2 from cement did not change the results since the same type of
cement was used for the references and the carbonated samples.
The carbon uptake calculations so far considered the entire sample as cement.
However, in reality the powder used for TGA also had some sand grains. Approximately 50 % of
the powder sample was found to be sand as explained in section 4.1.3.3. Thus, the actual
carbon uptake of the 2h and 18h carbonation were twice as much as the values presented in
Table 4-5. The correction for the carbon uptake measured by TGA-MS test was done with XRF
test as shown in section 4.1.3.3. The values in the table below are an average of two samples.

Table 4-5: TGA summary of crushed MB

sample CO2 from CO2 from calcareous CO2 from
calcareous aggregates, cement carbonation curing
aggregates and and carbonation (%)
cement (%) curing (%)
moist reference 19.22 — —
dry reference 18.71 — —
2h carbonation X 26.18 7.47
18h carbonation Y 28.56 9.85

Table 4-6: Calcium carbonate and calcium hydroxide dissociation temperature from MS of MB
compound molecular dissociation
mass (g) temperature ( C)
CO2 / calcareous aggregates 44 ~ 550 - 750
H2O from C-H 18 ~ 375 - 430

The moist and dry samples were not carbonated. Therefore, all the carbon dioxide
collected during the TGA-MS test was issued from the calcareous aggregates. On the other

- 62 -
hand, the carbon dioxide measured during the TGA-MS test of the carbonated samples was
coming from both the calcareous aggregates and the carbonation process.
The TGA-MS curve shown in Figure 4-4 determined the dissociation temperature ranges
of calcium hydroxide and calcareous aggregates in the moist reference samples.
The calcium hydroxide (CH) dissociated at a temperature range of approximately 375-
430 °C represented by the differential thermogravimetric curve (DTG) peak of 1.43 %. As
demonstrated in section 4.1.3.3, 50 % of the sample was composed of cement and the other 50
% was sand. Thus, the water loss % due to dissociation of CH was actually 2.86 % when
considering the mass of cement only. The total sample mass was 2.97 mg and the cement mass
was 1.485 mg. Using one-to-one molar conversion of water molecule (18.015 g/mol) to calcium
hydroxide molecule (74.093 g/mol) according to equation (2-19), the dissociated calcium
hydroxide represented 11.77 % of cement mass.
The dissociation temperature of CH has been reported to be approximately 430-530 °C
in the literature (Villain et al. 2007). The CH dissociation peak was also present in the DTG curve
of dry samples as shown in Figure 4-5. However, it was not present in the 2h and 18h
carbonated samples as demonstrated in Figure 4-6 and Figure 4-7, respectively. Thus, the
calcium hydroxide was consumed during the carbonation process.
The calcium carbonate dissociation temperature was roughly 550-750 °C as
demonstrated by the 17.57 % peak of the differential thermogravimetric curve (DTG). The mass
spectrometry curve was used to identify the nature of the dissociation product as shown by the
peak in Figure 4-8. The mass number identified by the mass spectrometry was 44
corresponding to CO2. Similarly, the nature of the dissociation compound was found to be
carbon dioxide for the dry, 2h and 18h carbonation batches as shown in Figure 4-9, Figure 4-10,
Figure 4-11. The calcium carbonate dissociation temperature has been reported to be
approximately 650-950 °C in the literature (Villain et al. 2007). The calcium carbonate
dissociation peaks were 17.57, 16.14, 24.36 and 27.22 % for the moist, dry, 2h and 18h
carbonation samples as shown in Figure 4-4, Figure 4-5, Figure 4-6 and Figure 4-7. The calcium
carbonate content was increased by the carbonation process as shown by the difference in DTG

- 63 -
peaks of the carbonated and the reference samples such as the moist and the dry. Hence,
calcium carbonate was produced during the early carbonation curing.
Provided that calcium hydroxide was consumed and calcium carbonate was produced
during the carbonation process, it can be concluded that calcium hydroxide reacted with
carbon dioxide to produce calcium carbonate as discussed in section 2.4.2.
The dissociation temperature depends on the nature of the sample and its composition.
Thus, calcium carbonate coming from two different cement or rock types may dissociate at
distinct temperature ranges. This theory can explain the difference between the experimental
results and the literature.

100 0.01

95 0
1.45 % -0.01
90
-0.02

DTG (%/sec)
85 water from Ca(OH)2
TG (%)

19.22 % -0.03
80
-0.04
75
-0.05

70 CO2 from calcareous aggregates and cement (limestone)

-0.06

65 -0.07
0 100 200 300 400 500 600 700 800 900 1000
temperature (°C)

TG DTG

Figure 4-4: Dissociation of moist reference sample of crushed MB during a TGA-MS test

- 64 -
 100 0.01

95 0

-0.01
90
1.43 %
-0.02

DTG (%/sec)
85
TG (%)

18.71 % -0.03
80 water from Ca(OH)2
-0.04
75
-0.05

70 CO2 from calcareous aggregates and cement (limestone)

-0.06

65 -0.07
0 100 200 300 400 500 600 700 800 900 1000
temperature (°C)

TG DTG

Figure 4-5: Dissociation of dry reference sample of crushed MB during a TGA-MS test

100 0.01

95 0

-0.01
90
-0.02

DTG (%/sec)
85
TG (%)

-0.03
80 26.18 %
-0.04
75
CO2 from calcareous aggregates, cement -0.05
(limestone) and carbonation curing
70 -0.06

65 -0.07
0 100 200 300 400 500 600 700 800 900 1000
temperature (°C)

TG DTG

Figure 4-6: Dissociation of 2h carbonation sample of crushed MB during a TGA-MS test

- 65 -
 100 0.01

95 0

-0.01
90
-0.02

DTG (%/sec)
85
TG (%)

-0.03
80 28.56 %
-0.04
75
-0.05
CO2 from calcareous aggregates, cement
70 (limestone) and carbonation curing
-0.06

65 -0.07
0 100 200 300 400 500 600 700 800 900 1000
temperature (°C)

TG DTG

Figure 4-7: Dissociation of 18h carbonation sample of crushed MB during a TGA-MS test

100 12

95 10
90

ion current (mA)

8
85
TG ( %)

6
80 peak = CO2 44
4
75

70 2

65 0
0 200 400 600 800 1000
temperature (°C)

TG H2O ion current CO2 ion current

Figure 4-8: TG and MS (ion currents) of moist reference sample of crushed MB

- 66 -
 100 12

95 10
90

ion current (mA)

8
85
TG ( %)

6
80 peak = CO2 44
4
75

70 2

65 0
0 200 400 600 800 1000
temperature (°C)

TG H2O ion current CO2 ion current

Figure 4-9: TG and MS (ion currents) of dry reference sample of crushed MB

100 12

95 10
90

ion current (mA)

8
85
TG ( %)

6
80 peak = CO2 44
4
75

70 2

65 0
0 200 400 600 800 1000
temperature (°C)

TG H2O ion current CO2 ion current

Figure 4-10: TG and MS (ion currents) of 2h carbonation sample of crushed MB

- 67 -
 100 14

95 12

90 10

ion current (mA)

85 8
TG ( %)

80 peak = CO2 44 6

75 4

70 2

65 0
0 200 400 600 800 1000
temperature (°C)

TG H2O ion current CO2 ion current

Figure 4-11: TG and MS (ion currents) of 18h carbonation sample of crushed MB

4.1.3.3 TGA-MS-XRF METHOD

Thermogravimetric coupled with mass spectrometry and X-ray fluorescence (TGA-MS-
XRF) was conducted to correct the carbon content measured by the thermogravimetric method
(TGA) alone. Four tracers such as SiO2, Al2O3, Fe2O3, and CaO were used to determine the
correct content of cement and aggregates in the samples used for TGA. The tracers’ content in
both the cement and fine aggregates were provided by the suppliers as shown in Table 4-7. The
chemical analysis of the TGA crushed mortar bars is tabulated in Table 4-8.
The samples contained unknown amounts of cement and fine aggregates. Thus, the
objective was to determine the tracer’s content in the sample and then, infer the cement and
fine aggregates content from the tracer’s content. Once the cement content was determined,
the carbon uptakes calculated in section 4.1.3.2 were divided by the cement content of samples
to determine the actual carbon uptakes of the samples. Refer to section 3.3.6.2 for equations
and details.
Table 4-7: Chemical analysis of cement and aggregates
SiO2 (%) Al2O3 (%) Fe2O3 (%) CaO (%)
cement (Ciment Quebec) 19.10 4.80 3.60 60.2
fine aggregate (Spratt) 7.72 0.43 0.26 48.7

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 The preferred tracer was aluminum oxide (Al2O3) since it had the lowest standard
deviation of 0.28 % as compared to the other tracers. The standard deviation for SiO2, Fe2O3
and CaO tracers were 1.85, 0.29 and 1.05 %. Silica oxide is not appropriate to determine the
cement content in carbonated samples since the solubility of silica oxide is reduced during
carbonation process. However, the solubility of Al2O3 is not affected by the early carbonation
process (Villain et al. 2007). Moreover, Platret and Deloye did not recommend the use of Fe2O3
as a tracer of cement since it is inaccurate due to the presence of its many forms (1994). Hence,
aluminum oxide was chosen to determine the correct content of cement in the samples.

Table 4-8: Chemical analysis of crushed MB by XRF

curing condition SiO2 (%) Al2O3 (%) Fe2O3 (%) CaO (%)
moist reference 16.02 2.88 3.46 58.04
dry reference 15.44 2.88 3.36 57.15
2h carbonation 12.92 2.62 3.16 57.07
18h carbonation 12.26 2.30 2.81 55.51
average 14.16 2.67 3.20 56.94
standard deviation 1.85 0.28 0.29 1.05

Table 4-9: Corrected average TGA-MS CO2 content of crushed MB by XRF

SiO2 (%) *Al2O3 (%) Fe2O3 (%) CaO (%)
average 14.16 2.67 3.20 56.94
chemical analysis
standard deviation 1.85 0.28 0.29 1.05
crushed MB cement 56.6 51.3 88.0 71.7
proportion (%) fine aggregate 43.4 48.7 12.0 28.3
corrected TGA-MS 2h carbonation 13.2 14.6 8.5 10.4
CO2 content (%) 18h carbonation 17.4 19.2 11.2 13.7
*Choice of tracer: Al2O3 (%)

- 69 -
 The correct carbon (CO2) content of the 2h and 18h carbonated samples were 14.6 and
19.2 % as demonstrated in Table 4-9. According to the mass gain method, the carbon content in
the mortar bars were 14.7 and 17.4 %. Hence, the corrected carbon content results were
comparable to the results obtained by the mass gain method. That is, the mass gain method
yielded 0.1 % higher carbon uptake for the 2h carbonated samples and 1.8 % lower carbon
uptake for the 18h carbonated samples as compared to the TGA-MS-XRF.
The differences in the measurement results are due to two main reasons. First, the TGA-
MS was based on an approximate dissociation temperature range. The dissociation
temperature range is not precisely defined, so the carbon uptake results changes depending on
the selected range. However, the mass gain method is independent of the temperature. It was
based on the mass increase after the carbonation exposure. Thus, it is more likely to provide
accurate results. The second reason for the difference was about the sampling technique. The
mass gain method used two entire mortar bars of 25 mm square cross-section by 285 mm per
curing condition to calculate the carbon content. For instance, two mortar bars were used for
each 2h carbonation and 18h carbonation curing condition. However, the TGA-MS-XRF used
two 25 mm square slices of 5 mm width to calculate the carbon uptake. The assumption made
for the TGA-MS-XRF was that the samples were carbonated homogenously. However, in reality,
the samples were not carbonated 100 % uniformly.

Table 4-10: MB CO2 content according to TGA-MS and TGA-MS-XRF

TGA-MS TGA-MS-XRF
(%) (%)
2h carbonation 14.7 14.6
18h carbonation 17.4 19.2

4.1.4 CRACK QUANTIFICATION METHOD AFTER AMBT

After the AMBT, the mortar bars (MB) were evaluated for cracks to validate the benefit
of the carbonation curing as compared to the moist and dry curing conditions. As demonstrated
in Figure 4-12, the cracks were not visible with a regular camera in any of the samples.

- 70 -
Therefore, the samples were examined under the microscope under 10x optical zoom with an
HDR option. The typical microscopic images are shown in Figure 4-13.

(a)

(b)

(c)

(d)

(a) Moist reference (b) Dry reference (c) 2h Carbonation (d) 18h Carbonation

Figure 4-12: Visual crack inspection of MB after AMBT

- 71 -
 No crack was visible for the carbonated samples up to an optical zoom of 10x as
demonstrated in Figure 4-13 c) and d). However, the moist and dry references showed cracks as
evidenced in Figure 4-13 a) and b).

(a) (b)

(c) (d)

(a) Moist reference (b) Dry reference (c) 2h Carbonation (d) 18h Carbonation

Figure 4-13: Microscopic crack inspection samples of MB after AMBT

For each curing condition, 30 images were processed for crack width, length and area
under the optical microscope with a 10x zoom. The crack width results are shown in Figure
4-14. The crack width varied between 2.02 to 5.16 µm with an average of 3.04 µm for the moist
reference samples. The crack width ranged from 1.50 to 3.20 µm with an average of 2.23 µm
for the dry reference samples. However, no cracks were visible for the carbonated samples.
Thus, the crack quantification results were in line with the AMBT results, confirming the benefit

- 72 -
of the carbonation curing in alkali-silica reactive mortar bars. Beyond 10x zoom, the images
became blurry due to the uneven surface of the mortar bars.

6
5.16
5
crack width (µm)

4
3.04 3.20
3
2.23
2.02
2 1.50

1
0 0 0 0 0 0
0
moist reference dry reference 2h carbonation at 1 bar 18h carbonation at 1
bar

min average max

Figure 4-14: Effect of carbonation on crack width of MB after AMBT

The cracked area formula was the crack width multiplied by the crack length divided by
the total image area. The cracked area results of the AMBT mortar bars are shown in Figure
4-15. The cracked area of the mortar bars validated the hypothesis that the carbonation curing
prevents cracks caused by ASR in AMBT. The cracked area varied between 0.26 to 0.29 % with
an average of 0.28 % for the moist reference samples. The crack area ranged from 0.05 to 0.29
% with an average of 0.15 % for the dry reference samples. However, the 2h and 18h
carbonated samples did not show any crack. The standard error for the moist reference and the
dry reference were 0.0016 and 0.0120, respectively.

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 0.35
0.29 0.29
0.30 0.28
0.26
crack area (%) 0.25

0.20
0.15
0.15

0.10
0.05
0.05
0.00 0.00 0.00 0.00 0.00 0.00
0.00
moist reference dry reference 2h carbonation at 1 18h carbonation at 1
bar bar

min average max

Figure 4-15: Effect of carbonation on crack area of MB after AMBT

4.1.5 SURFACE RESISTIVITY AFTER AMBT

Surface resistivity (SR) is a non-destructive test that quantifies the quality of mortar and
concrete. SR is proportional to mortar bar density and permeability. For instance, a well-packed
microstructure results in a high SR value and a poorly packed microstructure yields low SR
value. The theory behind SR is explained in section 2.6.2.
The carbonated samples yielded approximately 4.5 folds higher SR results as compared
to the moist and the dry reference samples as shown in Figure 4-16. More specifically, the SR
for the moist and the dry references were 40.3 and 57.3 kilohm-cm, respectively. In contrast,
the SR for the 2h and 18h carbonation samples were 272.9 and 260.3 kilohm-cm. The density of
the samples based on the curing condition in decreasing order was the 2h carbonation, the 18h
carbonation, the dry reference, and the moist reference. Thus, the optimal carbonation
exposure was 2 hours since it produced a higher SR than the 18 hours one.

- 74 -
 300.0

250.0
Surface Resistivity (kilohm-cm)

200.0

150.0
272.9
260.3

100.0

50.0

57.3
40.3
0.0
moist reference dry reference 2h carbonation at 1 bar 18h carbonation at 1
bar
Sample Batch

Figure 4-16: Effect of early carbonation on surface resistivity of 112 days old MB

4.1.6 COMPRESSIVE TEST AFTER AMBT

When using non-reactive aggregates, the carbonated samples have better compressive
strength as opposed to the hydrated samples according to the literature as shown in section
2.8. However, it was not clear if the carbonation curing would also yield better compressive
strength as compared to the hydrated (moist) reference when using alkali-silica reactive
aggregates. Figure 4-17 shows the compressive strength of the mortar bars made with alkali-
silica reactive after AMBT.
The moist and dry references samples showed compressive strengths of 46.3 and 41.9
MPa on average. In contrast, the 2h and 18h carbonation samples showed compressive
strengths of 63.6 and 59.3 MPa on average. Thus, the carbonated samples had approximately
1.4 folds higher compressive strengths as compared to the references on average.
Consequently, the hypothesis stating that the carbonation curing yields higher compressive

- 75 -
strength thanks to surface densification phenomenon in mortar bars as formulated in section
2.8 is validated. Furthermore, the 2h carbonation had the highest compressive strength that
was 51 % greater than the dry reference, 36 % better than the moist reference and 6 % higher
than the 18 h carbonation.

70.0

60.0

50.0

40.0
f'c (MPa)

63.3
30.0 59.3

46.3
20.0 41.9

10.0

0.0
moist reference dry reference 2h carbonation at 1 bar 18h carbonation at 1
bar
Sample Batch

Figure 4-17: Effect of early carbonation on compressive strength of MB cubes

4.2 XRD OF MORTAR BARS

The X-ray diffraction (XRD) test was conducted to validate that the carbonation curing
transforms the calcium hydroxide (reactive) content of the mortar bars (MB) to calcium
carbonate (stable). Figure 4-18 demonstrates the XRD patterns of the crushed MB. Positions “1”
denotes calcium hydroxide presence while positions “2” represents calcium carbonate. For
instance, the position at approximately 18.1 2Ɵ° represented the presence of calcium
hydroxide. In contrast, the position at approximately 29.5 2Ɵ° represented the calcium
carbonate’s presence.

- 76 -
 2 1: Calcium hydroxide
2: Calcium carbonate

1 2 1 2 2 2 2 2 1
intensity ( counts )

18 h carbonation

1 2 1 2 2 2 2 2 1
2 h carbonation

1 2 1 2 2 2 2 2 1
dry reference

1 2 1 2 2 2 2 2 1
moist reference

10 15 20 25 30 35 40 45 50 55
position ( 2θ °)

Figure 4-18: XRD patterns of crushed MB samples

The calcium hydroxide peak at 18.1 2Ɵ° is not present at 18h carbonation samples as
shown by the relatively straight baseline. On the contrary, the moist and the dry references
have clear calcium hydroxide intensity peaks at the same position as shown in Figure 4-18.
Thus, the theory of calcium hydroxide consumption during the carbonation curing is confirmed.
The calcium carbonate content increased thanks to the carbonation curing process as
demonstrated in Figure 4-18. For instance, the calcium carbonate peaks were relatively higher
in the carbonated samples as opposed to the reference samples. At approximately 39.4 2Ɵ°
position the calcium carbonate intensity peaks were taller in the 2h and 18h carbonation as
compared to the dry and moist references.

- 77 -
4.3 pH TESTS OF MORTAR BARS

The pH decrease due to the carbonation curing process was a concern since a pH below 9
promotes disintegration of the protective film around steel reinforcement in concrete and
mortar as discussed in section 2.4.1. Thus, the carbonated were tested with phenolphthalein
solution to validate that the carbonation curing did not decrease pH below passivation film
threshold.
A phenolphthalein solution was sprayed on the freshly fractured surface of mortar bars
immediately after the carbonation curing process and 28 days after subsequent hydration
curing. If the mortar bars stayed colorless after the spray, it was indicative of pH level below
9.5. In contrast, if the mortar bars changed color to pink, it was indicative of pH level above
approximately 9.5 (Dean 1985).
As demonstrated in Figure 4-20 “a)” and “c),” the 2h and 18h carbonated samples yielded
both colorless and pink zones when tested with phenolphthalein immediately after the
carbonation curing. The colorless zones indicated that the samples had been carbonated. The
pink zones indicated non-carbonated areas. The images “a)” and “c)” were captured
immediately after the 2h and 18h carbonation curing, respectively. As expected, the image “a)”
corresponding to the 2h carbonation showed less carbonated area than the image “c)”
representing 18h carbonation. The image “b)” and “d)” were captured after 28 days of
subsequent hydration for the 2h and 18h carbonation samples, respectively. Both of the
carbonation curing samples revealed almost entirely pink results. Thus, the carbonation curing
process lowers the pH of mortar bars only temporarily. The early carbonation decreased the pH
of the mortar bars up to a depth of 12.5 mm. The minimum cover of the steel reinforcement in
concrete or mortar is 20 mm which is higher than the carbonated depth. Thus, the cover
ensures that the environment does not corrode the steel reinforcement (CSA-A23.3-04 2005).
The corrosion process of the steel reinforcement usually requires a more extended period than
28 days (Nguyen et al. 2015). Hence, the early carbonation curing does not corrode the
reinforcement.

- 78 -
 (b)
(a)

(c) (d)

(e) (f)

(a) after 2h carbonation curing (b) 2h carbonation sample after 28 days’ subsequent hydration
(c) after 18h carbonation curing (d) 18h carbonation sample after 28 days’ subsequent hydration
(e) after 24h hydration curing (f) 24h hydration sample after 28 days’ subsequent hydration

Figure 4-19: Effect of early carbonation on MB carbonation depth

- 79 -
 The moist reference samples yielded pink surface color for the entire period of the test.
Hence, the hydration reference stayed at a pH above 8.6. The phenolphthalein test is simple to
conduct, and its’ results are easy to interpret. However, it only yields binary results; either
below 9.5 or above 9.5 pH. Therefore, pH EXTECH 150 meter was used to determine the precise
pH of the samples. The results are shown in Table 4-11 and Figure 4-20.
As demonstrated by Figure 4-14 and Table 4-11, the surface pH values of the 2h and 18h
carbonation samples immediately after the carbonation curing were 9.19 and 9.05. However,
the pH values at the core of the mortar bars were above the de-passivation threshold. The pH
values were 10.65 and 10.58 for the 2h and 18h carbonation, respectively. Moreover, the 2h
and 18h carbonated samples recovered their surface pH values above the de-passivation
threshold of 9.5. The average surface pH values of the 2h and 18h carbonated samples
increased to 10.25 and 10.39 after 28 days of subsequent hydration.
Furthermore, the pH values of the bottom surface were above 9.5 even immediately
after the carbonation process. The bottom surface of the mortar bars was not exposed to the
air during the preconditioning process. Thus, less water evaporated from the bottom surface as
compared to the top and sides. The pores filled with water inhabited the carbon dioxide to
react with the hydrated cement and lower the pH value. Therefore, the bottom surface was not
carbonated as much as the top and sides surfaces.

Table 4-11: MB pH after initial curing and subsequent hydration

after initial curing after 28 day's subsequent hydration
sample batch surfaces* core** bottom surfaces* core** bottom
moist reference 13.66 13.59 13.92 12.97 13.18 13.30
dry reference 12.63 13.44 13.10 12.87 13.14 13.12
2h carbonation 9.19 10.65 12.54 10.25 12.27 12.75
18h carbonation 9.05 10.58 12.66 10.39 12.32 12.68
*surfaces represent the average pH of the top, left and right surfaces of the mortar bars.
**core represents the average pH of two samples at the center of the mortar bars.

- 80 -
 14.00

12.00

10.00

8.00
pH

6.00

4.00

2.00

0.00
surface after core after initial surface after 28 core after 28
initial curing curing day's subs. day's subs.
hydration hydration

moist reference dry reference 2h carbonation 18h carbonation

Figure 4-20: MB pH after initial curing and subsequent hydration

4.4 MORTAR BARS (MB) FOR MAMBT

The cracks in mortar bars caused during the accelerated mortar bar test were not visible
to the naked eye. Both the carbonated and the references samples showed no crack results
during the accelerated mortar bar test that were visible by the naked eye. Thus, the test
environment was exacerbated to investigate the effect of carbonation on ASR cracking at
extremely hostile ASR environment. For the modified accelerated mortar bar test (MAMBT), the
test temperature was increased from 80 to 100 °C, and the duration was prolonged from 14 to
30 days. However, the mortar bars were carbonated at 5 bars pressure instead of 1 bar.

4.4.1 CARBON UPTAKE OF MORTAR BARS

As shown in Table 4-12, the average carbon uptake of three mortar bars carbonated at a
pressure of 5 bars was 23.9 % with 51.0 % water removal. Thus, there was an average of 8.1 %
increase as compared to the mortar bars carbonated at a pressure of 1 bar with 52.8 % water
removal.

- 81 -
 Table 4-12: CO2 content of MB according to mass gain method
sample batch mass gain (%) water removal (%)
18h carbonation 23.9 51.0

4.4.2 MODIFIED ACCELERATED MORTAR BAR TEST (MAMBT)

The evaluation criteria of the modified accelerated mortar bar test (MAMBT) results
were the same as the accelerated mortar bar test (AMBT). The criteria are tabulated in Table
4-13. An expansion below 0.10 % is considered harmless. An expansion ranging between 0.10
and 0.20 % is inconclusive, and further tests are needed to categorize the expansion. However,
an expansion above 0.20 % is expected to be reactive (ASTM C1260-14 2014).

Table 4-13: Evaluation criteria for AMBT and MAMBT

category expansion (%)
non-reactive below 0.10
inconclusive between 0.10 – 0.20
reactive above 0.20

According to the MAMBT, the 18h carbonated samples vacuumed to 0.95 bar and cured
at 5 bars pressure showed harmless expansion as compared to the moist reference samples. At
14 days, the average moist reference samples’ expansion was 0.72 % which is categorized as
reactive according to Table 4-13. In contrast, the average 14-days expansion of the carbonated
samples was 0.02 % which is considered non-reactive. Furthermore, the average 30-days
expansion of the carbonated samples was 0.04 % which is also considered harmless. However,
the average 30-days expansion of the moist reference samples was 0.83 % which is
characterised as reactive.
The average expansion of the reference samples was 20.75 folds higher than the
carbonated samples in the hostile ASR environment as shown in
Figure 4-21. According to the best fit line, the average reference sample expanded
linearly up to 13 days at a rate of 0.052 % per day with an R-squared value of 0.9922. Then, the

- 82 -
expansion slowed down until reaching a plateau at 27 days. The average carbonated sample
expanded linearly up to 30 days at a rate of 0.0013 % per day with an R-squared value of
0.8969. The moist reference expanded 40 folds faster than the carbonated samples. Hence, the
carbonation curing has demonstrated its capacity to decrease the ASR induced expansion in
concrete with very reactive aggregates.

Table 4-14: Summary of MAMBT

MAMBT 14 days MAMBT 30 days
curing condition expansion category expansion category
(%) (%)
moist reference 0.72 reactive 0.83 reactive
18h carbonation 0.02 non-reactive 0.04 non-reactive
*The expansion values are the average of three samples.

0.90

0.80

Moist Reference
0.70
average mortar bar expansion (%)

18H Carbonation at 5
bar
0.60 max innocuous limit (%)

0.50 y= 0.052x
R2=0.9922
0.40

0.30

reactive from 0.20 %

0.20

inconclusive zone between 0.10 %

0.10
non-reactive up to 0.10 %
0.00
0 5 10 15 0.0013x R2=0.8969
y= 20 25 30 35
age (days)

Figure 4-21: Expansion of MB (Spratt fines) according to MAMBT

- 83 -
4.4.3 CRACK QUANTIFICATION AFTER MAMBT

The images of the moist reference and the 18h carbonated samples after the MAMBT is
shown in Figure 4-22 a) and b). No crack was visible in the carbonated samples with the naked
eye. In contrast, the cracks were visible in the moist reference samples. The results are in line
with the expectations and the MAMBT. Hence, the carbonation curing process eliminates the
cracks caused in the hostile alkali-silica reaction environment.

(a)

(b)

(a) Modified moist reference (b) Modified 18h carbonation

Figure 4-22: Visual crack inspection of MB after MAMBT

- 84 -
 As demonstrated in Figure 4-23, the reference samples showed cracks ranging from
approximately 10 to 239 µm under the microscope with an optical zoom of 10x. The average
crack width of 30 moist reference images was 173.76 µm. However, the carbonated samples
did not show any crack under a microscope up to 30x optical zoom as shown in Figure 4-23 and
Figure 4-24 b). Thus, the microscopic observations validated that the carbonation curing
prevents cracks caused ASR reaction even under extremely hostile conditions as hypothesized
in section 2.

300

250 239.01
crack width (µm)

200
172.76

150

100

50
10.03
0 0 0
0
modified moist reference modified 18h carbonation at 5 bar

min average max

Figure 4-23: Effect of carbonation on crack width of MMB after MAMBT

- 85 -
 (a)

Crack

(b)

(a) Modified moist reference (b) Modified 18h carbonation

Figure 4-24: Microscopic crack inspection samples of MMB after MAMBT

- 86 -
 5 CHAPTER 5 - CONCLUSIONS AND RECOMMENDATIONS

5.1 CONCLUSIONS

Damage due to alkali-silica reaction (ASR) in concrete structures represents a significant

portion of rehabilitation cost worldwide. An early carbonation curing process was developed to
efficiently store carbon dioxide gas and alleviate the alkali-silica reaction in mortar using
reactive Spratt aggregates. The curing included four steps: air-drying, fan-drying, vacuuming
and carbonation. The carbon sequestration was maximized when about 52.5 % of the initial
water was removed in mortar bars.
The 2h and 18h carbonation cured samples with reactive Spratt aggregates showed
superior resistance to ASR as compared to the samples cured with the traditional moist
(hydration) curing process. The better resistance was indicated by lower expansion results in
the accelerated mortar bar test (AMBT or ASTM C1260) and the modified mortar bar test
(MAMBT).
The 2h and 18h carbonated samples yielded harmless expansions in the AMBT. However,
the moist and the dry references samples demonstrated deleterious expansions. In the AMBT,
the 2h carbonated samples expanded 94.3 % less than the moist samples. Similarly, the average
18h carbonated sample expanded 97.1 % less than the moist reference. The average dry sample
showed harmful expansion and expanded only 8.6 % less than the moist reference. Thus, the
carbonation curing decreased the expansions and not the drying process.
Even in the extreme conditions of higher temperature and longer duration exposure
(MAMBT), the 18h carbonated samples with reactive aggregates showed negligible expansion
as opposed to the moist-cured reference samples at the age of 30 days.
The carbonated mortar bars had shown significantly improved resistance to ASR induced
cracking. Contrarily, both hydration references (dry and moist curing) samples yielded average
crack widths of 3.04 and 2.23 µm, respectively.

- 87 -
 The quality of the mortar bars were evaluated with surface resistivity. The carbonated
samples showed higher surface resistivity than the dry and the moist references, indicating the
carbonated samples were more resistance to water permeation.
The 2h and 18h carbonated samples demonstrated better compressive strength as
compared to the moist and the dry references. The 2h carbonation cured samples performed
slightly better than the 18h carbonation cured samples in the compressive test.
The transformation of calcium hydroxide, a detrimental element in ASR, into calcium
carbonate, a stable product was validated from the X-ray diffraction (XRD), and the
thermogravimetric analysis coupled with mass spectrometry and X-ray fluorescence (TGA-MS-
XRF).
An elevated concentration of carbon dioxide, a greenhouse gas, is a substantial factor in
global warming. The early carbonation curing was able to sequester carbon dioxide gas in
mortar permanently. Both the mass gain and the thermogravimetric-mass spectrometry
coupled with X-ray fluorescence (TGA-MS-XRF) methods yielded similar carbon dioxide
sequestration results in mortar.
The early carbonation curing does not only alleviate ASR in mortar but also provide an
efficient way of storing a greenhouse gas inside mortar permanently.

- 88 -
5.2 RECOMMENDATIONS FOR FUTURE WORK

The following list could be beneficial to future research:

1- The effect of early carbonation curing on reactive aggregates in concrete should be
studied using the concrete prism test (CPT) also known as ASTM C1293.
2- The lowest carbon dioxide pressure in the chamber that yields harmless expansions in
AMBT and CPT with reactive aggregates should be determined to decrease the cost of
the early carbonation curing.
3- A cost-benefit analysis of the carbonation curing as compared to the traditional moist
(hydration) curing should be conducted.
4- The containers and sample holders used for AMBT and CPT should be made of either
polypropylene or polyethylene. Stainless steel containers and sample holders should not
be used in the AMBT and CPT since it will corrode in warm alkali environment after a
few days.

- 89 -
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