Construction and Building Materials 38 (2013) 829–836

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Construction and Building Materials

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Effect of free lime content on properties of cement–fly ash mixtures

Krittiya Kaewmanee a,⇑, Pitisan Krammart b, Taweechai Sumranwanich c, Pongsak Choktaweekarn d,
Somnuk Tangtermsirikul a
a
School of Civil Engineering and Technology, Sirindhorn International Institute of Technology, P.O. Box 22, Thammasat-Rangsit Post Office, Klong Luang District,
Pathumthani 12121, Thailand
b
Department of Civil Engineering, Rajamangala University of Technology Thanyaburi, 39 Moo 1 Rangsit-Nakhonnayok Road, Thanyaburi District, Pathumthani 12110, Thailand
c
Department of Civil Engineering, Burapha University, 169 Long-Hard Bangsaen Road, Saen Sook Sub-district, Muang District, Chonburi 20131, Thailand
d
Construction and Maintenance Technology Research Center, Sirindhorn International Institute of Technology, P.O. Box 22, Thammasat-Rangsit Post Office, Klong Luang District,
Pathumthani 12121, Thailand

h i g h l i g h t s

" The free lime particles have irregular shape and are distributed outside the fly ash particles.
" Higher free lime in fly ash leads to early setting and higher compressive strength especially at early age.
" The autoclave expansion and the expansion due to alkali-aggregate reaction increases as free lime in fly ash increases.
" Carbonation depth, chloride and sulfate resistances are only slightly affected by the content of free lime in fly ash.
" It is possible to utilize the tested fly ash with free lime content up to 4.51% as mineral admixture in concrete.

a r t i c l e i n f o a b s t r a c t

Article history: This research aims to clarify the limitation of free lime content in fly ash according to EN-450. The form
Received 12 March 2012 and existence of free lime in fly ash by SEM, EDX, and free lime content by a titration method, were
Received in revised form 13 September observed. Some basic properties of fly ashes with various free lime contents and durability properties
2012
of mortar incorporating the fly ashes were also preliminary studied. It was found that free lime particles
Accepted 19 September 2012
Available online 29 October 2012
were mostly distributed outside the fly ash particles and that a minor amount of free lime was encapsu-
lated inside the fly ash particles in the fly ash formation process, meaning that the originally high free
lime and added free lime similarly affects properties of fly ash mixtures. A free lime addition method
Keywords:
SEM
was selected by adding free lime to the originally collected fly ash in order to vary free lime content of
EDX the fly ash. The studied basic properties consisted of normal consistency, autoclave expansion, initial
Added free lime and final setting time, water requirement, and compressive strength. In terms of durability, alkali-aggre-
Fly ash gate reaction, carbonation, shrinkage, and chloride and sulfate resistances, were investigated. Test results
Durability revealed that physical properties such as normal consistency and water requirement were unaffected by
free lime, and that a free lime content up to 4.51% had only slight chemical effects on fly ash–cement mix-
tures, i.e., faster setting, higher compressive strength, especially at early age, and higher autoclave expan-
sion. However, the values of autoclave expansion were still within the standard limit. Regarding
durability, mixtures with the high free lime fly ash led to higher expansion due to alkali-aggregate reac-
tion. The expansion was smaller than that of a cement-only mixture. Carbonation depth, shrinkage, and
chloride and sulfate resistances were only slightly affected by the added free lime.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction industrial product, its chemical and mineralogical compositions

Fly ash, a by-product from electricity generating power plants,
has been widely used in the concrete industry. Since it is not an
⇑ Corresponding author. Tel.: +66 8 1754 8389; fax: +66 2 986 9009 x 1900.
E-mail addresses: krittiya@siit.tu.ac.th (K. Kaewmanee), pitisan.k@en.rmut
t.ac.th (P. Krammart), twc@buu.ac.th (T. Sumranwanich), pongsak@siit.tu.ac.th
(P. Choktaweekarn), somnuk@siit.tu.ac.th (S. Tangtermsirikul).
vary greatly depending on many factors such as the type of coal
and burning conditions. Other countries’ standards [1–3] cannot
be directly applied because of differences in characteristics and
properties of fly ashes produced in different countries.
Much research has been conducted in Thailand to develop fly
ash classification and standards for the country, i.e., TIS 2135 [4].
Recently, fly ash produced from Mae Moh electricity generating
power plant started to show signs of high free lime content. Too

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.09.035
830 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836

high free lime content fly ash may affect both mechanical proper-
ties and durability of concrete [5,6]. Antiohos and Tsimas [7] re-
ported that unusually high percentages of free lime and sulfur
trioxide are concentrated in the smaller size particles of fly ash.
The behaviors of concrete with high free lime content fly ash in
Thailand have not been sufficiently studied. With reference to
ASTM C618 [2], no limit is set for either total calcium oxide content
or free lime content of fly ash. Nonetheless, EN-450 [1] limits the
amount of free lime content of fly ash to 1%, or up to 2.5% if the re-
sult of an autoclave expansion test is satisfied.
This research was initiated to provide understanding and preli-
minary information on the effect of free lime content of fly ash in
Thailand on properties of concrete. The research consists of two
parts: (i) clarifying the form and existence of free lime in fly ash
and (ii) studying properties of cement–fly ash mixtures with differ-
ent free lime content. To eliminate effects of physical properties of
the fly ash and focus only on the effects of free lime, the addition of
free lime to originally collected fly ash was done in order to vary
free lime content. Fig. 2. EDX of particle #1.

2. Experiment

2.1. Form and existence of free lime in fly ash

Microscopic study of Mae Moh fly ash content was carried out by SEM (Scan-
ning Electron Microscope), EDX (Energy-dispersive X-ray), whereas free lime
content was determined by a titration method.
The SEM picture of Mae Moh fly ash with high free lime content, illustrated in
Fig. 1, shows that there are two types of particle shape, i.e., round (#1) and irregular
(#2). It is generally known that Mae Moh fly ash particles are spherical. Therefore,
there is no doubt that the round particles are fly ash. The irregular particles, often
found in Mae Moh fly ash with high free lime content, are assumed to be free lime.
To prove this hypothesis, it is necessary to determine the composition of the parti-
cles. The EDX technique was implemented on the selected areas of particles #1 and
#2 and the results are shown in Figs. 2 and 3, respectively. The main composition of
particle #1 is silica, which is common for fly ash. Unlike particle #1, particle #2
indicates a calcium rich particle. To reaffirm the outcome, an SEM picture of Mae
Moh fly ash (which is the oven-dried filtered residue of fly ash in the process of free
lime determination) was taken as depicted in Fig. 4. The round shape particles are
obviously observed while the irregular shaped particles, presumed to be free lime,
are absent. This indicated that free lime particles were washed out in the free lime
determination process. According to SEM and EDX techniques, it is concluded that
particles of free lime in Mae Moh fly ash have irregular shapes and are distributed Fig. 3. EDX of particle #2.
among the fly ash particles.
However, free lime may also be encapsulated inside fly ash particle during the
fly ash formation process. To quantitatively determine this amount of free lime, ori-
ginal Mae Moh fly ash (MM) was ground into two different finenesses, referred to as
MM1 and MM2. Free lime contents of all fly ashes were determined by a titration
method. Initially, 1 gram of fly ash was dissolved in 50 cm3 of ethylene glycol at
a temperature of 60–70 °C for 30 min. The solution was then filtered by #1 filter
paper. In this process, another 30 cm3 of ethylene glycol at the temperature of
60–70 °C was added to make sure that all particles were washed out. The filtrate

Fig. 4. SEM image of oven-dried filtered Mae Moh fly ash.

was titrated with 0.1 N hydrochloric acid using Bromocresol green as an indicator
while the residues on filter paper were collected and dried in an oven. These resi-
dues were later sampled and used for the second test of free lime determination.
The free lime content was computed from:

Fig. 1. SEM image of Mae Moh fly ash (particles #1 and #2). Free lime content ð%Þ ¼ ðMfl =M fa Þ  100 ð1Þ
 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836 831

M fl ¼ s  n  56:07  0:5  103 ð2Þ Table 3

Chemical compositions of ordinary Portland cement type I, Mae Moh fly ashes A and
where Mfl is weight of free lime (g), s is the amount of HCl acid used in the titration D.
(cm3), n is normality of HCl acid and Mfa is weight of the fly ash sample (g). Blaine
fineness, free lime content of the fly ashes in the first and the second free lime con- Chemical compositions (%) OPC type Fly ash Fly ash
tent determinations are tabulated in Table 1. Free lime content obtained from the I A D
first titration of fly ashes tends to increase with an increase of fineness. However, SiO2 20.48 41.43 32.43
the increase is quite small and is insignificant, and does not affect properties of fly Al2O3 5.25 23.96 17.89
ash concrete. Second free lime content tests of all fly ashes yield the same results, Fe2O3 3.82 12.57 15.62
which can be explained from the characteristics of the test method. Unlike ethylene CaO 65.00 13.65 21.60
glycol, the filtrate is not a pure chemical solution and may consist of a very small MgO 0.95 2.73 3.65
amount of lime. When Bromocresol is added to filtrate, the color of solution does SO3 1.90 1.62 4.80
not immediately turn into an emerald green as in the case of pure ethylene glycol. Na2O <0.01 0.91 1.33
A few drops of HCl acid is required in order to turn the color of solution to be the K2O 0.40 2.34 1.87
same as that of the comparative solution. This results in the same non-zero value LOI 1.89 0.16 0.23
of free lime content of the second test of all fly ashes. From the results of free lime Free lime 0.22 0.83 2.11
contents in Table 1, it can be concluded that a very small amount of free lime was Equivalent sodium oxide 0.26 2.45 2.55
encapsulated inside the fly ash particles. (Na2O + 0.658 K2O)
It is clear from the study that free lime particles are mostly distributed outside
the fly ash particles and that an insignificantly small amount of free lime is encap-
sulated inside the fly ash particles.

2.2. Properties of fly ash–cement mixtures with different added free lime content 2.2.2.2. Durability properties. The research focused on durability properties of
cementitious mixtures with fly ash having various free lime content. Durability
The study covered some basic properties of fly ashes with various free lime con- properties in terms of alkali-aggregate reaction, carbonation, shrinkage, chloride
tents and durability properties of mortar incorporating the fly ashes. The basic resistance and sulfate resistance, were studied.
properties included normal consistency, autoclave expansion, setting time, water For expansion due to alkali-aggregate reaction, the test was carried out accord-
requirement, and strength activity index at 7, 28 and 91 days. Durability properties ing to ASTM C1260 [13] using mortar bar specimens with dimensions of
such as expansion due to alkali-aggregate reaction, shrinkage, carbonation depth, 2.5  2.5  28.5 cm. The reactive gravel was crushed and sieved so that its size dis-
chloride resistance and sulfate resistance were observed in this study. tribution was conformed to the specified gradation. In each mixture, 30% by weight
of cement was replaced by each type of fly ash. The sand to binder ratio was 2.25
2.2.1. Materials and the water to binder ratio was controlled at 0.47 for all mixtures. The expansion
From the findings in 2.1, it is reasonably assumed that the content of free lime, of mortar bars submerged in sodium hydroxide solution at the control temperature
which is originally present in the fly ash, can be varied by adding free lime from an of 80 ± 2 °C was regularly recorded for 14 days.
external source. This enabled the authors to vary free lime content of the tested fly An accelerated carbonation test was selected in order to shorten the test period.
ashes by keeping the other properties constant. The carbonation environment was controlled such that the CO2 concentration, and
Two types of fly ash, namely A and D, having different free lime content, from the temperature and the relative humidity, were 4% (40,000 ppm), 40 ± 2 °C and
Mae Moh electricity generating power plant and ordinary Portland cement, were 50 ± 5%, respectively. The test was conducted on 5  5  5 cm mortar specimens.
used in this study. Physical properties and chemical composition of the ordinary In each mix proportion, 30% by weight of total binder was replaced by each type
Portland cement type I and the Mae Moh fly ashes A and D are shown in Tables 2 of fly ash. The sand to binder ratio was 2.75 and the water to binder ratio was fixed
and 3, respectively. According to TIS 2135 [4], fly ashes A and D were classified as at 0.55 for all mixtures. The specimens were cured in water for 7 days before sub-
fly ash Classes 2b and 3, respectively. Based on ASTM C618 [2], fly ashes A and D jecting to a CO2 environment. After 28 days of CO2 subjection, the specimens were
were also be classified as Class F and Class C fly ash, respectively. Although fly split into half, sprayed with 1% phenolphthalein solution and the carbonation depth
ash A was classified as Class F, it contains a high amount of calcium oxide. was measured.
Fly ashes B and C were made by adding free lime to fly ash A so that the total The mix proportions for the shrinkage test were the same as those of the car-
free lime contents were 2.43% and 3.81%, respectively. Similarly, fly ashes E and F bonation test. The tested specimens were mortar bars with dimensions of
were made by adding free lime to fly ash D so that the total free lime contents were 2.5  2.5  28.5 cm. The mortar bars were cured in water for 7 days and subjected
3.11% and 4.51%, respectively. to drying conditions at a temperature of 28 ± 2 °C and relative humidity of 50 ± 5%
River sand complying with ASTM C33-92a [8] was used as fine aggregate and its for 78 days. Shrinkage of mortar bars measured in term of total shrinkage was con-
specific gravity was 2.60. tinuously monitored.
Chloride permissibility, measured according to ASTM C1202 [14], and chloride
binding capacity were tested. The former was tested on mortar with sand to binder
2.2.2. Experimental programs
ratio of 2.75 and water to binder ratio of 0.50. The tested specimens had the diam-
2.2.2.1. Basic properties. Some vital basic properties were tested. The autoclave
eter of 10 cm and thickness of 5 cm. The portion of fly ash was 30% by weight of to-
expansion test was conducted in accordance with ASTM C151 [9]. Normal consis-
tal binder content for each type of fly ash. The charge passed was measured and the
tency and setting time were determined according to ASTM C187 [10] and ASTM
interpretation of chloride permissibility was made. Chloride binding capacity was
C191 [11], respectively. Water requirement and compressive strength were tested
tested on paste. Each type of fly ash was proportioned such that it accounted for
according to ASTM 311 [12]. The mix proportions were designed by replacing
30% by weight of total binder content, and the water to binder ratio of 0.40 was con-
20% by weight of cement by each type of fly ash, i.e., fly ashes A, B, C, D, E, and F.
trolled. For each mixture, 13 cylindrical disc specimens with a diameter of 5 cm and
The mortar was cast with sand to binder ratio of 2.75 by weight.
a thickness of 1 cm were cast and cured in water for 7 days. Then, they were sub-
merged in 3% sodium chloride solution for 91 days. After submersion, the speci-
mens were compressed and the pore solution was collected. Total chloride was
Table 1 determined from multiplying the volume of salt water with the difference between
Blaine fineness and free lime content of fly ashes. initial chloride content of the submerging salt water at the start of exposure and its
final chloride content at the end of exposure, and was assumed to be shared equally
MM MM1 MM2
to all specimens submerged in the salt water. The free chloride was determined
Blaine fineness (cm2/g) 3084 3403 3856 from chloride concentration of the pore solution multiplied with the evaporable
Free lime content (%) water. Finally, the fixed chloride content can then be computed from the subtrac-
1st test 3.28 3.30 3.34 tion of the free chloride content from the total chloride content.
2nd test 0.14 0.14 0.14 For sulfate resistance, the expansion of 2.5  2.5  28.5 cm mortar bar speci-
mens in sodium sulfate solution was measured. The mix proportions were the same
as those of the carbonation and shrinkage tests, except that the portion of each type
of fly ash was set at 40% by weight of total binder. All specimens were cured in
Table 2 water for 28 days and then immersed in sodium sulfate solution. The length change
Physical properties of ordinary Portland cement type I, Mae Moh fly ashes A and D. of mortar bar specimens was periodically recorded.
Details of mix proportions and sizes of specimen of all tests are summarized in
Physical properties OPC type I Fly ash A Fly ash D Table 4.
Specific gravity 3.15 2.08 2.40 The mix proportions were systematically designated as shown in Table 5. The
Blaine fineness (cm2/g) 3350 2390 1705 number after C represents the weight percentage of OPC type I cement in the total
binder whereas the number after FA represents the weight percentage of fly ash in
832 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836

Table 4
Details of mix proportions and specimen sizes.

Test items Paste/mortar Dimension of specimens Fly ash replacement ratio w/b Sand to binder ratio
Normal consistency Paste Ø6 top, Ø7 base  4 cm 0.2 NM –
Autoclave expansion Paste 2.5  2.5  28.5 cm 0.2 NM –
Setting time Paste Ø6 top, Ø7 base  4 cm 0.2 NM –
Water requirement Mortar – 0.2 WR 2.75
Compressive strength Mortar 5  5  5 cm 0.2 WR 2.75
Alkali-aggregate reaction expansion Mortar 2.5  2.5  28.5 cm 0.3 0.47 2.25
Drying shrinkage Mortar 2.5  2.5  28.5 cm 0.3 0.55 2.75
Carbonation depth Mortar 5  5  5 cm 0.3 0.55 2.75
Chloride permissibility Mortar Ø10  5 cm 0.3 0.50 2.75
Chloride binding capacity Paste Ø5  1 cm 0.3 0.40 –
Expansion due to Na2SO4 solution Mortar 2.5  2.5  28.5 cm 0.4 0.55 2.75

Remarks: NM = water to binder ratio that achieves normal consistency (10 ± 1 mm penetration depth determined by Vicat apparatus) and WR = water to binder ratio that
achieves flow of 110 ± 5%.

Table 5
Mix designation.

Mix designation OPC (%) Fly ash (%) Fly ash replacement ratio
Type I Type V A B C D E F
C100 100 – – – – – – – 0
C80FA(A)20 80 – 20 – – – – – 0.2
C70FA(A)30 70 – 30 – – – – – 0.3
C60FA(A)40 60 – 40 – – – – – 0.4
C80FA(B)20 80 – – 20 – – – – 0.2
C70FA(B)30 70 – – 30 – – – – 0.3
C60FA(B)40 60 – – 40 – – – – 0.4
C80FA(C)20 80 – – – 20 – – – 0.2
C70FA(C)30 70 – – – 30 – – – 0.3
C60FA(C)40 60 – – – 40 – – – 0.4
C80FA(D)20 80 – – – – 20 – – 0.2
C70FA(D)30 70 – – – – 30 – – 0.3
C60FA(D)40 60 – – – – 40 – – 0.4
C80FA(E)20 80 – – – – – 20 – 0.2
C70FA(E)30 70 – – – – – 30 – 0.3
C60FA(E)40 60 – – – – – 40 – 0.4
C80FA(F)20 80 – – – – – – 20 0.2
C70FA(F)30 70 – – – – – – 30 0.3
C60FA(F)40 60 – – – – – – 40 0.4
Type I 100 – – – – – – – 0
Type V – 100 – – – – – – 0

the total binder. Types of fly ash are indicated in the parenthesis after FA. Type I and 25
Normal consistency (%)

V represent the mixtures made from OPC type I and OPC type V, respectively, in the 24.31
sulfate expansion test. 24

23 22.77 22.77 22.77

3. Results and discussion 22.46 22.46 22.46
22
3.1. Basic properties
21
The results of normal consistency, autoclave expansion, setting
time, and water requirement of mixtures made with fly ash having 20
various free lime contents are illustrated in Figs. 5 and 6.
It is certain that mixtures with all types of fly ash required less
water than that of the cement-only mixtures in order to achieve
the same consistency and flow (Figs. 5 and 6) due to their spherical
Fig. 5. Normal consistency.
shape. Mixtures with fly ash A needed slightly higher amount of
water than that of mixtures with fly ash D since fly ash A is slightly
finer and thus can retain more water than fly ash D, resulting in
less free water to lubricate the mixture. Free lime added to the amounts of free lime and also sulfur trioxide in fly ash D are higher
mixtures had no effect on normal consistency and water require- than those in fly ash A. A higher free lime content of fly ash tends to
ment, as can be observed from the same normal consistency and cause higher expansion. The cement-only mixtures had very small
water requirement among mixtures with fly ashes A, B, and C expansion compared with the expansion of mixtures of all types of
and among mixtures with fly ashes D, E, and F. fly ash, except for fly ash A. Though the autoclave expansion of
The autoclave expansion results (Fig. 7) show that mixtures mixtures with fly ash is high, especially in case of fly ash with high
with fly ash D, having originally higher free lime content, had high- free lime and sulfur trioxide content, all results are still within the
er expansion than mixture with fly ash A. This is because the limit specified by ASTM C618 [2], i.e., not higher than 0.8%.
 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836 833

110 600

Compressive strength
Water requirement (%)

105 500
100 99.25 99.25 99.25 98.87 98.87 98.87

(kg/cm 2)
100 400 341 335 333 337 349
317 318
95 300
200
90
100
85
0
80

(a) 7 days
Fig. 6. Water requirement.
800

Compressive strength
700
600
C80FA(F)20 0.017 469 468 466 466 467 481

(kg/cm 2)
500 440
400
C80FA(E)20 0.014
300
C80FA(D)20 0.013 200
100
C80FA(C)20 0.015 0

C80FA(B)20 0.005
C80FA(A)20 -0.012
(b) 28 days
C100 0.0004
-0.03 -0.02 -0.01 0.00 0.01 0.02 0.03 800
Compressive strength

700
Expansion (%) 578 551
600 538 518 544 535 537
(kg/cm 2)

Fig. 7. Autoclave expansion. 500

400
300
Initial setting Final setting 200
100
C80FA(F)20 111 0
140
111
C80FA(E)20 140
111
C80FA(D)20 145
C80FA(C)20 114 (c) 91 days
160
C80FA(B)20 115 Fig. 9. Compressive strength of mortar specimens.
160
C80FA(A)20 115
165
C100 103 ash A to obtain the same workability. Moreover, fly ash D possesses
120
higher CaO content than fly ash A does, though fly ash D is coarser
0 30 60 90 120 150 180
than fly ash A. For mixtures with fly ashes having total CaO content
Time (mins) of 13.65 (fly ashes A, B and C), compressive strength increased as
free lime of fly ash increased. However, when free lime content
Fig. 8. Initial and final setting times.
of fly ash became too high (fly ash C), the compressive strength
did not show further increase. This can be observed at all tested
ages. In cases of mixtures with fly ashes having total CaO content
The initial and final setting times of all mixtures, as illustrated of 21.60 (fly ashes D, E and F), compressive strength increased as
in Fig. 8, reveal that the initial and final setting times of all types free lime of fly ash increased at 7 and 28 days. At 91 days, the in-
of fly ash mixtures were longer than that of cement-only mixtures. crease of strength was less significant when free lime of fly ash
Mixtures with fly ash D set slightly earlier than mixtures with fly was too high (fly ash F). The strength activity index of mixtures
ash A. This is likely to be caused by the originally higher amount with Class 2b fly ashes (fly ashes A, B, and C) were much greater
of calcium oxide and also free lime of fly ash D. The added free lime than 70% and 75% of the control mix at 7 days and 28 days, respec-
had a small effect on the setting of mixtures with fly ash. The mix- tively, which satisfied TIS 2135 [4] standard specification. In addi-
tures with higher free lime content tended to have slightly earlier tion, strength activity index of mixtures with Class 3 fly ashes (fly
initial and final setting times. ashes D, E and F) also showed higher value than that specified in
Results of compressive strength and strength activity index are the TIS 2135 [4] standard specification, i.e., >60% and >70% of the
expressed in Figs. 9a–c and 10a–c, respectively. Mixtures with fly control mix at 7 days and 28 days, respectively. As specified in
ash D had slightly higher compressive strength than mixtures with ASTM C618 [2], the strength activity index of Class C and Class F
fly ash A, due to the fact that fly ash D requires less water than fly fly ash with Portland mixture must be greater than 75% percent
834 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836

---- min. strength index for fly ash class 2b (70%, TIS 2135) 0.16
__ min. strength index for fly ash class 3 (60%, TIS 2135) 0.14

Expansion (%)
0.12
…. min. strength index for fly ash class C and class F (75%, ASTM C 618) 0.12
0.10
120
100 98 98 99 102 0.08 0.06 0.06 0.06
100 93 93 0.06
Strength index

0.04 0.03 0.03 0.03

80
0.02
60 0.00
40
20
0
Fig. 11. Expansion due to alkali-aggregate reaction.

D, E, and F were similar. Although fly ash with high free lime and
(a) 7 days sulfur trioxide made the mixture expand more, the expansion
was far less than that of the cement-only mixture. As it is generally
---- min. strength index for fly ash class 2b (75%, TIS 2135) understood, replacing a part of the cement by fly ash reduced the
__ min. strength index for fly ash class 3 (70%, TIS 2135) alkalinity of the mixtures since calcium hydroxide was consumed
…. min. strength index for fly ash class C and class F (75%, ASTM C 618) in the pozzolanic reaction.
120
100 100 99 99 100 103
100 94 3.2.2. Carbonation
Strength index

As shown in Fig. 12, free lime content, neither originally pos-

80
sessed nor added, had no influences on carbonation since carbon-
60 ation depths of mixtures with fly ashes A, B, C, D, E, and F were
40 equal. As is generally known, mixtures with all fly ashes resulted
in a higher carbonation depth than a cement-only mixture.
20
0
3.2.3. Shrinkage
It is quite obvious that mixtures with fly ash D shrink less than
mixtures with fly ash A, as can be seen from Fig. 13. This is possibly
due to the higher sulfur trioxide content in fly ash D than that of fly
(b) 28 days ash A. Since sulfur trioxide causes expansion which compensates
shrinkage, the mixture with higher sulfur trioxide content would
---- min. strength index for fly ash class 2b (85%, TIS 2135)
__ min. strength index for fly ash class 3 (75%, TIS 2135)
120 8
107 103
Carbonation depth

100 96 101 99 100 7

100 6 6 6 6 6 6
Strength index

6
80 5
(mm)

60 4 3
3
40 2
20 1
0
0

Fig. 12. Carbonation depth.

(c) 91 days
Fig. 10. Strength index of mortar specimens.
1200
Total shrinkage (x10-6 m)

of the control mix at 7 and 28 days. All the tested fly ashes in this 1000
research satisfied the standard. 800

3.2. Durability properties 600

400 C100 C70FA(D)30

3.2.1. Alkali-aggregate reaction C70FA(A)30 C70FA(E)30
It is clear from the results of AAR expansion shown in Fig. 11 200 C70FA(B)30 C70FA(F)30
that fly ash D, having originally higher free lime, sulfur trioxide, C70FA(C)30
0
and equivalent sodium oxide contents, caused higher expansion 0 10 20 30 40 50 60 70 80 90 100
than fly ash A. The addition of free lime content seemed to have Drying period (days)
no effect on the expansion since the expansion of mixtures with
fly ashes A, B, and C and the expansion of mixtures with fly ashes Fig. 13. Total shrinkage.
 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836 835

result in less shrinkage [15]. The addition of free lime seemed to 2.0
have more effect on mixtures with lower total calcium oxide con-

cementitious materials)
Fixed chloride content
tent fly ash. Less influences were found on the mixtures with high-

(% by weight of
1.5
er total calcium oxide content fly ash since shrinkage of mixtures
with fly ashes D, E, and F are insignificantly different. A clear expla-
nation for this behavior is still unknown and further study is 1.0
needed. However, mixtures with all type of fly ash showed lower C70FA(A)30 C70FA(D)30
total shrinkage than the cement-only mixtures. 0.5
C70FA(B)30 C70FA(E)30
C70FA(C)30 C70FA(F)30
3.2.4. Chloride resistance 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
The charge passed of mixtures with all fly ashes was less than
that of a cement-only mixture (see Fig. 14), meaning better chlo- Total chloride content
ride penetration resistance. Among mixtures with various free lime (% by weight of cementitious materials)
content of fly ash, the amount of charge passed slightly differed. Fig. 16. Relationship between total chloride content and fixed chloride content.
Therefore, it can be said that the tested range of free lime content
has little effect on chloride permissibility.
Results of total chloride content and fixed chloride content of all
mixtures are shown in Fig. 15 and the relationship between total 0.50
Type I-100 Type V-100
chloride content and fixed chloride content is plotted in Fig. 16. C60FA(A)40 C60FA(D)40

Expansion (%)
0.40
It is noticeable that the free lime content has no influences on chlo- C60FA(B)40 C60FA(E)40
ride binding capacity since the fixed chloride content of all fly ash 0.30 C60FA(C)40 C60FA(F)40

mixtures lies on the same line.

0.20

3.2.5. Sulfate attack 0.10

The expansion of all tested mixtures immersed in sodium sul- 0.00
fate solution is plotted in Fig 17. It is obvious that free lime content 0 100 200 300 400 500 600 700
of fly ash, either originally possessed or added, has little effect on Immersion period (days)
the expansion. The expansion of all fly ash mixtures is still smaller
Fig. 17. Expansion of mortar bars submerged in sodium sulfate solution.
than that of the cement type I-only and cement type V-only
mixtures.
Performances of high free lime content fly ash, compared with
those of low free lime content fly ash on various properties, are Table 6
Summary of performances of high free lime fly ash on various properties in
comparison with those of low free lime fly ash.
Charge passed (coulombs)

Properties Performance
12000
Worse Same Better
10000
8,087 Normal consistency 
8000 Autoclave expansiona 
6,071 Setting time 
6000 5,080 5,234 5,142 5,358 5,273
Water requirement 
4000 Compressive strength  
Alkali-aggregate reactiona 
2000 Drying shrinkage 
Carbonation 
0 Chloride resistance 
Sulfate resistance 
a
Though performances are worse than those of the low free lime fly ash mix-
tures, the performances are still better than those of cement-only mixtures.

Fig. 14. Chloride permissibility by charge passed at 28 days.

summarized in Table 6. It should be noted that although the auto-
clave expansion and the expansion due to alkali-aggregate reaction
of mixtures with high free lime fly ash were higher than those of
Chloride content (% by weight

low free lime fly ash, the expansions are still smaller than that of
of cementitious materials)

Total Chloride Fixed Chloride

3.00 the cement-only mixtures. From the summary shown in Table 6,
2.53
2.50 2.20 2.34 2.36 it can be mentioned that it is possible to utilize fly ash which has
2.02 2.06 2.06 a free lime content beyond 2.5% (up to 4.51% in this study) in con-
2.00
1.50 1.52 1.60 crete while still achieving the benefits normally obtained from fly
1.45
1.50 1.14 ash with free lime lower than 2.5%.
1.09 1.09
1.00 It should be noted here that fly ash is an industrial waste which
0.50 has relatively large property variation when compared to cement.
0.00 It is not possible to cover all natures of fly ash in this study. The re-
sults obtained from this study are the first of its type to verify that
the maximum limit of free lime content may not be as low as 2% as
allowed by EN-450 [1]. More intensive results are required to
establish a more appropriate limit of free lime content of fly ash
Fig. 15. Total and fixed chloride contents. in the future.
836 K. Kaewmanee et al. / Construction and Building Materials 38 (2013) 829–836
4. Conclusions
The existence of free lime in the tested fly ash and various prop-
erties of mixtures with the fly ash, having free lime content up to
4.51% by addition, were studied in this research. The following con-
clusions can be drawn from the results of this study:
(i) Free lime particles have irregular shape and are distributed
outside the fly ash particles. Very small amounts of free lime
may be encapsulated inside the fly ash particles.
(ii) Normal consistency and water requirement of mixtures with
fly ash are unaffected by the amount of free lime in fly ash as
long as fly ashes are of the same particle shape and fineness.
(iii) Higher free lime in fly ash leads to early setting and higher
compressive strength, especially at early age. When the free
lime content of fly ash is too high, the increase of compres-
sive strength becomes less significant. The compressive
strength results of mixtures with fly ashes having free lime
content up to 4.51% satisfy both TIS 2135 [4] and ASTM C
618 [2] standards.
(iv) Even though high free lime content of fly ash tends to cause
higher autoclave expansion, the expansion is still within the
allowable value specified by the ASTM standard [2].
(v) The expansion due to alkali-aggregate reaction increases as
free lime in fly ash increases. However, the expansions of
mixtures with all fly ashes are far less than that of the
cement-only mixture.
(vi) Drying shrinkage is prone to be affected more by free lime in
cases of low total calcium oxide content in fly ash. Shrink-
ages of all the tested fly ash mixtures are lower than that
of the cement-only mixture.
(vii) Carbonation depth, and chloride and sulfate resistances are
only slightly affected by the content of free lime in fly ash.
(viii) It is possible to utilize the tested fly ash with free lime con-
tent up to 4.51% as mineral admixture in concrete since
properties of mixtures with the fly ashes satisfy the relevant
standards. Although fly ashes with high free lime show some
poorer performances than fly ashes with lower free lime,
replacing a part of the cement with high free lime fly ashes
results in better performances when compared to that of the
cement-only mixtures.
Acknowledgements
Financial support from the Thailand Research Fund through the
Royal Golden Jubilee Ph.D. Program (Grant No. PHD/0124/2549) is
acknowledged. The authors would like to thank EGAT (Electricity
Generating Authority of Thailand) for providing research support
and fly ash samples for this study. The research is also partially
supported by the Higher Education Research Promotion and Na-
tional Research University Project of Thailand, Office of the Higher
Education Commission.
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