Académique Documents
Professionnel Documents
Culture Documents
SEMINAR REPORT
MASTER OF TECHNOLOGY
IN
CIVIL ENGINEERING
(STRUCTURAL ENGINEERING AND CONSTRUCTION MANAGEMENT)
Submitted by
NAJEEB.M
CERTIFICATE
This is to certify that the seminar report on Portland Limestone Cement is a
bonafide record of the seminar presented by Najeeb.M (Reg No. 84113) in partial
fulfilment for the award of the degree of Master of Technology in Civil Engineering
with specialisation in Structural Engineering and Construction Management
(Staff Advisor)
(P. G. Coordinator)
ACKNOWLEDGEMENT
NAJEEB.M
ABSTRACT
Portland-limestone cements (PLC) have been used in practice for a considerable
period of time in several countries. In 2008, the CSA A3000 cements committee approved
the addition of a new class of cement with up to 15% interground limestone.
The main advantage of producing Portland-limestone cement is its contribution
to sustainable development. By introducing limestone into cement, the total volume of
cement would increase, or in other words, the amount of clinker required to produce a
certain amount of cement would decrease. This would result in a substantial amount of
energy saving in the production of cement as the consumption of natural raw materials
and the fuel needed for production of clinker would be reduced. Moreover, it would
contribute to sustainable development due to the reduction in greenhouse gas emissions,
mostly CO2 and NOx, involved in the pyro processing of clinker. On this basis, the future
world production of Portland-limestone cement is expected to increase. Nevertheless, it
should be noted that all the aforementioned benefits can only be achieved provided that
Portland-limestone cement has similar performance characteristics to Portland cement,
and has no adverse effects on the properties of concrete.
The properties of Portland-limestone cements have been the subject of numerous
studies. Researchers have studied the effect of using Portland-limestone cement with
various limestone contents on fresh properties, mechanical properties, and durability of
concrete.
This seminar paper covers a brief introduction to Portland Limestone Cement, its
properties, equivalent strength, equivalent durability and Shrinkage properties
ii
CONTENTS
SL No
TITLE
ACKNOWLEDGEMENT
ABSTRACT
ii
LIST OF TABLES
iv
LIST OF FIGURES
INTRODUCTION
1.1 Initiatives
1.2.1 History
1.2.2
Current Situation
PAGE
No.
7
8
9
10
11
13
15
3.4 Carbonation
17
19
LIMESTONE CEMENT
20
22
25
25
26
27
CONCLUSION
30
REFERENCES
31
iii
LIST OF TABLES
Sl No.
NAME OF TABLES
PAGE No.
Table 1
Table 2
16
20
Table 4
20
Table 5
22
Table 6
22
Table 7
24
iv
LIST OF FIGURES
Sl No
NAME OF FIGURES
PAGE NO
Fig 1
Fig 2
component fractions
Fig 3
Fig 4
Fig 5
Fig 6
14
Fig 7
15
Fig 8
18
Fig 9
18
Fig 10
21
Fig 11
23
Fig 12
27
28
PLC-Slag systems with w/b of: (a) 0.39; and (b) 0.34
Fig 14
29
29
1.
INTRODUCTION
1.1. Initiatives
Concrete is the second most consumed material in the world after water. It is
estimated that approximately 10 km3 of concrete is required annually, which corresponds
to about 1.5 m3 per person. Ordinary concrete typically contains about 12% cement.
Currently, Portland cement is the most common type of cement used to bond concrete
in many parts of the world. Recent statistics indicate that about 3 billion tons of cement
is produced every year.
The main component of Portland cement is ground clinker, which mainly consists
of calcium silicates, with some aluminum- and iron-containing phases. Clinker is
manufactured by mixing limestone (calcium source), clay (silica and alumina sources)
and iron ore in a rotary kiln and heating the mix to over 1450 C. This high temperature,
which is usually reached by burning fossil fuels, leads to chemical reactions that transform
raw materials into clinker. This results in large emission of greenhouse gases, especially
carbon dioxide, both from the burning of fossil fuels and from decalcification of limestone.
It is often stated that the production of 1 ton of cement results in emission of 0.8
ton of CO2. In fact, estimations show that the manufacture of Portland cement is
responsible for between 5 to 8% of global CO2 emissions. In fact, production of cement
is expected to further increase because of the exponential growth rates in developing
countries, such as China and India, which are the major cement producers and consumers
in the world. Therefore, it is imperative that steps be taken in order to reduce the CO2
released into the atmosphere. This involves either incorporating new environmentally
friendly manufacturing technologies or finding substitute materials to replace a major
part of Portland cement for use in concrete industry. Due to the limitations involved in
reducing CO2 emissions from alternative raw materials and fuels or by improving kiln
efficiency, the first option seems to be not practical. Hence, probably the most effective
means of achieving significant reductions in CO2 emissions lies in the replacement of
Portland cement by other suitable materials, or alternatively by reducing the clinker
component of Portland cement.
Replacement materials that react with calcium hydroxide are commonly known as
Supplementary Cementitious Materials (SCMs). They include fly ash, ground
1
granulated blast furnace slag (GGBFS), pozzolans, silica fume, metakaolin, etc. These
replacement materials can be added separately to the concrete, allowing a reduction in the
cement content of concrete, or used to replace the clinker in blended/composite cements.
Blended cements, i.e. cements comprising of supplementary cementitious
materials such as ground granulated blast furnace slag, fly ash, pozzolans, and silica
fume, are being produced by many cement manufacturers, and are used extensively in the
concrete sector. According to Mehta (2007), the use of supplementary cementitious
materials has increased from 10% in 1990 to about 15% in 2005, and it is viable to
increase this number to about 50% in 2020. SCMs are beneficial not only in the sense
that they contribute to sustainability and reduction in CO2 emissions, but also due to the
potential ability of these materials to enhance the properties and performance of concrete.
In addition to that, some of the SCMs such as slag and fly ash are byproducts of other
industries, and their use could help preserve non-renewable resources.
1.2. Portland-Limestone Cements
One of the materials that has been introduced to Portland and blended cements as
a constituent is limestone or calcium carbonate (CaCO3). This has led to the production
of Portland-limestone cement, i.e. cements that have been interground with limestone.
Most Portland cement specifications allow the use of up to 5% limestone. Beyond that,
Portland-limestone cements are categorized based on the percentage of limestone added
to the cement. Portland-limestone cements consisting of limestone from 5% up to about
40% are being produced and used in various countries around the world, with the most
commonly used cement type in Europe being CEM II/A composite cement with 5-20%
limestone. Also, different standards have stated specifications with regards to the amount
of limestone used in Portland-limestone cements. In 2008, CSA A3001 adopted a new
class of Portland-limestone cements with up to 15% interground limestone.
Perhaps the main advantage of producing Portland-limestone cement is its
contribution to sustainable development. By introducing limestone into cement, the total
volume of cement would increase, or in other words, the amount of clinker required to
produce a certain amount of cement would decrease. This would result in a substantial
amount of energy saving in the production of cement as the consumption of natural raw
materials and the fuel needed for production of clinker would be reduced. Moreover, it
would contribute to sustainable development due to the reduction in greenhouse gas
2
emissions, mostly CO2 and NOx, involved in the pyro processing of clinker. On this basis,
the future world production of Portland-limestone cement is expected to increase.
Nevertheless, it should be noted that all the aforementioned benefits can only be achieved
provided that Portland-limestone cement has similar performance characteristics to
Portland cement, and has no adverse effects on the properties of concrete.
The properties of Portland-limestone cements have been the subject of numerous
studies. Researchers have studied the effect of using Portland-limestone cement with
various limestone contents on fresh properties, mechanical properties, and durability of
concrete. Overall, the data found in the literature seems to be inconsistent in some
specific areas, especially in cases where the limestone content of Portland-limestone
cement is greater than 5%. Data reported in the literature is apparently affected by the
quality and particle size distribution of the limestone used. Also whether the limestone
was interground, blended, or added at the mixer seems to have an influence on the results.
Hence, it is important that these factors be taken into consideration when interpreting the
data.
1.2.1. History
The use of Portland-limestone cements has been in practice for a considerable
period of time in several countries. It seems that European countries have been the
leaders in producing and using Portland-limestone cement. According to Schmidt (1992),
Heidelberg Cement, the main cement producer in Germany, used to produce an energysaving cement which contained 20% interground limestone and was used for special
applications as early as 1965. In 1979, a new standard introduced in France permitted the
incorporation of up to 35% of slag, fly ash, natural or artificial pozzolans, and limestone
in a new type of cement called CPJ.
Later on, a specific cement designated as PKZ which consisted of 85+/-5%
clinker and 15+/-5% limestone was specified in the 1987 draft of the European standard
EN 197 (Schmidt 1992). This type of Portland-limestone cement, along with other types
of blended cements, was reported to be commonly used throughout Germany by 1990. In
addition to that, the British Standard BS 7583 allowed use of up to 20% limestone in
cement in the United Kingdom in 1992 (Schmidt 1992). However, the use of it did not
become so popular until the concrete standard BS 5328 was amended in 1997 to include
its use in concrete. Nonetheless, the standard prohibited the use Portland- limestone
3
approved the use of PLC in concrete in 2009, and it was included in the National Building
Code of Canada in 2010 as well as several provincial building codes.
1.2.2. Current Situation
As mentioned before, there are four classes of composite cements with limestone
filler in the European Standard, namely CEM II/A-L or-LL (6-20% limestone) and
CEMII/B-L or -LL (21-35% limestone). It is interesting that except in Sweden and Italy,
none of these types of cement are allowed to be specified where sulfate resistance is
required (CEN, 2003). In Sweden, testing for sulfate resistance must be performed, and in
Italy, there are certain restrictions on the C3A content of the clinker and the severity of
sulfate environment. This fact reflects the concern over performance of Portlandlimestone cements in sulfate exposures.
The literature review on Portland-limestone cements (Hooton et al, 2007)
suggested that the literature was conflicting with respect to use of Portland-limestone
cements in sulfate exposures. They pointed out inconsistencies in the trends found by
different researchers as to whether limestone improved or worsened sulfate resistance of
cement, either for conventional sulfate attack or in regards with thaumasite related
deterioration. Moreover, data on the performance of Portland-limestone cements when
used in conjunction with SCMs is limited. The recommendation was that more work
needs to be done in the Canadian context (e.g. at CSA exposure levels and sulfate types)
on the performance of Portland-limestone cements at both 5C and 23C. This should
include use of plain Portland-limestone cement and its combination with levels of SCMs
currently known to provide good sulfate resistance as well as on CSA MS and HS
cements.
Due to this uncertainty about the performance of Portland-limestone cements in
sulfate environments, their use was not allowed in sulfate exposures in the 2008 revision
until further research had been conducted. By that time, the cement companies had
started trial grinds and testing the properties of Portland-limestone cement had been
initiated. However, the concern over the sulfate resistance of Portland-limestone cements,
especially in regards with thaumasite sulfate attack, became the driving force behind
several research studies. Based on the result of this research, including the present study,
the 2010 version of the CSA A3001 standard stated that Portland-limestone cements may
be used in sulfate environments provided that they are combined with the specified
6
Fig 2. Example fineness trends PLC vs. clinker and limestone component fractions
7
2.
when the water content is kept as low as possible, consistent with ensuring satisfactory
placing and thorough compaction.
Other factors affecting performance include conditions of curing as well as the
individual properties of the constituent materials and their proportions in the mix. The
potential performance of any Portland cement based product will only be best developed
under saturated conditions. Appropriate curing is necessary for optimum performance.
Loss of any water to the surroundings should be guarded against and for a period of at least
seven days precautions should be taken to keep the concrete moist and to prevent premature
drying. The rate of strength development will depend on ambient conditions and the initial
temperature of the mix. As a general rule, concrete should be placed within the range of
10C to 30C. In cold weather, freshly poured concrete should be protected against frost to
avoid damage.
At higher temperatures concrete should be protected to avoid increased risk of loss
of water by evaporation, which may lead to cracking caused by drying shrinkage and
thermal stresses, and reduced ultimate performance and strength.
Filler Content
Bulk Density
Chemistry
(Main Oxides)
Sulphate
Chloride
Declared Mean Alkali
Colour
Surface Area
Setting Time
Strengths
2.1.
Fresh Blown
Settled
900-1100 kg/m3
1100-1350 kg/m3
Compacted
1350-1450 kg/m3
CaO
SiO2
Al2O3
60-70 %
15-25 %
3-5 %
Fe2O3
2.0-3.5 %
MgO
0.5-1.5 %
SO3
Cl
Na2Oeq
Tri-stimulus Y
2 days
25-40
350-550 m2/kg
100-200 minutes
15-30 MPa
7 days
28 days
20-45 MPa
40-60 MPa
difference in water demand, slump loss, when PLC used. Also excellent finishing
properties are obtained for PLC. Generally no change for straight cement systems in case
of the setting conditions. Response to admixtures are similar to that of normal concrete.
Strength development is at least equivalent, though both rate of strength gain and ultimate
strength may be enhanced, especially in combination with SCMs. Shrinkage, heat of
hydration, and durability performance attributes all similar or even slightly improved.
However, there has been little research to show whether PLC concrete is as robust
as PC concrete in less-than- ideal situations, such as when poor construction
practices lead to increased water contents or improper finishing. Concrete produced
with PLC-SCM blends and a high water-cementitious material ratio (w/cm) may be
more vulnerable than similar concrete made with PC-SCM blends; and
Published research on the carbonation of concrete is ambiguous. The rate of
carbonation of concretes produced at the same w/cm increases with the amount of
limestone in the cement. However, the PLC and PC used in these studies were not
manufactured to produce equivalent strength. PC and PLC concretes proportioned
to achieve equivalent 28-day strength have about the same rate of carbonation;
however, the PLC concrete was proportioned with a lower w/cm than the PC
concrete to achieve equivalent strength. There are no published carbonation data
related to the performance of concrete with PLC that has been ground to produce
equivalent strength as PC at the same w/cm. Additionally, there is little information
on the carbonation of PLC with relatively high amounts of SCMs. High levels of
SCMs are known to render concrete more susceptible to carbonation.
Research results presented in this article address these unresolved issues. For each
study included here, PC and PLC came from the same mill circuit, the target limestone
content of the PLC was 12%, the limestone was inter- ground with the cement clinker,
and the fineness of the PLC was increased to achieve the same 28-day (mortar) strength as
the PC.
3.1. Alkali-Silica Reaction
It is well established that most types of SCMs can be used to control expansion due
to ASR, provided that the SCM is used at a sufficient level of replacement. However, there
is some controversy over the best test method for determining the amount of SCMs
required. Although the concrete prism test (ASTM C1293, Standard Test Method for
Determination of Length Change of Concrete Due to Alkali-Silica Reaction) is considered
by some to be the most reliable it requires a 2-year test duration. The accelerated mortarbar test (ASTM C1567, Standard Test Method for Determining the Potential Alkali-Silica
Reactivity of Combinations of Cementitious Materials and Aggregate (Accelerated
Mortar-Bar Method)) is thus being more commonly selected for evaluating preventative
measures, as it allows a much shorter exposure of the mortar bars to the test solution.
11
Fig 3. Concrete prisms stored for 2 years over water at 38C (100F)
12
14
(up to 22%). However, provided a sufficient level of SCM is used (50% slag cement in the
study), satisfactory performance is achieved irrespective of the limestone content up to
22%. Note. the CSA specifications prescribe minimum SCM replacement levels and
impose these higher w/cm values for concrete exposed to freezing and thawing. All
concretes were air-entrained with a target air content of 6%. Table 2 shows the results after
300 freezing-and- thawing cycles. Satisfactory durability factors (>90%) and small length
changes were observed for all mixtures regardless of w/cm, type of cement (PC or PLC),
or type and presence of SCM (fly ash or slag cement). All specimens exhibited mass loss
from the surface after 300 cycles. While the mass loss increased with increasing w/cm, it
was not significantly influenced by the type of cement or SCM used.
Table 2. Results of freezing-and-thawing tests (ASTM C666/C666M, Procedure A)
w/cm
0.74
0.80
0.90
PC
PLC
PC
PLC
35% Slag
Cement
PC
PLC
Durability factor %
Length increase, m/m
Mass loss, %
Durability factor %
99
28
4.43
98
100
24
4.11
99
100
12
2.88
95
100
8
3.63
99
95
10
3.17
95
97
8
2.45
96
24
22
27
42
Mass loss, %
Durability factor %
Length increase, m/m
Mass loss, %
4.43
99
22
5.56
5.11
94
22
9.93
6.09
95
17
9.40
5.39
100
7
9.74
4.81
96
10
4.43
4.25
96
7
5.18
Control
Property
Deicer salt scaling tests (ASTM C672/C672M, Standard Test Method for Scaling
Resistance of Concrete Surfaces Exposed to Deicing Chemicals) were conducted on
concrete mixtures with w/cm of 0.45, 0.50, and 0.55 and PC or PLC, with or without SCM
(fly ash or slag cement). The Canadian Specification (CSA A23.1-09) imposes a maximum
w/cm of 0.45 for concrete exposed to freezing and thawing in the presence of deicing salts.
Again, the increased values were selected to test the robustness of the PLC-SCM blends;
the authors recommend compliance with the CSA limit for concrete exposed to freezing
and thawing and deicing chemicals. Figure 3 shows the mass loss of concrete samples after
50 freezing-and-thawing cycles. The data show that the extent of scaling is dependent on
both the w/cm and the presence of SCM. The data also show that there is little significant
influence of the cement type (PC or PLC), although PLC mixtures with higher w/cm and
25% fly ash exhibited the most scaling.
16
The data in Figure are for slabs that were finished after bleeding and then moistcured for 14 days and air-dried for 14 days prior to exposure to freezing-and-thawing
cycles; this is a standard procedure set forth in ASTM C672/ C672M. Tests were also
conducted on slabs for which the standard procedure was modified; the modifications
included finishing immediately after striking off the concrete (before bleeding) and
shortening the air-drying period to 2 days. These modifications had a marginal impact on
the outcome of the test and the results were not significantly influenced by the use of PLC
compared with PC.
Concrete slabs (600 x 600 x 150 mm [24 x 24 x 6 in.]) were cast using the same
mixture proportions as those used for the laboratory scaling tests. The slabs were cast
outdoors (in southeast Ontario) and treated with a curing compound after finishing. Deicing
salt (predominantly NaCl) is applied regularly to the surface of these slabs during winter
months and the slabs are exposed to numerous freezing- and-thawing cycles per year.
Figure 4 shows the surface appearance of slabs (with the highest w/cm of 0.55) after two
winters of service. There has been minor scaling of all of the slabs at this w/cm but neither
the cement type (PC versus PLC) or the presence of SCMs (25% fly ash or 35% slag
cement) appears to have significantly influenced the scaling. The slabs produced at lower
w/cm are generally exhibiting lesser amounts of scaling.
3.4. Carbonation
Concrete mixtures used for carbonation testing were produced with a w/cm of either
0.45 or 0.55 and with PC or PLC. These cements were used alone or blended with relative
high amounts of SCMs (cement replacements of 40% using fly ash or 60% using slag
cement). Concrete prisms (75 x 75 x 300 mm [3 x 3 x 12 in.]), moist-cured for either 1, 3,
or 7 days, were subsequently stored in air at approximately 55% relative humidity (RH)
and 21C (70F). The depth of carbonation was determined by splitting the prisms at
regular intervals and spraying the freshly-fractured surface with phenolphthalein indicator.
17
18
4.
PLC Target
Limestone, %
3.8
14
Calcium carbonate, %
3.3
12
400
490
+9
The PLC was produced during industrial trials on two different milling circuits and
compared to PC. Results from the production trials are reported in Table 3. For PLC1
(produced on Mill Line 1), they are very close to target with a Blaine fineness increase of
+8 m2/kg per percent of additional limestone. However, for PLC2, the limestone content
achieved was too high because of an incorrect setting of the limestone feeding rate to the
mill. As a consequence, although the same overall Blaine fineness increase (+80 m2/kg
compared to the PC) was achieved for both PLC1 and PLC2, the increase for PLC2 only
translates to +6 m2/kg per percent of additional limestone for PLC2. This is significantly
lower than the target of +9 m2/kg per percent of additional limestone.
Table 4. Characteristics of produced cements
Control
Line 1
Line 2
Designation
PC
PLC1
PLC2
Limestone, %
3.6
13.5
16.9
Calcium Carbonate, %
3.2
11.7
14.6
+8
+6
94.4
99.5
92.8
Blaine fineness,
m2/kg/%L
Passing 45 m (No. 325)
sieve, %
20
The amount passing a 45 m (No. 325) sieve confirms the fineness results, as this
value increased relative to PC for PLC1 but decreased relative to PC for PLC2.
Compressive strength testing ASTM C109/C109M, Standard Test Method for
Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube
Specimens), compressive strength tests on mortar cubes were performed on mixtures
prepared from the three produced cements. Results obtained at 3, 7, and 28 days are
reported in Fig. 10. They confirm that equivalent strength performance is obtained for
PLC1. However, for PLC2, strength results are lower than the control PC by 3.9 MPa (565
psi) at 3 days and 4.9 MPa (710 psi) at 28 days, which represents a strength decrease of
approximately 13% compared to the control PC.
Fig 10. ASTM C109 mortar cube strength results (Note. 1 MPa = 145 psi)
Compressive strength was also measured on concrete prepared according to
Table.5. The results provided in Table6 confirm the PC-equivalent strength for PLC1 and
the lower strength of PLC2.
21
355(598)
1080 (1820)
Initial w/c
(adjusted for 100mm [4 in.] slump)
0.54
195 (3)
PLC1
PLC2
Average
Average
Average
Final w/c
0.54
0.56
0.54
2435
(152.0)
2428
(151.6)
2421
(151.1)
Air content, %
1.3
1.1
1.1
Slump, mm (in.)
110 (4.25)
107 (4.25)
108 (4.25)
374
401
386
1-day compressive
strength, MPa (psi)
18.0
(2610)
17.1
(2480)
13.5
(1960)
7-day compressive
strength, MPa (psi)
32.5
(4710)
31.4
(4550)
27.5
(3990)
28-day compressive
strength, MPa (psi)
398
(5770)
39.2
(5690)
35.9
(5210)
23
If we consider that (28 days) will be about 10 m on every cement particle, the
degree of hydration can be estimated for the tested cements as
85% for the control PC;
89% for PLC1; and
84% for PLC2.
It also should be noted that DOH can be calculated for any chosen value of
dissolved depth. The value of 10 m was selected as it corresponds to 85% DOH for a
hydration time of 28 days on the PC sample, which is a typical value.
As the different systems do not have the same clinker content, we apply this DOH
to the clinker fraction of each system to determine the quantity of reacted cement as given
in Table 7.
Table 7. Estimation of reacted cement for the three different systems
Control PC
PLC1
PLC2
Limestone, %
3.6
13.5
16.9
Gypsum, %
5.0
4.5
4.5
Clinker, %
91.4
82.0
78.6
DOH at 10 m dissolved, %
85
89
84
78
73
66
It is striking to see that, despite having about 10% less clinker than the control PC,
the PLC1 cement has only 5% less reacted cement than PC. The remaining 5% of the
reaction products can be attributed to the additional mechanisms listed at the beginning of
this section (such as heterogeneous nucleation and formation of carbo-aluminates). But the
results of this simple model are clear. the increased fineness of the clinker portion is a key
mechanism explaining the equivalent strength feature for the conditions investigated in the
present study.
Similarly, the gap in the amount of reacted cement between the control PC cement
and PLC2 is very large because clinker fineness did not compensate for the extra dilution
of clinker content by over dosage of the limestone.
24
5.
revolves around two central arguments. The first is that the finer cement has a higher
surface area, causing the hydration reaction to occur more quickly and leading to a more
rapid gain in stiffness, not providing time for stress to be relaxed out of the system.
The second is that the capillary stress that develops in the pore fluid is greater due to
the smaller pores in mixtures with finer cements (as described by the Young-Laplace
relationship, which states that the capillary stress is inversely related to the radius of the
pore being emptied). It should be noted, however, that when the pores are very large (bigger
than 50 nm), then relatively low stress levels are generated; and when the pores are very
small (smaller than a few nm), the concept of capillary stress due to the formation of a
meniscus loses physical meaning, at which point other mechanisms dominate the shrinkage
behavior.
Previous studies have also examined the shrinkage of cement-limestone blends. The
fineness of the limestone influenced the shrinkage and stress, it should be noted that the
evaluated systems consisted of cement with 10% additions of limestone of various sizes.
As such, the cement limestone blends were not interground and were not designed to have
similar performance (strength). When interground PLC mortar systems with similar
strength were evaluated, the PLC system was shown to have similar or slightly less
shrinkage than the OPC system. The PLC system also had no increased tendency to crack.
The purpose of the current study is to expand upon this work and investigate the potential
risk for shrinkage of interground PLCs containing up to 15% limestone and to better
understand why these engineered PLCs do not appear to exhibit increased shrinkage with
increased Blaine fineness.
5.1. Shrinkage Studies
Shrinkage was evaluated using mortar specimens comprising 55% fine aggregate
by volume and w/b of 0.34 and 0.39. For indirect evaluation of shrinkage using hydration
characterization tests, samples were prepared using graded silica sand complying with
ASTM C778, Standard Specification for Standard Sand, with a specific gravity of
25
2.65 and absorption of less than 0.1%. For direct shrinkage tests, mortar samples were
prepared using river sand with a specific gravity of 2.53 and absorption of 1.8%.
A high-range water-reducing admixture (HRWRA) was used at dosages of 1.2 and
0.6% by weight of binder for mixtures with w/b values of 0.34 and 0.39, respectively.
Indirect estimates of shrinkage were based on the Kelvin-Laplace relationship (that is,
capillary stress is an inverse function of the size of a pore that is emptied by self-desiccation
or external drying). Pore size distributions were estimated by measuring the water
desorption from mortar samples. Hydration rates were based on the results of chemical
shrinkage tests (ASTM 1608-07, Standard Test Method for Chemical Shrinkage of
Hydraulic Cement Paste) conducted at a constant temperature of 23 0.5C (73 1F).
Direct determinations of shrinkage included autogenous shrinkage tests per ASTM
C1698-09, Standard Test Method for Autogenous Strain of Cement Paste and Mortar
length-change tests per ASTM C157/C157M, Standard Test Method for Length Change
of Hardened Hydraulic-Cement Mortar and Concrete; and restrained shrinkage tests, in
which torus-shaped mortar samples were cast in contact with and restrained by
instrumented invar rings. Two restrained shrinkage test methods were used. single-ring
tests were conducted in accordance with ASTM C1581/ C1581M-09, Standard Test
Method for Determining Age at Cracking and Induced Tensile Stress Characteristics of
Mortar and Concrete under Restrained Shrinkage, and dual-ring tests. Ring test
specimens were maintained at a constant temperature and strain measurements were
automatically recorded and used to determine the stress build-up in the mortar samples.
5.2. Chemical Shrinkage
Our chemical shrinkage tests were performed on saturated mortar samples of
approximately 15g (0.53 oz.) and approximately 3 to 6 mm (0.1 to 0.2 in.) tall. Figure 12
shows the chemical shrinkage normalized to the mass of binder up to an age of 1 month.
During the first day, the three mixtures show an insignificant difference, after which point,
the chemical shrinkage of the PLC and PLC-Slag mortars are lower than the OPC. The
chemical shrinkage of the PLC and PLC-Slag mortars were reduced by 6 to 10% and 20 to
24%, with the reduction due to the increasing dilution effect, respectively. It can be noted
that when the chemical shrinkage is normalized by the mass of clinker, the results (not
shown) are nearly identical.
26
Fig 12. Chemical shrinkage plots of OPC, PLC, and PLC-Slag mortars at w/b of.
(a) 0.39 and (b) 0.34
5.3. Shrinkage and Cracking
The autogenous shrinkage from the time of set was measured per ASTM C1698-09.
Results are shown in Fig. 13. The data indicate that shrinkage varied inversely with w/b.
Also, the total shrinkage values for the PLC and OPC mixtures were very similar, but
the PLC-Slag system had slightly lower shrinkage. RH measurements on crushed mortar
samples taken from sealed samples using Rotronic humidity sensors at 23 0.1C (73
0.2F) confirmed this trend in shrinkage (as a function of RH in the pores) with a slightly
lower RH in the OPC system and the highest RH in the PLC-Slag system.
27
Fig 13.Autogenous shrinkage measurements for OPC, PLC, and PLC-Slag systems
with w/b of. (a) 0.39; and (b) 0.34
The PLC and OPC showed similar shrinkage behavior as other PLC systems. This
demonstrated similar shrinkage for other OPC and PLC systems over a wide range of RH
values. Figure 14 shows the stress that developed in the OPC, PLC, and PLC-Slag
specimens during dual-ring tests. While the PLC mixture exhibited a slightly higher initial
expansion, the tensile stresses that developed in all three mixtures were virtually the same.
As the vertical line on the plot indicates, the PLC cracked at a slightly earlier age than the
other specimens, despite having a similar stress level. Similar observations can be made
using results of the ASTM C1581/C1581M test (Fig. 15). It should also be noted that the
age of cracking determined from the ASTM C1581/C1581M test has a relatively high
scatter due to the nature of the test. Figure 15 shows the range of maximum to minimum
measured cracking times in the hashed bars, with one standard deviation from six samples
represented by the horizontal lines over each bar. The results from the single ring tests
indicate slightly earlier cracking ages for the PLC mortars. This difference in cracking age
would be consistent with the PLC having a 5% reduction in tensile strength, based on the
stress level reached when cracking occurred. It should be noted, however, that if a reduction
of tensile strength exists, it appears to be small. The PLC has a slightly higher expansion
28
than the other materials immediately after setting, and this may have contributed to the
observed slight difference in the age of cracking, as the shrinkage subsequent to this
expansion would be higher in the PLC system.
Fig 14. Stress development in the dual-ring tests of mortar specimens with w/b
values of 0.34 (Note. 1 MPa = 145 psi)
29
6. CONCLUSION
PLCs have the potential to significantly improve concrete sustainability with
performance equal to or better than C150 / M85 cements, similarly used. PLCs can be
used seamlessly as a substitution for OPCs in mix designs. PLCs hydrate with synergies
contributed by limestone that enable enhanced setting and strength performance, especially
in combination with SCMs. Limestone fineness is a key influence on the extent of synergy
benefits. The particle size distribution of PLC produced to optimum overall fineness in
finish grinding ball mills appears well suited for synergy-driven performance
enhancement.
The performance of PLC concrete will be equivalent to PC concrete provided that
the PLC is ground finer to produce equivalent 28-day (mortar) strength as the PC. Recent
research has shown that combinations of PLC and SCMs can be expected to provide similar
performance in ASR and sulfate attack tests as the same combinations of PC and SCMs.
Further- more, PLC concrete, with or without SCMs, is no less robust than PC concrete in
terms of resistance to freezing and thawing, deicer salt scaling, and carbonation, even when
subjected to poor practices such as the addition of water, improper finishing, and
inadequate curing. This is critical to permit a seamless transition from PC to PLC across
the concrete industry.
It was found that the limestone portion of the PLCs is very fine (>90% finer than
10 m) and that consequently, the Blaine fineness has to be increased significantly to
provide clinker that is ground finer. PLC, with an increased fineness of +8 m2/kg per
percent of additional limestone, was found to have a clinker fraction finer than the PC. Its
28-day DOH was estimated to be higher than the 28-day DOH for the PC, and ultimately,
PLC exhibited PC-equivalent strength.
The PLC-Slag system exhibited slightly lower autogenous shrinkage than either the
OPC or the PLC samples. While the three systems developed about the same levels of
restrained shrinkage stress, one of the PLC samples with w/b of 0.39 cracked at a slightly
earlier time. We observed that the slightly earlier age of cracking was consistent with a
measured tensile strength reduction of 5%.
30
REFERENCES
[1]
Michael D.A. Thomas, Anik Delagrave, Bruce Blair, and Laurent Barcelo,
Equivalent Durability Performance of Portland Limestone Cement, Concrete
International, December 2013, pp 39-45.
[2]
Laurent Barcelo, Michael D.A. Thomas, Kevin Cail, Anik Delagrave, and Bruce
Blair, Portland Limestone Cement Equivalent Strength Explained, Concrete
International, November 2013, pp 41-47.
[3]
Timothy Barrett, Hongfang Sun, Chiara Villani, Laurent Barcelo, and Jason Weiss,
Early-Age Shrinkage Behavior of Portland Limestone Cement, Concrete
International, February 2014, pp 51-57.
[4]
Gzde _nan Sezer, Oguzhan opuroglu & Kambiz Ramyar, Microstructure of 2 and
28-day cured Portland limestone cement pastes, Indian Journal of Engineering &
Materials Sciences, Vol. 17, August 2010, pp. 289-294
[5]
Amir Mohammad Ramezanianpour, Sulfate Resistance and Properties of PortlandLimestone Cement, Thesis, University of Toronto, 2012
[6]
Barcelo, L.; Thomas, M.D.A.; Cail, K.; Delagrave, A.; and Blair, B., Portland
Limestone Cement Equivalent Strength Explained, Concrete International, V. 35,
No. 11, Nov. 2013, pp. 41-47.
[7]
Tennis, P.D.; Thomas, M.D.A.; and Weiss, W.J., State-of-the-Art Report on Use of
Limestone in Cements at Levels of up to 15%, SN3148, Portland Cement
Association, Skokie, IL, 2011, 78 pp.
[8]
Thomas, M.D.A; Hooton, D.; Cail, K.; Smith, B.A.; de Wal, J.; and Kazanis, K.G.,
Field Trials of Concretes Produced with Portland Limestone Cement, Concrete
International, V. 32, No. 1, Jan. 2010, pp. 35-41.
[9]
Hossack, A.; Thomas, M.D.A.; Barcelo, L; Blair, B.; and Delagrave, A.,
Performance of Portland Limestone Cement Concrete Pavements, Concrete
International, V. 36, No. 1, Jan. 2014, pp. 40-45
31