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FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
               Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                Vol. 2, Issue 5, September- October 2012, pp.1953-1959
       Sorptivity Of Cement Combination Concretes Containing
              Portland Cement, Fly Ash And Metakaolin
                               FOLAGBADE, Samuel Olufemi
                  Department of Building, Faculty of Environmental Design and Management,
                          Obafemi Awolowo University, Ile-Ife, 0220005, Nigeria.


ABSTRACT
         To investigate the permeation resistance       bleeding and pore size[1] and ensure more
of cement combination concrete, this paper              nucleation sites to accelerate hydration reactions[2],
examined the sorptivity of Portland cement and          increase pore refinement[3, 4] and enhance the early
some binary and ternary cement concretes                and later age performance of concrete[5]. However,
containing fly ash and metakaolin at equal              its high specific surface and chemical reactivity
water/cement ratios and strengths. At equal             have caused workability problems in concrete[6]
water/cement ratio, fly ash binary cement               resulting in increased superplasticiser dosage of
concretes have higher sorptivity than Portland          about 0.6% for every 5% increase in its content[5].
cement and while their sorptivity increased with        Hence, it is used as replacements between 5-15% by
increasing content of fly ash, they decreased with      weight to increase the strength and reduce the
curing age. Metakaolin binary and ternary               permeability of concrete[7]. Due to its availability,
cement concretes have lower sorptivity than             low cost and quality control, fly ash constitutes the
Portland cement and fly ash binary cement               primary pozzolana for blended cements[8] and the
concretes at both early and later ages and their        use of gas-fired and co-combustion fly ash would
sorptivity reduced with increasing content of           ensure the availability of quality fly ash for future
metakaolin up to 15%. At equivalent strengths,          use in concrete[9]. Fly ash is characterised by low
cement combination concretes generally have             water demand and reduced water/cement ratio for
lower sorptivity than Portland cement and the           equal       consistence[10]       and       improved
sorptivity of the binary cement concretes reduced       workability[11]. This is due to the spherical
with increasing content of fly ash and metakaolin       shape[12, 1] and electronic dispersion of its
up to 55% and 10% respectively. While at a total        particles[13]. However, the reaction of fly ash
replacement level of less than 55%, the ternary         requires a higher alkalinity of the pore water than
cement concretes only performed better than the         metakaolin. Since this alkalinity would be reduced
fly ash binary cement concretes at a strength of        by metakaolin, the reactivity of fly ash in the
50 N/mm2, at a total replacement level of 55%,          presence of metakaolin would be reduced[14]. Also,
the ternary cement concretes have lower                 while fly ash concrete has relatively poor
sorptivity values than the fly ash binary cement        characteristics at early ages[15], its pozzolanic
concretes at all the strengths investigated.            reactivity improves with curing age to improve
                                                        concrete resistance in aggressive media[16].
Keywords:        Cement  additions;  cement
combination concrete; metakaolin; permeation                     While fly ash is cheaper and would
resistance; sorptivity.                                 improve the workability of concrete than Portland
                                                        cement and metakaolin, it would reduce hydration
1. Introduction                                         reactions at early ages. Hence, ternary combinations
          The use of cement combination would lead      of metakaolin and fly ash would perform better than
to reduced cost and improved performance and            their binary combinations with Portland cement.
environmental compatibility of concrete and it is       This is because, while metakaolin would support
supported by cement and concrete standards like BS      early age performance, fly ash would continue to
EN 197- 1, BS 8500 and BS EN 206- 1. Cement             refine the properties of the hardened concrete as it
combinations, by virtue of their delayed strength       matures[17]. Ternary cement combinations are also
development at early ages, would be more suitable       known to reduce admixture dosage[18].
for mass concreting and concrete work in hot
climate than Portland cement. With their long-term               Sorptivity measures the rate of water
pozzolanic reaction with curing age, they would also    absorbed by hydraulic cement concretes and
be good for under-water concrete structures which       therefore the susceptibility of an unsaturated
are prone to water sorption.                            concrete to water penetration by absorption when no
          Metakaolin is a highly reactive non-          head of water exist. Minimising sorptivity is
crystalline fine pozzolana and its fineness would       important in order to reduce the ingress of chloride
result in closer packing of materials and reduced       or sulphate into concrete[19]. But while sorptivity



                                                                                             1953 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
               Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                Vol. 2, Issue 5, September- October 2012, pp.1953-1959
would increase with increasing content of fly ash,
the incorporation of metakaolin as binary and             Table 1: Properties of Cements
ternary cement component would lead to a marked
reduction in sorptivity[17]. Despite their ability to                                      CEMENTS
perform better than Portland cement, cement
                                                          PROPERTY
combination concretes have been under-utilised in
construction. While BS EN 197- 1 permits the use                                           PC       FA           MK
of metakaolin and fly ash of up to 15% and 55%
respectively, data from the European Ready Mixed
Concrete Organisation[20] show a cement addition          Blaine fineness, m2/kg           395      388          2588
content of less than 20% in ready-mixed concrete.         Loss on ignition, % a)           1.9       6.1 b)      0.9
Also, while concrete in practice is prescribed on the     Particle density, g/cm3          3.17     2.26         2.51
basis of strength, most researches in literature were     % retained by 45µm sieve b)      -        11.0         -
conducted at equal water/cement ratio. Since at
equivalent strengths, the use of cement                   Particle size distribution, cumulative % passing by mass c)
combinations would result in better performance[21,       125 µm                           100     100        100
22], this paper examined the effect of cement             100 µm                           98.2    99.2       100
combinations containing fly ash (up to 55% content)       75 µm                            93.2    96.5       99.8
and metakaolin (up to 15% content) on the                 45 µm                            81.8    87.0       99.4
sorptivity of concrete at equal water/cement ratios       25 µm                            57.1    66.2       96.0
and strengths.                                            10 µm                            30.1    40.6       76.2
                                                          5 µm                             13.5    24.1       50.7
2. Experimental          Materials      and     Mix       2 µm                             5.6     10.9       18.2
Proportions                                               1 µm                             2.9     4.8        4.7
         The cements used were Portland cement            0.7 µm                           1.3     1.9        1.4
(PC, 42.5 type), siliceous or Class F fly ash (FA)        0.5 µm                           0.2     0.3        0.1
and metakaolin (MK). The properties of the cements
are presented in Table 1. The aggregates consisted        a) In accordance with BS EN 196-2
of 0/4mm fine aggregates and 4/10mm and                   b) In accordance with EN 450- 1
10/20mm coarse aggregates. The coarse aggregates          c) Obtained with the Laser Particle Sizer
were uncrushed and they come in varied shapes. The
4/10mm aggregates have rough texture and the                    Table 2: Properties of Fine and Coarse
10/20mm aggregates were smooth. The properties of        Aggregates
the aggregates are presented in Table 2.
                                                                                        AGGREGATES 1)
         Potable water, conforming to BS EN 1008,
was used for mixing, curing and testing the concrete                                                COARSE
specimens. In order to provide reasonably workable        PROPERTY
concretes and a uniform basis for comparing                                             FINE
concrete performance at equal water content and                                         0/4
                                                                                                    4/10         10/20
water/cement ratio, a superplasticiser based on                                         mm
                                                                                                    mm           mm
carboxylic ether polymer conforming to EN 934-2
was applied during mixing to achieve a consistence
level of S2 defined by a nominal slump of 50-             Shape, visual                 -           Varied       Varied
100mm in BS EN 206- 1. The yield corrected                Surface texture, visual       -           Rough        Smooth
concrete mix proportions, to the nearest 5 kg/m3,         Particle density 2)           2.6         2.6          2.6
based on the BRE Design Guide[23], a fixed free           Water absorption, % 3)        1.0         1.7          1.2
water content of 165 kg/m3 (to avoid an excessively       % passing 600 µm sieve        55.0        -            -
sticky mix) and saturated surface-dry (SSD)
aggregates are presented in Table 3 for 0.35, 0.50        1) Aggregates were obtained from Wormit Quarry.
and 0.65 water/cement ratios.                             2) In accordance with BS EN 1097- 6
                                                          3) In accordance with BS EN 1097- 6, Laboratory-dry
                                                             condition




Table 3: Yield Corrected Mix Proportions of Concrete at a Fixed Free Water Content of 165 kg/m3


                                                                                                1954 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
            Applications (IJERA) ISSN: 2248-9622 www.ijera.com
             Vol. 2, Issue 5, September- October 2012, pp.1953-1959

                                MIX     PROPORTION, kg/m3


                                CEMENTS                 AGGREGATES
MIX COMBINATION          w/c
                                                                               Free      SP,
                                                                               Water     % a)
                                                        0/4    4/10    10/20
                                CEM I     FA     MK
                                                        mm     mm      mm


                         0.35   475       -      -      650    375     755     165       0.41
100%PC                   0.50   330       -      -      740    385     770     165       0.33
                         0.65   255       -      -      820    380     765     165       0.25

                         0.35   375       95     -      640    370     745     165       0.37
80%PC+20%FA
                         0.50   260       65     -      735    385     765     165       0.30
                         0.65   200       50     -      815    375     760     165       0.23

                         0.35   375       70     25     640    370     745     165       0.43
80%PC+15%FA+5%MK
                         0.50   265       50     15     735    385     765     165       0.35
                         0.65   200       40     15     820    375     760     165       0.26

                         0.35   305       165    -      635    365     740     165       0.33
65%PC+35%FA
                         0.50   210       115    -      730    380     760     165       0.27
                         0.65   165       90     -      815    375     755     165       0.20

                         0.35   305       140    25     635    365     740     165       0.40
65%PC+30%FA+5%MK
                         0.50   210       100    15     730    380     760     165       0.35
                         0.65   165       75     15     815    375     755     165       0.27

                         0.35   305       115    45     635    365     740     165       0.45
65%PC+25%FA+10%MK
                         0.50   210       80     35     730    380     760     165       0.39
                         0.65   165       65     25     815    375     755     165       0.31

                         0.35   205       255    -      625    360     730     160       0.31
45%PC+55%FA
                         0.50   145       180    -      725    375     755     160       0.26
                         0.65   110       135    -      810    370     750     160       0.19

                         0.35   210       210    45     630    365     730     160       0.38
45%PC+45%FA+10%MK
                         0.50   145       145    30     725    380     755     160       0.34
                         0.65   115       115    25     810    375     750     160       0.27

                         0.35   210       185    70     630    365     730     160       0.41
45%PC+40%FA+15%MK
                         0.50   145       130    50     725    380     755     160       0.37
                         0.65   115       100    40     810    375     750     160       0.28

                         0.35   450       -      25     645    375     750     165       0.43
95%PC+5%MK
                         0.50   315       -      15     740    385     770     165       0.35
                         0.65   240       -      15     820    380     760     165       0.26

                         0.35   425       -      45     645    375     750     165       0.47
90%PC+10%MK
                         0.50   295       -      35     740    385     770     165       0.39
                         0.65   230       -      25     820    380     760     165       0.29

                         0.35   400       -      70     645    370     750     165       0.51
85%PC+15%MK
                         0.50   280       -      50     740    385     770     165       0.43
                         0.65   215       -      40     820    380     760     165       0.33



                                                                        1955 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
               Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                Vol. 2, Issue 5, September- October 2012, pp.1953-1959

 a) % Superplasticiser (SP) required for consistence class 2 (BS EN 206-1) is related to the total cement content.


3. Experimental Methods                                     cracking associated with reduced bleeding that
         Concrete was prepared to BS EN 12390- 2            normally characterise the use of fine materials
and the specimens were cast, cured under a layer of         would be avoided and the microstructure of the test
damp hessian covered with polythene for about 24            specimens would not be adversely affected to
hours, demoulded and cured in water tanks                   prevent the repeatability of the results.
maintained at about 20oC until the tests’ dates. Tests
were carried out on hardened concrete specimens to                    Sorptivity was carried out in accordance
determine their cube compressive strength and               with ASTM C1585- 05 using concrete specimens
sorptivity at equal water/cement ratios. The cube           100mm in diameter and about 50mm thick. After
compressive strengths were obtained in accordance           being cooled to room temperature in a dessicator,
with BS EN 12390- 3 using 100mm cubes at the                the oven-dried specimens were waxed on the side
curing age of 28 days. Since absorption into                and covered on one end with a loose plastic sheet
concrete is a function of the drying temperature and        attached with masking tape to allow the entrapped
immersion duration[24], sorptivity was determined           air to escape from the concrete pores while at the
with specimens oven-dried to constant mass at               same time preventing water loss by evaporation.
105±5oC to ensure a uniform basis for the                   After obtaining the initial mass, the test surface (i.e.
comparison and repeatability of the results. This is        uncovered end) of each sample was placed on two
because it is generally believed that at this               lines of roller support placed in water maintained at
temperature the pozzolanic reactions of the cement          3-5mm level above the top of the support
additions would be stopped, the plastic shrinkage           throughout the duration of the test (Fig. 1).




                                                                                                    Specimen covered at one
                                                                                                    end with loose plastic sheet




                                                                                                    Roller support placed in
                                                                                                    water




                                                                                                    Water level maintained at
                                                                                                    3-5mm above support

            Figure 1: A typical sorptivity test set-up


         The sorptivity test was conducted over six                    m
hours and the cumulative change in mass at                     i =                                                   (1)
specific intervals was determined. For each mass                       A
determination, the test specimen was removed from
water and the surface was cleaned with a dampened            where Δm = cumulative change in mass due to
paper towel to remove water droplets. The mass of            water absorption,
the sample was then measured and the sample was
replaced to continue the test. The cumulative                A = cross-sectional area of test specimen, mm2,
change in mass at one minute, five minutes, ten              ρ = density of water.
minutes, 20 minutes, 30 minutes, one hour, two
                                                                                             [29]
hours, three hours, four hours, five hours and six           It has been shown by Hall               that there exists a
hours were used to obtain the respective cumulative          relation of the form:
absorption values, i, expressed by:
                                                              i   =    St0.5 (Darcy’s Law)                          (2)



                                                                                                        1956 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
               Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                Vol. 2, Issue 5, September- October 2012, pp.1953-1959
where S = sorptivity in mm/√min (1mm/√min                also satisfy most of the strength requirements in BS
  = 1.29x10-0.4 m/√s) and                                EN 206-1 and BS 8500.
t = time in minutes
                                                         Table 4: Cube compressive strength and sorptivity
          Hence the cumulative absorption values         of concrete at equal water/cement ratios
were plotted against the square root of the times
and sorptivity (the initial rate of water absorption)
was obtained as the slope of the line that best fits                           STRE         SORPTIVITY
the plot.                                                                      NGTH         x 10-4, m/√s
                                                                               AT
4. Analysis and Discussion of Results                                          28
                                                          MIX         w/c
         Table 4 shows that the cube compressive                               DAYS
                                                                                            28      90    180
strength of concrete reduced with increasing                                   ,
                                                                                            Day     Da    Da
water/cement ratio and that while the addition of
                                                                                            s       ys    ys
fly ash would reduce strength with increasing                                  N/mm
                                                                               2
content, the addition of metakaolin as binary and
ternary cement component resulted in improved
strength at 28 days.                                                  0.35     80.0         200     160   135
                                                          100%PC      0.50     54.0         260     215   190
          The sorptivity of fly ash binary cement                     0.65     38.5         335     295   260
concretes which were slightly higher than that of
Portland cement concrete at 28 days reduced               80%PC       0.35     72.0         205     155   120
progressively such that at 180 days they became           +20%FA      0.50     46.5         265     220   185
lower. This is because fly ash would require a                        0.65     30.0         345     300   255
higher level of alkalinity which increased
progressively with the release of Ca(OH)2 by the          80%PC
                                                                      0.35     82.0         185     150   130
hydration reaction of Portland cement to improve          +15%FA
                                                                      0.50     53.0         245     205   170
the resistance of its concretes to sorption. Since the    +5%MK
                                                                      0.65     33.0         320     275   240
reductions at these ages increased with increasing
content of fly ash, sorptivity would reduce at equal      65%PC       0.35     60.0         210     155   120
water/cement ratio with increasing content of fly         +35%FA      0.50     35.0         270     220   180
ash. The Table also shows that the addition of
                                                                      0.65     20.0         360     295   250
metakaolin as binary and ternary cement
component reduced the sorptivity of concrete at the       65%PC       0.35     64.0         185     145   120
test ages. The resistance of the ternary cement           +30%FA
                                                                      0.50     42.0         250     200   165
concretes to sorptivity also increased with increase      +5%MK
in the total content of the cement additions. This                    0.65     24.0         340     275   235
must be due to the higher fineness of metakaolin          65%PC
(Table 2) resulting in more nucleation sites for          +25%FA      0.35     68.0         175     140   115
Ca(OH)2 and improved pozzolanic reactions to              +10%M       0.50     43.0         240     195   160
provide better packing between the cements and at         K           0.65     25.0         330     270   230
the interface zones between the cement paste and
the aggregates.                                           45%PC       0.35     42.0         210     150   110
                                                          +55%FA      0.50     24.0         275     210   155
         Table 4 shows that sorptivity of concrete                    0.65     12.0         375     295   250
reduced with increasing water/cement ratio and that       45%PC
equivalent sorptivity values of the concretes at          +45%FA      0.35     47.0         115     90    70
equal water/cement ratio would be achieved at             +10%M       0.50     32.5         215     155   105
different ages and compressive strengths. Since           K           0.65     18.5         325     240   175
concrete is usually specified in practice on the basis    45%PC
of strength at 28 days, the sorptivity of these           +40%FA      0.35     50.0         110     90    70
concretes has been investigated at equivalent             +15%M       0.50     33.0         180     130   100
strength at 28 days. Being the range of strengths         K           0.65     20.0         300     215   160
that would commonly be used in practice, the cube
compressive strength and sorptivity of the                95%PC       0.35     80.0         195     150   115
concretes at the water/cement ratios of 0.35, 0.50        +5%MK       0.50     56.0         240     185   135
and 0.65 at 28 days (Table 4) were used, by                           0.65     37.0         325     255   180
interpolation, to obtain the sorptivity of the            90%PC
concretes at the equivalent strengths of 30, 40 and       +10%M       0.35     78.0         190     145   115
50 N/mm2 at 28 days (Table 5). These strengths            K           0.50     54.5         220     175   130


                                                                                            1957 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
                         Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                          Vol. 2, Issue 5, September- October 2012, pp.1953-1959
                   0.65 38.0        310    245 175       5. Conclusion
                                                                          At equal water/cement ratio, fly ash binary
          85%PC
                      0.35     76.0          175   135     110   cement concretes have poor resistance against
          +15%M
                      0.50     54.0          215   170     125   sorption and the resistance reduced with increasing
          K
                      0.65     41.0          310   240     170   content of fly ash. However, the resistance
                                                                 increased with increasing age such that at 180 days
                  Table 5 shows that sorptivity reduced with     they became better than that of Portland cement
         increasing strength and all the cement combination      concrete. Metakaolin binary and ternary cement
         concretes now have lower sorptivity values than         concretes have better resistance to sorption than
         Portland cement concrete at the equivalent              Portland cement and fly ash binary cement
         strengths. Hence, the incorporation of the cement       concretes at both early and later ages and their
         additions at equivalent strengths reduced the           resistance increased with increasing content of
         sorptivity of concrete. While the sorptivity of the     metakaolin. The sorptivity of cement combination
         fly ash binary cement concretes reduced with            concrete is influenced by strength. Compared with
         increasing content up to 55%, the sorptivity of the     Portland cement concrete, the sorptivity of the
         metakaolin binary cement concretes only reduced         cement combination concretes were lower at the
         with increasing content up to 10%. At a total           equivalent strengths and they reduced with
         replacement level of less than 55%, metakaolin as a     increasing total content of fly ash and metakaolin
         ternary cement component only performed better          as binary cement components up to 55% and 10%
         than the fly ash binary cement concretes at the         respectively. Metakaolin ternary cement concretes,
         strength of 50 N/mm2. However, at a total               at equivalent strength, would only perform better
         replacement level of 55%, the addition of               than the fly ash binary cement concretes at a total
         metakaolin, as a ternary cement component,              replacement level of 55%. Hence, if appropriately
         resulted in concretes with sorptivity values lower      used, cement combination concrete would have
         than that of their respective fly ash binary cement     higher resistance against sorption than Portland
         concretes.                                              cement concrete and therefore would be preferred
                                                                 for concretes exposed to water and/or aggressive
         Table 5: Sorptivity of concrete at the equivalent       conditions.
         strengths of 30, 40 and 50 N/mm2 at 28 days
                                                                 References
                                                                   [1]    Mindess, S., Young, F. J. and Darwin, D.,
                             SORPTIVITY x 10-4, m/√s                      Concrete (Prentice-Hall, 2003).
                                                                   [2]    Mehta, P, K. and Aitcin P. C., Principles
MIX                                                                       underlying      production      of    high-
COMBINATION                                                               performance         concrete,       Cement
                             30        40          50
                             N/mm2     N/mm2       N/mm2                  Concrete and Aggregates, 12, 1990, 70-
                                                                          78.
                                                                   [3]    Khatib J. and Wild S., Pore size
100%PC                                                                    distribution of metakaolin paste, Cement
                             380       330         275                    and Concrete Research, 26 (10), 1996,
                                                                          1545-1553.
80%PC+20%FA                  345       295         255             [4]    Khatib J. M. and Clay R. M., Absorption
80%PC+15%FA+5%MK             330       300         255                    characteristics of metakaolin concrete,
                                                                          Cement and Concrete Research, 34 (1),
                                                                          2004, 19-29.
65%PC+35%FA                  295       255         230             [5]    Wild S., Khatib J. M., Jones A, Relative
65%PC+30%FA+5%MK             310       260         225                    strength pozzolanic activity and cement
65%PC+25%FA+10%MK            305       250         220                    hydration in superplasticised metakaolin
                                                                          concrete, Cement and Concrete Research,
                                                                          26 (10), 1996, 1537-1544.
45%PC+55%FA                  250       215         180             [6]    Bai J., Wild S., Sabir B. B. and Kinuthia J.
45%PC+45%FA+10%MK            240       160         100                    M., Workability of concrete incorporating
45%PC+40%FA+15%MK            200       150         110                    pulverized fuel ash and metakaolin,
                                                                          Magazine of Concrete Research, 51 (3),
                                                                          1999, 207-216.
95%PC+5%MK                   365       310         260             [7]    Advanced Cement Technologies available
90%PC+10%MK                  355       300         235                    at
85%PC+15%MK                  400       320         235
                                                                          http://www.advancedcementtechnologies.
                                                                          com.


                                                                                                     1958 | P a g e
FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and
               Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                Vol. 2, Issue 5, September- October 2012, pp.1953-1959
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[11] Thomas M. D. A., Shehata M. H.,                [25]   Hall C., Water sorptivity of mortars and
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[12] Concrete Society, The use of GGBS and
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[13] Helmuth, R., Fly ash in cement and
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[14] Fraay A. L. A., Bijen J. M. and De Haan
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[15] Hassan, K. E., Cabrera, J. G., Maliehe, R.
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[16] Naik T. R., Singh S., Ramme B.,
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[17] Bai J., Wild S. and Sabir B. B., Sorptivity
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 [18] Bouzoubaa         N.,    Bilodeau       A.,
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      high     performance      concrete,    ACI
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                                                                                     1959 | P a g e

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  • 1. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 Sorptivity Of Cement Combination Concretes Containing Portland Cement, Fly Ash And Metakaolin FOLAGBADE, Samuel Olufemi Department of Building, Faculty of Environmental Design and Management, Obafemi Awolowo University, Ile-Ife, 0220005, Nigeria. ABSTRACT To investigate the permeation resistance bleeding and pore size[1] and ensure more of cement combination concrete, this paper nucleation sites to accelerate hydration reactions[2], examined the sorptivity of Portland cement and increase pore refinement[3, 4] and enhance the early some binary and ternary cement concretes and later age performance of concrete[5]. However, containing fly ash and metakaolin at equal its high specific surface and chemical reactivity water/cement ratios and strengths. At equal have caused workability problems in concrete[6] water/cement ratio, fly ash binary cement resulting in increased superplasticiser dosage of concretes have higher sorptivity than Portland about 0.6% for every 5% increase in its content[5]. cement and while their sorptivity increased with Hence, it is used as replacements between 5-15% by increasing content of fly ash, they decreased with weight to increase the strength and reduce the curing age. Metakaolin binary and ternary permeability of concrete[7]. Due to its availability, cement concretes have lower sorptivity than low cost and quality control, fly ash constitutes the Portland cement and fly ash binary cement primary pozzolana for blended cements[8] and the concretes at both early and later ages and their use of gas-fired and co-combustion fly ash would sorptivity reduced with increasing content of ensure the availability of quality fly ash for future metakaolin up to 15%. At equivalent strengths, use in concrete[9]. Fly ash is characterised by low cement combination concretes generally have water demand and reduced water/cement ratio for lower sorptivity than Portland cement and the equal consistence[10] and improved sorptivity of the binary cement concretes reduced workability[11]. This is due to the spherical with increasing content of fly ash and metakaolin shape[12, 1] and electronic dispersion of its up to 55% and 10% respectively. While at a total particles[13]. However, the reaction of fly ash replacement level of less than 55%, the ternary requires a higher alkalinity of the pore water than cement concretes only performed better than the metakaolin. Since this alkalinity would be reduced fly ash binary cement concretes at a strength of by metakaolin, the reactivity of fly ash in the 50 N/mm2, at a total replacement level of 55%, presence of metakaolin would be reduced[14]. Also, the ternary cement concretes have lower while fly ash concrete has relatively poor sorptivity values than the fly ash binary cement characteristics at early ages[15], its pozzolanic concretes at all the strengths investigated. reactivity improves with curing age to improve concrete resistance in aggressive media[16]. Keywords: Cement additions; cement combination concrete; metakaolin; permeation While fly ash is cheaper and would resistance; sorptivity. improve the workability of concrete than Portland cement and metakaolin, it would reduce hydration 1. Introduction reactions at early ages. Hence, ternary combinations The use of cement combination would lead of metakaolin and fly ash would perform better than to reduced cost and improved performance and their binary combinations with Portland cement. environmental compatibility of concrete and it is This is because, while metakaolin would support supported by cement and concrete standards like BS early age performance, fly ash would continue to EN 197- 1, BS 8500 and BS EN 206- 1. Cement refine the properties of the hardened concrete as it combinations, by virtue of their delayed strength matures[17]. Ternary cement combinations are also development at early ages, would be more suitable known to reduce admixture dosage[18]. for mass concreting and concrete work in hot climate than Portland cement. With their long-term Sorptivity measures the rate of water pozzolanic reaction with curing age, they would also absorbed by hydraulic cement concretes and be good for under-water concrete structures which therefore the susceptibility of an unsaturated are prone to water sorption. concrete to water penetration by absorption when no Metakaolin is a highly reactive non- head of water exist. Minimising sorptivity is crystalline fine pozzolana and its fineness would important in order to reduce the ingress of chloride result in closer packing of materials and reduced or sulphate into concrete[19]. But while sorptivity 1953 | P a g e
  • 2. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 would increase with increasing content of fly ash, the incorporation of metakaolin as binary and Table 1: Properties of Cements ternary cement component would lead to a marked reduction in sorptivity[17]. Despite their ability to CEMENTS perform better than Portland cement, cement PROPERTY combination concretes have been under-utilised in construction. While BS EN 197- 1 permits the use PC FA MK of metakaolin and fly ash of up to 15% and 55% respectively, data from the European Ready Mixed Concrete Organisation[20] show a cement addition Blaine fineness, m2/kg 395 388 2588 content of less than 20% in ready-mixed concrete. Loss on ignition, % a) 1.9 6.1 b) 0.9 Also, while concrete in practice is prescribed on the Particle density, g/cm3 3.17 2.26 2.51 basis of strength, most researches in literature were % retained by 45µm sieve b) - 11.0 - conducted at equal water/cement ratio. Since at equivalent strengths, the use of cement Particle size distribution, cumulative % passing by mass c) combinations would result in better performance[21, 125 µm 100 100 100 22], this paper examined the effect of cement 100 µm 98.2 99.2 100 combinations containing fly ash (up to 55% content) 75 µm 93.2 96.5 99.8 and metakaolin (up to 15% content) on the 45 µm 81.8 87.0 99.4 sorptivity of concrete at equal water/cement ratios 25 µm 57.1 66.2 96.0 and strengths. 10 µm 30.1 40.6 76.2 5 µm 13.5 24.1 50.7 2. Experimental Materials and Mix 2 µm 5.6 10.9 18.2 Proportions 1 µm 2.9 4.8 4.7 The cements used were Portland cement 0.7 µm 1.3 1.9 1.4 (PC, 42.5 type), siliceous or Class F fly ash (FA) 0.5 µm 0.2 0.3 0.1 and metakaolin (MK). The properties of the cements are presented in Table 1. The aggregates consisted a) In accordance with BS EN 196-2 of 0/4mm fine aggregates and 4/10mm and b) In accordance with EN 450- 1 10/20mm coarse aggregates. The coarse aggregates c) Obtained with the Laser Particle Sizer were uncrushed and they come in varied shapes. The 4/10mm aggregates have rough texture and the Table 2: Properties of Fine and Coarse 10/20mm aggregates were smooth. The properties of Aggregates the aggregates are presented in Table 2. AGGREGATES 1) Potable water, conforming to BS EN 1008, was used for mixing, curing and testing the concrete COARSE specimens. In order to provide reasonably workable PROPERTY concretes and a uniform basis for comparing FINE concrete performance at equal water content and 0/4 4/10 10/20 water/cement ratio, a superplasticiser based on mm mm mm carboxylic ether polymer conforming to EN 934-2 was applied during mixing to achieve a consistence level of S2 defined by a nominal slump of 50- Shape, visual - Varied Varied 100mm in BS EN 206- 1. The yield corrected Surface texture, visual - Rough Smooth concrete mix proportions, to the nearest 5 kg/m3, Particle density 2) 2.6 2.6 2.6 based on the BRE Design Guide[23], a fixed free Water absorption, % 3) 1.0 1.7 1.2 water content of 165 kg/m3 (to avoid an excessively % passing 600 µm sieve 55.0 - - sticky mix) and saturated surface-dry (SSD) aggregates are presented in Table 3 for 0.35, 0.50 1) Aggregates were obtained from Wormit Quarry. and 0.65 water/cement ratios. 2) In accordance with BS EN 1097- 6 3) In accordance with BS EN 1097- 6, Laboratory-dry condition Table 3: Yield Corrected Mix Proportions of Concrete at a Fixed Free Water Content of 165 kg/m3 1954 | P a g e
  • 3. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 MIX PROPORTION, kg/m3 CEMENTS AGGREGATES MIX COMBINATION w/c Free SP, Water % a) 0/4 4/10 10/20 CEM I FA MK mm mm mm 0.35 475 - - 650 375 755 165 0.41 100%PC 0.50 330 - - 740 385 770 165 0.33 0.65 255 - - 820 380 765 165 0.25 0.35 375 95 - 640 370 745 165 0.37 80%PC+20%FA 0.50 260 65 - 735 385 765 165 0.30 0.65 200 50 - 815 375 760 165 0.23 0.35 375 70 25 640 370 745 165 0.43 80%PC+15%FA+5%MK 0.50 265 50 15 735 385 765 165 0.35 0.65 200 40 15 820 375 760 165 0.26 0.35 305 165 - 635 365 740 165 0.33 65%PC+35%FA 0.50 210 115 - 730 380 760 165 0.27 0.65 165 90 - 815 375 755 165 0.20 0.35 305 140 25 635 365 740 165 0.40 65%PC+30%FA+5%MK 0.50 210 100 15 730 380 760 165 0.35 0.65 165 75 15 815 375 755 165 0.27 0.35 305 115 45 635 365 740 165 0.45 65%PC+25%FA+10%MK 0.50 210 80 35 730 380 760 165 0.39 0.65 165 65 25 815 375 755 165 0.31 0.35 205 255 - 625 360 730 160 0.31 45%PC+55%FA 0.50 145 180 - 725 375 755 160 0.26 0.65 110 135 - 810 370 750 160 0.19 0.35 210 210 45 630 365 730 160 0.38 45%PC+45%FA+10%MK 0.50 145 145 30 725 380 755 160 0.34 0.65 115 115 25 810 375 750 160 0.27 0.35 210 185 70 630 365 730 160 0.41 45%PC+40%FA+15%MK 0.50 145 130 50 725 380 755 160 0.37 0.65 115 100 40 810 375 750 160 0.28 0.35 450 - 25 645 375 750 165 0.43 95%PC+5%MK 0.50 315 - 15 740 385 770 165 0.35 0.65 240 - 15 820 380 760 165 0.26 0.35 425 - 45 645 375 750 165 0.47 90%PC+10%MK 0.50 295 - 35 740 385 770 165 0.39 0.65 230 - 25 820 380 760 165 0.29 0.35 400 - 70 645 370 750 165 0.51 85%PC+15%MK 0.50 280 - 50 740 385 770 165 0.43 0.65 215 - 40 820 380 760 165 0.33 1955 | P a g e
  • 4. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 a) % Superplasticiser (SP) required for consistence class 2 (BS EN 206-1) is related to the total cement content. 3. Experimental Methods cracking associated with reduced bleeding that Concrete was prepared to BS EN 12390- 2 normally characterise the use of fine materials and the specimens were cast, cured under a layer of would be avoided and the microstructure of the test damp hessian covered with polythene for about 24 specimens would not be adversely affected to hours, demoulded and cured in water tanks prevent the repeatability of the results. maintained at about 20oC until the tests’ dates. Tests were carried out on hardened concrete specimens to Sorptivity was carried out in accordance determine their cube compressive strength and with ASTM C1585- 05 using concrete specimens sorptivity at equal water/cement ratios. The cube 100mm in diameter and about 50mm thick. After compressive strengths were obtained in accordance being cooled to room temperature in a dessicator, with BS EN 12390- 3 using 100mm cubes at the the oven-dried specimens were waxed on the side curing age of 28 days. Since absorption into and covered on one end with a loose plastic sheet concrete is a function of the drying temperature and attached with masking tape to allow the entrapped immersion duration[24], sorptivity was determined air to escape from the concrete pores while at the with specimens oven-dried to constant mass at same time preventing water loss by evaporation. 105±5oC to ensure a uniform basis for the After obtaining the initial mass, the test surface (i.e. comparison and repeatability of the results. This is uncovered end) of each sample was placed on two because it is generally believed that at this lines of roller support placed in water maintained at temperature the pozzolanic reactions of the cement 3-5mm level above the top of the support additions would be stopped, the plastic shrinkage throughout the duration of the test (Fig. 1). Specimen covered at one end with loose plastic sheet Roller support placed in water Water level maintained at 3-5mm above support Figure 1: A typical sorptivity test set-up The sorptivity test was conducted over six m hours and the cumulative change in mass at i = (1) specific intervals was determined. For each mass A determination, the test specimen was removed from water and the surface was cleaned with a dampened where Δm = cumulative change in mass due to paper towel to remove water droplets. The mass of water absorption, the sample was then measured and the sample was replaced to continue the test. The cumulative A = cross-sectional area of test specimen, mm2, change in mass at one minute, five minutes, ten ρ = density of water. minutes, 20 minutes, 30 minutes, one hour, two [29] hours, three hours, four hours, five hours and six It has been shown by Hall that there exists a hours were used to obtain the respective cumulative relation of the form: absorption values, i, expressed by: i = St0.5 (Darcy’s Law) (2) 1956 | P a g e
  • 5. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 where S = sorptivity in mm/√min (1mm/√min also satisfy most of the strength requirements in BS = 1.29x10-0.4 m/√s) and EN 206-1 and BS 8500. t = time in minutes Table 4: Cube compressive strength and sorptivity Hence the cumulative absorption values of concrete at equal water/cement ratios were plotted against the square root of the times and sorptivity (the initial rate of water absorption) was obtained as the slope of the line that best fits STRE SORPTIVITY the plot. NGTH x 10-4, m/√s AT 4. Analysis and Discussion of Results 28 MIX w/c Table 4 shows that the cube compressive DAYS 28 90 180 strength of concrete reduced with increasing , Day Da Da water/cement ratio and that while the addition of s ys ys fly ash would reduce strength with increasing N/mm 2 content, the addition of metakaolin as binary and ternary cement component resulted in improved strength at 28 days. 0.35 80.0 200 160 135 100%PC 0.50 54.0 260 215 190 The sorptivity of fly ash binary cement 0.65 38.5 335 295 260 concretes which were slightly higher than that of Portland cement concrete at 28 days reduced 80%PC 0.35 72.0 205 155 120 progressively such that at 180 days they became +20%FA 0.50 46.5 265 220 185 lower. This is because fly ash would require a 0.65 30.0 345 300 255 higher level of alkalinity which increased progressively with the release of Ca(OH)2 by the 80%PC 0.35 82.0 185 150 130 hydration reaction of Portland cement to improve +15%FA 0.50 53.0 245 205 170 the resistance of its concretes to sorption. Since the +5%MK 0.65 33.0 320 275 240 reductions at these ages increased with increasing content of fly ash, sorptivity would reduce at equal 65%PC 0.35 60.0 210 155 120 water/cement ratio with increasing content of fly +35%FA 0.50 35.0 270 220 180 ash. The Table also shows that the addition of 0.65 20.0 360 295 250 metakaolin as binary and ternary cement component reduced the sorptivity of concrete at the 65%PC 0.35 64.0 185 145 120 test ages. The resistance of the ternary cement +30%FA 0.50 42.0 250 200 165 concretes to sorptivity also increased with increase +5%MK in the total content of the cement additions. This 0.65 24.0 340 275 235 must be due to the higher fineness of metakaolin 65%PC (Table 2) resulting in more nucleation sites for +25%FA 0.35 68.0 175 140 115 Ca(OH)2 and improved pozzolanic reactions to +10%M 0.50 43.0 240 195 160 provide better packing between the cements and at K 0.65 25.0 330 270 230 the interface zones between the cement paste and the aggregates. 45%PC 0.35 42.0 210 150 110 +55%FA 0.50 24.0 275 210 155 Table 4 shows that sorptivity of concrete 0.65 12.0 375 295 250 reduced with increasing water/cement ratio and that 45%PC equivalent sorptivity values of the concretes at +45%FA 0.35 47.0 115 90 70 equal water/cement ratio would be achieved at +10%M 0.50 32.5 215 155 105 different ages and compressive strengths. Since K 0.65 18.5 325 240 175 concrete is usually specified in practice on the basis 45%PC of strength at 28 days, the sorptivity of these +40%FA 0.35 50.0 110 90 70 concretes has been investigated at equivalent +15%M 0.50 33.0 180 130 100 strength at 28 days. Being the range of strengths K 0.65 20.0 300 215 160 that would commonly be used in practice, the cube compressive strength and sorptivity of the 95%PC 0.35 80.0 195 150 115 concretes at the water/cement ratios of 0.35, 0.50 +5%MK 0.50 56.0 240 185 135 and 0.65 at 28 days (Table 4) were used, by 0.65 37.0 325 255 180 interpolation, to obtain the sorptivity of the 90%PC concretes at the equivalent strengths of 30, 40 and +10%M 0.35 78.0 190 145 115 50 N/mm2 at 28 days (Table 5). These strengths K 0.50 54.5 220 175 130 1957 | P a g e
  • 6. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 0.65 38.0 310 245 175 5. Conclusion At equal water/cement ratio, fly ash binary 85%PC 0.35 76.0 175 135 110 cement concretes have poor resistance against +15%M 0.50 54.0 215 170 125 sorption and the resistance reduced with increasing K 0.65 41.0 310 240 170 content of fly ash. However, the resistance increased with increasing age such that at 180 days Table 5 shows that sorptivity reduced with they became better than that of Portland cement increasing strength and all the cement combination concrete. Metakaolin binary and ternary cement concretes now have lower sorptivity values than concretes have better resistance to sorption than Portland cement concrete at the equivalent Portland cement and fly ash binary cement strengths. Hence, the incorporation of the cement concretes at both early and later ages and their additions at equivalent strengths reduced the resistance increased with increasing content of sorptivity of concrete. While the sorptivity of the metakaolin. The sorptivity of cement combination fly ash binary cement concretes reduced with concrete is influenced by strength. Compared with increasing content up to 55%, the sorptivity of the Portland cement concrete, the sorptivity of the metakaolin binary cement concretes only reduced cement combination concretes were lower at the with increasing content up to 10%. At a total equivalent strengths and they reduced with replacement level of less than 55%, metakaolin as a increasing total content of fly ash and metakaolin ternary cement component only performed better as binary cement components up to 55% and 10% than the fly ash binary cement concretes at the respectively. Metakaolin ternary cement concretes, strength of 50 N/mm2. However, at a total at equivalent strength, would only perform better replacement level of 55%, the addition of than the fly ash binary cement concretes at a total metakaolin, as a ternary cement component, replacement level of 55%. Hence, if appropriately resulted in concretes with sorptivity values lower used, cement combination concrete would have than that of their respective fly ash binary cement higher resistance against sorption than Portland concretes. cement concrete and therefore would be preferred for concretes exposed to water and/or aggressive Table 5: Sorptivity of concrete at the equivalent conditions. strengths of 30, 40 and 50 N/mm2 at 28 days References [1] Mindess, S., Young, F. J. and Darwin, D., SORPTIVITY x 10-4, m/√s Concrete (Prentice-Hall, 2003). [2] Mehta, P, K. and Aitcin P. C., Principles MIX underlying production of high- COMBINATION performance concrete, Cement 30 40 50 N/mm2 N/mm2 N/mm2 Concrete and Aggregates, 12, 1990, 70- 78. [3] Khatib J. and Wild S., Pore size 100%PC distribution of metakaolin paste, Cement 380 330 275 and Concrete Research, 26 (10), 1996, 1545-1553. 80%PC+20%FA 345 295 255 [4] Khatib J. M. and Clay R. M., Absorption 80%PC+15%FA+5%MK 330 300 255 characteristics of metakaolin concrete, Cement and Concrete Research, 34 (1), 2004, 19-29. 65%PC+35%FA 295 255 230 [5] Wild S., Khatib J. M., Jones A, Relative 65%PC+30%FA+5%MK 310 260 225 strength pozzolanic activity and cement 65%PC+25%FA+10%MK 305 250 220 hydration in superplasticised metakaolin concrete, Cement and Concrete Research, 26 (10), 1996, 1537-1544. 45%PC+55%FA 250 215 180 [6] Bai J., Wild S., Sabir B. B. and Kinuthia J. 45%PC+45%FA+10%MK 240 160 100 M., Workability of concrete incorporating 45%PC+40%FA+15%MK 200 150 110 pulverized fuel ash and metakaolin, Magazine of Concrete Research, 51 (3), 1999, 207-216. 95%PC+5%MK 365 310 260 [7] Advanced Cement Technologies available 90%PC+10%MK 355 300 235 at 85%PC+15%MK 400 320 235 http://www.advancedcementtechnologies. com. 1958 | P a g e
  • 7. FOLAGBADE, Samuel Olufemi / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.1953-1959 [8] Antiohos S. K., Papadakis V. G., [19] McCarter W. J., Ezirim H., Emerson M., Chaniotakis E., Tsimas S., Improving the Absorption of water and chloride into performance of ternary blended cements concrete, Magazine of Concrete by mixing different types of fly ashes, Research, 44 (158), 1992, 31-37. Cement and Concrete Research, 37 (6), [20] European Ready Mixed Concrete 2007, 877-885. Organisation available at [9] Jones M. R., Sear L. K. A., McCarthy M. http://www.ermco.eu/documents. J. and Dhir R. K., Changes in coal fired [21] Dhir R. K. and Byars E. A., PFA power station fly ash: Recent experiences Concrete: Near surface absorption and use in concrete, paper presented at properties, Magazine of Concrete the Ash Technology Conference Research, 43 (157), 1991, 219-232. organized by the UK Quality Ash [22] Dias W. P. S., Nanayakkara S. M. A. and Association, Birmingham, 2006, available Ekneligoda T. C., Performance of concrete at: mixes with OPC-PFA blends, Magazine of Concrete Research, 55 (2), 2003, 161-170. www.ukqaa.org.uk/index_htm_files/AshT [23] Teychenne D. C., Franklin R. E. and echA01ChangesInCoalFiredPowerStationJ Erntroy H. C., Design of normal concrete onesEtAl.pdf. mixes, 2nd Ed., amended by B. K. Marsh [10] Dhir R. K., McCarthy M. J. and Paine K. (Building Research Establishment, A., Use of fly ash to BS EN 450 in 1997). structural concrete (Thomas Telford, [24] Lea F. M., Lea’s chemistry of cement and 2002). concrete, 4th Ed. (Arnold, London, 1998). [11] Thomas M. D. A., Shehata M. H., [25] Hall C., Water sorptivity of mortars and Shashiprakash S.G., Hopkins D. S. and concretes: A review, Magazine of Cail K., Use of ternary cementitious Concrete Research, 41 (147), 1989, 51-61. systems containing silica fume and fly ash in concrete, Cement and Concrete Research, 29 (8), 1999, 1207-1214. [12] Concrete Society, The use of GGBS and PFA in concrete- Technical Report No 40 (The Concrete Society, London, 1991). [13] Helmuth, R., Fly ash in cement and concrete (Portland Cement Association, Skokie, Illinois,1987). [14] Fraay A. L. A., Bijen J. M. and De Haan Y. M., The reaction of fly ash in concrete: a critical examination, Cement and Concrete Research, 19 (2), 1989, 235-246. [15] Hassan, K. E., Cabrera, J. G., Maliehe, R. S., The effect of mineral admixtures on the properties of high-performance concrete, Cement and Concrete Composites, 22 (4), 2000, 267-271. [16] Naik T. R., Singh S., Ramme B., Mechanical properties and durability of concrete made with blended fly ash, ACI Material Journal, 95 (4), 1998, 454-462. [17] Bai J., Wild S. and Sabir B. B., Sorptivity and strength of air-cured PC-PFA-MK concrete and the influence of binder composition on carbonation depth, Cement and Concrete Research, 32 (11), 2002, 1813-1821. [18] Bouzoubaa N., Bilodeau A., Sivasundaram V., Fournier B and Golden D. M., Development of ternary blends for high performance concrete, ACI Material Journal, 101 (1), 2004, 19-29. 1959 | P a g e