THE EFFECT OF SILICA FUME ON DIELECTRIC CONSTANT OF ORDINARY
PORTLAND CEMENT AND HIGH ALUMINA CEMENT PASTE
1
P. Saritha, 2*S. Barathan and 3G. Sivakumar
1
Engineering Physics Division, Annamalai University, Annamalai nagar-608002, India.
2
Department of Physics, Annamalai University, Annamalai nagar -608002, India.
3
CISL, Department of Physics, Annamalai University, Annamalai nagar -608002, India.
*psarithaau@yahoo.com
ABSTRACT
AC-Impedance Spectroscopy has been applied for the study of the dielectric properties of
High Alumina Cement (HAC), Ordinary Portland Cement (OPC) and Silica Fume (SF)
admixture in the frequency region from 10 Hz to 10 MHz. The real and imaginary dielectric
constant (ε) has been computed for the cement paste containing Pure 100%HAC,
85%HAC+10%OPC+5%SF, 80%HAC+10%OPC+10%SF, 75%HAC+10%OPC+15%SF and
70% HAC + 10% OPC + 20% SF using GW in a W/C of 0.4. The dielectric constant (ε) value
increases non-linearly and the compressive strength values reversibility up to 6.4 Mpa, although
the reversibility is not complete. It is observed that an increase in HAC substitution by silica
fume in the OPC-HAC blend decreases the aggressive attack of sulphate ions. The values of
dielectric constant at a constant temperature of – 30º C, were dominated by properties of C-S-H
gel percolation threshold at a volume fraction of approximately 15% - 20%. It is also evidenced
that increasing the aluminium content beyond the percolation threshold decreases the relative
dielectric constant.
The dielectric properties of concrete can be used to characterize the
development of the microstructure of the cement paste. During hydration the microstructure
changes and so does the amount of water in the pore structure.
Keywords: OPC; HAC; SF; Characterization; AC-Impedance Spectroscopy; Dielectric
Constant.
1
INTRODUCTION
Impedance spectroscopy (IS) is an electrical technique that has been used to characterize
the microstructure of cement paste, providing useful information about the relationships between
microstructure and chemical processes during the hydration of cement paste.
Due to the
presence of ionic bonding and moisture in cement, electric dipoles are present and dielectric
constant has been measured for the purpose of fundamental understanding of cement based
materials [1].
The dielectric measurement is a non destructive and it can be performed
irrespective of the state of the sample (fluid slurry or solid). Hence the hydration reaction and
structural changes can be monitored over an extended period after initial mixing. The hydration
reaction of HAC produces CAH10 and C2AH8. However the stable phases are C3AH6 and AH3
and the other phases will inevitably convert to this [2],
Conversion reaction are shown schematically below
3CAH10→ C3AH6+2AH3+18H
------- (1)
3C2 AH8 → 2C3AH6+AH3+9H
------- (2)
High early strength is one of the major advantages of HAC over OPC. This high early
strength may mislead designers into ignoring the conversion effect during its service life.
The use of a siliceous material in this combination with a HAC and OPC was recently
reported to be more effective than the siliceous material alone in promoting formation of
stratlingite instead of hydro garnet Siliceous materials including natural zeolites, fly ash, slag and
silica fume were effective in inhibiting hydro garnet formation and preventing strength reduction
in HAC and OPC. SF is preferred because it is highly pozzolanic due its particle nature and
improves the properties of paste/concrete in fresh as well as hardened state. Generally the
additions of SF increase the strength and improve the resistance to sulfate attack [3,4].
In the present investigation it has been planned to mix the proportions of HAC, OPC and
SF in different combination. A particular permutation and combination of this blend is expected
to bring a maximum strength development. The dielectric measurement using microwave
technique in the AC impedance may give some useful information regarding the state of
hardening of the cement paste and mortars at different time intervals since mixing. The present
work explains the results and measurements of change in the dielectric constant and conductivity
of the prepared blended cement paste when mixed with GW for the first 24h of the hydration in
the microwave frequency range from 1 MHz to 12 GHz.
2
MATERIALS AND METHODS
High Alumina Cement (HAC), Ordinary Portland Cement (OPC) and Silica Fume (SF)
supplied by Coromondal Ltd, Chennai, Ace Refractory, Chennai and Polygon Chemicals Ltd,
Mumbai respectively. Chemical composition of raw materials is presented in table 1. The
admixture cement pastes were prepared in the w/c ratio of 0.4 being this formulation
85%HAC+10%OPC+5%SF, 80%HAC+10%OPC+10%SF, 75%HAC+10%OPC+15%SF and
70%HAC+10%OPC+20%SF Ground Water (GW) was used as medium. The prepared samples
were analyzed by dielectric measurements used AC Impedance Spectrometer, Novo control
technologies, Central Instrumentation Facility Lab at Pondicherry University. In these.
Technique input AC 1V, Impedance ranges from 0.1 to 100 Ohm, Capacitance ranges from
0.1PF to 1F and Frequency ranges from 10Hz to 10 MHz.
The Chemical Oxide compositions of the HAC, OPC and SF materials are given in Table – 1.
TABLE-1
Chemical Oxide
Composition (%)
CaO
SiO2
Al2O3
Fe2O3
SO3
MgO
K2O
Na2O
LOI
OPC
HAC
Silica Fume
64.0
21.1
4.9
3.0
2.1
1.6
0.78
0.18
2.1
39.8
4.5
41.2
11.3
0.6
0.05
0.05
-
0.23
95.17
0.21
0.13
0.12
0.15
0.25
0.15
-
RESULTS AND DISCUSSIONS
For OPC, the dielectric constant decreases within 20 minutes after gauging with water.
At 4-5 hours the dielectric constant decreases. At 2 hours the value of dielectric constant is 34.
The dielectric constants of HAC are very much different from that of the OPC [5]. Comparing
with the OPC, the HAC has a higher initial value of dielectric constant at 2 hours 39 and a much
3
smaller values at 28hours. We noted that for the HAC the slow change period lasts for about 6
hours. At 6 hours the dielectric constant drops dramatically [6]. For the paste containing 100%
HAC, the curves are similar to that of the HAC. But the values of dielectric constant are smaller
than that of the HAC at 2 hours and greater at 28hours
7.00E+01
4.50E+01
4.00E+01
6.00E+01
3.00E+01
imag.die.const.
real.di.const.
3.50E+01
2.50E+01
2.00E+01
1.50E+01
5.00E+01
4.00E+01
3.00E+01
2.00E+01
1.00E+01
1.00E+01
1.73E+01
2.99E+01
5.16E+01
8.92E+01
1.54E+02
2.66E+02
4.60E+02
7.95E+02
1.37E+03
2.37E+03
4.10E+03
7.09E+03
1.22E+04
2.12E+04
3.66E+04
6.32E+04
1.09E+05
1.89E+05
3.26E+05
5.63E+05
9.74E+05
1.68E+06
2.91E+06
5.02E+06
8.68E+06
1.00E+07
5.02E+06
2.42E+06
1.17E+06
5.63E+05
2.72E+05
6.32E+04
1.31E+05
3.05E+04
1.47E+04
7.09E+03
3.42E+03
7.95E+02
1.65E+03
3.83E+02
1.85E+02
8.92E+01
4.30E+01
0.00E+00
2.07E+01
1.00E+01
0.00E+00
1.00E+01
5.00E+00
freq[hz]
freq[hz]
(a)
(b)
Figure 1 Plot of (a) real dielectric constant and (b) Imaginary dielectric constant with frequency
for paste prepared 100% HAC using GW
85% HAC+10% OPC+5% SF
In addition of 5% SF, the relative dielectric constant (ε) decreases with increasing
frequency as expected. In initial stage begins immediately after the cement mixing with water.
The initial dissolution of cement grains into water and the formation of CAH10, C2ASH8 etc.
Make dielectric constant changes quickly. The formation of stratlingite (C2ASH8) is an important
consequence of SF addition [7,8].
Using silica fume increases the strength of concrete at all ages, but it is apparent that
much of the increase is realized at early ages and the rate of strength development at later ages is
similar for silica fume concrete and Portland cement and alumina cement.
The setting of cement is controlled by the formation of a network of partially hydrated
cement practices connected by hydration products [9] that can resist a shear force.
4
4.50E+02
1.40E+02
4.00E+02
imag.die.const.
5.00E+02
1.60E+02
1.20E+02
1.00E+02
8.00E+01
6.00E+01
3.50E+02
3.00E+02
2.50E+02
2.00E+02
1.50E+02
1.00E+01
1.73E+01
2.99E+01
5.16E+01
8.92E+01
1.54E+02
2.66E+02
4.60E+02
7.95E+02
1.37E+03
2.37E+03
4.10E+03
7.09E+03
1.22E+04
2.12E+04
3.66E+04
6.32E+04
1.09E+05
1.89E+05
3.26E+05
5.63E+05
9.74E+05
1.68E+06
2.91E+06
5.02E+06
8.68E+06
1.00E+07
5.02E+06
2.42E+06
1.17E+06
5.63E+05
2.72E+05
1.31E+05
6.32E+04
3.05E+04
1.47E+04
7.09E+03
3.42E+03
1.65E+03
7.95E+02
3.83E+02
1.85E+02
0.00E+00
8.92E+01
5.00E+01
0.00E+00
4.30E+01
1.00E+02
2.00E+01
2.07E+01
4.00E+01
1.00E+01
real.die.const.
1.80E+02
freq[hz]
freq[hz]
Figure 2 Plot of (a) real dielectric constant and (b) Imaginary dielectric constant with frequency
for paste prepared 85% HAC+10% OPC+5% SF using GW.
80% HAC+10% OPC+10% SF
In ternary cement pastes, ettringite can be formed in the first few minutes of the hydration
mainly through the following reactions
CA+3CSH2+2C+26H → C6 AS3H32
----- (3)
C3A+3CSH2+26H →
----- (4)
C6AS3H32
In this stage, the rapid drop in dielectric constant, changes in both electric parameters
slow down. Effects of SF on the rate and amount of heat evolution may be attributed to its
physical and chemical effects on the cement hydration process. GRUTZECK et al., observed
that the addition of SF underwent rapid dissolution in the calcium hydroxide solution and formed
a new phase on the SF particles in a matter of minutes. This new phase is a calcium poor silica
rich layer and may serve as a substrate for the formation of conventional CASH gel. In the first
few minutes of hydration there is a rapid release of Ca2+ and alkali ions from the cement
compounds, the reduction in Ca2+ in the solution increases the rate of release and amount of heat
evolution i.e. hydration at this stage is accelerated by SF [10].
This may be due to the principal reaction between the metakaolin and the calcium
hydroxide derived from cement additional, cementations aluminium containing CSH gel together
with crystalline products which include calcium aluminates hydrates and alumina silicate
hydrates (C2ASH8, C4AH13 and C3AH6) the formation of CAH and CASH phases increases the
compressive strength [11].
5
60
5.00E+02
imag.die.const.
real.die.const.
50
40
30
20
10
4.00E+02
3.00E+02
2.00E+02
1.00E+02
4.30E+01
2.22E+02
1.14E+03
5.91E+03
3.05E+04
1.57E+05
8.11E+05
4.19E+06
0.00E+00
1.44E+01
2.99E+01
6.19E+01
1.28E+02
2.66E+02
5.52E+02
1.14E+03
2.37E+03
4.92E+03
1.02E+04
2.12E+04
4.39E+04
9.10E+04
1.89E+05
3.91E+05
8.11E+05
1.68E+06
3.49E+06
7.23E+06
0
freq[hz]
freq[hz]
Figure3. Plot of (a) real dielectric constant and (b) Imaginary dielectric constant with frequency
for paste prepared 80% HAC+10% OPC+10% SF using GW
75% HAC+10% OPC+15% SF
Fig. shows the addition of 15% SF observes the decrease of the dielectric constant with time can
be ascribed to three phenomena; 1. Modification of the chemical nature of the constituents (2)
change of the relative amount of individual phases and (3) variation of local topology the first
effect seems to be of little importance because the concentration of ionic components in the free
water does not change significantly in time and the dielectric constants of clinker and of CSH are
substantially similar [12,13]. The 2 and 3 are strictly related to each other. The hydration of
cement is accompanied by a decrease of the free water content and an increase of the volume of
the solid phase. The downward shift of the spectra of the dielectric constant has also been
attributed to the thickening of layers in the CSH [14,15,16]. In general, factors that either
increase the porosity (e.g., high W/C ratios) or decrease the thickness of the gel layers (e.g., short
hydration times) increases the dielectric constant.
6
Figure 4. Plot of (a) real dielectric constant and (b) Imaginary dielectric constant with frequency
for paste prepared 75% HAC+10% OPC+15% SF using GW.
70% HAC+10% OPC+20% SF
Silica fume adsorbs the calcium ions to its surface and reduces the concentration of Ca2+
in the solution of this effect may accelerate the process of diffusion as shown by the results
[17,18]. SF is composed of very small particles which when mixed with water may form
agglomerations and are soon covered with a gel-like layer. Water may become enclosed in this
layer, which has been suggested as the cause of the rapid water consumption of SF mixtures
[19,20].
Chatterji et.al stated that around each cement particle there were approximately 100,000
grains of SF. Clearly this number depends on the size of the cement and SF particles and the
percentage of SF in the mixture. Water required for the hydration of the cement grains will have
to percolate the rough the layers of SF. The resistance to this water flow would increase with an
increase in the thickness of the SF layer with a lowering of the w/c ratio. At higher w/c ratios the
voids between particles are originally filled with water and the particles may be fully separated
by a water film. In this case SF will dissolve and move into the solution instead of adhering to
the cement particle surfaces as both surfaces have a silica rich layer (negative Charge). SF even
though it adsorbs some water, does not reduce the amount of water available for cement
hydration therefore the retarding effect reduces. The addition of 15% SF develops very low
strengths and high levels of porosity.
It implies that the formation and interlacing of
microcrystal and the agglutinative “gel of alumina” remain incomplete.
6.00E+01
5.00E+01
5.00E+01
4.00E+01
imag.die.const.
real.die.const.
6.00E+01
4.00E+01
3.00E+01
3.00E+01
2.00E+01
2.00E+01
1.00E+01
1.00E+01
5.02E+06
freq[hz]
5.02E+06
1.68E+06
5.63E+05
1.89E+05
6.32E+04
2.12E+04
7.09E+03
2.37E+03
7.95E+02
2.66E+02
8.92E+01
2.99E+01
0.00E+00
1.00E+01
1.68E+06
5.63E+05
1.89E+05
6.32E+04
2.12E+04
7.09E+03
2.37E+03
7.95E+02
2.66E+02
8.92E+01
2.99E+01
1.00E+01
0.00E+00
freq[hz]
Figure 5. Plot of (a) real dielectric constant and (b) Imaginary dielectric constant with frequency
for paste prepared 70% HAC+10% OPC+20% SF using GW
Conclusion
The combination of silica fume and Portland cement and high alumina cement should
result in a number of synergistic effects, some of which are obvious as follows.
 Silica fume increases the long term strength development of cement/concrete.
 To obtain the dielectric capacitance of cement paste free of contributions from the solid
sample phase and determined the various frequency and real and imaginary dielectric
constants are calculated. It is expected that their study will allow gathering information
related to diffusion mechanisms in concrete.
 A higher water-cement ratio promotes greater ion dissolution. The dissolution depends
on the water quality and impurities present in the water.
 Increase in pore size or a decrease in product layer thicknesses leads to a higher dielectric
constant.
 During the initial period of hydration the water evaporation is higher for higher W/C
ratio.
 Dielectric constant decrease with increasing frequency from 100 Hz to 10 KHz and then
decreased slowly and become almost constant up to 1 MHz, this is due to the inability of
the electric dipoles relaxation.
8
 The value of dielectric constant is water content dependent.
 Dielectric constant values for hardened Portland cement pastes in the RF range show a
rapid decrease in the interval 1 MHz to 100 MHz. They reach relatively constant values
at higher frequencies.
 Increase of HAC substitution by silica fume to complete substitution in the 10% OPC
80% HAC 10% SF composite decreases the aggressive attack of sulphate ions on the
hardened cement pastes.
 The dielectric properties can very well be used to characterize the changes in the
microstructure during hydration.
The dielectric properties can be linked to the
microstructure with the degree of hydration. The degree of hydration, in its turn, is
directly related to properties like strength.
9
References
1. X.Zhang, Y.Yang, C.K.Ong, study of early hydration of OPC-HAC blends by microwave
and calorimetry technique, Cement and concrete Research, 27, (1997) 1419-1428.
2. S.Bhanja, B.Sengupta, Modified water-cement ratio law for silica fume concretes, Cement
and concrete Research, 33, (2003), 447-450.
3. Sihai Wen, D.D.L. Chung, Effect of admixtures on the dielectric constant of cement paste,
Cement and concrete Research, 31, (2001), 673-677.
4. S.J.Ford, J.H.Hwang, J.D.Shane, R.A.Olson, G.M.Moss, H.M.Jennings, T.O.Mason,
Dielectric amplification in cement pastes, J.Am.Ceram.Soc. 81, (1998), 213-216.
5. N.Miura, N.Shinyashiki, S.Yagihara, M.shiotsubo, Microwave dielectric study of water
structure in the hydration process of cement paste, J.Am.Ceram.Soc. 81, (1998), 213-216.
6. P.Gu, J.J.Beaudoin, Dielectric behaviour of hardened cement paste systems, J.Mater.Sci. 15,
(1996), 182-184.
7. C.Alonso,
C.Andrade,M.Keddam,
X.R.Novoa,H.Takenouti,
study of
the
dielectric
characteristics of cement paste, Mater.Sci. Forum 289-292, (1998), 15-28.
8. X.Zhang, X.Z.Ding, C.K.Ong, B.T.G.Tan, J.Yang, Dielectric and electrical properities of
mortar in early hydration period at microwave frequencies,J.mater,Sci.,31, (1996), 339-5345.
9. S.S.Yoon, H.C.Kim, R.M.Hill, Dielectric response of hydrating porous cement paste,
J.Phys.D.Appl.Phys.29, (1996), 869-875.
10. M.Cabeza, P.Merino, A.miranda, X.R.Novoa, I.Sanchez, Impedance spectroscopy study of
hardened Portland cement paste, Cement and concrete Research, 32, (2002), 881-891.
11. Yan Fu, Jian Ding, J.J.Beaudoin, Effect of different calcium aluminate hydrates on ettringite
formation and expansion of High Alumina Cement – based expansive cement pastes, Cement
and concrete Research, 26, (1996), 417-426.
12. R.H. Haddad, I.L. Al-Qadi, Measuring dielectric properties of concrete over low RF, Mater.
New Millennium, Proc. Mater. Eng. Conf., 4th 2, ASCE, New York, NY, (1996), 1139-1149.
13. Sihai Wen, D.D.L. Chung, Cement-based materials for stress sensing by dielectric
measurement, Cement and Concrete Research 32, (2002), 1429-1433.
14. J. Devais, Y.Hung, Determination of dielectric properties of institute concrete at radar freq –
Non Destructive Testing in civil engineering. 2003 (NDT-CE).
10
15. T.M. El Sokkary, H.H. Assal, A.M.Kandeel, Effect of silica fume or Granulated slag on
sulphate attack of OPC and alumina cement blend, Ceramics International 30, (2004) 133138.
16. Dr. S. Barathan, D. Govindarajan, G. Sivakumar and K. Raghu, Microwave study of
hydration of cement with different waters, Indian Journal of Pure & Applied Physics, 44,
(2006), 334-338.
17. G. Sivakumar, K. Mohanraj and S. Barathan, Dielectric study on fly ash blended cement, EJournal of Chemistry, 6, (2009), 231-236.
18. W.L. Lai, S.C.Kou, W.T. Tsang, C.S.Poon, Characterization of concrete properties from
dielectric properties using ground penetrating radar, Cement and Concrete Research 39,
(2009), 687-695.
19. V. Picandent, D. Rangeard, A. Perrot, T. Lecompte, Permeability measurement of fresh
cement paste, Cement and Concrete Research 41, (2011), 330-338.
20. I. Sancheq, X.R. Novoa, Micro structural modifications in Portland cement concrete due to
forced ionic migration tests – study by impedance spectroscopy, Cement and Concrete
Research 38, (2008), 1015-1025.
11