Journal of Ceramic Processing Research. Vol. 13, No. 2, pp.

174~177 (2012) J O U R N A L O F

Ceramic
Processing Research

Comparison of the microstructure and compressive strength of Type 1 Portland

cement paste between accelerated curing methods by microwave energy and auto-
claving, and a saturated-lime deionized water curing method
Natt Makul * and Dinesh Agrawal
a, b

a
Department of Construction Technology, Faculty of Industrial Technology, Phranakhon Rajabhat University, Changwattana
Road, Bangkhen Bangkok 10220, Thailand
b
Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA

The microstructure and compressive strength of a 0.38 water-to-cement mass ratio (w/c) cement paste when subjected to
accelerated-curing by microwave energy and autoclave curing were compared with a normal curing method by soaking in
saturated-lime deionized water at 25 oC. The morphology, atom ratio of Si/Ca versus Al/Ca, phase composition by XRD, and
compressive strength were measured in this study. The results indicate the presence of needle-like ettringite (Aft) in pastes that
had been cured using the autoclave method. However, the saturated-lime deionized water cured paste showed lath-like or
plate-like shapes and did not appear to produce ettringite (Aft). In addition, the microwave-cured paste indicated some
evidence of ettringite. The range of Si/Ca and Al/Ca ratios of the autoclave-cured paste were 0.039 − 0.052, and 0.207 − 0.234,
respectively, while in the microwave-cured paste the ratio shifted to 0.079 − 0.091. The compressive strength of the autoclave-
cured cement paste showed an increase in strength at an early age, while the strength decreased after 7 days of hydration.
Key words: Autoclave curing, Cement paste, Compressive strength, Microwave accelerated curing, Microstructure.

Introduction This is because concrete-making materials, like hyd-

raulic Portland cement, aggregates, water, and admix-
Curing is the process by which hydraulic-cement- tures have a good dielectric behavior; they can absorb
based materials develop strength hardening over time microwave energy very effectively. Water, in particular,
[1]. And, this process ensures that the degree of has a higher relative dielectric constant ( ε ) and loss
r′

hydration is sufficient to reduce porosity enough that tangent (tanδ) than the other components in cemen-
the desired properties of a concrete can be achieved. titious material. As a result, when the electric com-
There are various curing methods to accelerate the ponent ( E ) of the microwave electromagnetic field,
development of strength in concrete during the early- interacts with concrete’s constituents, energy is quite
age phase. However, these methods often cause draw- dramatically transferred and converted into heat. This
backs in their properties. For example, a lack of water mechanism causes the bonds to vibrate, and the energy
in the water-curing process causes concrete to shrink is, therefore, dissipated as heat and transferred within
which leads to tensile stresses within the concrete. As a the concrete to be processed, providing an elevated
result, surface cracking may occur, especially if the temperature and effecting accelerated hydration re-
stresses develop before the concrete achieves adequate actions. Consequently, free water molecules in the
tensile strength. Over heating in the autoclave curing capillary pores of the concrete are quickly removed
method reduces the concrete’s final strength. Selecting from the internal concrete structure before setting,
an appropriate curing method and process helps to which means that plastic shrinkage takes place, and
control the temperature during hydration. Curing by an leads to the collapse of the capillary pores with the
admixture may encounter long-term durability pro- simultaneous densification of the microstructure.
blems [2-8]. This study focuses on establishing how well micro-
As described above, thermal-curing methods affect wave curing performs, some other curing methods and
concrete’s properties adversely both at an early age
− their related properties have also been considered for a
and long term. Considering this, a crucial question comparative analysis. In this section, a normal curing
arises: Can microwave heating be applied in the con- method that uses lime-saturated deionized water at
crete industry for curing? Theoretically, it is possible. 25 oC defines the optimal performance by current
established standards. While an autoclave curing with a
*Corresponding author: temperature rate increase of 75 oC per hour and a
Tel : +662-544-8000
Fax: +662-544-8000 maximum temperature of 150 oC was also used for the
E-mail: [email protected] purposes of comparison.
174
Comparison of the microstructure and compressive strength of Type 1 Portland cement paste between accelerated... 175

Experimental Autoclave curing setup and procedures

Samples were cured in an autoclave chamber at a
Specimen preparation maximum temperature of 150 oC with a heating rate of
The chemical composition in weight percent of the 75 oC per hour. As shown in Fig. 2, this apparatus
Type 1 Portland cement was 20.30 SiO2, 5.67 Al2O3, includes a heat pump, a Chromalox precision heat and
60.43 CaO, 6.23 Fe2O3, 3.14 MgO, 0.90 K2O, 0.36 control electric boiler (model CHPES-036AOF10-203),
Na2O, 2.80 SO3. The Portland cement had a loss on a pump circuit consisting of a motor of 560 Watt, and a
ignition (LOI) of 2.80%, a specific gravity of 3.12, and chamber. A micro-computer with a feedback tempera-
a surface area (BET method) of 0.85 m2/g. Deionized ture control program was used to control the heat inlet
water was used to mix with Portland cement to make of and, therefore, the temperature within the chamber.
pastes. The pastes used were proportioned at a w/c Under autoclave curing, specimens were introduced
ratio of 0.38 by weight. After mixing and molding, into the cavity after having been mixed for 30 minutes
they were cured at room temperature by wrapping with under conditions whereby the initial temperature of
polyethylene plastic until a delay time (time after 75 oC increased until reaching a maximum temperature
mixing until introducing microwave energy with a of 150 oC.
multi-mode cavity) for 30 minutes. A Hobart mixer
was used to mix the solids and liquids according to Testing procedures
ASTM C109 [9]. Cylinderical samples of dimensions A scanning electron microscope (SEM) associated
of 69.0 mm 4.0 mm were cast.
φ × with an energy dispersive X-ray spectroscope, speci-
fically an International Scientific Instruments ISI-130
Curing methods electron microscope, was used to determine the micro-
Normal curing structure and morphology of the samples.
The paste samples were cured until the testing time The crystalline phase identification of the various
by saturated-lime deionized water at 25 oC. samples was performed on a Scintag X-ray diffrac-
tometer. This differactometer is equipped with a copper
Microwave curing target X-ray source, a monochromator, and a Tl-drifted
The microwave heating system used in this study is NaI scintillation detector. Dried-powder samples were
shown in Fig. 1, which includes an industrial micro- packed into a cavity of a zero-background quartz slide
wave generator model S56F manufactured by Cober and placed on a goniometry. Most of the subsequent
Electrics, Inc., Stanford Conn., USA. This model can scans were taken from 25 to 45o 2θ at a rate of 2o 2θ
generate microwave energy at 2.45 ± 0.05 GHz and a per minute.
maximum power of 6.0 kW into a multimode appli- The compressive strengths of the cement pastes were
cator. This microwave apparatus does not provide real- tested using a compressive strength apparatus in
time monitoring of temperature changes during micro- accordance with the ASTM C39 [10] at 8 and 24
wave curing; therefore, the temperature of the sample hours, and 3 and 28 days.
was measured at the start and end of the curing
process. In order to measure the temperature of the Results and Discussion
sample subjected to microwave energy, the positions of
measurement were determined. The temperature of the Morphology
top surface and the bottom surface was measured The morphology of the cement paste at 28 days when
5 times for each; likewise, the sample was immediately subjected to autoclave curing is shown in Fig. 3(c).
fractured and the inside temperature was also measured
5 times.

Fig. 1. Configuration of the microwave curing package. Fig. 2. Configuration of the autoclave apparatus.
176 Natt Makul and Dinesh Agrawal

Atom ratio of Si/Ca versus Al/Ca of the cement pastes at the

Fig. 5.

age of 28 days subjected to microwave and autoclave curing

compared to saturated-lime deionized water curing.

Fig. 3. Micrographs of the cement pastes subjected to : (a) water

curing, (b) microwave curing, and (c) autoclave curing.

Fig. 6. X-ray diffraction of the cement pastes at the age of 28 days

subjected to microwave and autoclave curing compared to
saturated-lime deionized water curing.

ettringite (Fig. 3(b)).

From the plot of the atom ratio of Si/Ca versus Al/Ca
of the cement paste at an age of 28 days subjected
to microwave and autoclave curing compared to
saturated-lime deionized water curing as shown in
Figs. 4-5, the values of the Si/Ca and Al/Ca ratios
subjected to autoclaving showed more clustering than
does the paste under saturated-lime deionized water
curing. The range of Si/Ca and Al/Ca ratios of the
autoclave-curing paste are 0.039 0.052, and 0.207
− −

0.234, respectively. For the microwave-cured paste,

Fig. 4.Spectra of cement pastes subjected to various curing the ratios have a similar character, but the Al/Ca ratio
methods
shifts to 0.079 0.091.
.
−

This shows the presence of needle-like ettringite (Aft) Phase identification

in the specimens that had been cured using the The X-ray diffraction technique was used to examine
autoclave method because it had already formed at a the phase composition of the cement pastes at the age
temperature of 60 oC [11]. However, the morphology of of 28 days when subjected to microwave and autoclave
the saturated-lime deionized water-cured paste (Fig. curing as compared to saturated-lime deionized water
3(a)) showed lath-like or plate-like shapes and did not curing. The XRD patterns (Fig. 6) showed a com-
appear to produce ettringite (Aft). In addition, the position of calcium silicate hydrate (Ca3SiO5), calcium
microwave-cured paste showed some evidence of hydroxide (Ca(OH)2), residual lime (CaO), and Xeno-
Comparison of the microstructure and compressive strength of Type 1 Portland cement paste between accelerated... 177

and did not appear to produce ettringite (Aft), whilst

the microwave-cured and autoclave-cured pastes
showed the presence of needle-like ettringite (Aft).
The range of Si/Ca and Al/Ca ratios of the autoclave-
cured paste was 0.039 – 0.052, and 0.207 – 0.234,
respectively. For the microwave-cured paste, the ratios
have a similar character, but the Al/Ca ratio shifts to
0.079 – 0.091.
The cement paste specimens at the age of 28 days
when subjected to microwave and autoclave curing and
saturated-lime deionized water curing, showed a phase
composition of calcium silicate hydrate (Ca3SiO5),
calcium hydroxide (Ca(OH)2), residual lime (CaO), and
Fig. 7.Compressive strengths of the cement pastes at the age of 28 Xenotile (Ca6(SiO3)6(H2O)).
days subjected to microwave and autoclave curing compared to The compressive strength of the autoclave-cured
saturated-lime deionized water curing. cement paste showed an increase in strength at an early
age, while the strength decreased after 7 days of
tile (Ca6(SiO3)6(H2O)). However, by examining the hydration.
peaks at 18o and 34.5o of the calcium hydroxide phase,
the intensity of the autoclave-cured cement paste Acknowledgements
indicated that this phase crystallized at a rapid rate.
This was different from the case of microwave curing, The authors gratefully acknowledge the Thailand
under which conditions these phases appear crystalline Research Fund (TRF) for supporting this research.
with an uncertain and complicated shape that makes
their elements difficult to identify. References
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