Author’s Accepted Manuscript

MICRO-STRUCTURAL BEHAVIOUR OF
INTERFACIAL TRANSITION ZONE OF THE
POROUS SINTERED FLY ASH AGGREGATE

Manu S. Nadesan, Pasla Dinakar

www.elsevier.com/locate/jobe

PII: S2352-7102(17)30371-6
DOI: https://doi.org/10.1016/j.jobe.2017.12.007
Reference: JOBE379
To appear in: Journal of Building Engineering
Received date: 7 July 2017
Revised date: 12 December 2017
Accepted date: 13 December 2017
Cite this article as: Manu S. Nadesan and Pasla Dinakar, MICRO-
STRUCTURAL BEHAVIOUR OF INTERFACIAL TRANSITION ZONE OF
THE POROUS SINTERED FLY ASH AGGREGATE, Journal of Building
Engineering, https://doi.org/10.1016/j.jobe.2017.12.007
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 MICRO-STRUCTURAL BEHAVIOUR OF INTERFACIAL TRANSITION ZONE

OF THE POROUS SINTERED FLY ASH AGGREGATE

Manu S Nadesan1, Pasla Dinakar2*

1
PhD Scholar
2
Associate Professor, School of Infrastructure, Indian Institute of Technology
Bhubaneswar, India

Abstract

The interfacial transition zone (ITZ) has a significant influence on the hardened

concrete behaviour. The behavior of ITZ is not well established in the case of sintered

fly ash aggregate (SFA) concrete compared to normal aggregate concrete. The present

study emphasizes to quantify the characteristics of ITZ of the SFA concrete. To

understand the influence of water-cement ratio on the ITZ behavior, various water-

cement ratios ranging from 0.25 to 0.75 were employed and the ITZ characteristics

were assessed both at 28 and 90 days through various experimental methods such as

microhardness test, SEM-EDX and impedance spectroscopy. Also, a comparison is

made with the ITZ of the normal granite aggregate concrete. The results indicate that

the ITZ formed in the SFA aggregate concrete is denser than the normal aggregate

concrete.

Keywords: ITZ; SFA; SEM; microhardness; Impedance spectroscopy.

*Email: pdinakar@iitbbs.ac.in
 1. Introduction

Cement concrete became one of the integral parts of infrastructure development in

modern days. Even though concrete is neither an energy efficient nor a green material,

it is the most consumed construction material in the world [1]. To make concrete more

energy efficient, the structural efficiency (compressive strength to density ratio) of

concrete has to be increased. One way to increase the structural efficiency is the

development of structural lightweight concrete [2]. Replacement of natural quarried

aggregate with lightweight aggregate (LWA) is one of the best practice adopted to

develop lightweight concrete, and these concretes are categorized as lightweight

aggregate concrete (LWAC). Production of structural grade concrete is possible only by

using limited type of LWAs. Sintered fly ash aggregate (SFA) is one of the suitable

materials towards this effort. Besides reducing self-weight of the structure there is a

significant environmental and economic benefits that can also be availed by utilizing

this material [3]. The strength and durability characteristics of the fly ash LWACs were

examined earlier and found that their performance is equal to or higher as compared to

the normal aggregate concretes [4 -6].

It is often considered that hardened concrete is a three-phase composite material which

contains cementitious paste, aggregate and the boundary layer between them. The

boundary layer between cement paste and aggregates is commonly referred as

interfacial transition zone (ITZ). It is believed that ITZ plays a significant role on the

mechanical and durability characteristics of the matured concrete. Usually ITZ is

considered to be the weakest link in normal aggregate concrete. The thickness of ITZ in

normal aggregate concrete is around 40 µm and it occupies around 20 to 40% of the

total volume of the cementitious matrix [7]. But in case of LWAC the scenario may be
totally different; it was reported that the ITZ of the porous aggregate concretes are

dense and homogeneous compared to normal aggregate concrete [8, 9]. The average

ITZ thickness of LWAC reported earlier using microhardness study was 60 µm [10].

However, the nature of ITZ of the sintered fly ash aggregate concrete is not well

understood to date.

The type and nature of the interfacial zone depends on the microstructural

characteristics of the individual aggregates also [11]. A strong bond exists between

paste and porous aggregate due to enhanced mechanical interlocking [11]. Apart from

mechanical interlocking, chemical interaction was also reported between the fly ash

aggregates and the cement paste [12]. It was reported that, in the case of SFAs there

exhibits a pozzolanic reaction between the aggregates and the surrounding cement paste

and the pozzolanic reactivity of this is less than that of the individual fly ash and the

cement paste [13]. Also, reduction in Ca(OH)2 content at the vicinity of the aggregate

again reconfirms the fact that there exists a pozzolanic reaction between the aggregate

and the surrounding cement paste [13]. Fagerlund [14, 15] suggest that the ITZ

enhancement in the case of porous aggregate is due to the ‘filtration effect’; wherein

only the water in the cement paste can infiltrate into the aggregate, which could

facilitate the formation of a dense layer around the LWA and may further reduce the

ingress of water. ‘Wall effect’ is another phenomenon that occurs generally in normal

aggregate concrete ITZ, making it porous in nature [16]. Apart from this the ITZ in

normal aggregates is porous and the amount of anhydrous grains available is lesser

compared to bulk cement paste [17].

Therefore, proper characterization of the ITZ has been a topic of immense attention in

recent times. Experimental techniques such as scanning electron microscopy (SEM)

with an energy dispersive X-ray detector (EDX), microhardness, impedance

spectroscopy etc., are useful to arrive at some meaningful conclusions [12, 18, 19].

Electrochemical impedance spectroscopy is relatively a new and reliable nondestructive

procedure to understand the hydration process of cement and the role of several

influencing parameters [20-22]. Most of the available studies are concentrated on

particular water content only. The effect of different water-cement ratios on the ITZ of

SFA is not yet studied well. As the water-cement ratio varies the viscosity of the paste

also getting varied [23, 24], and this may lead to the penetration difference in the

amount of paste to the porous aggregates. Till date there are no proper experimental

investigations conducted in this direction.

The present investigation is aimed to carry out a comparative study on the ITZ behavior

of the sintered fly ash aggregates and granite aggregates at different water-cement

ratios using various experimental techniques. The experimental techniques like

microhardness, SEM-EDX and impedance spectroscopy were employed to quantify the

ITZ behavior of the specimens. The obtained results are expected to provide a

quantitative measure of the microhardness, thickness and resistivity of the ITZ in case

of SFAs. The outcome of the present investigation may enhance the cement hydration

modeling in the case of SFA concretes.

2. Materials and specimen preparation

Ordinary Portland cement (UltraTech 53 grade) confirming to IS 12269 [25] is used as

binder, SFA supplied by IMFA Chowdwar plant located in Odisha state, India and

locally available normal granites were used as coarse aggregates in the present

investigation. The average size of the aggregates adopted in this study is 12 mm. The
manufactured aggregates are nearly spherical in shape. In order to maintain similar test

conditions, the granite aggregates are also transformed into similar shape and size as

shown in Fig. 1. The water-cement ratios adopted in this investigation are 0.25, 0.35,

0.45, 0.55, 0.65 and 0.75. The physical and chemical properties of cement and the fly

ash aggregates are mentioned in Table 1.

Table 1: Physical and chemical characteristics of cement and LWA

Chemical composition Cement LWA

Silica [SiO2] (%) 34 61.23

Alumina [Al2O3] (%) 5.5 14.68

Ferric Oxide [Fe2O3] (%) 4.4 8.05

Calcium oxide [CaO] (%) 63 9.05

Magnesium oxide [MgO] (%) 1.26 0.68

Sodium oxide [Na2O] (%) 0.1 0.72

Potassium oxide [K2O] (%) 0.48 0.58

Sulphur trioxide [SO3] (%) 1.92 0.42

Loss on ignition (LOI) 1.3 -

Blaine (m2 / kg) 360 -

Specific gravity 3.15 1.25

The size of the test specimen in the present investigation is fixed as 2 cm×2 cm×2 cm.

Well mixed cement paste is poured into the mould and the single aggregate grain is

inserted in such a way that it is located at the center of the specimen. Three different

types of specimens were prepared for each water-cement ratio. One of the specimen is

fully prepared with cement paste; and for the other two specimens, SFA and granite

aggregate were inserted within the paste matrix. The casted specimens were kept at 100
% humidity till 24 hours. After that the specimens were kept at 27 0C and 95 % relative

humidity till the date of testing. The designation ‘M’ stands for the specimen fully

prepared with paste, also L and G represents specimen containing SFA and granite

aggregate, respectively. Also, the numbers 25, 35, 45, 55, 65 and 75 designates the

corresponding water-cement ratios 0.25, 0.35, 0.45, 0.55, 0.65 and 0.75, respectively.

Figure 1: Aggregates used in the present investigation

3. Experimental methods

3.1 Microhardness

In this test method, the sample is cut through its center such that the specimen became

2 cm×2 cm×1 cm using diamond cutter. The polished specimens were tested at the age

of 28 and 90 days. Zwick Roell ‘ZHVµ’ Micro Vickers hardness tester was used to

determine the microhardness of the samples. The microhardness readings were taken at

10 µm interval up to 100 µm from the surface of the aggregate using microhardness

tester and 25 g force was used for indention. It is difficult to measure the microhardness
value exactly at the boundary point. Considering this the starting reading was taken at a

distance of 10 µm from the surface of the aggregate.

3.2 SEM and EDX

The microstructural assessment of the interfacial region by using a field emission

scanning electron microscope (FESEM ‘Carl Zeiss MERLIN II compact’) with an X-

ray microanalysis detector (Oxford Instruments 51-XMX1004) can determine the

elemental composition and that will indicate the behavior of the ITZ. The specimens

were cut using diamond cutter through its center such that the specimen becomes 2

cm×2 cm×1 cm. Subsequently by means of epoxy resin cold mounting was done for

proper holding of the specimen. The cut sections were polished using an automatic

polishing machine with a series of 6, 3, 1, and 0.25 µm diamond pastes, by exerting 20

N force on a low-speed lap wheel for about 3 minutes with iso-propylene as a lubricant.

A thin layer of gold was evaporated onto the surface to facilitate proper conductivity.

The readings were taken at 10 µm interval. From the obtained atomic percentage, the

Ca/Si ratio can be calculated.

3.3 Impedance spectroscopy

The basics of impedance spectroscopy is to measure the alternating current (AC)

response of the applied alternating voltage. By varying frequency range of the AC

impedance spectra, a plot known as Nyquist can be obtained. Typical plot obtained

during scanning of a concrete specimen is depicted in Fig. 2.

 Figure 2: Typical Nyquist plot for concrete [26]
To interpret the AC impedance spectra an equivalent circuit (a combination of resistors

and capacitors) is employed. In the present investigation equivalent circuit proposed by

Song [26] is adopted to interpret the behavior of impedance spectra obtained during the

impedance spectroscopy. The equivalent circuit diagram of the adopted Song’s model

is shown in Fig.3. According to the adopted equivalent circuit model, R0 is the overall

resistance of all micro-pores that are filled with water, R1 is the kinetic parameter of the

cement hydration, RCCP is the impedance of the entire continuous conduction path

(CCP) and RCP is the impedance of remaining portion of discontinuous conduction path

(DCP). Parameters R0 and R1 can be obtained from the Nyquist plot that was obtained

during scanning of the specimen, whereas RCCP and RCP were calculated from the

Song’s model.
 Figure 3: Equivalent circuit model for concrete [26]
Due to limitation of scope the detailed theoretical background of the adopted model is

not included in the present manuscript. Two electrode arrangements were adopted in

the present study to conduct the impedance spectroscopy using ‘ACM instruments- Gill

AC’. The amplitude of the sinusoidal voltage was chosen to be 32 mV and the

frequency is varied from 5 MHz to 1000 Hz. The impedance of the specimen was

measured in three different directions and the average values were reported. Vacuum

saturated samples were tested at the age of 28 and 90 days. To facilitate proper

conductivity filter paper saturated with 0.3 M NaOH solution was used.

4. Results and discussion

4.1 Microhardness

Microhardness study mainly concerned over two parameters, one is hardness value and

the other is the thickness of the ITZ. During the microhardness test the hardness value

obtained near to the surface of the aggregate is reported as the hardness value of the

ITZ. Whereas the thickness of the ITZ is obtained from the microhardness profile along
the ITZ. The profile obtained for all the specimens at 28 days and 90 days were

presented in Fig. 4 and Fig. 5, respectively. As the microhardness values stabilizes it is

assumed that there is a shift from the ITZ to the bulk cement paste.

Figure 4: Microhardness of the ITZ around the aggregate surface at 28 days

 Figure 5: Microhardness of the ITZ around the aggregate surface at 90 days

Fig.6 illustrates the thickness of the ITZ of various specimens that were obtained in the

present investigation. In Fig. 6 and Fig. 7 the designation ‘G’ and ‘L’ represents granite

and SFA specimens, respectively and ‘28’ and ‘90’ represent the curing periods.

Microhardness study conducted on specimen having w/c 0.25 with granite aggregate

indicates that there is a negligible presence of the ITZ around the aggregate grain.

Whereas a thicker ITZ is observed in the case of SFA for the same w/c. This may be

due to the ‘internal curing’ [27] and ‘filtration effect’ [14, 15] facilitated by the SFA.

Due to the filtration effect the water-cement ratio around the SFA aggregate may

reduce further than the bulk paste. Also, it is noticed that the thickness of the ITZ

increases with age. It is observed that the thickness of ITZ of LWA is 60 to 70 µm at

the age of 28 days and 70 to 80 µm at 90 days. Whereas in granite aggregate, these

ranges shifted to 20 to 40 µm at 28 days and 30 to 40 µm at 90 days, respectively. This

is may be due to the impact of prolonged internal curing that happens at the periphery
of the LWA [27]. From the above observation it can be noticed that the thickness of

ITZ decreases for granite aggregate with age whereas, for the LWAs it increases. Also,

it was observed that as the water-cement ratio decreases the thickness of ITZ also

decreases irrespective of the aggregate type. This may be due to the fact that at lower

water-cement ratio the cementitious particles are packed closely. Stroeven and Stroeven

[28] found that as the contacts area between the gel products of neighbouring particle

increases, the surface area that is available for the product deposition will decrease,

thus less surface area signifies a thicker deposit of the product layer. Another

interesting observation is that in case of SFA the thickness of ITZ remained same from

w/c 0.25 to 0.55 at 28 and 90 days. Similar trend was also exhibited in case of granite

aggregate; however, the w/c ratios varied from 0.45 to 0.75. Comparable results were

also established earlier [8].

Figure 6: Variation of thickness of ITZ according to w/c

Fig.7 illustrates the variation of the hardness value (though the unit is N/mm2, it usually

expressed as HV) of all the investigated specimens at the interface region (within 10

µm). After 28 days of curing the hardness values varied from 12 to 62 for granite

aggregates, whereas the range lies in between 59 to 168 for SFA. Similarly, after 90

days of curing these values varied for granite and SFA as 13 to 81 and 64 to 241,

respectively. It is clear that the hardness value of SFA paste interface is much higher

than that of the granite aggregate paste interface. Also, for the specimens having water-

cement ratio less than 0.45 a steep increase in the hardness value for both granite and

fly ash aggregates were observed. Water-cement ratios less than 0.45 were generally

considered for the development of high strength concretes. Except for w/c 0.25 all the

granite aggregate specimen possesses similar hardness value at all ages irrespective of

water-cement ratios adopted.

Figure 7: Variation of hardness value with water-cement ratio

Also in case of SFAs, it is noticed that some of the paste penetrated inside the SFA.

While conducting the hardness test on the penetrated paste within the aggregate, the

hardness values obtained were within 450 to 600. These values are nearly similar to

that of the granite aggregates. So, from this experiment it can be observed that most of

the open pores of the LWA were getting sealed due to the intrusion of cement paste. It

is also noticed that the impregnated cement paste possesses very high hardness value

similar to granite aggregate. This indicates that pore refinement occurred in SFA, and

consequently enhances its performance potential of the concrete made up from these

porous aggregates.

4.2 SEM and EDX

The obtained SEM images of all the specimens at 90 days were configured in Fig. 8.

The configuration is in such a way that the numeral indicates the order of w/c from 0.25

to 0.75, the alphabet ‘G’ stands for granite aggregate whereas ‘L’ stands for LWA. For

example, L 25 indicates LWA specimen having water-cement ratio 0.25. From SEM

images (Fig. 8) it can be noticed that most of the granite aggregate specimen having

water-cement ratios 0.65 and 0.75 (G 65, G 75), the paste matrix split apart from the

aggregate surface; this probably happens because of the shrinkage that takes place

within the paste phase during drying, at the time of specimen preparation. At the same

time, no such failure is observed in LWAC; this is probably because of the better bond

between the cement paste and the LWA surface. Fig.8 also indicates that LWA having

water-cement ratio 0.75 (L 75) tend to start the cracking at the ITZ.
 Figure 8: SEM images of specimens [G: Granite aggregate, L: LWA, P: Paste]

The SEM images (Fig.8- L 45) indicate that the cement paste is perfectly merged with

the porous SFAs. While the presence of loosely packed paste can be observed on the

surface of granite aggregate; as can be seen in Fig.9. This may be due to the fact that,
the stiffness of the LWA is much less than the granite aggregate; so it can

accommodate certain level of deformation that occurs during drying without failure.

Similar behavior was also observed by Wegen and Bijen [4], while studying the

shrinkage performance of the SFA concretes.

Figure 9: a) Typical SEM images of ITZ of the specimen b) Enlarged view of marked
area of Fig. 9-a

According to Scrivener [17] the specimen configuration adopted in the present

investigation is not a good model for concrete as the aggregate is not present during the

mixing process. To eliminate this adverse effect on the paste specimen the study further

extended to the use of concrete specimen having similar water-cement ratio. These

concrete specimens were used in backscattered electron (BSE) images to quantify the

amount of anhydrous cement grains around the LWAC. From BSE images (Fig. 10) of

the ITZ of all specimens, it has been observed that the Ca(OH)2 is absent around the

periphery of LWA at all the water-cement ratios studied. This may be due to the

alteration in the normal hydration process that happens in normal aggregate concrete.

Cement hydration usually takes place by a three-step cyclic process such as dissolution,

diffusion and reaction [29]. During these processes in the case of normal aggregate
concrete, the fast moving Ca2+ will normally align near to the aggregate surface where

the w/c is higher. Also, the deficiency of anhydrous cement grains near to the interface

in fresh paste will increase the amount of water filled space and subsequently paves

path for the growth of more Ca(OH)2 crystals [17]. From Fig. 10, in the BSE images,

the anhydrous cement grain area is analyzed using image analyzer. From the analysis, it

was found that for LWAC the percentage area of anhydrous cement within the matrix

increases from 7.28 % to 19.47 % as the water-cement ratio decreases from 0.75 to

0.25. It is known fact that the lack of sufficient anhydrous grains will increase the

porosity [17].
 Figure 10: BSE image of the concrete samples [S: Sand, L: LWA, A: Anhydrous
cement grain, C: Ca(OH)2]
In the present investigation the homogeneity of the paste matrix is identified using

calcium to silica ratio (Ca/Si). The obtained results indicate that the Ca/Si ratio of the

bulk paste increases as the w/c ratio decreases. It is also observed from the results that

the thickness of ITZ obtained from the EDX analysis after 90 days for granite aggregate

is around 20 to 30 µm whereas the thickness obtained from the microhardness study

was between 20 to 40 µm. Also from Fig. 9 it can be noticed that the Ca/Si ratio near to

the granite aggregate surface is increasing. This may be due to the accumulation of fast

moving Ca2+ ions during the diffusion process around the granite aggregate surface

[29]. From Fig. 11 it is also noticed that the Ca/Si ratio for w/c 0.65 and 0.75 increases

drastically within the ITZ. This may be due to the fact that higher the w/c ratio more gel

pores will exist within the paste matrix which facilitates the easy movement of the Ca2+

ions. More Ca2+ ions aligned around the aggregates increases the Ca/Si ratio. For w/c

0.25 and 0.35 this change is minimum, this may be because of the presence of more

anhydrous grains that exists throughout the paste.

Figure 11: Variation of Ca/Si ratio of granite aggregate with distance

By analyzing the EDX plot depicted in Fig. 12 it has been noticed that the behavior of

calcium-silica ratio in SFAs matrix is different from that of the granite aggregate.
From the obtained results a reduction in Ca/Si around the SFA surface has been

observed. This may be due to the pozzolanic reaction that may have taken place during

the hydration around the vicinity of the SFAs. Also, an increase in Ca/Si is noticed at

around 20 µm from the aggregate surface. This may be due to the reduction of w/c

around the SFA surface due to the absorption of water from the paste. It is observed

that this increment diminishes as the w/c ratio decreases. From the earlier studies, it is

understood that the presence of supplementary cementitious materials during the

hydration process decreases the Ca/Si [30]. The thickness of ITZ obtained for SFA

specimen from EDX study is 20 to 40 µm, whereas using microhardness the thickness

obtained is around 60 to 80 µm. By analyzing results obtained from the specimens it is

noticed that the thickness obtained from EDX analysis is different from microhardness

study. Similar trends were also observed in case of LWAs studied earlier by Kong et al

[8]. Even though the thickness values obtained are different, both the studies show that

the thickness of the ITZ of the SFA is higher than the granite aggregate.

The major elemental composition of the hydrated cement consists of Ca, Al and Si.

Among these the domination of Si indicates the presence of aggregate whereas the

domination of Ca indicates the presence of cement. The Ca mapping done by EDX

indicated that some of the cement paste infiltrated within the LWA as shown in Fig. 13,

this could eliminate some of the open pores present in the LWA. From the EDX images

it is observed that the depth of penetration of the cement paste can be up to 40 µm.
 Figure 12: Variation of Ca/Si ratio of LWAC with distance

Figure 13: Typical image showing infiltrated cement paste within the LWA (L 25)

4.3 Impedance spectroscopy

All the impedance parameters of the entire specimens were depicted in Table 2. From

the obtained results it can be noticed that both R0 and R1 increases with time, and the

increase in the value of R1 is more than that of R0. This may be due to the fact that as

the hydration process increases, most of the CCPs will be hindered by the hydration
 products. Similarly, the hardness of the hydration products also gets increased so

consequently R0 also increases. From the obtained results it is also noticed that

specimen containing SFA possess higher resistance than the specimen contains paste

alone and with granite aggregate. Similar trends were also reported earlier by Kong

et.al also [8]. There is a difference in resistances offered by the specimen containing

different aggregates even though the w/c, shape and size of the aggregate are the same.

This may due to the difference in the nature of ITZ formed in both the cases.

Table 2: Impedance parameters of specimens

Aggregate 28 day (Ω) 90 day (Ω)

w/c
type R0 R1 RCCP RCP R0 R1 RCCP RCP
G 368 1916 2284 439 410 2052 2462 492
0.25 L 373 1924 2297 446 417 2062 2479 502
M 280 1748 2028 325 313 1872 2185 365
G 189 1852 2041 209 248 1909 2157 280
0.35 L 198 1861 2059 219 259 1916 2175 294
M 171 1648 1819 188 204 1714 1918 229
G 128 1356 1484 140 147 1788 1935 159
0.45 L 132 1363 1495 145 152 1798 1950 165
M 113 1218 1331 124 133 1598 1731 144
G 96 1098 1194 105 109 1198 1307 119
0.55 L 102 1109 1211 111 116 1202 1318 127
M 89 995 1084 96 95 1080 1175 103
G 87 763 850 97 99 858 957 111
0.65 L 93 773 866 104 112 862 974 126
M 70 717 787 77 80 798 878 88
G 64 642 706 71 71 684 755 79
0.75 L 67 654 721 74 74 701 775 82
M 57 607 664 62 62 641 703 68
G- Granite aggregate, L- SFA aggregate, M- Cement paste without aggregate
From the impedance analysis electrical resistivity of the sample can be easily

determined using the well-known following relation:

ρ = RA/l (1)

where, ‘ρ’ is the resistivity of the pore solution in Ω cm, ‘R’ is the resistance offered by

the pore solution in CCP, ‘A’ is the area of cross section perpendicular to the applied

electrical field and ‘l’ is the thickness of the sample parallel to the applied electrical

field. If the aggregate in concrete sample, solely plays the role of occupying the volume

without any interaction, then resistivity of the paste sample and the concrete sample

will remain same. If they are not same, it can be considered that the difference in the

resistivity of the two samples indicate the presence of ITZ. To describe the existence of

ITZ, Yang and Shi [31] established a relation between the resistance of the cement

paste and the paste containing aggregate as given below:

δ = Rc-Ra (1-V/8) (2)

where, ‘δ’ is the parameter that indicates the nature of ITZ (in other words difference in

resistivity), Rc and Ra represents the resistance of the cement paste (RCCP of M) and

paste containing aggregate (RCCP of G or L), respectively and ‘V’ represents volume of

the aggregate inserted. Here paste matrix is considered as the datum to assess the nature

of ITZ of different types of aggregate. If the value of ‘δ’ is not zero it can be considered

that the inclusion of aggregate may lead to the formation of ITZ within the matrix. If

the value of ‘δ’ increases, it means that the inclusion of that particular type of aggregate

causes the reduction in resistivity of the matrix. In other words, a positive increase in

the value of ‘δ’ indicates, the increase in the porosity within the sample [32].
 Figure 14: Variation of δ with water-cement ratio at different ages

The characteristic parameter of ITZ (δ) of both the aggregates calculated based on the

impedance parameters summarized in Table 2 are presented in Fig. 14. From Fig. 14 it

is clear that the value of ‘δ’ is less for specimen containing SFAs compared to that of

the specimen containing granite aggregates. It is also noticed that the porosity of the

ITZ is decreasing with increase in curing period for both types of aggregates.

Irrespective of the type of aggregate the value of ‘δ’ decreases as the w/c decreases at

all the ages. In case of granite aggregate for w/c 0.25 the value of ‘δ’ is approaching

towards 0; this means that the ITZ is almost similar to the paste matrix. Also, there is

no significant change in the values of ‘δ’ with age observed for the specimens having

w/c less than 0.45. Whereas, in case of SFAs for w/c below 0.45 the value of ‘δ’ is

negative; this clearly indicates that the inclusion of aggregate increases the overall
resistivity compared to that of the paste matrix. This shows that the porosity formed by

the SFA is less than that of the granite aggregate.

5. Conclusions

After conducting the experimental investigation on LWA and granite aggregate at

different water-cement ratios at 28 day and 90 day the following conclusions were

obtained.

 The thickness of ITZ obtained from microhardness test and SEM-EDX analysis

are different. But the trends that were followed by the specimens having

different water-cement ratios is similar in nature. The trend is well maintained

at different ages also.

 It is found that thickness of the ITZ is higher in the case of SFA compared to

granite aggregates. It is also noticed that the microhardness value of the ITZ of

the granite aggregate concrete is less than that of the bulk paste, whereas the

microhardness value of the ITZ of SFA concrete is higher than that of the bulk

paste for all the water-cement ratios studied.

 The study concludes that the microhardness and resistivity offered by the ITZ of

the SFAs is higher than that of the granite aggregates for all the water-cement

ratios studied at 28 day and 90 day. The impedance spectroscopy study

indicates that the porosity present in the ITZ of the SFA concrete is less than

that of the granite aggregate concrete.

 The cement paste penetrated in to the porous SFA aggregates seals some of the

open pores and the microhardness value of the hardened penetrated paste is
much higher than the individual bulk paste for any of the water-cement ratios

studied.
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Highlights

 The thickness and hardness values of ITZ of the SFA aggregate is greater than

granite aggregate for all the water-cement ratios studied from 0.25 and 0.75.

 The thickness of ITZ is reducing in granite aggregate concrete, while the value

is increasing in SFA aggregate concrete with age.

 Impedance spectroscopy is easy and a reliable method to study the ITZ of

lightweight aggregate concrete.