Accepted Manuscript

Chloride ingress and steel corrosion in geopolymer concrete based

on long term tests

Chandani Tennakoon, Ahmad Shayan, Jay G Sanjayan, Aimin Xu

PII: S0264-1275(16)31547-7
DOI: doi: 10.1016/j.matdes.2016.12.030
Reference: JMADE 2575
To appear in: Materials & Design
Received date: 21 August 2016
Revised date: 11 November 2016
Accepted date: 11 December 2016

Please cite this article as: Chandani Tennakoon, Ahmad Shayan, Jay G Sanjayan, Aimin
Xu , Chloride ingress and steel corrosion in geopolymer concrete based on long term tests.
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 ACCEPTED MANUSCRIPT

Chloride ingress and steel corrosion in geopolymer concrete based on long

term tests
Chandani Tennakoona,1, Ahmad Shayanb, Jay G Sanjayana, Aimin Xub
a
Centre of Sustainable Infrastructure, Faculty of Science, Engineering and Technology,
Swinburne University of Technology, Hawthorn, Victoria, Australia.
b
ARRB Group Ltd, Vermont South, Victoria, Australia.

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Abstract

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Alkali activated binders (geopolymer) is an emerging technology to produce concrete without
the use of any Ordinary Portland Cement (OPC) by alkali activation of alumino-silicate source

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materials such as fly ash and/or slag. Limited knowledge on durability issues like corrosion
behaviour of reinforced geopolymer concrete impedes the usage of this technology in structural
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applications.

This study explored the chloride permeability and initiation of chloride induced corrosion of
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geopolymer concrete in accelerated chloride environment using longer test period. Corrosion
initiation was also monitored in embedded rebar in 2% chloride contaminated concrete.
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Corrosion state of the rebar was monitored using non-destructive test method using Cu/CuSO4
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reference electrode.
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The results showed that the apparent chloride diffusion coefficient of blended fly ash and slag
geopolymer concrete is lower than that of OPC concrete. The diffusion coefficient also
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decreased with the increase of slag content in the binder. Blended fly ash and slag geopolymer
concrete also exhibited higher aging factor than OPC concrete indicating improved resistance to
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chloride ingress with time. The study also showed that the embedded rebar in fly ash and slag
based geopolymer concrete has higher protection against corrosion than a rebar in OPC concrete
even when the concrete is contaminated with significant levels of chloride.

1
Corresponding author; email: ctennakoon@swin.edu.au

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Highlights

 Chloride ingress rate in geopolymers containing slag is low

 Age factor of geopolymer is significantly higher than OPC

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Geopolymer can hinder corrosion in steel rebar

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Keyword: Age factor, Chloride ingress, Corrosion, Fly ash, Geopolymers, Slag
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1. Introduction
The term geopolymer describes a broad class of synthetic zeolite materials that are produced by a
series of reactions between alumina-silicate source materials and alkali activators. Due to the
reduced carbon foot print and low embodied energy, geopolymer concrete technology has gained
significant attention in recent years as an alternative to Ordinary Portland cement (OPC) concrete

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for production of structural and non-structural elements. To date, geopolymer concrete has had
relatively minor application in field concrete due to the limited knowledge base on its durability

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[1]. Its long-term durability properties as well as its protection against reinforcements corrosion
are yet to be fully investigated [2]. Some studies of marine-exposed concrete specimens have

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shown that the performance of geopolymer concrete specimens is comparable to that of OPC
concrete with respects to reinforced corrosion [3-5].
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The main cause of corrosion in concrete structures, particularly in concrete structures in marine
environment is the chloride ingress [6, 7]. Ganesan et al. [8] studied the chloride diffusion of
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100% fly ash based geopolymer and reported that chloride diffusion of geopolymer and OPC
concrete are similar. In their study authors employed AgNO3 spraying to identify the depth of
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chloride penetration, as suggested by ASTM C1556 [9]. In contrast, the study by Olivia et al.
[10] reported that the rate of chloride penetration in 100% fly ash based geopolymer concrete is
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higher than that of OPC concrete. Shayan et al. [11] characterised the properties of a 100%
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slag-based geopolymer concrete after having been in service for five years in the retaining walls
of a bridge structure on the Yarra river in Melbourne, Australia. The rapid chloride permeability
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test ASTM 1202 [12] showed very low chloride permeability. Based on NT Build 443 [13]
chloride diffusion coefficient was an order of magnitude lower than that of blended slag cement
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concrete used in the retaining walls of the same bridge. More recently, Ma et al. [14] followed
NT build 443 test method [13] to evaluate the chloride diffusion coefficient of 100% slag-based
geopolymer and found that chloride diffusion rate of slag based geopolymer concrete is lower
than OPC concrete. However, in the same study, Ma et al. [14] found that the corrosion rate of
rebar inside prism specimens is similar to that of the embedded rebar inside OPC concrete.

The above studies were mainly focused on corrosion due to chloride ingress. There are also a
few studies on chloride induced corrosion in contaminated concrete. Monticelli et al. [15] added

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2% chloride by mass of binder to 100% class F fly ash based geopolymer during the mixing
process. The authors reported that the availability of silicate ions in the pore solution of
contaminated geopolymer concrete can provide additional protection for the passivity of rebar.
Miranda et al. [16] observed that addition of 2% chloride by mass of binder to fly ash based
geopolymer mix increase the corrosion rate by 100 times compared to uncontaminated
geopolymer concrete. They also found that the steel embedded in contaminated geopolymer did
not have the protective passive layer and show similar corrosion behaviour to OPC. The result of

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Bastidas et al. [17] is in agreement with the previous observations. More recently, an innovative
technique for repair and strengthening of reinforced concrete members with deteriorated cover

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concrete and/or corroded steel rebars was proposed and named inhibiting-repairing-strengthening

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(IRS) technique [18, 19]. It consists in the installation of a stainless steel fabric in the cover
concrete, restoring this latter with a geopolymer-based matrix which also act as a corrosion
protection.
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Blending of class F fly ash and slag enables geopolymers modifies the reaction phases and the
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microstructure of geopolymer compared to 100% fly ash or 100% slag based geopolymer leading
to different level of chloride binding and electro chemical mechanisms. Slag leaches sulphate
ions into pore solution leading to high negative half-cell redox potential in the embedded rebar
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[20]. Corrosion mechanism of embedded rebar in slag blended geopolymer concrete has not been
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discussed in the litreture. In the present study chloride ingress of slag blended geopolymer
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concrete is evaluated using potentiometric titration method [14, 21]. This study also examines
the change in chloride diffusion rate with time in blended fly ash and slag geopolymer which can
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be used to quantify the age factor of concrete. The corrosion state of embedded rebar using
electrochemical method (half-cell potential and corrosion current) was evaluated. These results
are compared with the actual corrosion state of the rebar. Finally, the study evaluates the
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corrosion state of the embedded rebar in blended fly ash and slag geopolymer concrete
contaminated with 2% (by mass of binder) The purpose is to accelerate the corrosion so that the
investigation can be completed in realistic time period.

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2. Materials and methods

2.1.Materials

Precursor materials

A class F fly ash (FA) which was a 50/50 mixture of Gladstone and Callide fly ashes (FA) and
granulated ground blast furnace slag (Slag), with the chemical compositions shown in Table 1
were used as the alumino-silicate precursor materials. The bulk chemical compositions were

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determined by X-ray florescence (XRF) analysis. The main component of class F fly ash is SiO2
(over 51%) whereas slag contains high amount of CaO (41.5%). It is important to note that fly

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ash contains twice as much Al2O3 as slag does. The particle size distributions of fly ash and slag,
obtained using a Cilas laser diffraction particle analyser are shown in Figure 1. The particle size

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analysis shows that both fly ash and slag have small particle sizes which are desirable for the
geopolymer reaction. It also shows that class F fly ash has 10% of very fine particles (< 1µm),
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while slag has about 2.5% of finer than 1µm.
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Table 1: Bulk chemical composition of materials (wt. %)

Oxides GP Cement Slag FA

SiO2 19.30 32.00 51.50
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TiO2 0.30 0.51 1.50

Al2O3 5.50 13.00 27.60
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Fe2O3 2.90 0.40 11.80

Mn3O4 0.20 0.30 0.15
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MgO 1.40 4.90 1.30

CaO 62.00 41.50 2.20
Na2O 0.06 0.20 0.40
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K2O 0.40 0.33 0.60

P2O5 0.11 0.02 0.73
SO3 2.46 2.10 0.2
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S2- 0.00 0.60 0.00

LOI 5.3 4.9 1.8

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(a) (b)

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Figure 1: Particle size distribution of (a) Slag (b) Fly ash. 1-10 g of source material was
dispersed in water in order to obtain the particle size.

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Alkali activator NU
Granular sodium metasilicate penta-hydrate (28.7 wt% Na2O, 28.5 wt% SiO2 and 42.8 wt%
H2O) was used as solid activator to activate the precursors. Usage of solid alkali activators in
geopolymer systems is less hazardous than commonly used liquid activators and more
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convenient for field applications. The amount of activator used was calculated to provide an
alkali content of 4% Na2O by mass of precursor materials.
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Aggregates
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A coarse basalt aggregate of 14 mm nominal particle size and river sand were used in the
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geopolymer concrete mix. The particle density of coarse aggregates and the sand in saturated
surface dry condition (SSD) was 2830 and 2620 kg/m3, respectively. The moisture absorption of
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coarse aggregates and the sand were 2.2 and 0.3% respectively.
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2.2.Preparation of geopolymer concrete

The mix designs for the geopolymer concretes employed in this work are shown in Table 2. The
concrete mixing procedures consistent of: Sand, coarse aggregate and precursor materials were
mixed thoroughly for 1 minute. Water was added to the mix and mixing was continued for
another 2 minutes. Alkali activator (solid form) was added into wet mix and mixed for around 7
minutes to obtain workable geopolymer concrete. The workability of geopolymer concrete mix
was measured using the standard slump test according to AS1012.3.1 [22]. The target slump was
80-100 mm.

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Two identical concrete prisms (95 × 95 × 300 mm) were cast from each, mix embedding a 20
mm diameter carbon steel rebar. A sample prism is shown in Figure 2. The concrete mixes were
also used to cast two cylindrical specimens (100×200 mm) for NT build 443 testings. The cast
specimens were transferred into a standard fog room (23°C, 100% RH). After 24 hours, concrete
specimens were de-moulded and stored inside fog room until 28 days. During the storing period
in the fog room, the samples were covered with plastic sheets to avoid the water dropping on the
sample.

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To identify the corrosion behaviour in contaminated concrete, 50/50 FA/Slag geopolymer

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concrete specimens were cast with added 2% NaCl by mass of binder and partially immersed in
water. The temperature during the immersion test was maintained at 23°C. An OPC concrete

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prism was also cast with added 2% NaCl by mass of binder as a control.
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Table 2: Mix design for concrete (Alkali content = 4% for geopolymers)

FA Slag OPC Aggregate (kg/m3) Water/

Mix Solid
(kg/m3) (kg/m3) (kg/m3)
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Sand 14mm 10mm ratio

60/40 FA/Slag 240 180 0 680 630 450 0.390
50/50 FA/Slag 200 200 0 680 630 450 0.425
40/60 FA/Slag 180 240 0 680 630 450 0.449
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OPC 0 0 400 680 630 450 0.464

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(a) (b)
Figure 2: (a) Specimens used for chloride induced corrosion testing (b) Gecor8 instrument

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2.3.Testing procedure

Chloride diffusion tests

After 28 days of moist curing at 23°C each concrete cylinder was segmented to three parts with
heights 51, 51 and 98 mm respectively. The curved surfaces of the cylindrical segments were
then coated with quick setting epoxy which prevented chloride transportation into the concrete
from the sides.

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Chloride diffusion coefficients of geopolymer and OPC concretes were measured using NT
Build 443 [13] method. The 98 mm cylindrical section was immersed in 2.826 M sodium

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chloride solution vertically such that approximately 1/4 of the height was submerged inside the

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solution. Cylindrical specimens were mounted on PVC rings in order to maintain uniform
chloride exposure through the bottom surface. The chloride solution was stirred frequently in
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order to have a uniform solution. After 5 weeks of immersion, the concrete specimens were
drilled in 1 mm depth increments using a profile grinder to obtain fine concrete powder from
each 1 mm layer (75 mm diameter circular area is drilled). The obtained concrete powder was
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dried at 105°C for 24 hours (powder was covered properly avoiding direct heat exposure).
Approximately, 5 g mass of the dried concrete powder was mixed with distilled water (1:5 solid
to water ratio) and HNO3. The resulting solution was boiled and filtered to extract the chloride
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ions from concrete powder. Potentiometric titration was conducted on the filtered solution using
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standard 1N AgNO3 solution to obtain the chloride content (acid soluble chloride) of each layer.
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The rapid chloride permeability of concretes was measured using ASTM 1202 standard [12]. In
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this test each ends of a 51 mm (2 inch) thick concrete disk is embedded between two cells each
fitted with a stainless steel mesh. One cell is filled with a 0.6 M NaCl solution and connected to
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the negative terminal and the other filled with 0.3 M NaOH solution. A DC potential of 60 Volts
is applied across the concrete specimen for 6 hours during which the current is recorded every 5
minutes, and the total charge after 6 hours is reported by the testing device. Chloride
permeability of geopolymer concrete was measured at three ages, namely 28 days, 180 days and
500 days.

Measurements of corrosion state of embedded rebar using electrochemical measurements

After 28 days of ambient curing at 23°C, the concrete prisms were partially immersed in 2.826
and 0.6 M NaCl solutions up to 500 days. Temperature of the storing room was 23°C. The

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corrosion rate meter was used to measure the corrosion current. It measures the corrosion current
over a confined length of steel bar, the half-cell potential (copper-copper sulphate) of the steel
and the electrical resistance of concrete. This instrument uses the “linear polarization” technique
and calculates the polarization resistance and obtains the corrosion current according to Stern
and Geary relationship [23].

Gecor6 instrument was used to measure the half-cell potential of embedded rebars with reference

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copper-copper sulphate electrode. As prescribed in ASTM C876 standard for Cu/CuSO4
reference electrode [24], the corrosion state of rebar can be assessed as follows: the half-cell

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potential < -200 mV (less negative) is an indication of 90% chance of having no corrosion while
if the potential<-350 mV (more negative) it is an indication of 90% probability of having

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corrosion (half-cell potential limits are marked in the figure). Previously it was also reported
that, if the corrosion rate is higher than 1 µA/cm2 it is an indication of a higher corrosion activity
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(high risk of corrosion). Instead, if the corrosion rate is in between 0.1 and 0.5 µA/cm2 it is a
sign for low to moderate corrosion activity [25].
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After 500 days, immersed concrete prisms were split to observe the corrosion state of embedded
rebar. Chloride penetration depth and chloride content at the rebar were calculated using
potentiometric titration [13].
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3. Results and Discussion

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3.1.Chloride diffusion rate of concrete in unsaturated condition

Corrosion due to chloride ingress is initiated when sufficient amount of chloride ions penetrate to
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the depth of reinforcement steel [7]. The resistance against chloride transportation into concrete
is quantified using the chloride diffusion coefficient [26]. To determine the rate of chloride
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diffusion into concrete NT build 443 test as described in section 2.3 was conducted. The
apparent diffusion coefficient of a concrete (Da mm2/year) can be calculated using the Fick’s
second Law of Diffusion. According to this law the relationship between the calculated chloride
content of concrete (C(t,x) ), and the depth from the exposed surface (𝑥) is as follows:

𝑥
𝐶(𝑡,𝑥) − 𝐶0 = (𝐶𝑆 − 𝐶0 )erfc⁡( )]
t (1)
√∫t 𝐷(𝑡) 𝑑𝑡
s

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Where CS ⁡ is the chloride concentration at the surface (x=0), C0 is the chloride concentration in
concrete before immersion and t is time in years and t s age of concrete when exposure started.
The chloride profile of concrete specimens obtained using the above procedure was then used to
calculate the chloride coefficient of each concrete type.

Figure 3 shows the chloride profiles obtained for the geopolymer and OPC concretes while Table
3 shows the calculated chloride diffusion coefficients. The chloride profile and the chloride

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diffusion coefficient results show that the chloride diffusion rate decreases significantly when the
slag content of the geopolymer binder is increased.

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Geopolymer concrete containing significant level of slag has the following main reaction

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products: calcium silicate hydrate (C-S-H), calcium aluminate silicate hydrate (C-A-S-H),
sodium aluminate silicate hydrate (N-A-S-H) and hydrotalcite phases [27-29]. When the slag
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content of the geopolymer blends increases, the resulting binder consists more C-S-H, C-A-S-H
than N-A-S-H and higher amount of hydrotalcite phases [27, 30]. It is known that C-A-S-H
products have higher a binding capacity for chloride ions (and accompanied Na ions) compared
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to N-A-S-H which can limit the ingress of those ions [27]. Hydrotalcite
(Mg6Al2(OH)16CO34H2O) has a layered double hydroxide structure. This layered crystal
structure consists of an outer layer with hydroxide and an inner layer with anions and water
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molecules [30-32]. Therefore, hydrotalcite has large specific area which increase its capability to
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exchange ions with the concrete pore solutions and absorb anions to its structure [32]. Previous
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studies have shown that the addition of hydrotalcite into a chloride contaminated system
externally result in the reduction of chloride content in the concrete without changing the
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structure of hydrotalcite [30, 33].

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The X-ray diffraction patterns on slag blended geopolymer show the indication of hydrotalcite
type phases with significant magnesium level in fly ash and slag based geopolymer which is also
confirmed in literature (Figure 13) [30]. Geopolymer containing lower slag content mainly
produces N-A-S-H type phases which have high pore volume [27, 28]. Provis et al.[34] and
Lloyd et al. [35] showed that increasing fly ash content, the porosity of the geopolymer is
increased significantly. They stated that geopolymer containing high slag content have high
bound water (induced by calcium) which leads to more pore-filling capacity than geopolymer
containing high fly ash [34]. This is in agreement with the studies by Yang et al. [36] and Li et

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al. [37]. Since fly ash based geopolymer has lower density than slag blended geopolymer, it can
absorbs more external chloride ions and deposit in the binder pore solution. Previously it has
been reported that geopolymers containing higher fly ash content (>50%) has halite (NaCl) in
their pore solution than that of high slag based geopolymers [27].

The chloride diffusion coefficients results in Table 3 also show that slag blended geopolymer has
higher resistance to chloride ingress compared to OPC based concrete. Geopolymer concrete

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containing significant level of calcium produces cross-linked tobermorite-like C-A-S-H which
are high density structures compared to non-cross linked tobermorite-like C-S-H phases formed

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in OPC concrete [38]. These cross linked structures reduce the chloride ingress in slag blended
geopolymer concrete compared to that of OPC concrete. OPC binder also contains calcium

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aluminates and calcium aluminoferrite phases that can absorb chloride ions forming
3CaO·Al2O3·CaCl2·10H2O (Friedel’s salt). However, the study by Florea and Brouwers [39]
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stated that Friedel’s salt formation in OPC binder is significant only in chloride contaminated
concrete during the initial hydration process. The Friedel’s salt formation after cement hydration
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is very slow hence this process would not be effective in absorbing chloride coming from the
external sources in the long term [40, 41]. This explains the higher chloride diffusion in OPC
concrete.
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Figure 3: Chloride profiles of concrete cylinders after 5 weeks of immersion test

Table 3: Chloride diffusion coefficient and surface chloride content of concrete

Geopolymer Surface Cl-. % Apparent chloride

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formulation (Cs ) (%wt. by diffusion coefficient (Da )

concrete mass) 10-12 m2/s
60/40 FA/Slag 0.80 5.17
50/50 FA/Slag 0.89 2.38
40/60 FA/Slag 0.81 1.01
OPC 0.80 6.70

Table 4 shows the chloride content (Cl-% by mass of concrete) at the different depth of
geopolymer and OPC concrete after 500 days immersion in 2.83 M NaCl solution. The results

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show that the chloride content of OPC concrete is higher than geopolymer concrete at all depths.
At the rebar (40 mm depth), OPC concrete has 0.070% chloride (by mass of concrete) which is

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above the threshold chloride value that initiates corrosion [42]. On the other hand, geopolymer
concrete shows 10 times lower chloride content at the rebar after 500 days which is not sufficient

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to initiate chloride induced corrosion. NU
The resistance to chloride ingress rate into concrete is reduced upon aging of the geopolymer
concrete. It is well known that chloride diffusion rate of OPC concrete decreases with the age of
concrete as a result of chloride binding and refinement in the pore structure [43]. It was reported
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that a 1 day old OPC binder has pore size range 8 nm to 700 nm while more than 365 days old
OPC binder has pores in the range of 16 nm to 64 nm [43] which significantly affects the
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chloride diffusion coefficient of concrete. Ignoring this effect can result in overestimation of the
chloride penetration rate [44]. Resistance to chloride ingress into concrete can vary due to
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modified microstructure and additional reaction products formed during extended curing.
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Geopolymerisation is a continual reaction process that can have different microstructure and new
reaction phases in the later stages compared to premature age of concrete. Puertas et al. [29],
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showed that when blended fly ash and slag geopolymer matures, FTIR (T-O-T T: tetrahedral Si
or Al) band shifted towards a higher value indicating higher degree of cross-linking in
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geopolymer than in early age concrete. This is attributed to the continual development of N-A-S-
H and C-A-S-H cross-linking and increase of number of reaction products. Their results are in
agreement with several other studies [45, 46].

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Provis et al. [34] reported that longer curing of blended fly ash and slag geopolymer increases
the pore-network tortuosity and decreases the porosity due to space filling nature of C-(N)-S-H
phases. Xu et al. [45] reported that in the presence of slag, geopolymerisation is continual as slag
provides hydroxyl buffering to react with the precursors in the later age. Moreover, the authors
found that channels in the pore structure are disconnected due to maturity of geopolymer
concrete. These studies show that resistance to chloride ingress into concrete is expected to be
lower in the later age of geopolymer concrete. In the next section, the age factor of geopolymer

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concrete will be quantified and analysed the factors affecting it.

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Table 4: Chloride percentage in the different depth of concrete after 500 days of immersion in
2.83 M NaCl solution

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Measured
Average depth
Concrete type chloride (%wt. by
of the concrete (mm)
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concrete mass)
1 0.880
15 0.300
50/50 FA/Slag
35 0.020
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40 0.007
1 0.989
OPC 15 0.364
35 0.299
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40 0.077
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3.2.Properties of geopolymer concrete

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3.2.1. Compressive strength

Figure 4 (a) and (b) show the compressive strength development of 60/40 FA/Slag, 50/50
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FA/Slag and 40/60 FA/Slag geopolymers. 40/60 and 50/50 FA/Slag based geopolymers showed
the highest strength during first year. 60/40 FA/Slag based geopolymer had the maximum
strength at 100 days and thereafter compressive strength is slightly reduced. Ismail et al. [47]
found that the main reaction phase in geopolymer with slag percentage in the range of 50-100%,
is calcium silicate hydrated gel (C-S-H) and calcium aluminate silicate hydrate (C-A-S-H).
Moreover, in these binders, the number of reaction product formations and degree of cross-
linking increased with extended curing time. The geopolymer with lower than 50% slag has a
combination of C-A-S-H and N-A-S-H reaction products, and the reaction product formation and

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development of additional cross-linking of the geopolymer is slower compared to geopolymer

containing higher slag (>50%). This reveals that geopolymer concrete synthesised using fly ash
and slag under ambient curing has stable compressive strength within the test period of two
years. Higher compressive strength indicates the denser microstructure that has lower gas
permeability. Therefore, oxygen cannot be penetrated into concrete and the level of rebar.

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Figure 4: Compressive strength development of fly ash and slag blended geopolymers

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3.3.Quantifying the age factor for geopolymer concrete

The influence of the age on the chloride diffusion coefficient is an important parameter for
service-life modelling of any concrete structure [48]. The chloride diffusion of concrete D(t)
varies with the time as shown in the equation (2) [48]:

ts
D(t) = Dref [ ]m (2)
t

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Where, 𝒎(> 𝟎) is the age factor, 𝐃𝐫𝐞𝐟 is the chloride diffusion rate obtained using NTBuild 443
test (Table 3) and⁡𝐭 is exposure time in years and 𝐭 𝐬 age of concrete when exposure started.

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Rapid permeability test results at several ages of concrete can be used to obtain the value of
𝐦(> 𝟎) for concrete. The rapid chloride permeability test (RCPT) ASTM C1202 [12] provides

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information on the instantaneous chloride diffusion of concrete as it is conducted within a short
period of time (6 hours), whereas NTBuild 443 [12] test involves 35 days immersion period.
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Previous studies have shown that the changes in RCPT results upon aging would reflect the
changes in the chloride diffusion change [49, 50]. In order to calculate the ′𝐦′⁡factor of concrete,
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rapid chloride permeability of concrete was conducted at three ages of concrete (i.e. 28, 180 and
500 days) and total charges passed through the concrete is calculated according to the procedure
described in section 2.3 [26, 51]. The charges passed through concrete obtained from ASTM
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C1202 [12] test method is used to calculate the 𝐦⁡factor as shown in the equation (8) [52, 53].
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G(t) = G0 t −m
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(3)

Where G(t)= charge passed through concrete at age t of concrete, GO = charge passed through
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concrete at age⁡t o .

Figure 5 shows the charges passed through concrete at different ages of concrete. The results
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show that the charges passed through 28 days old geopolymer concrete is in the range of 1000-
2000 Coulumb which is classified as low permeable concrete [12]. Even though, 28 days old
OPC concrete can be also classified as low permeable concrete, the number of charged passed
through OPC concrete is slightly higher than the corresponding value for geopolymer concrete.
At 180 days, the charges passed through geopolymer concrete are significantly lower than in 28
days. This changes the permeability classification of geopolymer concrete to “very low”
permeable concrete range [12]. The charges passed through geopolymer concrete after one year
is only slightly lower than that at 180 days. All the geopolymer concretes reached to the same

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level of permeability level after one year, with charges passed through concrete being 300-330
Columb. On the other hand, the 180 days old OPC concrete had the same permeability category
(low) as the 28 days old OPC concrete. When the OPC concrete was older than one year the
change in the permeability level was not significant.

The calculated age factors are presented in Table 5. The results show that the age factor of
geopolymer concrete is in the range of 0.40-0.60. On the other hand age factor of OPC concrete

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is only 0.192 which is half of the age factor of geopolymer concrete. The value obtained for
100% OPC concrete is similar to the values reported in previous studies [53, 54]. This shows

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aging improves the resistance of geopolymer concrete for chloride diffusion more significantly
than for OPC concrete. As mentioned previously, when fly ash and slag geopolymer concrete

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matures, a higher degree of cross-linked structure is achieved than in early age, more reaction
products (like hydrotalcite) are formed from unreacted fly ash and slag particles and pore
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structure of the binder is refined [27, 30, 34]. The combination of these parameters reduced the
chloride diffusion of the concrete upon aging at a higher rate than for OPC concrete. Even
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though the pore structure is refined upon aging of OPC binder, not as much additional products
are formed for binding chloride [40, 41, 43] in turn a lower age factor is obtained.

Previous studies [55, 56] have reported that, when used on geopolymer binders, the outcome of
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the RCPT test is greatly influenced by the ion mobility of the pore solution rather than the
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chloride permeability. However, current study found that RCPT results correlates well with the
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chloride induced corrosion.

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Figure 5: The change of charged passed through concrete for concrete specimens of different
ages NU
Table 5: Age factor of concrete

Mix proportions Age factor of concrete (m)

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60/40 FA/Slag 0.407

50/50 FA/Slag 0.604
40/60 FA/Slag 0.509
OPC 0.192
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3.4.Service life prediction of concrete

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Evaluation of the time to initiate corrosion on the embedded rebar in concrete is essential in
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modelling the service life of concrete structures. The results in Table 4 and the state of rebar
(section 3.3) show that in OPC corrosion has initiated at a chloride level of 0.077% by mass of
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concrete. This chloride level has also been identified as the threshold level of the chloride to
initiate corrosion process in rebar embedded in OPC concrete [42].
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Assuming the same threshold level for geopolymer concrete, the time taken to initiate the
corrosion can be calculated using the equations Fick’s Law [57]. The following assumptions are
used in the calculation of the corrosion initiation time.

1. The threshold chloride level for the initiation of the steel corrosion is 0.077% by weight
of concrete.
2. The diffusion rate only changes during the initial 10 years. There after it is assumed to be
constant [53].

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The results presented in Table 6 shows the time taken to initiate chloride induced corrosion when
the cover thickness of concrete is 25 and 40 mm and the environment chloride concentration is
2.826 M. According to the calculations, OPC concrete initiates corrosion in 0.69 years which is
consistent with the observations. OPC concrete takes 1.95 years to initiate corrosion when the
cover thickness is 40 mm.

On the other hand geopolymer concrete has very high corrosion initiation time, particularly the

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geopolymer concrete containing higher slag (>50%). The time taken to initiate chloride induced
corrosion is increased with the slag content in the geopolymer concrete. This results show that

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geopolymer concrete structures would have higher service life in chloride environment compared
to OPC concrete structures. It should be noted that a typical marine environment has a chloride

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concentration of around 0.6% which is approximately a quarter of the concentration used for the
calculations (2.8%). Therefore, the initiation time will be much longer. The corrosion state of the
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rebar is consistent with the chloride calculations.

Table 6: Number of years to reach chloride level of 0.077% in 2.826 M NaCl solutions.
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(Chloride (%) = mass of chloride/ concrete mass)

Number of years to reached 0.077%

Mix
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chloride in different concrete depths

proportions
25 mm 40 mm
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60/40 FA/Slag 1.28 5.26

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50/50 FA/Slag 7.87 37.28

40/60 FA/Slag 13.19 41.39
OPC 0.69 1.95
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Results presented in the previous section showed that chloride diffusion in blended fly ash and
slag geopolymer concrete is lower than in OPC concrete. Therefore, the initiation time for
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corrosion is expected to be longer in geopolymer concrete than in OPC. To determine the

corrosion state of the rebar, the specimens which had been immersed in the 2.826 M NaCl
solution for 500 days were split, and immediately 0.1M AgNO3 solution was sprayed to measure
the chloride penetrated depth, based on the depth of white colour observed due to formation of
AgCl. In general, when the chloride content of concrete is in the range 0.02-0.23, the colour
change is observed [58, 59]. Figure 6 shows the concrete samples after spraying AgNO3 solution
and Table 7 shows the measured chloride penetrated depth of concrete obtained from AgNO3.
The depth obtained using AgNO3 colorimetric method is based on the apparent chloride content

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of the concrete. Geopolymer concrete immersed in 2.826 M NaCl solution has very low chloride
penetrate depth (lower than 5 mm). Moreover, when the geopolymer concrete prisms were
immersed in 0.600 M NaCl solution, apparent chloride penetration depth is further reduced to 2
mm. On the other hand, OPC concrete immersed in 2.826 M and 0.600 M NaCl solutions
showed 35.0 mm and 18.0 mm chloride penetration depth respectively which is significantly
higher than that of geopolymer concrete samples. Since all the geopolymer concrete types had
similar corrosion and chloride penetrated depth, only the 50/50 FA/Slag geopolymer concrete

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was samples are shown in the Figure 6.

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(a) (b)
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(c) (d)
Figure 6: Chloride penetration depth of concrete (a) 50/50 FA/S geopolymer immersed in 2.832
M NaCl solution (b) 50/50 FA/S geopolymer immersed in 0.6 M NaCl solution (c) OPC concrete
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immersed in 2.826 M NaCl solution (d) OPC concrete immersed in 0.6 M NaCl solution

Table 7: Depth of chloride obtained from AgNO3 colorimetric method

Depth in 2.826 M Depth in 0.6 M NaCl

Sample ID
NaCl solution (mm) solution (mm)
60/40 FA/S 4.2 1.2
50/50 FA/S 4.0 2.5
40/60 FA/S 4.1 1.8
OPC 35.0 18.0

3.5.Corrosion state of rebar

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Figure 8(a) and Figure 8(b) respectively show half-cell potential and corrosion current of
embedded rebar. The electrochemical indicate that embedded rebar in geopolymer concrete has
90% probability of having corrosion which is not consistent with the actual corrosion state of the
rebar. 50/50 FA/S geopolymer has half-cell potential around -700 mV consistently in entire
measuring period. Furthermore, rebar in 60/40 FA/S shows the half-cell potential around -600
Mv. Rebar in OPC concrete shows the half-cell potential -200 mV which is an indication of
uncertainty in corrosion. 40/60 FA/S geopolymer also shows high negative value that indicates

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corrosion activity. In the previous section, it has been observed that chloride was not reached to
the level of the rebar in geopolymer concrete while chloride was reached to rebar level in OPC

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concrete when they are in 2.83 M NaCl solution.

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Half-cell potential and corrosion current of embedded rebar in geopolymer concrete when they
are immerged in 0.6 M NaCl solution shows scattered behaviour (Figure 8). Rebar in OPC
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concrete shows lower negative half-cell potential than the samples in 2.83 M NaCl solution.
Despite the fact the chloride is not reached to the level of rebar for initiating corrosion, the
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corresponding half-cell potential for embedded rebars in geopolymer concrete pushed towards
high negative values (>-300 mV). Slag blended geopolymer release sulphide ions into pore
solution of concrete leading significant reduction in redox potential. Slag-rich blends can reduce
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100 mV of rebar in OPC concrete to minus 200-225 mV [Glaser, 1988 #58]. The similar
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observations were made by Yeau and Kim [60] for the half-cell potential in slag blended OPC
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concrete. They stated that sulphur species in slag-rich binders (S2-, SO3- and S2O32-) resulted
higher negative half-cell potential in embedded rebar. The half-cell potential of slag blended
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geopolymer concrete is also high negative. The actual corrosion state of the embedded rebar in
slag blended geopolymer concrete is not consistent with the half-cell potential. Half-cell
potential of rebar embedded in OPC when immerge in 2.83 M NaCl solution, indicates
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uncertainty in corrosion. It has been observed that the embedded rebar is initiated to corrode.
Corrosion state can be seen in the Figure 9 and Figure 10.

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(a)

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(b)
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Figure 7: Corrosion state of embedded rebar when concrete is immersed in 2.826 M NaCl
solution (a) half-cell potential (b) corrosion rate
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(a)

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(b)

Figure 8:Corrosion state of embedded rebar when concrete is immersed in 0.6 M NaCl solution

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(a) half-cell potential (b) corrosion rate

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Figure 9 shows the corrosion state of rebar inside 50/50 FA/Slag geopolymer and OPC concrete
after immersion in 2.826 M NaCl solution. Rebar inside geopolymer concrete retained its
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passivity after 500 days (Figure 9(b)), while chloride induced corrosion was initiated in rebar
embedded in OPC and rust products are evident in Figure 9(d). No rust products formed in either
geopolymer concrete or OPC concrete for immersion in 0.6 M NaCl solution for 500 days
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(Figure 10). This shows that the corrosion state based on the electrochemical measurements and
the corrosion activity observed in the rebar do not have direct relationship. Therefore, the
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electrochemical measurements can over-estimate the corrosion of embedded rebar in geopolymer

concrete.
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(a) (b)

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(c) (d)
Figure 9: (a) geopolymer concrete with rebar (b) embedded rebar in geopolymer concrete (c)
OPC concrete with rebar (d) embedded rebar in OPC concrete immersed in 2.826 M NaCl

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(a) (b)
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(c) (d)
Figure 10: (a) geopolymer concrete with rebar (b) embedded rebar in geopolymer concrete (c)
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OPC concrete with rebar (d) embedded rebar in OPC concrete immersed in 0.60 M NaCl

3.6.Corrosion rate of rebar embedded in chloride contaminated geopolymer concrete

As observed in the previous section, the chloride ions take a long time to reach the embedded
rebar in geopolymer concrete. Therefore, to accelerate the chloride induced corrosion the authors
prepared specimens with added chloride. The half-cell potential and corrosion current of
embedded rebar was measured using Cu/CuSO4 (CSE) reference electrodes [61].

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Again half-cell potential of embedded rebar in geopolymer concrete is higher negative than that
of embedded rebar in OPC concrete (Figure 11(a) and (b). This is an indication of severe
corrosion activity in embedded rebar in geopolymer concrete. The corresponding corrosion
current for the rebar inside 50/50 FA/Slag geopolymer concrete is lower than the current
obtained for rebar in OPC concrete [25]. According to electrochemical measurements, embedded
rebars in both types of concrete expected to have corrosion.

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Figure 12 shows the corrosion products of the rebar embedded in contaminated concrete. Figure
12(a) and (c) show the corrosion products in rebar embedded in OPC concrete. The rebar

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embedded in OPC shows significant corrosion activity after 150 days while the rebar embedded
in geopolymer concrete does not show any pitting corrosion products. As observed in previous

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section, electrochemical measurements obtained for the rebar in contaminated geopolymer
concrete misinterpret the corrosion state.
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Slag rich concrete has high content of sulphide species (S2- and S2O32-) in the concrete pore
solution [14, 20, 62]. These sulphide ions can oxidize into sulphur consuming locally available
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oxygen [14, 62]. The absence of oxygen in the rebar inhibits the cathode reaction in turn the
corrosion is controlled. Ma et al. [14] reported higher sulphide ion concentration in the slag
based geopolymer concrete pore solution than OPC concrete which leads to reduction in the
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embedded rebar. Hollway et al.[62] concluded that oxidation of sulphide ions inot sulphur
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prevents potential rising into the pitting regimes which inhibits the oxygen cathode reaction.
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(a) (b)
Figure 11: (a) Half-cell potential (b) Corrosion current of rebar in chloride contaminated
geopolymer and OPC concrete

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(a) (b)

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(c) (d)

Figure 12: Corrosion state of rebar embedded in chloride contaminated concrete (a) rebar in OPC
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closer image (b) rebar in 50/50 FA/Slag geopolymer closer image (c) rebar in OPC (d) rebar in
50/50 FA/Slag geopolymer after 150 days
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3.7 XRD patterns of geopolymer

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The XRD patterns of the blended fly ash and slag geopolymer binders at two ages i.e. 28 and 270
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days are shown in Figure 13. The results show that geopolymer binders containing higher than
50% slag have C-S-H phases indicated by the peak at 29°2θ. C-S-H has a disordered structure
similar to riversideite and do not have 3-dimensional cross linking.
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When the Fly ash percentage is increased beyond 50% the resulting binders show a peak
corresponding to N-(C)-A-S-H type garronite phases and N-A-S-H type zeolite crystalline
phases. The high fly ash binders also showed a hump between 25-30°2𝜃 corresponds to the
amorphous geopolymer gel. The XRD patterns at 28 days also show the presence of crystalline
phases corresponding to unreacted particles from the original fly ash (mullite, quartz, and
hematite). However, at 270 days, the height of these peaks decreased indicating continual
geopolymerisation reaction.

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Above XRD results shows that geopolymers containing higher slag content produce higher
content of calcium bearing phases including disordered calcium silicate hydrate phases. These
phases do not have 3-dimensional cross linking like N-A-S-H phases which are produced in high
fly ash binders. The disorderly structure in high slag binders can be easily attacked by
chemically.

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(a)
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(b)
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(c)

Figure 13: XRD patterns of geopolymer binders (a) 70/30 FA/S (b) 50/50 FA/S (c) 30/70 FA/S

4. Conclusions
On the basis of obtained results, the following concluding remarks can be drawn:

1. Apparent chloride diffusion coefficient of blended fly ash and slag geopolymer concrete is

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lower than that of OPC concrete. The diffusion coefficient decreased with the slag content
in the binder.

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2. Blended fly ash and slag geopolymer concrete has higher age factor than in OPC concrete
indicating improved resistance to chloride ingress with time. The lower permeability is

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attributed to the higher binding capacity in the hydrolacite phases and higher degree of
geopolymerisation in blended fly ash and slag which have been reported in the literature.
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3. The time taken to initiate the corrosion in the rebar in blended fly ash and slag geopolymer
concrete is significantly higher than that of OPC concrete. The time is longer when the slag
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in the geopolymer is higher.

4. Chloride induced corrosion started in the rebar in OPC concrete exposed to 2.826 M NaCl
solution for 500 days while the blended fly ash and slag geopolymer concrete bar did not
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corrode. The chloride content at the rebar in geopolymer is ten times lower than chloride
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content in OPC concrete. The results are consistent with the calculated initiation time.
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5. Geopolymer concrete containing slag provides greater protection against reinforced

corrosion than that of OPC concrete when concrete is contaminated with chloride. This is
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due to reduction in oxygen around the rebar in the presence of slag in the binder (which
has been confirmed by the previously reported work).
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6. Electrochemical measurements (i.e. Half-cell potential and corrosion current) of the

embedded rebar in geopolymer concrete do not correlate well with the corrosion activity.

Acknowledgements
The authors gratefully acknowledge the financial support provided by Austroads.

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MA
E D
PT
CE
AC

35
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Graphical Abstract

PT
RI
SC
NU
MA
DE
PT
CE
AC

36