Reproduced from the proceedings of the 14th fib International PhD Symposium in Civil Engineering

- 5-7 September 2022 - Rome, Italy , page NUMBER 241- “ Paper « Prediction of the time of corrosion
initiation of reinforced geopolymer concrete hollow piles»: with permission from the International Federation
for Structural Concrete (fib).
Prediction of the time of corrosion initiation of
reinforced geopolymer concrete hollow piles
Ali Abdulhasan Khalaf1 and Katalin Kopecskó1
1Department of Engineering Geology and Geotechnics ,
Budapest University of Technology and Economics,
Műegyetem rakpart 3, Budapest 1111, Hungary

Abstract
Geopolymer concrete can be a solution in the future as a sustainable green construction material due to
its low carbon footprint. Therefore, it is vital to understand its durability in a severe environment such
as chloride exposure. The related data are collected from the peer-reviewed literature and analysed for
the binding capacity of chloride ions and apparent diffusion coefficient. The binding capacity shows a
concise increase by increasing slag content when ground granulated blast furnace slag, GGBFS, is
added to fly ash geopolymer concrete. On the other hand, the binding capacity fluctuates in a wide
range when fly ash is used alone due to the absence of chemical binding in this case. The apparent
diffusion coefficient results are analysed to its mixing and exposure variables. The relative apparent
diffusion coefficient, RDa, with respect to Portland cement has been introduced to eliminate the varia-
bility of exposure type and time. According to the literature, the remaining variables are the same as
the compressive strength, CS, variables. However, samples with comparable CS values show signifi-
cantly different relative apparent diffusion coefficient values as a result of the difference in the slag
content in the mixture. Therefore, it is concluded that the primary role in the chloride resistance is
played by slag content.Furthermore, a statistical model of RDa have been proposed and utilised to pre-
dict the time of the corrosion initiation of reinforced geopolymer concrete hollow piles based on three
simple parameters: GGBFS%, CS, and alkali activation solution-binder ratio (AAS/B).

1 Introduction
Reinforced concrete hollow piles are highly preferred to be used in marine structures, including piers,
bridges, since they have a higher bearing capacity and better adaptability to foundation soils than the
traditional piles [1]. From a sustainable point of view, cement manufacturing involves high carbon
dioxide emission (CO2), which are very harmful to the environment. As a result, researchers have been
seeking alternatives that have less impact on the environment. One of the most promising alternative
materials is geopolymer [2]. The source of geopolymer binders can be natural, by-product or synthetic
amorphous aluminosilicate. The idea of geopolymerisation is that the chemical reaction between alu-
minosilicate oxides and alkali polysilicates produces polymeric (Si-O-Al) bonds of amorphous to semi-
crystalline three-dimensional silico-aluminate structures [2,3]. Evidently, since Portland cement con-
crete practice manuals and design codes have been established over decades, most cement alternatives
at the first stage are compared with cement properties to examine their validation [4–6]. Portland ce-
ment concrete is widely used in construction mainly due to its exceptional durability. However, material
design and practice limitations can lead to concrete deterioration, especially under severe exposure
conditions such as marine surroundings [4]. When concrete is exposed to such severe environments, it
will be vulnerable to some deterioration induces, and one of the most critical deterioration factors is
chloride-induced pitting corrosion of steel reinforcement. Ingress of chloride ions upto the steel rein-
forcement will destroy the passive protective layer and leave steel susceptible to pitting corrosion.
Therefore, it is quite acceptable to govern the concrete durability by the resistance to the penetration of
chloride ions [4,7]. There are three groups of chloride ions involving the chemical attack of concrete:
free, bound, and total chloride ions. Free chloride is the type responsible for the initiation of reinforcing
steel corrosion. The free chloride is dissolved in the pore water of concrete. The bound chloride can be
physically bound to the pore walls of cement stone or chemically bound with hydrates or ion exchange
binding. It is believed that the free and bound chlorides are in equilibrium, and the concentration of free
chloride is equal to the concentration in the surrounding environment. The total chloride content is
equal to the sum of free and bound chloride [8].

Proc. of the 14th fib International PhD Symposium in Civil Engineering 1

Sep. 5 to 7, 2022, Rome, Italy
14th fib International PhD Symposium in Civil Engineering

According to the ASTM C1556 standard results [9], the primary chloride binding is the reaction
product of mixtures containing ground granulated blast furnace slag (GGBFS). Ismail et al. [10] studied
GGBFS, fly ash, and different percentages of GGBFS/fly ash geopolymer concretes and mortars. The
mortar samples are mixed with a w/b ratio of 0.4 and cured at 30 ºC. The period of immersion was 180
days of 3.5% NaCl solution. The binding capacities of all geopolymers were comparable to Portland
cement concrete. Furthermore, Lee and Lee [11] inferred that increasing the slag content decreased the
binding capacity for geopolymer paste samples with the immersion period of 28 and 91 days of a 10%
NaCl solution. Tittarelli et al. [12] studied the binding capacity under wet-dry cycles of fly ash and
metakaolin geopolymer mortars for 12 weekly cycles in a 3.5% NaCl solution. The curing temperature
was 20 ºC. The specimens were in three classes of strength R1 <10 MPa, R2 < 15 MPa and R3 < 20
MPa. Only R3 is a structural class. The geopolymer specimens show no binding capacity except for the
R2 class. Therefore, statistical analysis of all published results in the peer-reviewed literature will pro-
vide a comprehensive understanding of the relationship between chloride binding capacity and GGBFS
content.
The diffusion process occurs when there is a concentration gradient, and concrete provides a con-
tinuous liquid phase [8]. "The chloride diffusion coefficient defines the capacity of any specific con-
crete to resist chloride penetration and is used to predict the service life of reinforced concrete struc-
tures" [13]. Therefore, the apparent (steady state) diffusion coefficient of chloride was taken as a repre-
sentative to evaluate the chloride ingress resistance of geopolymer concrete in this study. The apparent
diffusion coefficient of concrete is determined by the relationship between chloride content (C (t, r))
and the radius of the exposed surface (r). There are many methods to evaluate C (t, r), such as NT Build
443 [14] or ASTM C1556 [9] tests, which have similar procedures [15].
The study aimed to prove the correlation between the chloride binding capacity of geopolymer
concrete and GGBFS content. Since there was no proposed model in the literature to evaluate the chlo-
ride ion ingress resistance of geopolymer concrete, the goal has been extended to construct a statistical
model to predict the resistance against chloride ingress in geopolymer concrete based on the GGBFS
content and compressive strength (CS) as a percentage of the chloride ion ingress resistance of Portland
cement concrete. Furthermore, the proposed model is used in an analytical model to predict the time of
the corrosion initiation of reinforced geopolymer concrete hollow piles (RGPCHP) by determining an
additional simple parameter of geopolymer concrete (alkali activation solution-binder ratio, AAS/B).

2 Data description

2.1 Chloride binding capacity data

The relevant data have been collected from the peer-reviewed literature [10–12,15–17] to obtain 22
samples. The chloride binding capacity of geopolymer (GPBC), chloride binding capacity of Portland
cement corresponding to the assigned geopolymer (PCBC), and GGBFS content are statistically ana-
lysed to calculate the statistical parameters such as mean median range and standard deviation (STD).
The statistical summary are shown in Table 1. Since there was a high range of variability in the immer-
sion period, conditions, and type of testing, a new parameter is introduced in this research based on the
corresponding chloride binding capacity of Portland cement calculated by Eq. (1).

Table1 Chloride binding capacity data and statistical summary.

Variable
GPBC (%) PCBC (%) GGBFS (%)
Statistical parameter

Mean 42.5 35.4 15.9

Median 33.7 30.6 0.0
Range 94.4- 0.0 95.5- 9.7 100.0- 0.0
STD 40.2 29.1 28.3

𝐺𝑃𝐵𝐶
𝑅𝐵𝐶 = ∗ 100% (1)
𝑃𝐶𝐵𝐶

2 Durability and materials

 Prediction of the time of corrosion initiation of reinforced geopolymer concrete hollow piles

where RBC is the relative binding capacity in percentage; GPBC is the geopolymer
chloride binding capacity; PCBC is the Portland cement chloride binding capacity.

2.2 The apparent chloride diffusion coefficient data

In a similar manner to chloride binding capacity, 42 samples have been collected from the peer-re-
viewed literature [10,15,17–25] [14,19,21,25-32] to investigate the apparent diffusion coefficient. The
statistical summary of the apparent diffusion coefficient of geopolymer concrete, the corresponding
apparent diffusion coefficient of Portland cement concrete, and the cylindeical compressive strength
(CS) of geopolymer concrete are shown in Table 2. The relative apparent diffusion coefficient (RDa)
has also been introduced here to overcome the high variability in the exposure conditions as follows:
𝐺𝑃𝐷𝑎
𝑅𝐷𝑎 = ∗ 100% (2)
𝑃𝐶𝐷𝑎

where RDa is the relative apparent diffusion coefficient in percentage; GPDa is the geopolymer concrete
apparent diffusion coefficient; PCDa is the Portland cement concrete apparent diffusion coefficient.
Moreover, by looking at the other variables to the literature, it can be inferred that these variables
are the same that control CS of geopolymer concrete [26–28]. As a result, CS has been taken as a
representative for the other variables and their effect on RDa.

Table 2 Chloride apparent diffusion coefficient data statistical summary.

Variable GPDa PCDa GGBFS CS

Statistical parameter *10-12 m2/s *10-12 m2/s % MPa

Mean 35.1 16.0 26.6 44.4

Median 9.3 9.5 5.0 43.4
Range 215.0-0.01 71.3- 0.95 100.0- 0.0 68.0- 21.5
STD 54.7 20.3 35.5 11.7

3 Results and discussion

3.1 Relative chloride binding capacity of geopolymer concrete

The curve fitting tool in Matlab software has been run to evaluate the best curve fitting between RBC
and GGBFS content. The fourth degree polynomial is found to have the best description of the relation-
ship between RBC and GGBFS with a positive correlation. Generally, increasing the GGBFS increases
the RBC. Moreover, the evidence from the literature stated that the binding capacity of fly ash geopol-
ymer concrete is considered highly disturbed physical binding [17]. Furthermore, another study con-
cluded that 10% of GGBFS was not enough to improve the chloride ingress resistance of geopolymer
concrete [19]. Therefore, the samples with high RBC that fulfilled the abovementioned conditions have
been excluded and considered outliers in the curve fitting process. The goodness of fitting was evalu-
ated based on the root mean squared error (RMSE = 20.47 %) and determination coefficient (R 2 =
0.8251). Therefore, the correlation between RBC and GGBFS content is clearly strong as depicted in
Fig. 1. It can be inferred that increasing GGBFS increases RBC. Due to limited data on chloride binding
capacity, the GGBFS content can be used to replace it in the investigation of chloride ingress resistance
of geopolymer concrete. The relationship is represented by Eq. (3):

𝑅𝐵𝐶 = 1.503 ∗ 10−6 ∗ 𝐺𝐺𝐵𝐹𝑆 4 + 5.566 ∗ 10−5 ∗ 𝐺𝐺𝐵𝐹𝑆 3 − 0.051 ∗ 𝐺𝐺𝐵𝐹𝑆 2

(3)
+ 3.877 ∗ 𝐺𝐺𝐵𝐹𝑆 + 13.04

Ali Abdulhasan Khalaf1 and Katalin Kopecskó1 3

14th fib International PhD Symposium in Civil Engineering

Fig. 1 Correlation between RBC and GGBFS content.

3.2 Relative apparent chloride diffusion coefficient of geopolymer concrete

RDa has been analysed by the curve fitting tool in Matlab software with respect to GGBFS content and
CS simultaneously. After investigating all possible relationships, the polynomial fourth degree and
quadratic were the best performance to describe the relationship between RDa as a dependent variable
and GGBFS content and CS, respectively, as depicted in Eq. (4):

𝑅𝐷𝑎 = 𝑝00 + 𝑝10 𝐺𝐺𝐵𝐹𝑆 + 𝑝01 𝐶𝑆 + 𝑝20 𝐺𝐺𝐵𝐹𝑆 2 + 𝑝11 𝐺𝐺𝐵𝐹𝑆 ∗ 𝐶𝑆 + 𝑝02 𝐶𝑆 2 +
𝑝30 𝐺𝐺𝐵𝐹𝑆 3 + 𝑝21 𝐺𝐺𝐵𝐹𝑆 2 ∗ 𝐶𝑆 + 𝑝12 𝐺𝐺𝐵𝐹𝑆 ∗ 𝐶𝑆 2 + 𝑝40 𝐺𝐺𝐵𝐹𝑆 4 + 𝑝31 𝐺𝐺𝐵𝐹𝑆 3 ∗ (4)
𝐶𝑆 + 𝑝22 𝐺𝐺𝐵𝐹𝑆 2 𝐶𝑆 2

where GGBFS and CS is normalised by their means and standard deviations. The model and the good-
ness-of-fit parameters are shown in Table 3.

Table 3 Model and the goodness of fitting parameters.

95% Confidence interval
Parameter Estimate
Lower bound Upper bound
p00 190.3 100.4 280.2
p10 -250.9 -380.8 -120.9
p01 -38.04 -175.2 99.1
p20 -134.5 -275.7 6.8
p11 20.16 -37.1 77.5
p02 -19.64 -86.8 47.5
p30 280.0 73.2 486.8
p21 53.6 -137.1 244.3
p12 13.5 -44.2 71.2
p40 -83.59 -158.8 -8.4
p31 -29.3 -111.9 53.3
p22 -4.9 -50.9 41.2
Goodness of fitting
R-square Adjusted R-square RMSE
0.6106 0.4916 65.74 %

4 Durability and materials

 Prediction of the time of corrosion initiation of reinforced geopolymer concrete hollow piles

Fig. 2 The response surface for the RDa model. Fig. 3 The contour map of the RDa model.

The response surface for the RDa model is depicted in Fig. 2. At 0% of GGBFS (only fly ash geopo-
lymer concrete), the RDa was generally higher than 100.0 %. However, there were regional decreases
at very low compressive strength and very high compressive strength, which are very different from
the behaviour of Portland cement concrete in such a way that increasing compressive strength reduces
the PCDa [29].There is evidence from the literature that reports that the chloride binding capacity of the
fly ash geopolymer depends on the compressive strength class [12]. For fly ash-GGBFS blended geopo-
lymer concrete, there were three main surface regions. The first surface region underwent high RD a,
even higher than only fly ash geopolymer, which is designated with low GGBFS content up to 37.5%
to achieve 100.1 of RDa value as shown in Fig. 3.

The calculated value of RDa corresponding to 40 % of GGFBS content from the literature [21] was
found 77.2. The GGBFS values of 39.58 % and the 40.0% and RDa values of 80.78 and 77.2 for the
proposed model and calculated based on the literature, respectively, are not far from each other, but
they are comparatively in the same vicinity, taking into consideration that increasing the GGBFS con-
tent reduces the RDa. The effect of CS in this region is that increasing CS decreased the RDa slightly
until it reached 65.0 MPa of CS, as shown in Fig. 3. The second surface region is where the minimum
RDa is achieved. The GGBFS content in this region is in the interval [53.0 – 80] to produce a minimum
RDa range. These results are confirmed by the literature [24] that reported a significant shift in the
apparent diffusion coefficient after 50.0 % of GGBFS. The effect of CS strength in this region was
opposite to that of the first region. Increasing the CS increased the RDa values slightly. The third region
is where the GGBFS precursor is dominant. The RDa values showed a continuous increase as the
GGBFS content. This behaviour has been explained by Davidovit [30], who stated that GGBFS alkali-
activated concrete is exposed to alkali cation leaching, which could reduce chloride ingress resistance.
The effect of CS in this region is that increasing CS reduced the RDa values. CS had only an obvious
influence on RDa results in the first and second stages, where GGBFS% was between (0-37.5). The
reason behind these results can be related to the changing of the gel formation in the geopolymer matrix
when GGBFS increased to produce coexistence of N-A-S-H and C-S-H gel types [31].

3.3 The analytical model for the time of the corrosion initiation stage
The time of the corrosion initiation stage Ti is the time from the ingress of chloride ion to the initiation
of corrosion in steel reinforcement. In case of the initial chloride content in the geopolymer concrete
hollow piles is zero and assuming the saturated situation, the limit state function of this stage S(t) is as
follows Eqs. (5-6):
𝑆𝑡= 𝐶𝑡ℎ𝑟−C(𝑟,𝑡)
(5)
𝑇𝑖 =[𝑆(𝑡) ≤ 0]
(6)
where; r is the diffusion radius; 𝐶𝑡ℎ𝑟 is the threshold level of the chloride with the lowest value of 0.2
% and the mean value of 0.6 % [32]; C(r,t) is the chloride concentration (%) based on Fick's second
law and taking into consideration hollow sections is calculated [1] as follows Eqs. (7-9):

Ali Abdulhasan Khalaf1 and Katalin Kopecskó1 5

14th fib International PhD Symposium in Civil Engineering

𝐶(𝑟, 𝑡) = 0, ( 𝑡 = 0, 𝑎 < 𝑟 < 𝑏)

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠 { 𝐶𝑠 (a, t) = 𝐶𝑠 𝑡 𝑘 , ( 𝑡 > 0, 𝑟 = 𝑎) } (7)
𝐶𝑠 (b, t) = 𝐶𝑠 𝑡 𝑘 , ( 𝑡 > 0, 𝑟 = 𝑏)
𝜋𝐽0 (𝛼𝑛 𝑎)𝑈0 (𝛼𝑛 𝑟) −𝛼 2 (𝐺𝐷 )𝑡
𝐶(𝑟, 𝑡) = 𝐶𝑠 𝑡 [1 − ∑∞
𝑘
𝑛=1 (𝛼 (𝛼
𝑒 𝑛 𝑎 ] (8)
𝐽0 𝑛 𝑎)+ 𝐽0 𝑛 𝑏)

𝑈0 (𝛼𝑛 𝑟) = 𝐽0 (𝛼𝑛 𝑟)𝑌0 (𝛼𝑛 𝑏) − 𝐽0 (𝛼𝑛 𝑏)𝑌0 (𝛼𝑛 𝑟) (9)

where a is the internal radius of the pile, b is the external radius of the pile, r is the diffusion radius, C s
is the surface chloride concentration at time t (s), and k is the empirical coefficient = 0.37, J0 and Y0
are the Bessel functions of the first and second kind of order zeros, respectively, and αn is the positive
root of the equation U0(αn a) = 0.
Eq. 8 shows that the GDa has to be known to evaluate the C(r,t) value. Returning to Eq. 2, the GDa
value is calculated by applying a corresponding known value of PCDa. Therefore the value of PCDa
can be calculated [1] as follows Eqs. (10-16):

𝑃𝐶𝐷𝑎 = 𝑃𝐶𝐷𝑐 . 𝑓(𝑡). 𝑓(𝜎). 𝑓(𝑇). 𝑓(ℎ)

(10)
𝑤 2 𝑤
[ −0.79( ) +0.340( )−13.10]
𝑃𝐶𝐷𝑐 = 10 𝑐 𝑐 (11)
𝑡𝑟𝑒𝑓 𝑚
𝑓(𝑡) = ( ) (12)
𝑡
(8𝜎 3 )
𝑓(𝜎) = 1 + 5.98𝑒 (13)
𝑈 1 1
[ 𝑐 ( − )]
𝑓(𝑇) = 𝑒 𝑅 𝑇1 𝑇2 (14)
(1−ℎ)4 −1
𝑓(ℎ) = [1 + (1− ℎ𝑐 )4
] (15)
𝑤
𝑚 = 2.5 ( ) − 0.6 (16)
𝑐
where PCDc is the Portland cement concrete initial diffusion coefficient; w/c is the water-cement ratio;
the functions f(t), f (σ), f(T), and f(h) reflect the dependence of PCDa on the concrete ageing, stress
level, current absolute temperature, and relative humidity, respectively; tref is the reference time (28
days), t is the exposure time (days); σ is the imposed tensile stress (MPa); U c is the activation energy
(Uc = 35 kJ/mol), R is the gas constant (R = 8.314 J mol-1 K-1), T1 is the reference temperature (296 K),
T2 is the current absolute temperature of the pile (K); h is the relative humidity, and hc is the critical
humidity level (75%); m is the age reduction factor calculated based on w/c.
The w/c of Portland cement concrete that corresponds to geopolymer concrete is calculated based
on the alkali activator solution-binder ratio (AAS/B) [33] as follows Eq. (17) :

𝑤 𝐴𝐴𝑆
= (17)
𝑐 𝐵

The procedure to calculate the time of the corrosion initiation for RGPCHP is as follows:
1. Determining the GGBFS %, CS, and AAS/B of the geopolymer concrete.
2. Utilising the proposed prediction model (Eq. 4) to determine RDa and w/c from Eq. 17.
3. Calculating PCDa by applying Eqs. 10-16 based on the exposure and load conditions of the
pile and GDa is determined by applying Eq. 2.
4. C(r,t) value is determined by applying Eqs. 7-9 in time interval and subtituted in Eq. 5.
5. Applying Eq. 5 on the results of C (r,t).
6. Determining the time of the corrosion initiation by applying Eq. 6.

4 Conclusions
In this study, data relevant to chloride binding capacity and apparent diffusion coefficient of geopoly-
mer concrete have been collected from the peer-reviewed literature. A comprehensive understanding
was developed from a statistical point of view to predict the time of the corrosion initiation of reinforced
geopolymer concrete hollow piles. As a result, the key findings are as follows:

6 Durability and materials

 Prediction of the time of corrosion initiation of reinforced geopolymer concrete hollow piles

▪ The correlation between RBC and GGBFS was positively quite strong since R2 value equals
0.8251. Hence, increasing GGBFS content increased chloride binding capacity.
▪ The proposed RDa model to evaluate the chloride ion ingress resistance of geopolymer con-
crete in terms of GGBFS and CS put future research steps in the right way since it has a mod-
erate R2 value equals 0.6106.
▪ According to the proposed model, geopolymer concrete with only fly ash or less than 37.5 %
of GGBFS had higher chloride ingress than Portland cement concrete. By increasing GGBFS
from 37.5 to 80.0%, geopolymer concrete had quite lower chloride ingress than Portland ce-
ment concrete. When the GGBFS % was more than 80.0%, geopolymer concrete underwent
an increase of chloride ion ingress but was still lower than Portland cement concrete had.
▪ CS has an influence on the chloride ion ingress resistance of geopolymer concrete only with
the first and second stages, where the GGBFS% is between (0-37.5).
▪ RDa has been successfully utilised to predict the time of the corrosion initiation of reinforced
geopolymer concrete hollow piles based on knowing simple parameters (GGBFS%, CS, and
AAS/B) by an analytical model.

Acknowledgement
Stipendium Hungaricum Scholarship Programme is highly acknowledged for supporting the PhD study.

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8 Durability and materials