Characteristics of alkali activated material (geopolymer) in sulfuric acid solution

Partogi H. Simatupang

Citation: AIP Conference Proceedings 1887, 020028 (2017); doi: 10.1063/1.5003511

View online: https://doi.org/10.1063/1.5003511
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Published by the American Institute of Physics

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 Characteristics of Alkali Activated Material (Geopolymer)
in Sulfuric Acid Solution
Partogi H. Simatupang1, a)
1
Civil Engineering Department, Faculty of Science and Engineering, University of Nusa Cendana, Indonesia.
a)
Corresponding author: partogihsimatupang@gmail.com

Abstract. Alkali Activated Material (AAM) or Geopolymer is a solid material which made by mixing rich silica alumina
material with alkaline activator. AAM is a well known candidate to replace cement based material. Many researches
have claimed that AAM has better durability compared to cement based material in agressive environment. However,
there was rare paper presented the direct comparison of material characteristics between Class F fly ash based AAM and
Class C fly ash based AAM in such aggresive environment. Because of that, this paper present material characteristics of
Class F fly ash based AAM and Class C fly ash based AAM if the materials were immersed in 10% sulfuric acid solution
for 65 days. Material characteristics evaluated were (1) weight loss, (2) mineral of the material which evaluated by XRD
(X-Ray Diffraction), (3) morphology and oxide compounds of material which evaluated by SEM/EDXA (Scanning
Electron Microscopic/Energy Dispersive X-Ray Analyzer) and (4) compound bond which evaluated by FTIR (Fourier
Transform Infra Red) Spectroscopy Testing. Alkali Activated Material used were Class F fly ash based AAM Mortar and
Class C fly ash based AAM Mortar. The result is a quite difference of material characteristics between Class F fly ash
based AAM and Class C fly ash based AAM.

INTRODUCTION
Degradation of material can be happened as a consequences of physical and chemical attacks, which are occured
internally or externally. However, durability problems in material concern especially on externally chemical attacks
on material which come from aggressive environment. Researches on durability of Class F fly ash based AAM or
geopolymer in aggressive environment have been conducted.

Wallah and Rangan [1] has conducted the research on durability of Class F fly ash based concrete and mortar
AAM in 5% Na2SO4 solution and 0.5%-2% sulfuric acid solution. They concluded that concrete and mortar AAM
had better durability compared to cement based material. There were no gypsum or ettringite found as a
solidification product of sample which immersed natrium sulfate solution. Meanwhile, there was weight loss 3% of
the sample which immersed in sulfuric acid solution after 1 year.

Bakharev [2], [3] conducted the research on durability of Class F fly ash based mortar in acetic acid solution and
sulfuric acid solution 5% and sodium and magnesium sulfat solution. Bakharev found that geopolymer material had
superior durability compared to cement based material. Bakharev [2], [3] concluded that geopolymer material which
activated by NaOH solution had better durability than geopolymer which avtivated by Na 2SiO3 solution. This was
occured because geopolymer activated by NaOH solution had more crystalline solidification product.

Chanh et al [4] reported the research on durability of Class F fly ash based concrete AAM (using alkaline
activator Na2SiO3+NaOH solution) in HCl 5% and H2SO4 solution for 7 weeks (49 days). They reported that
weight loss was about < 1% with moderate compressive strength loss about 19,2 %.

Green Construction and Engineering Education for Sustainable Future

AIP Conf. Proc. 1887, 020028-1–020028-8; doi: 10.1063/1.5003511
Published by AIP Publishing. 978-0-7354-1570-6/$30.00

020028-1
 Song et al [5] conducted the research on durability of Class F fly based mortar AAM (activated by
Na2SiO3+NaOH solution) in sulfuric acid 10% for 56 days. They reported that weight loss was about < 3% with
moderate compressive strength loss about 37% for ambient curing and 32% for dry curing (70OC for 12 hours).

Sata et al [6] have conducted the research on durability of bottom ash lignite based mortar geopolymer in 5%
sodium sulfate solution and 3% sulfuric acid solution for 120 days. They reported that weight loss was about <
3,6%. This result was less than weight loss of OPC based mortar about > 15% for just 50 days. Resume of the prior
researches on durability AAM or geopolymer material in aggressive environment is given in Table 1.

They have claimed that AAM or geopolymer material had superior durability compared to cement based
material. Nevertheless, there is rare paper present the durability of Class C fly ash based AAM in aggressive
environment. Because of that, this paper will present the characteristics of mortar AAM which is consisted of Class
F fly ash and Class C fly ash in 10% sulfuric acid solution as an aggressive environment for 65 days.

TABLE 1. Resume of the researches on Durability of AAM (geopolymer) in aggressive environment

Size of
Aggressive
Reference Phase Sample Material AAM Result
Environment
(cm)
Wallah and Concrete, Cylinder FAF+Na2SiO3+NaOH Acid, 0.5-2% Weight loss <3%
Rangan Mortar 10x20 sulfuric acid Compressive
(2006) Cube strength loss 40-
7,5x7,5x7,5 50% in 52 weeks.
Sulfat, 5% Na2SO4 Weight increase
1.5%.
Strength better
than OPC.
Bakharev Mortar Variation FAF+Na2SiO3+NaOH 5% acetic acid and Better than mortar
(2005a, sulfuric acid OPC
2005b) solution,
5% sodium and
magnesium sulfat
solution
Sata V et al. Mortar Cube, LBA+ Sulfuric acid, 5% Better than OPC
(2012) 2,5x2,5x29, Na2SiO3+NaOH Sodium Sulfat, mortar
5x5x5 Sulfuric Acid, 3%
Sulfuric Acid
Chanh et Concrete variaton FAF+Na2SiO3+NaOH Acid, 5% HCl, Weight loss <1%
al.(2008) Sulfat, 10% H2SO4
Song et Mortar Cube, FAF+Na2SiO3+NaOH Sulfuric Acid, 10% Weight loss < 3,0%
al.(2005) 5x5x5 Sulfuric Acid
Solution
Note : FAF + Fly Ash Class F; FAC = Fly Ash Class C; LBA = Lignite Bottom Ash

METHODS
Method of the research will present raw material used, sample made, and testing taken. There was no treatment
to fly ash as a raw material. Mortar samples were used in this research. Testings taken were (1) weight loss and (2)
microscopic characteristics of material. Compressive strength was not taken in this research. It will be described as
follows.

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 Material
Raw materials used to make mortar AAM were : (1) Class F fly ash, (2) Class C fly ash (as precursor), (3)
natrium silicate solution and natrium hydroxide solution (as alkaline activator) and (4) sand (as filler). Sand used
was from Galunggung West Java. Sand was in Saturated Surface Dry (SSD) condition.

Class F fly ash was from Suralaya Coal Fired Power Plant in Cilegon Banten Province and Class C fly ash was
from Batu Hijau (Newmont Nusa Tenggara) Coal Fired Power Plant in Sumbawa West Nusa Tenggara Province.
Oxide composition of Class F and Class C fly ash is given in Table 2. There is a significant difference of amount of
SiO2 and Al2O3 between Class F fly ash and Class C fly ash. The amount was 78,87% for Class F fly ash and
57,50% for Class C fly ash. Meanwhile, the amount of CaO was 6% for Class F fly ash and 15,85% for Class C fly
ash.

TABLE 2. Oxide Composition of Class F fly ash and Class C fly ash
Material SiO2 Al2O3 CaO Fe2O3 Na2O SO3 Method
Class F Fly Ash 52,30 26,57 6,00 7,28 1,41 0,70 XRF
Class C Fly Ash 40,18 17,32 15,85 14,11 0,93 0,93 XRF

XRF = X-Ray Fluorescence Test

Sample
Sample used was cubic mortar with size 5 cm x 5 cm x 5 cm. Mortar made was conformed to ASTM C 109-92.
After fresh mortar made, the sample was cured with dry curing method with 80 OC for 24 hours. The detailed method
of making the mortar AAM with dry curing can be referred to Simatupang [7] and Simatupang et al [8].
Composition of mortar AAM used in this paper is given in Table 3.

TABLE 3. Composition of Mortar AAM (Simatupang [7], Simatupang et al [8])

Sample [NaOH] Fly Ash Sodium Natrium Sand Added Type of Curing Compressive
(gr) Silicate Hidroxide (gr) Water Fly Ash strength 7 days
Solution Solution (gr) (MPa)
(gr) (gr)
M-3 16 1260 420 210 1890 0 F Dry 80
M-24 8 1260 315 315 1890 126 F Dry 33,9
N-9 12 630 157,5 157,5 1134 0 C Dry 61,4
N-18 16 630 157,5 157,5 945 63 C Dry 32,1

Each sample was divided in two pieces using stone cutter. For microscopic characteristics testing, after sample
immersed for 65 days, sample was dried using ambient curing for 24 hours and then mortar was wiped by dry
napkin. Then, the mortar was broken and milled depend on the kind of testing taken.

Testing
Immersion method was used to evaluate characteristics of material in aggressive environment. Aggressive
environment used was 10% sulfuric acid solution. Ratio of volume of sample and sulfuric acid solution was 4,0 and
retained constant for 65 days. Weight loss measurement was taken every 5 days. At that time, every old sulfuric acid
solution was replaced with new sulfuric acid solution to keep the concentration of the solution was constant. As
immersed in sulfuric acid solution, the immersion container was always wrapped with clipped plastic bag.
Compressive strength was not measured in this research.

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 Weight loss was measured by digital scales. Microscopic characteristics testings conducted were : (1) XRD (X-
Ray Diffraction) to evaluate mineral of material, (2) SEM/EDXA (Scanning Electron Microscopic/Energy
Dispersive X-Ray Analyzer) to find morphology and compound oxide of material, and (3) FTIR (Fourier Transform
Infra Red) Spectroscopy Testing to evaluate compounds bonding. XRD testing was conducted at Mining
Department of ITB (Institute of Technology Bandung) using Philips Diffractomer PW 1710 XRD. SEM/EDXA was
done at Centre of Geology Laboratory Bandung using JEOL JSM 6360LA. And, FTIR testing was done at Chemical
Department of ITB (Institute of Technology Bandung) using Prestige 21 Shimadzu FTIR Spectroscopy equipment.
All testings were taken after 65 days immersion.

RESULT AND DISCUSSION

Weight Loss
Weight loss development of AAM mortar immersed in 10% sulfuric acid solution for 65 days is given in Fig 1.
This figure presents the contrary condition. After immersed for 65 days, weight loss of Class F fly ash based AAM
mortar was not happen. As contrary, there was weight addition. Weight additions were 3,61% for sample M-24
(33,9 MPa) and 0,89% for sample M-3 (80 MPa). Meanwhile, there was weight loss of Class C fly ash based AAM
mortar, Weight loss were 2,44% for sample N-9 (61,4 MPa) and 3,96% for sample N-18 (32,1 MPa). These results
are confirmed by prior researches. Wallah and Rangan [1] reported the weight increase on Class F fly ash AAM
mortar immersed in 5% Na2SO4 solution about 1,5%. Meanwhile, other researches reported weight loss of Class F
fly ash AAM or geopolymer material were about < 3% [5], [6].

110
100
90
Weight Loss (%)

80
70 M-3
60 (FAF)
50 M-24
40 (FAF)
30 N-9
20 (FAC)
10
0
0 10 20 30 40 50 60 70
Time of Immerse (days)

FIGURE 1. Development of weight loss of fly ash based AAM mortar versus time of immerse

Photo of the sample before and after immersed in 10% sulfuric acid solution for 65 days is given in Fig 2. After
immersed for 65 days, there was less cracks on sample M-3 (80 MPa) compared to sample M-24 (33,9 MPa). Cracks
on mortar M-24 had spread on all surfaces of mortar. Meanwhile, M-3 mortar just got local cracks. It means both
mortars have expanded because of a new product of solidification. This is the reason of weight addition on mortar
M-3 and M-24 as explained in Fig 1 before. There were no colour changing in sulfuric solution for sample M-3 and
M-24. It means there were no leaching on both mortar.

Contrary to Class F fly ash based AAM mortar, Class C fly ash based AAM mortar was leached by 10% sulfuric
acid solution. There were colour changing in sulfuric solution for sample N-9 and N-18. There were no crack on all
surfaces of N-9 and N-18 as shown on Fig 2 (e) and Fig 2 (f). This is the reason of weight loss on samples N-9 and
N-18 as explained in Fig 1.

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 (a) (b)

(c) (d)

(e) (f)
FIGURE 2. Samples were immersed in 10% sulfuric acid solution, left side just immersed and right side after immersed for 65
days : (a) and (b) for Class F AAM mortar sample M-24 (33,9 MPa); (c) and (d) for Class F AAM mortar sample M-3 (80 MPa) ;
(e) and (f) for Class C AAM mortar sample N-9 (61,4 MPa).

Characteristics of XRD Results

Based on XRD patterns as shown in Fig 3, there is a new product of solidification on both mortar AAM, Class F
fly ash based AAM mortar and Class C fly ash based AAM mortar. The new product was gypsum (Calcium Sulfate
Hydrate/ Ca(SO4)(H2O)2). Neverheless, amount of gypsum in M-3 was less than M-24 and N-9. This mineral
(gypsum) is the reason of cracks on surfaces of Class F fly ash based AAM material. Gypsum have made mortar
expanses and cracks. This result is contrary to Wallah and Rangan [1] that reported there were no gypsum in product
solidification of geopolymer immersed in natrium sulfate solution. Main minerals as well known on solidification
products of fly ash based AAM or geopolymer such as Quartz (SiO2), Mullite (Al6Si2O13), Albite (Na(Si3Al)O8) and
Sodium Alumino Silicate Hydrate (Na6(AlSiO4)6.4H2O) were still remained and not changed.

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 (a)

(b)
FIGURE 3. XRD patterns of fly ash based AAM Mortar before and after immersed in 10% sulfuric acid solution for 65 days, (a)
Class F AAM mortar dan (b) Class C AAM mortar

Characteristics of SEM/EDXA Results

Photos SEM (Scanning Electron Microscopic) of Class F fly sh based AAM mortar and Class C fly ash based
AAM mortar immersed in 10% sulfuric acid solution for 65 days are given in Fig 4. Figures 4 (a) and 4 (c) reveal
that there are gypsum as a solidification product of AAM. The cracks are also seen in sample M-24 (Class F fly ash
based AAM mortar). Meanwhile in Class C fly ash based AAM mortar (sample N-9), the gypsum was leached from
sample surface and made the hole. These results confirm the weight addition in Class F fly ash based AAM mortar
and the weight loss in Class C fly ash based AAM mortar that explained before in Fig 1.

From EDXA (Energy Dispersive X-Ray Analyzer) on the spot as seen in Fig 4(b) and 4(d), it has been confirmed
that the new product was gypsum (Calcium Sulfate Hydrate/ Ca(SO4)(H2O)2).

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 (a) (b)

(c) (d)
FIGURE 4. SEM photo shown new mineral (gypsum or ettrengite) in mortar AAM after immersed in 10% sulfuric acid solution
for 65 days : (a), (b) Class F fly ash based AAM mortar (sample M-24) and (c), (d) Class C fly ash based AAM mortar (sample
N-9)

Characteristics of FTIR Spectroscopy Results

The result of Fourier Transform Infra Red (FTIR) Spectroscopy Testing of fly ash based AAM mortar is given in
Fig 5. Based on FTIR Spectroscopy Testing of Class F fly ash based AAM mortar as in Fig 5 (a), wavelength
number of bonding ±OH, H-O-H, Si-O-Al, Si-O-Si and O-Si-O were remained and not changed. Significant
changing of wavelength number was happen on stretching Si-O-Si and Si-O-Al. This wavelengths tend to increase
which are 1068,37 cm-1 for sample M-24-H2SO4 and 1106,94 cm-1 for M-3-H2SO4, compared to 1018,41 cm-1 for
sample M-24 and 1080,14 cm-1 ; 1018,41 cm-1 for sample M-3.

Meanwhile, based on FTIR Spectroscopy Testing of Class C fly ash based AAM mortar as in Fig 5 (b),
wavelength number of bonding ±OH, H-O-H, Si-O-Al, Si-O-Si and O-Si-O were also remained and not changed as
on Class F fly ash based AAM mortar. Significant changing of wavelength number was also happen on stretching
Si-O-Si and Si-O-Al. This wavelengths tend to increase which are 1118,7 cm-1 for sample N-9-H2SO4 compared to
1024,2 cm-1 ; 1010,70 cm-1 for sample N-9). These patterns are like the patterns in Class F fly ash based AAM
mortar.

It means main compounds in either Class F fly ash AAM or Class C fly ash AAM were still exist. However,
main product of AAM which represented by wavelength number of stretching Si-O-Si and Si-O-Al had been
attacked or changed by severe environment 10% sulfuric acid solution.

020028-7
 (a) (b)
FIGURE 5. The result of FTIR Spectroscopy Testing of fly ash based AAM mortar before and after immersed in 10% sulfuric
acid solution for 65 days : (a) Class F fly ash AAM mortar and (b) Class C fly ash AAM mortar

Conclusions
According to this research, many conclusions can be given such as : (1) new mineral, gypsum, was found in
either Class F fly ash based AAM mortar or Class C fly ash based AAM mortar immersed in 10% sulfuric acid
solution for 65 days, (2) weight loss was happen to Class C fly ash based geopolymer but contrary, weight addition
was happen to Class F fly ash based AAM mortar, and (3) weight loss or weight addition were about < 4%.

In addition, either Class F fly ash based AAM mortar or Class C fly ash based AAM mortar immersed in 10%
sulfuric acid solution for 65 days, the same characteristics found are (1) the main mineral of AAM or geopolymer
was remained and not changed, (2) wavelength number of bonding ±OH, H-O-H, Si-O-Al, Si-O-Si and O-Si-O
were also remained and not changed and (3) significant changing of wavelength number was happen on stretching
bonding Si-O-Si and Si-O-Al.

As a general conclusion, there is a quite difference of material characteristics between Class F fly ash based
AAM and Class C fly ash based AAM immersed in 10% sulfuric acid solution for 65 days.

ACKNOWLEDGMENTS
This research was funded by Directorate General of Higher Education Indonesia (Dikti) through National
Strategic Competitive Research Grant 2009 and 2010.

REFERENCES
1. S.E. Wallah and B. V. Rangan, Concrete 107 (2006).
2. T. Bakharev, Cement and Concrete Research 35(4), 658±670 (2005).
3. T. Bakharev, Cement and Concrete Research 35(6), 1233±1246 (2005).
4. N. Van Chanh, B.D. Trung, and D. Van Tuan, Civ. Eng. 235 (2008)..
5. X.J. Song, M. Marosszeky, M. Brungs and R. Munn, ³Durability of Fly Ash Based Geopolymer Concrete
Against Sulphuric Acid Attack´, The 10nh International Conference on Durability of Building Materials and
Components Proceedings (2005).
6. V. Sata, J. Tangpagasit, C. Jaturapitakkul, and P. Chindaprasirt, Cem. Concr. Compos. 34, 94 (2012)..
7. P.H. Simatupang, I. Imran, I. Pane and B. Sunendar, J. Eng. Technol. Sci Vol 47, No. 3, 231±249 (2015).
8. P.H. Simatupang, ³The Development of Alkali Activated Material to make Green Infrastructure Material ,´
Ph.D. thesis, Institut Teknologi Bandung, 2013 (in Bahasa Indonesia).

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