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Determination of Excess Sodium Hydroxide in Geopolymer by Volumetric

Analysis

Article  in  Procedia Engineering · December 2016

DOI: 10.1016/j.proeng.2016.06.621

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Procedia Engineering 148 (2016) 298 – 301

4th International Conference on Process Engineering and Advanced Materials

Determination of Excess Sodium Hydroxide in Geopolymer by Volumetric

Analysis
Nur Ain Mohd Sania,*, Zakaria Mana, Rashid M. Shamsuddina, Khairun Azizi Azizlia, Ku Zilati Ku
Shaaria
a
Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 32610, Perak, Malaysia

Abstract

Efflorescence in geopolymers can be a significant issue as the binder contains much higher soluble alkali metal concentrations than
conventional cements. This paper reports the quantification method used to evaluate efflorescence potential on fly ash based geopolymer from
the leaching behaviour of alkali metal in the solution followed by volumetric analysis. In this study, NaOH was used as the only alkaline
activator. Geopolymer synthesis at higher molarity of NaOH gives higher percentage of excess sodium hydroxide content in geopolymer,
indicating the higher potential of efflorescenece. Meanwhile, the effect of hydrothermal curing condition at the same alkaline molarity results
in the lowest percentage of 4.84% excess sodium hydroxide content in geopolymers compared to others. The systems were subjected to 65%
relative humidity at 80˚C for 5 days. An optimum Na2O content along with hydrothermal curing condition can results in optimization of
geopolymerization reaction.
© 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2016 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016.
Peer-review under responsibility of the organizing committee of ICPEAM 2016
Keywords: Efflorescence; excess sodium hydroxide (NaOH),

1. Introduction

Sodium hydroxide (NaOH) is the most commonly used alkaline activators in geopolymer synthesis. The extensive use of
NaOH as an activator in geopolymer synthesis, from both fly ash and metakaolin precursors is due to its low cost, abundance and
low viscosity. Furthermore, leaching of Al 3+ and and Si4+ ions are generally high with NaOH solution compared to potassium
hydroxide (KOH) solution [1]. As an activator, NaOH accelerates the reaction more rapidly. Sodium hydroxide provides both
hydroxide anion (OH-), which act as a catalyst for dissolution of the aluminosilicates in the first stage and sodium cation (Na +)
which acts as structure-forming element, balancing the negative framework charge carried by tetrahedral aluminium in the last
stage [2]. NaOH was found to significantly affect both the compressive strength and structure of the geopolymers [3].
However, sodium aluminosilicate geopolymers, can suffer from unsightly efflorescence caused by excess sodium hyroxide
unreacted in the material, particularly those synthesized at high Na2O/Al2O3 ratio [5]. The reason for efflorescence in geopolymer
is due to the open microstructure of some materials which have a lower extent of reaction, resulting in access or unreacted
alkaline solution. It is partly due to the weak binding or exchangeability of sodium in the geopolymer structure as well [6].
Temperature and humidity influence the content of water (H2O) in efflorescence product (hydrous alkali carbonates). The
mechanism of efflorescence formation is outlined below [4]:

* Corresponding author.
E-mail address: ainsani2669@gmail.com

1877-7058 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016
doi:10.1016/j.proeng.2016.06.621
 Nur Ain Mohd Sani et al. / Procedia Engineering 148 (2016) 298 – 301 299

CO2 (g) + 2OH- (aq) ÎCO32- (aq) + H2O (l)

Na+ (aq) + CO32- (aq) + xH2O ÎNa2CO3.xH2O (s)

Under natural carbonation condition, dissolved CO2 acts as an acid and consumes hyroxides and therefore a partial
neutralization process. The main factor for efflorescence in the geopolymer synthesis is due to the availability of mobile Na+ and
OH- in geopolymers binders [4].
Thus, a research had been done to evaluate the excess of sodium hydroxide in geopolymer formation. This work quantified the
excess NaOH in fly ash geopolymer by direct leaching analysis and indirectly by volumetric analysis. In this work, fly ash and
sodium hydroxide were used as raw materials to produce geopolymer. Besides, this present work examined the effect of curing
condition to the excess sodium hydroxide content in geopolymer synthesis at constant Na2O/Al2O3 ratio.

2. Methodology

2.1. Materials

Fly ash (FA) of class F was obtained from a nearby coal power. Research-grade NaOH (99%) was purchased from Merck and
made into 6,8,10,12,14 and 16M solutions using distilled water. The solutions were kept for 24 hours prior to use. In volumetric
analysis acid-base titration, 1M of hydrocloric acid (HCl) solution were used as a titrant.

2.2. Geopolymer Synthesis

All geopolymer prepared were synthesized by maintaining the solid to liquid ratio of 3:1 by weight. 20g of sodium hydroxide
solution as alkaline activator was added into the 60g fly ash. The samples were mixed using mechanical mixer for 5 minutes. The
fresh geopolymer paste was quickly casted in 178 x 175 x 3 mm flexural mold and was cured at 60˚C for 24 hours in a drying
oven. The temperature was selected based on previous work to obtain the optimum compressive strength of geopolymer.

2.3. Leaching of Alkali and Acid-base titration

The produced geopolymer was crushed into powder. The powdered sample then was mixed with 100 mL of distilled water.
The pH of the solution was monitored twice a day using a MeterLab 450 pH analyser until the reading is stabilized, implying the
equilibrium leaching of NaOH into the solution. The final solutions then were filtered using Filters Fioroni, Grade 601 filter
paper. A 20 mL of the filtrate solution was titrated using 1M of hydrocloric acid (HCl). The moles of sodium hydroxide in titrate
solution is equal to the excess of NaOH in the geopolymer formed. This is expressed in percentage (%) and was calculated using
the Equation 1:

% excess NaOH = weight of NaOH in titrate x 100

weight of NaOH in geopolymer
Equation 1

2.4. Hydrothermal Curing

The effect of curing condition at the similar molarity of alkaline activator to the leaching of excess sodium hydroxide in
geopolymers also been studied. Based on previous study, the using of 10M NaOH as alkaline activator produces optimum
compressive strength. Therefore, 10M NaOH is used to synthesis the geopolymer cured at 60˚C. After 24 hours, the samples
were taken out and were put in humidifier for 1, 2, 3 and 5 days. The systems were subjected to 65% relative humidity at 80˚C.
Finally, all the samples will undergo the same procedure of alkali leaching and acid-base titration.

3. Results and Discussion

Volumetric analysis is used to determine the concentration of analyte. It is a quantitative analytical method that involves the
measurement of volume of a solution of known concentration. Since the sodium hydroxide is a strong base, the concentration of
excess sodium hydroxides can be measured by direct acid-base titration. The acid and base react quantitatively with each other
where the product are water and salts and a neutralization reaction. So, it is possible to determine the concentration of excess
sodium hydroxide in aqueous solution with high accuracy.
300 Nur Ain Mohd Sani et al. / Procedia Engineering 148 (2016) 298 – 301

3.1. Effect of Different NaOH Molarity

Figure 1 shows the percentage of excess NaOH in geopolymer at different NaOH concentration used in geopolymer synthesis.
At higher concentration, NaOH appears to leach more in the solution but was found to have the highest compressive strength [7].
Similar trend was also observed where increasing the amount of alkali activators in speciments will increase the severity of
efflorescence (A.Allahverdi et.al). This is due to high charge density of ions at high concentration with limited binding site on
the solid-phase of tetrahedron network. The unbound aquoues ions therefore leach into the solution as free cations and anions
resulting in the high excess sodium hydroxide content.

Figure 1: Percentage of excess sodium hydroxide vs Molarity of NaOH solution

3.2. Effect of Hydrothermal Curing

The severity of efflorescence decreases in most system by applying hydrothermal curing conditions [5]. As shown in the
figure 2, longer curing times in humidifier results in decreasing of excess sodium hydroxide content in geopolymer synthesis The
percentage of excess NaOH in geopolymer in 5 days of humidifier gives the lowest percentage of 4.84% compared to others.
This similar trend was reported in previous study where the pH values in the leaching solution of hydrothermally cured sample
are lower than those of the room temperature [4]. The decrease percentage of excess NaOH content in geopolymer may be
associated with higher temperature used for curing at 80°C which attributed to higher extent of geopolymerization reaction.

Figure 2: Percentage of excess sodium hydroxide vs curing time in humidifier

4. Conclusion

The excess of alkaline activator used in the synthesis of geopolymer can be determine using leaching analysis of alkali
content followed by acid-base titration as a quantitative measure. Thus, a feed forward measure can be taken during mixing to
avoid un-utilized alkaline activator, which results in waste and undesirable product appearance. The hydrothermal curing
condition was an effective ways in development of suitable geopolymer system as the results in five days hydrothermal curing
condition give lowest percentage of 4.84% of excess sodium hydroxide content in geopolymer.

Acknowledgements

The authors acknowledge Ministry of Higher Education (MOHE) for funding under Long Term Research Grant Scheme
(LRGS) for the project of OneBaja and would like to thank Universiti Teknologi PETRONAS for providing research facilities.
 Nur Ain Mohd Sani et al. / Procedia Engineering 148 (2016) 298 – 301 301

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