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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012024 doi:10.1088/1742-6596/2315/1/012024

Properties of red-mud-based geopolymers in the light of their

chemical composition

Ali Abdulhasan Khalaf1, Katalin Kopecskó1

1
Budapest University of Technology and Economics, Faculty of Civil Engineering,
Dept. of Engineering and Geotechnics, Hungary

E-mail: ali.abdulhasan.khalaf@emk.bme.hu, kopecsko.katalin@emk.bme.hu

Abstract. Utilizing industrial waste materials such as red mud as alternatives to high emissions
of CO2 materials such as Portland cement will help to produce integrated sustainable construction
materials. Statistical analysis has been performed on the major oxides of red mud to understand
the relationship between chemical composition and properties (e.g., workability, setting time,
compressive strength, etc.) of red mud-based geopolymer composite. Therefore, red mud can be
a suitable binder by blending with other geopolymer source materials to achieve the desired fresh
and mechanical properties. Moreover, a proposed equation has been derived on the basis of the
outcomes from the literature to determine the required extra water that can compensate for the
workability loss due to red mud addition.

1. Introduction
Red mud, RM, is a by-product material produced from alumina manufacturing. Alumina is usually
extracted from bauxite by Bayer Process. Bauxite ore is the raw material of the Bayer process. It is
treated with sodium hydroxide and an appropriate temperature to isolate the aluminate from the solid
phase. In this, the remaining part is called the red mud or bauxite residue, BR. The production of 1 ton
of alumina could generate 0.5 – 2.0 tons of red mud depending on the chemical composition of bauxite.
The primary disposal method of red mud is storing it in landfills. The high alkalinity and massive amount
of accumulated red mud become a series threat to the environment and human safety, imposing high
risk with the continuing Storage. The turning point that brought attention to red mud as a hazardous
material is the tragic accident of the Ajka factory in Hungary in 2010 [1, 2]. Therefore, utilizing red mud
is becoming a necessity to retain human safety and environmental sustainability.
Portland cement is well known for its high emission of CO2 gas. It can generate cca. one ton of CO2
gas to produce one ton of cement. This high emission is due to the required energy to generate high
temperature and decarbonation of lime. From an environmental point of view, seeking alternatives of
cement with less required energy or raw materials different from limestone will help reduce the emission
of CO2 gas. Geopolymers are promising alternative materials for Portland cement. The backbone of
geopolymers binders is three-dimension structures of amorphous aluminosilicate [3-5].
Red mud does not have the required amount of aluminosilicate to produce an appropriate
geopolymerization process. However, it can still be utilized in geopolymer production by blending with
other precursors [6-8]. Therefore, this is strong evidence of the importance of valorisation of red mud
based geopolymers. Statistical analysis was conducted based on the results from the literature review,

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012024 doi:10.1088/1742-6596/2315/1/012024

to obtain and widen more knowledge of red mud-based geopolymer composites as a construction
material to enhance environmental sustainability.

2. Chemical composition of red mud

The produced gel in the geopolymerization process is substantially dependent on the calcium oxide
content in the geopolymer precursor. Hence, the geopolymer precursors are divided into two main
groups: low calcium (CaO < 8%) and high calcium (CaO ≥ 8%). Low calcium-based geopolymers
undergo the formation of N-A-S-H type of gel, while high calcium-based geopolymers undergo the
formation of C-A-S-H kind of gel [9]. It is noticed that red mud could be either low calcium or high
calcium precursor by surveying the chemical composition for the researches in the literature.
Ten different sample compositions are categorized as low calcium RM collected from the literature
[7, 10-18]. From a statistical point of view, the average can be taken as the mean or median value
depending on the existence of outliers [19]. The statistical analysis of the major oxides and loss on
ignition yields no outliers for Al2O3, Fe2O3, and CaO. As a result, the mean values have been taken into
consideration. The other values show outliers; therefore, the median values have been considered. All
the considered average values of low calcium red mud composition are shown in Figure 1.a. The
dominant oxide is Fe2O3, with a value of 40%. The Fe ions can only replace 25% of Al ions in the
geopolymerization process, and the remaining will act as unreacted inert particles [15]. The SiO2 and
Al2O3 are 10.6 and 19.4, respectively. In other words, SiO2/Al2O3 is 0.55, which is out of the
recommended range (3.5-4.5) in geopolymer practice in construction materials [20, 21]. The other
obstacle is the content of Na2O is considerably high, which equals 5.4%. This value represents high
alkalinity before adding the alkaline activation solution.
Moreover, the loss on ignition content is very high (10.2). With this high percentage of LOI, the
water demand will be much higher than other geopolymer precursors [22]. It is also noted that the low
calcium red mud has a considerable amount (8.8%) of TiO2.

a. Low calcium red mud b. High calcium red mud

Figure 1. The average values of low and high calcium red mud compositions.

Another ten different sample compositions are categorized as high calcium RM collected from the
literature [8, 23–31]. The statistical analysis for the major oxides and loss on ignition yields no outliers
for Al2O3, CaO, Na2O, MgO, K2O, SO3 and LOI. As a result, the mean values have been taken into
consideration. The other values show outliers; therefore, the median values have been considered. All
the considered average values of high calcium red mud composition are shown in Figure 1.b. The
relatively high content of CaO, 13.1%, promotes the red mud to some hydraulic reactions. The number
of non-bridge oxygen atoms and structural units into the glassy phase is determined by the condensation
degree of network formers (SiO4 tetrahedra) as in Eq. (1) [32].

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012024 doi:10.1088/1742-6596/2315/1/012024

𝑆𝑖𝑂4
𝑓𝑆𝑖 = (1)
𝑀𝑒2 𝑂 + 𝑀𝑒𝑂 + 3𝑀𝑒2 𝑂3 + 2𝑀𝑒𝑂2 + 5𝑀𝑒2 𝑂5

Eq. 1 yields that the condensation degree (0.1) of high calcium red mud is insufficient and out of the
recommended range (0.286-0.333). As in low calcium red mud, the high calcium red mud also shows
high values of Na2O and LOI, which are 7.9% and 10.4%, respectively. Therefore, it is expected to
choose low molarity of NaOH solution and higher water demand in the synthesis process of
geopolymerization [21, 22, 33]. It is also noted that the high calcium red mud has a considerable amount
(4.0%) of TiO2.

3. Solutions to utilize red mud in the geopolymer production

The adopted feasible steps to resolve the inadequate chemical composition requirements of red mud to
be utilized in geopolymer production are:
o Red mud can be used to replace other geopolymer precursors partially [7, 8].
o The high content of LOI can be resolved by pre-treatment by igniting or increasing water
content [22, 25].
o The high sodium hydroxide content can be resolved by reducing the NaOH dosage or
utilizing mechanical activation [12, 33].

4. Setting time
The low calcium red mud has been investigated by adding to fly ash in different partial replacement
percentages. At first, the red mud addition reduces the initial and final setting times until reaching the
optimum decrease at 15% of red mud. After increasing the percentage of red mud, the initial and final
setting times start rising to surpass fly ash values at 40% red mud. The increase of setting time by
increasing red mud content above 15% can be attributed to the high content of LOI in red mud due to
absorbing more water. Therefore, the optimum percentage is 15%. The reduced initial setting time has
reached 196 minutes, and the final setting time has come 300 minutes with the 15% red mud added to
fly ash geopolymers [10, 14], as shown in Figure 2.

Figure 2. Effect of substitution of fly ash, FA by 0 or 15% RM on

geopolymer setting times [10,14].

The final setting time has been tested for the high calcium red mud combined with other geopolymer
precursors, fly ash and ground granulated blast furnace slag. In fly ash, the red mud is added in 20% and
thermally treated to reduce a final setting time to 140 minutes [29]. On the other hand, adding 75% of
red mud to ground granulated blast furnace slag, GGBS, shows a continuous increase of the setting time,
reaching 146 minutes [31]; both outcomes are presented in Figure 3. Adding 20% red mud to fly ash
and 75% red mud to GGBS gives comparable final setting time results. Therefore, it can be inferred that
GGBS can utilize more amount of red mud than fly ash.

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012024 doi:10.1088/1742-6596/2315/1/012024

5. Workability of red mud based geopolymers

The effect of low calcium red mud addition on the workability of fly ash geopolymers has been
investigated by S.Y. Kim et al. [14] and R. Bajpai et al. [34]. The increase of red mud percentage reduces
geopolymer workability almost in a linear relationship. Every 5% red mud increase corresponds to a
17% decrease in flow diameter (Eq. 2) [14]. These results are not surprising because red mud has a high
percentage of LOI. Most LOI materials are classified as unburnt/non-calcined residues that have a high
capability of water absorption. The less water availability in a mixture, the less workability is. Increasing
water content or water-to-binder ratio by 20% will increase the flow diameter by ~ 17% (Eq. 3) [34]. As
a result, we are proposing the following equation (Eq. 4) to calculate the required increase in the water-
to-binder ratio to eliminate the impact of red mud on workability.
5% ∗ 𝑅𝑀 𝛼 − 17% ∗ 𝐷𝑓𝑙𝑜𝑤 (2)
𝑤
20% ∗ ( ) 𝛼 17% ∗ 𝐷𝑓𝑙𝑜𝑤 (3)
𝑏 𝑖𝑛𝑐.
𝑤
( ) = 4 ∗ 𝑅𝑀% (4)
𝑏 𝑖𝑛𝑐.
𝑤
; where RM% is the red mud percentage in the binder; 𝐷𝑓𝑙𝑜𝑤 is the flow diameter, and ( 𝑏 )𝑖𝑛𝑐. is the
required increase of the water-to-binder ratio. It should be noticed that the above equation is derived
based on the observations where the low calcium red mud and fly ash are blended. However, it is
expected that high calcium red mud will show a similar effect on workability because it also has
comparable content of LOI to the low calcium red mud, 10.2 and 10.4, respectively. This assumption is
based on the findings describing water demand in geopolymer synthesis [22].

Figure 3. Effect of red mud addition on the fly ash

and GGBS geopolymer setting times [29,31].

6. Compressive strength of red mud based geopolymer mortars

To obtain optimal compressive strength in red mud based geopolymers, the partial replacement can be
controlled by ferrous ions [15] and sodium hydroxide concentration [35]. It is reported that the ferrous
ions can only replace 25% of aluminium ions in the geopolymerization reaction. The remaining ferrous
ions act as unreactive inert particles [15]. In addition, red mud has a considerably high content of Na2O,
as reported from the statistical analysis. Consequently, the alkalinity of red mud is high. Therefore, the
optimal compressive strength requires a lower concentration of sodium hydroxide in the alkali activator.
Low calcium red mud has been utilized to replace metazeolite, fly ash and ground granulated blast
furnace slag in geopolymer mortar production [11, 13, 15, 17, 18, 35]. In the case of ground granulated
blast furnace slag, the red mud is added without an alkali activator. Increasing red mud percentage
decreases the compressive strength of geopolymer mortar continuously. The maximum compressive
strength achieved was 8.0 MPa with 10% red mud under 70⁰C for 24 hours [13]. This low value of

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012024 doi:10.1088/1742-6596/2315/1/012024

compressive strength can be linked to the absence of the alkali activator. In another study [18] conducted
on metazeolite as a low-calcium geopolymer binder with different percentages of quartz sand as waste
sand to replace standard sand, the geopolymer mortar shows significantly high compressive strength (57
MPa) with 25% red mud. Nevertheless, this value could reach 66.8 MPa by replacing 40% of the
standard sand with quartz sand. Replacing 100% of standard sand by waste sand does not change the
compressive strength, and its value remains at 57 MPa under 60 ⁰C for 48 hours [18]. In the case of fly
ash, the compressive strength of geopolymer mortars ranges from 4.66 to 32.7 MPa [11, 15, 17, 35].
The effect of sodium hydroxide molarity on compressive strength can be noticed. The compressive
strength drops from 32.7 to 23.86 MPa by increasing NaOH concentration from 8M to 10M. The effect
of waste sand comes in a positive way. Compressive strength increases 40% by replacing 50% of
standard sand with ground granulated blast furnace slag sand. The optimum percentage of red mud with
fly ash geopolymer mortars ranged from 20 to 30 percent with a standard sand and cured at 60 ⁰C for
(24-72) hours [15, 17, 35].
High calcium red mud has been investigated to replace ground granulated blast furnace slag [24, 31]
and stand-alone geopolymer binder [30]. In the case of GGBS, red mud addition shows a reasonable
decrease until 50% (85% MPa). After 50% red mud, compressive strength shows high degradation; for
example, at 75% red mud, the compressive strength drops to 30 MPa. The optimal curing temperature
varies depending on the red mud percentage. The ambient curing, 40 ⁰C, and 60 ⁰C fit the 25%, 50%,
and 75% red mud, respectively [31]. The high calcium red mud stand-alone binder at ambient curing
shows deficient compressive strength (6.6 MPa) [30]. This low compressive strength may be because of
the absence of heat curing. This assumption is based on the finding that the desired curing temperature
increases with increasing red mud percentage [31]. Moreover, red mud has an inadequate condensation
degree, as is stated previously in Eq. 1.

7. Conclusions
The statistical analysis of the chemical composition for low and high calcium red mud shows elevated
sodium oxide and LOI percentages. The synthesis oxide proportions are insufficient to produce an
appropriate geopolymerization process, so red mud is used as a partial replacement of other geopolymer
precursors. Low calcium red mud reduces setting time when it is added to fly ash geopolymers at an
optimum percentage of 15; while high calcium red mud optimum percentage is 20. The high calcium
red mud addition has a moderate increase on GGBS geopolymer setting time to the range of 75. The
required water-to-binder percentage to eliminate the workability loss can be calculated by applying our
proposed equation (Eq. 4) (without application of superplasticizer). The compressive strength of low
calcium red mud – fly ash-based geopolymer mortars have an optimum red mud percentage in the range
of 20% to 30%. The optimum sodium hydroxide concentration can reach 10 M. The curing conditions
are between 24-72 hours and 60-70 ⁰C. The compressive strength of high calcium red mud – GGBS
geopolymer mortars have a practical range to utilize red mud from 25 to 75% with curing conditions
from 25 to 60 ⁰C. The waste sand replacement can enhance the compressive strength of RM geopolymer
mortar.

Acknowledgment
Stipendium Hungaricum Scholarship Programme is highly acknowledged for supporting the Ph.D. study
and research work. The authors acknowledge the support by the Hungarian Research Grant NVKP_16-
1-2016-0019, “Development of Concrete Products with Improved Resistance to Chemical Corrosion,
Fire or Freeze-Thaw”.

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