BCR - From Byproduct To Brick: Using Red Mud Waste As A Construction Material

BCR - From Byproduct To Brick:
Using Red Mud Waste as a

Construction Material
August 6, 2000
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Figure 1. X-ray diffraction of the red mud sample.
Table 1. Chemical analysis of the red mud sample.

The Bayer Process is widely used throughout the world to produce alumina and aluminum. In this process, ground bauxite is reacted
with caustic soda under heat and pressure. The yield of this treatment, a sodium alumina solution, is then cleaned and decomposed.
The aluminum hydrate decomposition product is then transformed into alumina by a calcination process. Finally, liquid aluminum is
produced from alumina in electrolysis cells using direct current.1,2
At the end of the Bayer Process, a waste material called red mud is separated from the sodium alumina solution. This byproduct
contains iron, titanium oxides and undissolved sodium alumina, and, depending on the nature of the starting raw material, may also
contain elements such as Ca, Mg, V, Zr, Th, U, La and Se.
Approximately 35% to 40% per ton of bauxite treated using the Bayer Process ends up as red mud waste. In other words, for each ton
of alumina or half ton of aluminum, approximately one ton of red mud (based on dry weight) is produced. Disposal of the red mud is a
major problem due to the large amounts that are created1-in Seydisehir, Turkey, for example, more than 3 million tons of red mud
have accumulated over the past few decades. Dust from the red mud, which contains caustic soda, pollutes the air and creates severe
environmental problems.
Many researchers have examined this issue. Most of the studies so far have focused on dehydrating the red mud waste to reduce its
detrimental effects on the environment, or on extracting all or some of the compounds present in the red mud for use in the civil
engineering, metallurgy and chemical industries (see Figure 1).3 However, many of these processes have proved uneconomical, and
research in this field continues.4-12
Meanwhile, a different approach may hold the answer: using the red mud as a raw material in the manufacture of brick and structural
clay products.
Table 2. DTA analysis results of the red mud sample.*
What About Quality?

Quality is a logical question when using a waste product to manufacture other products-one that several researchers have endeavored
to answer. Studies examining the mechanical properties of structural brick and clay products made with red mud had three different
starting points in terms of the raw material used. In one group of studies, red mud was used with no additives or extraction from the
as-received state.6 A firing temperature range between 1000-1100C was used. This method generally gave higher porosity and lower
strength values compared to the other methods.
A greater number of studies used red mud that contained mineral additions, such as sand, calcium carbonate or fly ash;7 slag, volcanic
ash, refractory clay, brick clay, amorphous silicic acid or boric acid;8 caolinitic clay;9,10 or serpantine, wolastonite, silimanite,
zirconia, fosterite, ortoclas or anortite.11 In these studies, a somewhat wider firing temperature range, between 950-1400C, was used,
and considerably higher strength and lower porosity values were achieved.
The third approach to manufacturing construction materials from red mud required the extraction of Na2O from the raw material
before it was processed. This regeneration treatment enhanced the resulting mechanical properties and gave the lowest water
absorption ratios.12
However, adding and extracting minerals adds to the cost of the material, making it less desirable for use in brick manufacturing. For
this reason, some of the researchers decided to try to improve upon the first method, using the red mud without additives or
extractions.
Table 3. Grain size distribution of the red mud sample.
Experiments: Round 1
The Etibank Aluminum Plant in Seydieshir, Turkey, supplied the red mud samples for the experiments in this study. The samples were
taken from the pulp as it came out of the thickener, before it was pumped into the waste storage facility. The chemical analysis of the
samples is shown in Table 1.
To remove the organic matter and other undesirable residues, the red mud, in the form of pulp, was "washed"-i.e., diluted with water,
sieved through a 45-mm sieve, precipitated, decantated, and finally dried. Bar specimens with dimensions of 5 x 10 x 60 mm were
compacted in a laboratory-scale steel die. The samples were molded at room temperature using a uniaxial hydraulic press at a constant
pressure of 32 kg/cm2, and were fired in an electric furnace at 950-1150C, at a heating rate of 300C per hour.
Figure 2. The mechanical properties of red mud samples fired at various temperatures (molding pressure: 32 kg/cm2).
The thermal weight loss of the red mud samples was measured using Netzsch DTA-TG (Differential Thermal Analysis/Thermal
Gravimetry) and XRD analysis. These numbers are given in Table 2 and Figure 1, respectively.
Figure 3a. SEM micrograph of the red mud fired at 950C.

A Philips 1050/25 SW X-ray diffraction (XRD) instrument, a Jeol 840 JSM scanning electron microscope (SEM), and a Perkin Elmer
983 infrared spectroscopy (IR) instrument were used to determine the constituent minerals of the red mud samples. Hematite and
sodium aluminum hydrosilicate minerals were shown to be the major components of the red mud used in this study. The grain size
distribution of the dried samples, determined by Micromeritics Sedigraph 5000D, showed that 94% of the red mud sample was finer
than 10 mm (see Table 3).
Figure 3b. SEM micrograph of the red mud fired at 1050C .

Mechanical tests were carried out using an Instron 1115 test machine. The load during the compression tests was applied onto the
larger surface of the samples, with the dimensions of 5 x 10 x 30 mm. The mechanical properties and water absorption ratios of the
samples are shown in Figure 2. As seen from this figure, a noticeable increase in the mechanical properties occurs around the firing
temperature of 1050C.
Figure 3c. SEM micrograph of the red mud fired at 1150C.

As seen in Table 1, red mud contains oxides, such as Na2O, SiO2, CaO. These oxides form a glassy phase after sintering-a property
that can be exploited to develop strong ceramics. The high amorphous content of red mud tends to reduce this strength, but in these
experiments, the amorphous hematite was crystallized in the heating and cooling cycles, rendering it harmless.4
Figure 4. X-ray diffraction of the red mud sample fired at 1000C (a) and 1150C (b).
The microstructural evolution can be followed through the SEM micrographs given in Figure 3. In each micrograph pair, the one on
the left is a secondary electron image, and the one on the right is a back-scattered electron image representing the compositional
variation. These electron images show that sintering and the formation of the glassy phase take place more effectively at 1150C,
confirming the findings of the mechanical tests. The ultrafine particles seen in the micrograph of the sample fired at 950C are no
longer present in the sample fired at 1150C.
Figure 5. The mechanical properties of red mud samples molded at various pressures (firing temperature: 1150C). (a) Variation of the
compressive and three-point bending strengths with the molding pressure. (b) Variation of the water absorption ratio, porosity and
density with the molding pressure.
A more distinctive compositional image was also obtained from the sample fired at a higher temperature, as the smearing effect of the
ultrafine particles have been removed (i.e., regions of different contrast are better delineated). The glassy phase was thought to be
nepheline, as its presence was revealed by X-ray diffraction (see Figure 4).
Figure 6a. SEM micrograph of the red mud samples at 20 kg/cm2.
Experiments: Round 2
In the second set of experiments, the red mud samples were molded at various pressures (20 to 60 kg/cm2) and were fired at 1150C,
the temperature that gave the highest strength values in the previous set of experiments. The mechanical properties and water
absorption ratios of these samples are shown in Figure 5.
Figure 6. SEM micrographs of the red mud samples at 40 kg/cm2.

SEM micrographs of the samples pressed at 20, 40 and 60 kg/cm2 are given in Figure 6. Again, the back-scattered and secondary
electron images are given in the first and the second halves of each photograph, respectively. It appears from the figures that
increasing the pressure does not change the compositional images of the samples; that is, compositionally similar particles do not
necessarily agglomerate together. As expected, however, higher pressure gave lower porosity and higher strengths due to better
packing of the particles, and also enabled the glassy phase formed during firing to bind the particles more effectively.
Figure 6. SEM micrographs of the red mud samples at 60 kg/cm2.

In the experiments with washed red mud, the compression strength was found to increase as the firing temperature and the molding
pressure increased. For instance, 49I6 MPa compressive strength and about 9% water absorption ratio were achieved when 60 kg/cm2
molding pressure and 1150C firing temperature were used.
In many applications, a maximum 18% water absorption ratio is required for porous and non-porous bricks. When molding pressures
higher than 30 kg/cm2 are used, water absorption values generally lower than 18% have been achieved with washed red mud.
High-Strength Bricks
With the correct molding pressure and firing temperature, red mud-a waste product-can be successfully used to make quality bricks.
These experiments showed that the bricks made from washed red mud have higher strength values than red mud that has not
undergone the washing process. To reduce costs even further, it is possible to make bricks using the red mud as-received, without
washing. In either case, the achievable compressive strength levels are higher than those in the related Turkish standards of bricks (on
average 5-15 MPa and 30 MPa, respectively13). Moreover, the water absorption ratios are lower (18%) than those given in the related
Turkish standards.13
It may also be possible to make high-strength ceramic materials from red mud. However, further research is needed on this issue.
For More Information

For more information about using red mud to manufacture bricks, contact Mustafa Kara at the Tubitak-Marmara Research Center, P.O.
Box 21, TR-41470, Gebze-Kocaeli, Turkey; phone: (90) 262-6412300; fax: (90) 262-6412309; e-mail mustafa@mam.gov.tr.
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Using Red Mud Waste as a

Figure 1. X-ray diffraction of the red mud sample.

Table 1. Chemical analysis of the red mud sample.

Table 2. DTA analysis results of the red mud sample.*

What About Quality?

Table 3. Grain size distribution of the red mud sample.

Figure 3a. SEM micrograph of the red mud fired at 950C.

Figure 3b. SEM micrograph of the red mud fired at 1050C .

Figure 3c. SEM micrograph of the red mud fired at 1150C.

Figure 6a. SEM micrograph of the red mud samples at 20 kg/cm2.

Figure 6. SEM micrographs of the red mud samples at 40 kg/cm2.

Figure 6. SEM micrographs of the red mud samples at 60 kg/cm2.

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