Construction and Building Materials 166 (2018) 554–563

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Strength properties of Bayer red mud stabilized by lime-fly ash using

orthogonal experiments
Shutang Liu a, Zhuozhi Li a, Yingyong Li b, Weidong Cao a,⇑
a
School of Civil Engineering, Shandong University, No. 17923 Jingshi Road, Jinan, Shandong Province 250061, PR China
b
Highway Bureau, Shandong Province Transport Department, No. 19 Shungeng Road, Jinan, Shandong Province 250002, PR China

h i g h l i g h t s

The Bayer red mud (RM) was stabilized by lime and fly ash.

The UCS of stabilized RM was studied using orthogonal experiments.

The reaction mechanism of stabilized RM was analyzed through microscopic tests.

Stabilized RM can meet the requirement for the UCS of highway base material.

a r t i c l e i n f o a b s t r a c t

Article history: Bayer red mud (RM) was produced from aluminum ore according to Bayer process. In order to study the
Received 9 November 2017 feasibility of stabilized Bayer RM for use in road construction, strength properties of RM stabilized by
Received in revised form 28 January 2018 lime-fly ash using orthogonal experimental method were evaluated. In test design, the normalized
Accepted 30 January 2018
orthogonal table of L9 (34) was adopted. The influence of ratio of lime-ash, the dosage of lime and fly
Available online 22 February 2018
ash, and the type of Bayer RM (Two kinds of Bayer RM from different producers) on the unconfined com-
pressive strengths (UCS) of 7-day and 28-day curing age were studied. The experimental results showed
Keywords:
that these factors significantly influenced the UCS. The principal factors influencing 7-day UCS was ratio
Bayer red mud (Bayer RM)
Lime
of lime-ash, followed by chemical compositions of Bayer RM and the dosage of lime and fly ash in last.
Fly-ash The principal influencing factor of 28-day UCS was chemical compositions of RM, followed by ratio of
Unconfined compressive strength (UCS) lime-ash and the dosage of lime and fly ash in last. Then the optimum proportion for the UCS was deter-
Orthogonal experiments mined through the orthogonal analysis. The X-ray fluorescence (XRF) showed that chemical compositions
Hydration and contents of two types of RM were significantly different in iron, silicon and calcium. The microscopic
analysis of the raw material and stabilized material employed X-ray diffraction (XRD), scanning electron
microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS) showed that C3A(Ca3Al2O6), C2S, and
calcium carbonate increased under the optimal conditions of lime-fly ash stabilization, and hydrated sil-
ica aluminate and CSH were gradually generated. The stabilization mechanism of Bayer RM by lime-fly
ash is related to hydration like aluminate cement. There is no essential difference in reaction mechanism
for two kinds of Bayer RM and the difference in the strength properties is essentially originates from the
active material content.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction The component content of RM generated from different producing

Red mud (RM) is the main industrial waste from the alumina/
aluminium industry, and the history of Bayer RM can be retrospect
to the late nineteenth century. Bauxite is main mineral raw mate-
rial for production of alumina by utilizing the Bayer process [1].
⇑ Corresponding author.
E-mail addresses: gtreesl@sdu.edu.cn (S. Liu), lzz8786138@foxmail.com (Z. Li),
sgljliyyong@Shandong.cn (Y. Li), cwd2001@sdu.edu.cn (W. Cao).
area ore is quite different, and this can be seen from the colour of
the ore. The main chemical reaction occurred in Bayer process is
shown in equation (1) and RM is the alkali insoluble solid residue
after filtration [2].
½Al2 O3  nH2 O þ ½NaðOHÞ  3H2 O
¼ NaAl2 O3 ðOHÞ þ ð3 þ nÞH2 O þ RM ðinsolubleÞ ð1Þ
The amount of RM generated per ton of aluminium manufac-
tured is ranged between 1.9 and 3.6 tons hinge on the type of

https://doi.org/10.1016/j.conbuildmat.2018.01.186
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563 555

exploiting bauxite ore [3]. It is reported that the global RM residue
has reached 2.7 billion tons in 2007 with an annual growth of 120
million tons [4]. The accumulated storage volume of RM is approx-
imately 350 million tons by 2017 in China, whereas the rate of
multipurpose utilization is only 5.24% [5]. Currently, most RM is
disposed by means of heap storage or dumped into the sea, which
not only spends about 5% of alumina production value, but also
induces a range of environmental issues [6]. The most serious dam-
age caused by disposing in heap storage is the dam-breach of the
western dam, which is a part of the residue reservoir of the alu-
minium manufacturer at Ajka (Hungary) in 2010. A territory of
1017 ha was spilled and covered by about 0.8–1 million cubic
metre of highly-alkalic RM sludge in this failure [7]. Therefore, it
is an urgent need to address issues on the efficient multi-purpose
use of RM. In addition to a focus on environmental interest, there
are great potentials in economic interest for RM which contains
abundant oxides of the metals such as iron, silicon, aluminium,
and titanium [8], and considerable amount of rare earth elements,
such as zirconium, uranium, niobium, vanadium and thorium
[9–11]. Various explorations concerning extraction of valuable oxi-
des or utilization of RM have been put forward in many areas, such
as in construction material [12–15], ceramics [16–20], catalyst
[21–24], modified asphalt [25], and other fields [26,27]. Provided
that Bayer RM mix could attain the specified strength after stabi-
lization, it may be used in road construction.
Studies on the Bayer RM are generally performed with a single-
factor method (SFM) to obtain the optimum experimental param-
eters. But it cannot be used for identifying the effect degree of each
factor on the experimental results and the relationship among fac-
tors. Orthogonal test design is an experiment design procedure
applied to study multi-factor method (MFM), which can suppos-
edly avoid the weakness of SFM. At present, orthogonal experiment
has been widely used in many fields of research, but only a few
studies on RM have been conducted using orthogonal test design
method [28,29]. The main objectives of this research were to study
the strength properties of RM stabilized by lime-fly ash using
orthogonal experiments, and to demonstrate the feasibility of the
application of RM mix in road construction. Firstly, the unconfined
compressive strength test (UCS) was conducted and discussed.
Then the reaction mechanism was analysed through X-ray fluores-
cence (XRF), X-ray diffraction (XRD) and scanning electron micro-
scopy (SEM) methods.
2. Materials and experimental program
2.1. Raw materials
2.2. Orthogonal experiment design
Orthogonal experiment design is a method to arrange and anal-
yse multi-factor test using normalized orthogonal table. The
orthogonal table is a kind of normalized table designed according
to the orthogonality principle. The orthogonality is the guiding
principle of experiment design, which means that the main
impacts among all these factors can be derived without consider-
ing the influence of their interactions since the interactions are
uniformly distributed in each column [30,31]. The symmetry array,
a kind of orthogonal table, was employed in this paper, and it can
be represented by the symbol of Ln (rm).
Where L is mark of orthogonal table; n is line number of orthog-
onal table (number of experiment); r is level of each factor; m is
column number of orthogonal table (number of factor).
The processes of orthogonal experiment design can be summa-
rized as follows: determining evaluation property, selecting factors
and levels, choosing the orthogonal table and assigning the table
headers; determining the experimental scheme; statistically ana-
lysing the data (range analysis and variance analysis).
The critical advantage of orthogonal design relative to SFM is
that it allows the researcher to test the effectiveness of many fac-
tors simultaneously in a single experiment with far fewer experi-
mental units than it would take to exhaust all possible
intervention combinations [32]. Through statistical analysis on
the fewer certain experimental data, the optimum scheme could
be obtained, which may usually not be included in the fewer
experiments [33].
The table of L9 (34) was adopted in this test design, which
means results of 9 proportions of tests were able to represent the
information of total test plan (27 proportions). The orthogonal
table of L9 (34) was selected because it could be used for research-
ing 3 factors, and each factor with 3 levels. The three levels for
three factors were respectively as follows: 0.1:1 (A1), 0.5:1 (A2)
and 1.5:1 (A3) for ratio of lime-ash, 25% (B1), 50% (B2) and 75%
(B3) for the dosage of lime and fly ash, and SRM (C1), WRM (C2)
and 70%SRM + 30%soil (C3) for chemical compositions of RM. The
experiment scheme was shown in Table 5. The influences of ratio
Table 2
Characterization of lime.
Item Test values
Effective content of CaO and MgO/% 55.12
Moisture content/% 29.34
Fitness Residue on 0.60 mm sieve/% 18.9
Residue on 0.15 mm sieve/% 17.6

Two kinds of Bayer red mud were obtained from Shandong alu-
minium industry Co. Ltd. (named SRM) and Shandong Weiqiao Table 3
pioneering group Co. Ltd. (named WRM), respectively. The liquid Characterization of fly ash.
limit, plastic limit and natural moisture content of two kinds of Item Test values
RM were measured as shown in Table 1. Lime and fly ash used in Contents of SiO2、Al2O3 and Fe2O3/% 80.20
this study were supplied by Shandong Taihe highway Co. Ltd. Soil L.O.I/% 7.90
was used as a reference of RM in orthogonal experiment which was Percent passing of the 0.3 mm sieve /% 98.30
obtained from Shandong Taihe highway Co. Ltd. The characteriza- Percent passing of the 0.075 mm sieve /% 81.59
Moisture content/% 0.75
tion of the lime, fly ash and soil used in the experiments are shown
in Tables 2–4.

Table 4
Characterization of soil.

Table 1 Item Test values

Liquid limit and plastic limit of SRM and WRM. Moisture content/% 18.20
Liquid limit/% 34.0
Item Liquid limit/% Plastic limit/% Natural moisture content/%
Plastic limit/% 23.2
SRM 50.9 44.0 41.40 Plasticity index 10.8
WRM 48.0 33.4 40.73 Organic matter & inorganic salt content/% 0.13/0.36
556 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563

Table 5
Orthogonal experiment proportion.

Experiment No. Lime/% Fly ash/% RM/% Soil/% Ratio of lime-ash (A) The dosage of lime and fly ash/% (B) The type of RM (C)
1 2.3 22.7 75.0 0.0 10.00 25 SRM
2 4.6 45.4 50.0 0.0 9.96 50 WRM
3 6.8 68.2 17.5 7.5 10.00 75 SRM + SOIL
4 8.3 16.7 75.0 0.0 2.00 25 WRM
5 16.7 33.3 35.0 15.0 2.00 50 SRM + SOIL
6 25.0 50.0 25.0 0.0 2.00 75 SRM
7 15.0 10.0 52.5 22.5 0.67 25 SRM + SOIL
8 30.0 20.0 50.0 0.0 0.67 50 SRM
9 45.0 30.0 25.0 0.0 0.67 75 WRM

of lime-ash, the dosage of lime and fly ash and chemical composi-
tions of RM on 7-day and 28-day UCS were analysed in this
approach.
2.3. Experiments program and test methods
The orthogonal table was set for four factors – Three levels, with
another one column of the orthogonal table be remained as error
term. For pre-processing, natural curing and sieving by the 4.75
mm sieve were performed for RM raw materials. The moisture con-
tent of RM was measured, and then sealed and reserved.
The experimental program and processes are illustrated in
Fig. 1. The process includes the following major steps: mixing of
RM, lime and fly ash; material infiltration; compaction test; deter-
mining the optimum moisture content (OMC) and maximum dry
density; specimens fabricating; specimens curing and immersion;
UCS test and obtaining optimum proportion by orthogonal analy-
sis; microscopic analysis of the optimum proportion and raw RM
through XRD, SEM and EDS.
2.3.1. Heavy compaction test
In the raw material mixing and infiltrating stage, nearly 2 kg of
17.5–75%RM, 2.3–45% of line, 22.7–30% of fly ash and proper
dosage of soil were mixed and blended according to 9 kinds of pro-
portion. Water with 5 different proportions was then added and
blended. Afterwards, the mixtures were sealed with double PVC
plastic bags for 10 h. In the heavy compaction test stage, the test
pieces of compaction could be obtained with electric compaction
apparatus, and the weight of test pieces was ranging from 1.7 kg
to 2 kg. Thus, the curve of moisture content vs. dry density was
made and the OMC and maximum dry density were determined.
Chinese LD-III multi-function electric compaction apparatus
was employed in heavy compaction test. The mass of driving ham-
mer is 4.5 kg and drop height was 45 cm, with 27  5 times ham-
mering for each proportion. The picture of compaction test process
is as shown in Fig. 2.

2.3.2. Unconfined compressive strength (UCS) test

According to the compaction parameters determined by com-
paction tests, specimens of UCS test were fabricated. In the speci-
mens fabricating stage, nearly 200 g of raw materials were mixed

Fig. 1. Technological process of orthogonal experiment of Bayer RM. Fig. 2. Compaction test process.
 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563 557

and blended, and then 50 mm  50 mm cylindrical specimens 2.3.3. X-ray fluorescence (XRF) spectroscopy
were fabricated in the mould as shown in Fig. 3. Before UCS test, XRF analysis was performed to determine the chemical compo-
the specimens were stored for the predetermined age curing in a sitions of the all raw RM materials using the Japanese Rigaku ZSX
curing chamber that maintain the temperature at 20 ± 2 °C and rel- Primus II fully automatic scanning X-ray fluorescence spectrome-
ative humidity of 95% at the ages of 7 and 28 days, and then stored ter, with detection range from 6C to 92U, with accuracy from
immersion in water with the temperature of 20 ± 2 °C for 24 h as 0.0001% to 100%.
Chinese criterion JTG E51-2009. In the strength test stage, the test-
ing apparatus used for measuring pavement material strength with 2.3.4. X-ray diffraction (XRD)
loading rate 1 mm/min was employed and each mixing proportion XRD analysis was conducted to analyse the phase changes of
was conducted on six cylindrical specimens and then the average the lime-fly ash stabilized material using the Netherlands PANalyt-
within the error range was recorded. The results of each proportion ical EMPYREAN X-ray diffraction system with a Cu Ka radiation
were arranged and summarized for range analysis and variance source (Lambda = 0.15418 nm) and scanning speed of 5(°)/min.
analysis. The pictures of specimens and immersion condition are The power rating of X-ray generator was set up to 60 kV and 60
presented in Fig. 4. mA. A PIXcel3D detector was applied with a guaranteed resolution
UCS test was conducted to characterize compressive capacity of of 0.028° and pixels size of 55 mm  55 mm. The measurements
stabilized materials using Chinese LD-127s multi-function paving were conducted in the range of 2h values of 10–90° with a step size
material strength testing apparatus. The optimum mix proportion
of 7 and 28 days could be obtained through orthogonal analysis.
After that, the specimens of optimum mix proportion were ground Table 7
Range analysis to 7-day UCS.
and drying at 105 °C for the samples of XRD, SEM and EDS, then the
reaction mechanism was deduced. Item A B C NULL
Mean1/% 0.407 0.686 0.963 0.874
Mean2/% 0.845 1.074 0.655 0.864
Mean3/% 1.412 0.905 1.046 0.926
Range 1.005 0.388 0.391 0.062
Influence factor ranking A>C>B
Optimal scheme A3B2C3

Table 8
Range analysis to 28-day UCS.

Item A B C NULL
Mean1/% 0.417 1.170 1.326 1.147
Mean2/% 1.329 1.445 0.351 1.182
Mean3/% 1.614 0.745 1.682 1.030
Range 1.197 0.700 1.331 0.152
Influence factor ranking C>A>B
Optimal scheme A3B2C3
Fig. 3. Schematic diagram of cylindrical mold.

Fig. 4. Specimens before immersion (a) and after immersion (b).

Table 6
Experimental results of heavy compaction and UCS tests.

Experiment No. Optimum moisture content (OMC)/% Maximum dry density/g/cm3 7-day compressive strength/MPa 28-day compressive strength/MPa
1 37.0 1.377 0.265 0.701
2 32.0 1.429 0.336 0.035
3 32.2 1.309 0.619 0.515
4 31.4 1.544 0.448 0.520
5 33.0 1.359 1.175 2.244
6 33.5 1.285 0.913 1.222
7 34.3 1.388 1.344 2.288
8 36.0 1.260 1.710 2.056
9 31.0 1.328 1.182 0.497
558 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563

of 0.0001°. ICDD PDF-4 2014 database was applied to identify the
phase.
2.3.5. Scanning electron microscopy (SEM/EDS)
Scanning electron microscopy (SEM) coupled with energy-
dispersive X-ray spectroscopy (EDS) analysis using the German
Carl Zeiss SUPRATM 55 thermal field emission scanning electron
microscopy were conducted to study the microstructure and com-
ponent of the raw materials and stabilized RM. Pre-processed sam-
ples were analysed under the operating condition of ultra-high
vacuum with working distances of 6.0–8.6 mm, an accelerating
voltage of 3–5 kV, and secondary electron detector. Micrographs
were obtained at magnifications of 2000, 5000 and 20000. EDS
analysis was employed by Bruker X-Flash 5010 EDS detector with
132 eV @ Mn Ka resolution and the analysable elements range
from 4 Be to 94 Pu.
3. Results and discussion
3.1. Orthogonal experiment
The results of the orthogonal experiments on 7-day and 28-day
UCS are shown in Table 6, respectively.

Fig. 5. Trend chart of each factor for 7-day UCS.

Fig. 6. Trend chart of each factor for 28-day UCS.

Table 9
Variance analysis to 7-day UCS.

Variance source Deviance quadratic sum Degree of freedom Mean square F value p- value Significance
A 1.5242 2 0.7621 233.6111 0.0043 **
B 0.2271 2 0.1135 34.8012 0.0279 *
C 0.2540 2 0.1270 38.9321 0.0250 *
Error 0.0065 2 0.0033
Total 2.0118 8
*
Means significant under the significant level of 0.05.
**
Means significant under the significant level of 0.01.

Table 10
Variance analysis to 28-day UCS.

Variance source Deviance quadratic sum Degree of freedom Mean square F value p- value Significance
A 2.3444 2 1.1722 62.0704 0.0159 *
B 0.7469 2 0.3735 19.7752 0.0481 *
C 2.8520 2 1.4260 75.5105 0.0131 *
Error 0.0378 2 0.0189
Total 5.9810 8
 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563 559

The range analysis results of 7-day and 28-day UCS are shown
in Tables 7 and 8, respectively. The factors influencing 7-day UCS
in sequence are ratio of lime-ash, RM compositions and the dosage
of lime and fly ash; whereas, those influencing 28-day UCS are RM
compositions, ratio of lime-ash, and the dosage of lime and fly ash.
Moreover, each factor significantly influences both 7-day UCS and
28-day UCS. Since UCS is the major parameter for the selection of
pavement material, the optimal scheme of stabilized Bayer RM
mainly depends on the range analysis to UCS at the ages of 7-day
and 28-day. For factor A, A3 was selected, while as for factors B
and C, B2 and C3 were the optimum for both 7-day and 28-day
UCS, respectively. Hence, the best scheme for experiments is
A3B2C3, i.e., ratio of lime-ash is 1.5:1; the dosage of lime and fly
ash of 50%; and RM composition is 70%SRM + 30% soil. Besides,
RM compositions serve a primary role for 28-day UCS.
According to the principle of range analysis, the trend chart of
each factor for 7-day UCS and 28-day UCS are drawn, as in Figs. 5
and 6. From Figs. 5 and 6, it can be seen that increase in lime pro-
portion of ratio of lime-ash and addition of soil to modify RM com-
position could improve 7-day and 28-day UCS, while with the

Table 11
Chemical composition of SRM and WRM mass/%.

RM types CO2 Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O

SRM 20.72 6.21 0.31 17.37 14.03 0.22 0.45 0.14 0.15
WRM 17.77 5.84 0.44 22.25 10.78 0.19 0.91 0.26 0.10
RM types CaO TiO2 V2O5 MnO Fe2O3 SrO ZrO2 PdO TeO2
SRM 9.56 4.87 0.66 0.04 24.87 0.01 0.08 0.22 0.09
WRM 2.90 4.91 0.22 0.06 33.16 0.02 0.01 0.08 0.07

Fig. 7. XRD patterns of the SRM raw materials.

Fig. 8. XRD patterns of the WRM raw materials.

560 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563

increase of the dosage of lime and fly ash, a turning point of UCS
appears, after that the strength decrease. Furthermore, the rela-
tionship between the dosage of lime and fly ash and UCS showed
that the optimum proportion of lime-fly ash stabilized Bayer RM
can be further tapped to reach a higher strength. Hence, a further
study on mix proportion should be conducted in the next step.
The variance analysis results of 7-day and 28-day UCS are
shown in Tables 9 and 10, respectively. Table 9 shows that when
the value of a is 0.05, FA, FB and FC are greater than F0.05 (2, 2),
which value is 19. Factor A significantly influences 7-day UCS,
meanwhile factors B and C distinctly influence 7-day strength. This
result further proved that ratio of lime-ash, followed by RM com-
position and the dosage of lime and fly ash, are the main factor
influencing 7-day UCS. Similarly, Table 10 shows that factor A, B
and C could distinctly influence 28-day UCS, further proving that
RM composition, followed by ratio of lime-ash and the dosage of
lime and fly ash, are the main factor influencing 28-day.
The UCS of the optimum scheme, named A3B2C3, was tested
under the same condition. The results of 7-day and 28-day strength
are 1.799 MPa and 2.341 MPa, respectively. Hence, above results
also could surely be proof positive of orthogonal experiment.
The UCS of optimum scheme meets Chinese criterion require-
ments for 7-day UCS of base layer and subbase layer [34]. So the
optimum scheme of the stabilized Bayer RM can be used as base
layer and subbase layer materials from the point of view of the
compressive strength. While the environmental effect of the stabi-
lized Bayer RM needs further research in the next step.
3.2. Microscopic analysis and reaction mechanism
3.2.1. Component analysis
Chemical composition of SRM and WRM were determined by
XRF and the results are shown in Table 11. The result showed
the main compositions of RM are: Fe-oxides, Al-oxides, C-oxides,
Si-oxides, Na-oxides, Ca-oxides and Ti-oxides, and hematite are
major phases both in the SRM and WRM. It can be seen that the
content of Ca and Si in SRM is greater than in WRM, and their def-
erence is approximately 6.66% and3.25%, respectively. Also, Fe and

Fig. 9. XRD patterns of the optimum proportion under 7-day curing storage.

Fig. 10. XRD patterns of the optimum proportion under 28-day curing storage.
 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563 561

Al of WRM are obviously higher than SRM, which is approximately
8.29% and 4.88%, respectively. All the results above prove that the
SRM contain more hydrated active material compared with WRM,
in which has high content of Fe2O3.
3.2.2. Phase analysis
The crystalline phases in the SRM and WRM were performed by
XRD, and the results are shown in Figs. 7 and 8. The main crystalline
phases of iron in both SRM and WRM are hematite (Fe2O3), while
goethite (FeO(OH)), maghemite (c-Fe2O3) exist in SRM and pyrite
(FeS2) exist in WRM. Other crystalline phases are mainly
calcite (CaCO3), quartz (SiO2), perovskite (CaTiO3), gismondine
(CaAl2Si2O84(H2O)), Amesite ((Mg2Al)[SiAlO5](OH)4) and boehmite
(c-AlO(OH)) in SRM while boehmite (c-AlO(OH)), gibbsite
(Al(OH)3), perovskite (CaTiO3), morimotoite (Ca3TiFeSi3O12),
mayenite (Ca12Al14O33) and a few calcite (CaCO3) are in WRM.
The XRD analysis results of the optimum proportion under
curing condition at the ages of 7 and 28 days are shown in

(a-2000X) (a-5000X) (a-20000X)

(b-2000X) (b-5000X) (b-20000X)

(c-2000X) (c-5000X) (c-20000X)

(d-2000X) (d-5000X) (d-20000X)

Fig. 11. SEM micrographs of SRM (a), WRM (b), 7-day (c) and 28-day (d).
562 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563
Figs. 9 and 10, respectively. The main crystalline phases of 7-day
optimum scheme are quartz (SiO2), calcite (CaCO3), gismondine
(CaAl2Si2O84(H2O)), calcium aluminium oxide (Ca3Al2O6), hema-
tite (Fe2O3), perovskite (CaTiO3) and yeelimite (Ca4Al6O12SO4). By
comparison with Figs. 7 and 9, the characteristic peaks of boehmite
(c-AlO(OH)) and some phases like goethite (FeO(OH)), maghemite
(c-Fe2O3) and Amesite ((Mg2Al)[SiAlO5](OH)4) were not detected,
but the peak of calcium aluminium oxide (Ca3Al2O6) was observed.
In term of composition, the calcium aluminium oxide (Ca3Al2O6)
bears a resemblance to boehmite (c-AlO(OH)), which may illus-
trates the calcium aluminium oxide (Ca3Al2O6) is one of hydration
products of boehmite (c-AlO(OH)) and Ca(OH)2 from lime. The
intensity of gismondine (CaAl2Si2O84(H2O)) diffraction peak is
accordingly increased and many new peaks appear in the current
curve, which may infer that calcium aluminium silicate hydrate
is boosted by curing agent and NaOH from Bayer process.
Within the curing period, more hydration products were
generated, including not only existing phases, such as gismondine
(CaAl2Si2O84(H2O)) tricalcium aluminate (Ca3Al2O6), but also
newly formed phases, such as calcium silicate hydrate (Ca2 (SiO4)
nH2O) in Fig. 10. The locations of the main diffraction peaks in
Figs. 7, 9 and 10 are similar, but diffracted intensity wore off and
dispersion strengthening, which indicates that the hydration pro-
duct is basically amorphous substance, such as calcium aluminium
silicate hydrate and calcium silicate hydrate (CaOSiO2H2O, C–S–H).
Intergranular space of RM was filled with multiple newly generated
crystalline state and amorphous substances, which enhanced the
strength of stabilized material.
3.2.3. Microstructure analysis
The hydration products are divided into crystalline state and
amorphous state. The XRD analysis shows that crystalline sub-
stance can be gradually generated and form the strength. For
amorphous substance, SEM and EDS were used to find the products
like CSH. The specimens of SRM, WRM, optimum scheme for 7-day
and 28-day were analysed after grinding and drying, and the
results of SEM are shown in Fig. 11. The microscope whose magni-
fications are 2000, 5000 and 20000 from left to right,
respectively.
Table 12
Component analysis of prism-shaped crystal.
Element Weight percentage/% Atomic percentage/%
C 0.41 0.67
O 54.15 66.98
Al 42.75 31.35
Ti 0.60 0.25
Fe 2.10 0.74
Total 100.00 100.00
Fig. 12. EDS analysis of prism-shaped crystal.
Fig. 11(a) and (b) showed the differences of SRM and WRM in
form and composition. Prism-shaped, schistose and layered parti-
cles exist widely in SRM but rarely in WRM, the sizes of which
are ranging from 300 to 400 nanometres up to 1–2 micrometres
in diameter. For WRM, crystal druses with rose-shaped and
scale-shaped are the main form ranging from 200 nanometres to
4 micrometres in diameter. A rough, multiporous and
unconfined-bonding film is formed, which determines their low
compressive strength. Fig. 11(c) and (d) performed the morpho-
logic change with the addition of lime-fly ash. Growth of crystal
was surrounded by the schistose and layered particles, while the
particles were become greater in size. Part of the pore was filled
with tiny crystals and amorphous substance. The diameter of the
particle could grow to 20–30 micrometres while the surface was
become smoother over time. Some reticulate, flocculent and
threadiness amorphous body appear in 28-day micrographs, which
exist in the big particles and connect different parts, like Fig. 11 (d-
20000X). Thus, this threadiness amorphous is consistent with the
characteristic of CSH, and net structure increases the mechanical
strength of stabilized Bayer RM. Then, the schistose particles may
be Ca(OH)2, tricalcium aluminate (Ca3Al2O6) or calcite (CaCO3).
The Prism-shaped particles was analysed by EDS and the result
is shown in Table 12 and Fig. 12. The atomic ratio of Al/O is about
1/2, while there are almost no other elements except hydrogen.
Hence, this prism-shaped particle may well be boehmite (c-AlO
(OH)). It proved that SRM has more active substance than WRM
integrated with microstructure analysis.
To sum up, when lime and fly ash were added, strength was
improved by hydrating reactions similar to cement. Firstly, boeh-
mite and goethite participated in a reaction and tricalcium alumi-
nate was the main short-term product. Then the time went on,
hydrated silica aluminate and CSH were gradually generated,
which play a major role of the long-term strength. The resem-
blance of reaction mechanism between SRM and WRM is shown
in reactants and the products, which suggested the similar strength
law is consisted in Bayer RM.
4. Conclusions
On the basis of analyses of experimental results on the strength
properties of Bayer RM stabilized by lime-fly ash using four factors
– Three levels orthogonal experiments and reaction mechanism
analysis, the main findings and conclusions are summarized as
follows:
(1) The factors of ratio of lime-ash, the dosage of lime and fly
ash, and the type of RM significantly influence both 7-day
UCS and 28-day UCS of RM stabilized by lime-fly ash.
The principal factors influencing 7-day UCS are ratio of
 S. Liu et al. / Construction and Building Materials 166 (2018) 554–563
lime-ash, followed by chemical compositions of RM and the
dosage of lime and fly ash in last. While, the principal factors
influencing the 28-day UCS are chemical compositions of
RM, followed by ratio of lime-ash and the total dosage of
lime and fly ash.
(2) The optimum scheme of orthogonal experiments is ratio of
lime-ash of 1.5:1, the dosage of lime and fly ash of 50%,
and RM composition of 70%SRM + 30%soil. At the standard
curing conditions with the temperature of 20 ± 2 °C and
95% of relative humidity, the UCS of the optimum scheme
are 1.799 MPa and 2.341 MPa at the ages of 7 and 28 days,
respectively. From the perspective of compressive strength,
the stabilized Bayer RM can be used for base and subbase
materials in highway construction.
(3) Boehmite (c-AlO(OH)) and goethite (FeO(OH)), as active
materials in RM, are cooperative with active material in lime
and fly ash such as Ca(OH)2, participating in co-participation
reaction. Tricalcium aluminate (Ca3Al2O6) is the main short-
term product making significant contribution to the
strength. Afterwards, hydrated silica aluminates like gis-
mondine (CaAl2Si2O84(H2O)) and CSH are gradually gener-
ated, which play a major role in the long-term strength.
The strength of Bayer RM stabilized by lime and fly ash is
improved by hydrating reactions, which is similar to the
hydration of cement.
(4) There is no fundamental distinction in reaction mechanism
between SRM and WRM. The strength of stabilized RM
depends on the active material such as c-AlO(OH), FeO
(OH) and CaO (generate CaCO3 in heap storage), which is
the deciding factor for effective hydrate. The different con-
tent of active materials in two kinds of RM is the main rea-
son for their different strengths.
Acknowledgements
This work was supported by Primary Research & Development
Plan of Shandong Province in China (2016GSF116001) and Natural
Science Fund of Shandong Province in China (ZR2013EEM028), and
the authors would like to acknowledge their financial support.
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