Nano Hybrids and Composites Submitted: 2019-02-13

ISSN: 2297-3400, Vol. 25, pp 46-68 Revised: 2019-03-12

doi:10.4028/www.scientific.net/NHC.25.46 Accepted: 2019-03-13
© 2019 Trans Tech Publications, Switzerland Online: 2019-04-23

A Novel Method for Mixing Nanomaterials with Soil

Ali Akbar Firoozi1, Mohd Raihan Taha1,2, Tanveer Ahmed Khan3*,
Farzad Hejazi4, Ali Asghar Firoozi1, Jamal M.A. Alsharef1
Department of Civil & Structural Engineering, Universiti Kebangsaan Malaysia (UKM), Bangi,
1

Selangor, Malaysia.
2
Institute for Environment and Development (LESTARI), Universiti Kebangsaan Malaysia (UKM),
Bangi Selangor, Malaysia.
Department of Civil Engineering, Bahauddin Zakariya University Multan, Pakistan.
3

Email: tanveerkhan@bzu.edu.pk
Department of Civil Engineering, Faculty of Engineering, Universiti Putra Malaysia (UPM),
4

Serdang Selangor, Malaysia. Email: farzad@upm.edu.my

*
Corresponding author, Email: tanveerkhan@bzu.edu.pk

Keywords: Mixing; Nano-copper; kaolinite; Horizontal ball mill; De-agglomeration; Distribution

Abstract. Mixing of nano-sized powders with soils (macro-sized powders) is a noteworthy issue for
geotechnical projects. Thus, this study examined the horizontal ball mill mixing of nano-copper oxide
with kaolinite. Ball milling parameters (rotation speed, weight ratio of balls to powder and milling
time) of the planetary ball milling were optimized for proper mixing of nano-copper oxide and
kaolinite powder. Results showed that increase in mixing time decreased the agglomeration of nano-
copper powders and kaolinite and increased the homogeneity of nano-copper powder with kaolinite
particles. The quality of mixing was assessed through intensity and scale of segregation using
concentration data obtained through energy dispersive X-ray spectroscopy (EDS) and X-ray
diffraction (XRD) analyses. It was observed through these two tests that, increase in ball milling time
after 6 hours resulted in grain size reduction. Field emission scanning electron microscopy analysis
showed that nano-coppers were regularly found on the surface of kaolinite particles after 6 hrs. of
horizontal milling at 4:1 ratio of balls to powder mixture. Furthermore, 24 hrs. mixing resulted in
grinding of kaolinite particles and hence their size was reduced. Particle size analysis confirmed these
results, as the highest size span value of 3.417 was observed after 6 hrs. milling with speed of 200 rpm.

1. Introduction
High-performance structural materials of next-generation will regularly employ nanoparticles and
nanocomposites because of their advantageous qualities, such as mechanical strength, hardness, and
corrosion resistance [1-7]. In this regard nanotechnology has gathered considerable interest from
industries and implements an important function in fundamental research [8]. A part of this broad
field comprises nanomaterials, that are materials with one or more dimensions in the range of 1–100
nm. The properties of these materials can be significantly different from the behavior of their parent
materials [9]. When a particle is reduced to the nano-size range, a substantially larger surface area
per unit volume is attained; and more importantly, a prominently increased percentage of atoms or
molecules are found to be present on its surface [1, 7].
Cui et al. [10] showed that the addition of carbon-nano tubes in concrete increases the hydration rates
and stronger bonds build up between the carbon-nano tubes and the cement paste, while Petrunin et
al. [11] recorded increase of 70% in the compressive strength of carbon-nano tubes reinforced
concrete and reduction of 12% in the heat conductivity. Moreover, numerous researchers evaluated
the influence of nano-clay on asphalt mixture and it was found that nano-clay can substantially
improve the mixture properties. Nano-clay makes the clay complexes well-matched with organic
monomers and polymers. These nano-composites comprise of one or polymers with layered silicates
having layer thickness in the order of 1 nm. Common clays are natural minerals and are subjected to

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 Nano Hybrids and Composites Vol. 25 47

natural dissimilarities in their formation. Nano-clay with big active surface area (up to 700 to
800 g /m2) helps to have an intensive interaction between the bitumen and the nano-clay [12-16].
Fine particles frequently flocculate to produce powdered agglomerates with sizes that are
considerably larger than that of the chief particles. This conduct makes it difficult to obtain a
uniformly dispersed powder mixture due to the atomic bond [17]. Concurrently, aggregate ions or
homogeneities introduced at the initial step may continue in all the stages and influence the final
properties of the product [6, 18].
Though, the mixing of particulate solids is one of the oldest and most important jobs in process
industries, yet it is one of the least understood [19]. The energy of the milling media is dependent
upon the internal mechanics of the specific mill, the power supplied to drive the milling process, and
the size, composition and size distribution of the balls. Kinetic energy of the balls is a function of
mass and velocity, thus, dense materials (steel or tungsten carbide) can provide more energy than
lighter materials (such as ceramic balls). Ball size and size distribution can be optimized for a given
mill. Dense packing of balls decreases the mean free path of the ball motion, while thinned
distribution reduces collision frequency. Planetary ball mills, Spex shaker mill, specially designed
mills and vibratory mills etc. are laboratory-scale equipment. Whereas, at commercial scale the
quantities are milled in attritors or large tumbler ball mills [20, 21].
De-agglomeration can be achieved through two possible mechanisms, first; rupture, that is
characterized by an abrupt splitting of agglomerates into several fragments; and second; erosion, that
is characterized by a continuous detachment of small fragments from the agglomerate which occurs
at a lower stress than rupture [22]. Studies on de-agglomeration, which is related to powders, have
been executed on ceramic systems, such as alumina and titanium [23-27].
The main objective of this research is to evaluate the potential of horizontal ball milling and mixing
characterization of nanoparticles (nano-copper) in clayey soil (kaolinite) to utilize more advantages
of nanoparticles properties and to obtain homogenous mixing with less agglomeration. This area of
research is relatively new and presents a high potential for numerous applications; both in research
and the industry.

2. Material and Methods

The presented work is a part of research project entitled as “Evaluation of improvement potential of
nanomaterials for stabilizing clayey soils”. While, nanomaterials (nano-copper, nano-alumina, nano-
magnesia and nano-clay) were employed as stabilizing agents for clays (kaolinite and illite) for this
project. Whereas, the clay mineral used in this study was kaolinite with a white color, and nano-
copper as additive for mixing with soil (kaolinite). Nano-copper was selected because of its black
color, thus, during mixing, nanoparticles are easily visible in the mixture. The details of two materials
and mixing method are discussed below.
2.1 Kaolinite
Kaolinite was obtained from L & T Mineral Sdn. Bhd., Kuchai Lama, Malaysia, under the trade name
of “S-300” from “Kaolin, Malaysia”, Perak, Malaysia. Table 1 presents the physical and chemical
properties of kaolinite, which were determined during this study by performing a series of chemical
and geotechnical laboratory experiments and using procedures that are recommended by relevant
standards. Figures 1 and 2 show the scanning electronic microscopy image and X-ray diffraction
results of kaolinite particles, respectively.
48 Nano Hybrids and Composites Vol. 25

Table 1 Physical and chemical properties of kaolinite

Physical properties Chemical compositions
Moisture content Below 1.5% Formula Cont. (%)
pH 4.35 SiO2 85.76
100 mesh residue Below 10% Al2O3 9.11
60 mesh residue Below 0.5% Fe2O3 0.38
Specific gravity (Gs) 2.723 K2O 1.34
Average particle size 2-3 µm Heat loss 3.41
LL 47 - -
PL 26 - -
PI 21 - -
The morphology of the kaolinite particles, as shown in Figure 1, reveals well defined pseudo-
hexagonal and in some deposits relatively thick books or stacks and some long-vermicular-shaped
crystals. Kaolinite has a relatively low surface area and a low surface charge compared to illite. Thus,
it exhibits low absorption and adsorption. Kaolinite particles of 2 to 3 µm thickness are thin plates
that orient on a coated surface because of their flat two-dimensional nature.

Figure 1 Kaolinite particles under SEM @ Mag = 1.00 KX

The kaolinite particles were also characterized using X-ray diffraction. The X-ray diffraction result
for kaolinite is shown in Figure 2. X-ray diffraction patterns of kaolinite sample show high intensity
and broad peaks of silica at 20.85° and 26.62°. Kaolinite is the predominant mineral in kaolinite
sample as expected, which can be identified by its characteristic X-ray diffraction peaks at 8.94°,
12.75°, 24.61° and 35.27°.
 Nano Hybrids and Composites Vol. 25 49

Figure 2 XRD pattern of kaolinite

2.2 Nano-copper oxide
The nano-copper oxide powder used in this research was 99.99% pure and supplied by Inframat
Advanced Materials, Manchester, CT, USA. The nano-copper powder is insoluble in water and
dissolves slowly in alcohol or ammonia solution. It is also soluble in dilute acids, NH4Cl, (NH4)2CO3,
and potassium cyanide solution at high temperature. Nano-copper oxide is a widely used material and
is applied as catalyst for superconducting materials, sensing materials, thermoelectric materials,
ceramics, glass and others. The properties of nano-copper oxide as provided by the company is shown
in Table 2.

Table 2 Properties of nano-copper oxide

Property Value
Formula CuO
Particle density (gr/cm3) 6.3-6.49
2
Surface area (m /g) N/A
Average particle size (nm) 100
Solubility in water (%) Insoluble
o
Melting point ( C) 1,326
Purity 99.99 %
Black powder
Appearance and odor
Odorless
Crystal structure N/A
A field emission scanning electron microscopy image of nano-copper is shown in Figure 3 and an
X-ray diffraction pattern for nano-copper is given in Figure 4. The field emission scanning electron
microscopy image shows that nano-copper possesses needle-like shape, and the average particle
diameter is approximately100 nm. The result of X-ray diffraction pattern shows that nano-copper can
be identified at 35.44°, 38.61°, 48.75°, 61.53°, 66.28°, and 68.05° peaks.
50 Nano Hybrids and Composites Vol. 25

200 nm

Figure 3 FESEM image of nano-copper oxide powder @ Mag = 20.00 KX

Figure 4 XRD pattern of nano-copper oxide

2.3 Mixing procedure
Three mixing methods were examined. In the first method, the nanomaterials (nano-coppers) were
mixed with required quantity of water and then the mixture was put in a beaker. The beaker was then
placed in an ultrasonic bath of water for two hours (sonication) to agitate particles to lose adhering to
surfaces as suggested by Wei et al. [28]. After ultra-sonication, the suspension was mixed with the
soil (Figure 5). However, it was found difficult to obtain a homogeneous mixture of the soil-
nanomaterial mixture by this method.
 Nano Hybrids and Composites Vol. 25 51

Figure 5 Typical ultrasonic bath used in this study

In the second method, the dry soil was mixed with nanomaterials and then the water was added to the
mixture. In this method, mixing was carried out into two stages. Initially premix or hand mixed [29]
where the quantity of soil was divided into ten portions and each portion was spread in a square pan
(50×50 cm) then the required amount of nanomaterial was sprayed using sieve number 200 as shown
in Figure 6. Each portion was mixed alone manually for 5 minutes then put in a bowl (Figure 7) and
the mixture was mixed by a horizontal cylindrical mixer machine at 139 rpm for one, three, five, and
seven hours [30]. Yet this procedure was not able to obtain completely homogeneous mixture of the
soil-nano-copper as some particles of soils and nano-coppers remained agglomerated.

Figure 6 Spraying of nano-copper on the soil layer

52 Nano Hybrids and Composites Vol. 25

Figure 7 Mixing full quantity in a pot

In the third method, the dry soil (792 gm) was mixed with nano-copper (8 gm) by horizontal ball mill.
Mixing of the elemental powders (99% kaolinite and 1% nano-copper) was performed at laboratory
scale. To determine the feasibility of a mixing process for nanoparticles, forces generated during
mixing should be estimated. It is then determined that these forces are larger than the cohesive or
adhesive forces acting on powder particles.
Inter particle forces can be classified into two groups: first, mechanical interlocking forces, such as
Van der Waals, electrostatic and magnetic attraction, and chemical forces, or those that do not require
material bridges; and second, forces such as capillary bonding forces and immobile liquid bridges, or
those where a material bridge is present. In general, at low humidity, the first group is important, and
the second becomes dominant at high humidity. Consequently, for dry particle mixing, the cohesive
and adhesive forces acting between particles depend on molecular forces, and their importance
decreases with increasing particle size.
Body forces (gravity) are proportional to the cube of the particle diameter, whereas Van der Waals
forces are proportional to the particle diameter. Thus, for relatively large particles (greater than 10–
20 µm), the inter particle forces are small in comparison to particle weight. The function of these
forces in mixing can be neglected, and the effectiveness of a dry mixing process can be analyzed in
terms of the applied macroscopic forces. Precisely, these powders can be mixed, provided that the
applied macroscopic forces, that is, the shear and extensional/compressive stresses, are sufficiently
large to break any loosely formed aggregates. In most cases, mixing can be achieved by simply
agitating the powder, and the only concern in mixing of these powders is the mixing efficiency. The
overall motion of particles must be appropriate for obtaining efficient mixing and can be quantified
in terms of the spatial distribution of the particle trajectories.
To optimize the mixing process, filling ratio and media ratio (Equations1 and 2) were determined in
the first part of investigation, and then the kinetics of mixing was determined in the second part.
Vfeed Vnano − copper + Vkaoliniite + Vballs
Filling Ratio (FR) = = (1)
Vchamber Vchamber
Vnano − copper + Vkaolinite
Media Ratio (MR) = (2)
Vnano − copper + Vkaolinite + Vballs
Dry kaolinite was mixed with nano-coppers into two stages. Initially, premixing or hand mixing was
conducted for 20 min, then, the sample was loaded in a 1.5 L plastic jar. After that steel balls of three
sizes (5,8, and 12 mm) were used to grind the mixture for 1–24 h (Figures 8-10). Selected variable
parameters and their levels are provided in Figure 11 and Table 4. The weights of the balls were 4.1,
13.8 and 32.5gm for 5, 8 and 12mm diameter balls, respectively.
 Nano Hybrids and Composites Vol. 25 53

ball (12mm)
ball (5mm)

ball (8mm)

Figure 8 Planetary steel ball mills

Nano-copper

Kaolinite

Figure 9 Powder hand mixing process

Figure 10 Horizontal ball mill process

54 Nano Hybrids and Composites Vol. 25

X Y Z (Sample code)

Milling speed in rpm Balls to powder ratio Milling time in hr.

1 for 200 rpm 1 for 1:1 1 for 1 hr.

2 for 400 rpm 2 for 2:1 2 for 2 hr.

3 for 4:1 3 for 6 hr.

4 for 24 hr.
Figure 11 Variable parameters and their level in design experiment
Table 3 Different conditions of designed experiment
Mix soil Milling
masses of balls Duration
No. code amount speed
(gr) (hour)
(gr) (rpm)
1 111 800 800 200 1
2 112 800 800 200 2
3 113 800 800 200 6
4 114 800 800 200 24
5 121 800 1600 200 1
6 122 800 1600 200 2
7 123 800 1600 200 6
8 124 800 1600 200 24
9 131 800 3200 200 1
10 132 800 3200 200 2
11 133 800 3200 200 6
12 134 800 3200 200 24
13 211 800 800 400 1
14 222 800 1600 400 2
15 223 800 1600 400 6
16 234 800 3200 400 24
2.4 Microstructural characterization
The powders (kaolinite, nano-copper, and kaolinite + nano-copper) were subjected to standard
characterization techniques. Field emission scanning electron microscopy armed with energy
dispersive X-ray (EDX) spectroscopy was used to determine the physical geometries and the
elemental contents of powders. The chemical composition of both powders (nano and micro) was
explored through the results of X-ray diffraction. Particle size and distribution of the powders were
determined by Malvern Mastersizer 2000 for micro-sized powders and Malvern Zeta Sizer for nano-
sized powders.
In addition, specific surface area was measured by the Brunauer, Emmett, and Teller (BET) gas
adsorption theory using nitrogen PSCAL 440 Series under liquid nitrogen temperature (77.2 K)
conditions. Nitrogen adsorption (N2–BET) method was used independently to test the kaolinite,
nano-copper, and powder mixture to obtain the SSA [31, 32]. N2–BET method was employed to
calculate external surface area [33].
Finally, the liquid and plastic limit test were conducted as per ASTM D4318-17 [34]. These tests
were conducted to examine the effects of nano-copper addition on consistency.
 Nano Hybrids and Composites Vol. 25 55

3. Results and Discussion

The optimum operating conditions of ball mill method for mixing kaolinite with nano-copper were
investigated in terms of ball-to-powder ratio, rotation speed, and milling time (Table 3). Several runs
were conducted to determine the optimum conditions (Table 4). The optimum milling conditions
were for code 133 (milling speed, 200 rpm; ratio of ball to powder, 4:1; and milling time, 6 h).
Figure 12 shows the scanning electronic microscopy image of undispersed nano-copper. The
agglomerate size of the undispersed powders appears to be relatively large and anomalistic, as
explicitly provided by the factory. As shown in Figure 13, the average particle size of nano-copper
oxide powder is considerably larger than that of the primary particles (100 nm). The shapes of certain
particles are quadrangular, whereas others are anomalous.

Agglomeration of nano-copper particles

200 nm

Figure 12 Undispersed nano-copper oxide powder under SEM @ Mag = 20.00 KX

3.1 Effect of Ball Mill on Particle Characteristics
Particle characteristics are affected by mixing efficiency. Particle size also affects the relative
importance of triboelectric forces within powders, as the average charge per unit mass and Coulomb’s
forces decrease with increasing particle size [35]. After milling, particle size becomes smaller. In this
study, the particle size of kaolinite started to reduce after 6 hrs. of milling. After 24 hrs. of milling
with speed of 20rpm and ball to powder ratio of 4:1, the size of kaolinite particles decreased to less
than 2 µm (Figure13). Furthermore, as observed from Figure 14, agglomeration starts to occur again
after 24 h because of the increase in Van der Waals forces between particles.
56 Nano Hybrids and Composites Vol. 25

2 µm

Figure 13 SEM image of mixture after 24 hrs. ball milling @ Mag = 10.00 KX

Agglomeration

Figure 14 Agglomeration of particles after 24 hrs. ball milling–sample code:133

3.2 Comparison of the Performance of Different Mixing Methods
For comparison of the performance of the methods/devices employed in this research, experiments
were designed so that each device is operated close to its maximum capability in terms of providing
kinetic energy for de-agglomeration and enough processing time for mixing to occur. Figure 15 shows
a sequence of images of the powder during milling (that is, Figure15, a: hand mixing; b, c, d, and e,
after ball milling for 1, 2, 6, and 24 hrs., respectively). The progress of the powder can be observed.
The initial powder was simply hand mixed for 30 min (Figure15 a). Nano-copper oxide particles are
easily discernible and keep the original shape and size. These particles are surrounded by kaolinite
particles. Furthermore, the color after mixing is mostly white, showing that nano-copper particles are
agglomerated and did not disperse with kaolinite particles. In Figure 15 b, after 1 hr. milling, the color
changes to brown and becomes black to dark brown after 2 hrs. milling (Figure 15 c). As shown in
Figures.15 d and e, the color of the mixture did not significantly change and remained dark brown
after further milling (6 and 24 hrs.).
 Nano Hybrids and Composites Vol. 25 57

Figure 15 Images of samples during milling

3.3 Effect of Ball Milling on Chemical Composition and Homogeneity Levels
Figures 16-22 and Tables 4-8 present the chemical composition of the powders based on achieved
results of X-ray diffraction to understand the compositional homogeneity levels of the powders.
Furthermore, energy dispersive X-ray spectroscopy analyses were executed at different
magnifications. Figure 16 shows the X-ray diffraction patterns for the elemental powder mixture after
each milling time. The results show high intensity and broad peaks of silica at 20.85° and 26.62°.
Kaolinite is the predominant mineral in kaolinite sample as expected, which can be identified by its
characteristic X-ray diffraction peaks at 8.94°, 12.75°, 24.61° and 35.27°. Furthermore, nano-copper
can be identified at 35.44°, 38.61°, 48.75°, 61.53°, 66.28°, and 68.05° peaks. The results did not
report any chemical reaction between kaolinite particles and nano-copper during mixing. However,
as shown in Figure 16, the intensities of peak corresponding to reflection vary after ball-milling and
become broader, indicating the decrease of grain size of kaolinite particles due to the micro strain
induced peak broadening. After 1, 2 and 6 hrs. of milling, the sample still contained the three forms
of elemental powders, but with further milling (24 hrs.), peaks were reduced, showing that increasing
ball mill time after 6 hrs. led to grain size reduction.
58 Nano Hybrids and Composites Vol. 25

Figure 16 XRD pattern of mixture powder in different period of ball milling

Tables 4-8 and Figures 17-22 show the energy dispersive X-ray spectroscopy analysis of nano-
copper, kaolinite, and powder mixture after 2, 6, and 24 hrs. of ball milling. The results from Tables
6-8 demonstrate that the amount of nano-copper increased with increasing mixing time, indicating
that the distribution of nano-copper through kaolinite particles was increased. Figures 17-21 show the
randomly selected area of EDX analysis. From Figure17, it is seen that the main elements of nano-
copper were C, O, and Cu. Figure 18 shows the elements of kaolinite particles, namely, O, Mg, Al,
Si, and K. Furthermore, Fe (Figures 19-21) originated from balls that remained on the powder during
milling. Thus, the amount of Fe element was low.
Table 4 Copper oxide powder composition
Element Weight% Atomic%
C 14.51 33.76
O 21.90 38.26
Cu 63.59 27.97
Totals 100
Table 5 Kaolinite powder composition
Element Weight% Atomic%
O 46.28 60.88
Mg 1.73 1.49
Al 16.40 12.79
Si 26.92 20.17
K 8.67 4.67
Totals 100.00
 Nano Hybrids and Composites Vol. 25 59

Table 6 Powder mixture composition after 2 hrs. milling

Element Weight% Atomic%
C 14.78 24.94
O 52.49 57.18
Mg 1.73 1.49
Al 16.40 12.79
Si 26.92 20.17
K 8.67 4.67
Cu 0.52 0.44

Table 7 Powder mixture composition after 6 hrs. milling

Element Weight% Atomic%
C 14.78 24.94
O 52.49 57.18
Mg 1.73 1.49
Al 16.40 12.79
Si 26.92 20.17
K 8.67 4.67
Cu 1.1 0.44

Table 8 Powder mixture composition after 24 hrs. milling

Element Weight% Atomic%
C 14.78 24.94
O 52.49 57.18
Mg 1.73 1.49
Al 16.40 12.79
Si 26.92 20.17
K 8.67 4.67
Cu 1.85 0.44

Figure 17 Local elementary analysis of copper oxide powder before ball milling
60 Nano Hybrids and Composites Vol. 25

Figure 18 Local elementary analysis of kaolinite particle before ball milling

Figure 19 Local elementary analysis of powder mixture after 2 hrs. ball milling

Figure 20 Local elementary analysis of powder mixture after 6 hrs. ball milling
 Nano Hybrids and Composites Vol. 25 61

Figure 21 Local elementary analysis of powder mixture after 24 hrs. ball milling

Figure 22 EDS spectrum of distribution nano-copper on kaolinite particle surface after 6hrs. milling
3.4 Particle Size and Distribution
Mixing of particles of sizes ranging between several nanometers and micro particles (1% nano-copper
and 99% kaolinite) is extremely difficult, as inter-particle forces are significantly higher than those
between particles of within a size range higher than 1 µm. The most important observation from these
images (Figures 23-26) is that as the two powder constituents differ clearly in particle shape, the high-
resolution field emission scanning electron microscopy employed in this study is capable of
characterizing mixing at this scale, although in a qualitative manner. A sophisticated image analysis
procedure is required to extract any quantitative information. Breakup of agglomerates after 6 hrs. of
ball milling is apparent from the images of the agglomerates of different specimens. The field
emission scanning electron microscopy images of the samples, which were milled for a period of 1–
24 hrs., are shown in Figures 23-26.
Figure 23 presents that, with 1 hr. of milling, only a small quantity of nanoparticles was present on
the surface of kaolinite particles. After an increase in mixing time (2 hr.), higher amounts of
nanoparticles were observed, nevertheless some of these amounts were still agglomerated and
required dispersion (Figure 24). However, Figure 25 shows that, after 6 hrs. of mixing, the
nanoparticles were present on whole kaolinite particle surfaces, indicating a good distribution of
nanoparticles. Furthermore, after increasing mixing time to 24 hrs. (Figure 26) kaolinite particles
started to grind, and their size was reduced. In addition, Figure 26 reveals that nanoparticles become
agglomerated after 24 hrs. of mixing because of increasing Van der Waals forces between particles.
62 Nano Hybrids and Composites Vol. 25

Nano-copper

1 µm

Figure 23 Lower distribution after 1 hr. milling under SEM @ Mag = 10.00 KX

Nano-copper

200 nm

Figure 24 Agglomerated copper oxide powder after 2 hrs. milling under SEM @ Mag = 30.00 KX
 Nano Hybrids and Composites Vol. 25 63

Nano-copper

1 µm

Figure 25 Distributed copper oxide powder after 6 hrs. milling under SEM @ Mag = 10.00 KX

Nano-copper

1 µm

Figure 26 Agglomerated nano-copper and reduced kaolinite particles after 24 hrs. milling under
SEM @ Mag = 10.00 KX
To investigate the effect of different ball milling conditions on size distribution of the soil mixture,
volume mean size and size span were studied by Mastersizer at the Concrete Laboratory, Department
of Civil and Structural Engineering, UKM, Malaysia. The span is a measure of the size distribution,
which may be defined as follow:
 d (0.9) − d (0.1) 
Span =   (4)
 d (0.5) 
64 Nano Hybrids and Composites Vol. 25

where:
d(0.9) : at which, 90% by volume of particles in ground samples are smaller than these sizes
d(0.1) : at which, 10% by volume of particles in ground samples are smaller than these sizes
d(0.5) : at which, 50% by volume of particles in ground samples are smaller than these sizes
Notably, smaller span corresponds to narrower size distribution (Table 10). The particle size
distribution of mixture powder as milled according to conditions provided in Table 9 and measured
by means of laser beam scattering is revealed in Figure 27. As seen in Table 9, the span of selected
mixtures was 3.252, 3.308, and 3.417 for mixtures with code 113 (milling speed, 200 rpm; ratio of
ball to powder, 1:1; and 6hrs. milling time), 123 (milling speed, 200 rpm; ratio of ball to powder, 2:1;
and 6hrs. milling time), and 133 (milling speed, 200 rpm; ratio of ball to powder, 4:1; and 6hrs.
milling time), respectively. The high span reported for the mixture by code 133 confirms high
distribution particles in comparison with other selected mixtures.
Table 9 Particle size distribution of the powder mixture
Code d (0.9) µm d (0.1) µm d (0.5) µm Span
113 133.182 7.420 38.667 3.252
123 135.968 6.945 38.999 3.308
133 63.784 3.720 17.578 3.417

Figure 27 Volume particle size distribution under different milling conditions

 Nano Hybrids and Composites Vol. 25 65

3.5 Atterberg’s limits

The results of Atterberg’s limits (plastic and liquid limits), of kaolinite and its powder mixtures (99%
kaolinite and 1% nano-copper), are shown in Figure 29. The figure shows that the plastic limit (PL)
and liquid limit (LL) increased with nano-copper mixing. However, as the increase in the liquid limit
is less than that of plastic limit, the plasticity index (PI) decreased. This finding is important in
geotechnical engineering, as compaction of high-plasticity soils will generally result in high shrinkage
upon drying [36]. Finally, the soil will have high hydraulic conductivity, which is a disadvantage for
structures such as landfill liners and caps. Therefore, the addition of nanoparticles, such as nano-
copper, could enhance the properties of soil even at low doses.

Figure 28 Atterberg’s limits of kaolinite and powder mixture (99% kaolinite + 1% nano-copper)

4. Conclusion
In this study potential of horizontal ball milling to mix dry nanomaterials (i.e. nano-copper) with soil
(i.e. kaolinite) was examined. Based on the findings, the following conclusions can be drawn:
• Nano-carbon and kaolinite were mixed using three methods: sonication, rotating cylinder and
horizontal ball milling. Horizontal ball milling was found the most effective method to
uniformly distribute nano-carbon with kaolinite.
• Field emission scanning electron microscopy showed breakup of agglomerates after 6 hrs. of
ball milling and nanoparticles were found on whole kaolinite particle surface. Furthermore, a
mixing time to 24 hrs. ground the kaolinite particles and their size was reduced. This resulted
in agglomeration of nanoparticles because Van der Waals forces between particles were
increased.
• Size distribution of the soil mixture was studied by “size span” which is a measure of the size
distribution. The highest size span value of 3.417 was found for mixture with code 133
(milling speed, 200 rpm; ratio of ball to powder, 4:1; and 6hrs. milling time).
• Finally, the result of Atterberg’s limits show that even a small addition of nano-copper
particles will result in a marked enhancement in soil behavior (plasticity index decreased to
37% from 44%).
This research is an effort to introduce thorough and uniform mixing of nanoparticles with soil to gain
advantages for soil improvement. Nanomaterials can be planned to advance the behavior of soils to
suit design and practice requirements.
66 Nano Hybrids and Composites Vol. 25

5. Acknowledgement
We appreciate the financial support and facilities provided by Geotechnical Engineering Laboratory
of Universiti Kebangsaan Malaysia (UKM) for this study and Fuel Cell Institute at UKM, particularly
for the scanning electronic microscopy and X-ray diffraction tests. The contributions of Ministry of
Higher Education, Malaysia is acknowledged with gratitude.

Competing interests
The authors declare that they have no competing interests.

Ethics approval and consent to participate

The presented work is a part of research project entitled “Evaluation of improvement potential of
nanomaterials for stabilizing clayey soils”. There is no any ethical conflict. Authors on behalf of an
associated organization fully authorize to publish research.

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