coatings

Article
Coating Sand with New Hydrophobic and
Superhydrophobic Silica/Paraffin Wax Nanocapsules
for Desert Water Storage and Transportation
Ayman M. Atta 1, * , Mahmood M. S. Abdullah 1 , Hamad A. Al-Lohedan 1 and
Nermen H. Mohamed 2
1 Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia;
altaiar90@yahoo.com (M.M.S.A.); hlohedan@ksu.edu.sa (H.A.A.-L.)
2 Refining Department, Egyptian Petroleum Research Institute (EPRI), Nasr City, Cairo 11727, Egypt;
nermenhefiny@yahoo.com
* Correspondence: aatta@ksu.edu.sa; Tel.: +966-056-155-7975




Received: 6 January 2019; Accepted: 13 February 2019; Published: 17 February 2019


Abstract: Paraffin wax emulsions have gained immense attention as a cheap, environment-friendly,
and aroma-free material for preparing superhydrophobic coatings. In this work, paraffin wax (PWs)
capsules consisting of hydrophobic silica nanoparticles were used for coating desert sand. Different
types of the hydrophobic silica nanoparticles, modified with new oleylamino- and oleylamide silane
precursors, were prepared in the presence and absence of paraffin waxes. The particle sizes, surface
charges, thermal stability, surface morphologies, and wetting characteristics of these nanoparticles
were investigated. The combination of these superhydrophobic silica nanoparticles and desert sand,
showed excellent water repellency; stable water droplets remained on the sand surface, without
any wetting or permeation. Furthermore, the mixing of the superhydrophobic sand with untreated
sand (mixing ratio 1:10 wt %), with a thickness of 2 cm, sustained a great water-holding capacity
with a water column height of 35 cm. The good thermal stability of the PWs capsules containing
hydrophobic silica nanoparticles, along with their good water-holding capacity, make them potential
candidates for developing superhydrophobic sand for desert water storage and transportation.

Keywords: superhydrophobic silica nanoparticles; superhydrophobic sand; superhydrophobic

coatings; desert water storage

1. Introduction
Sand dunes are an abundant natural resource in the desert, are characterized with a low water
storage capacity and suffer from a temporary shortage of water especially when cultivated under
arid conditions. Sand consists of hydrophilic silica, which attracts water and facilitates its flow to
the ground, thus, adversely affecting the plantation, even under expensive irrigation systems such
as sprinkling or trickling. Previously, hydrogels were used to increase the water holding capacity of
sandy soils [1–6]. Their biodegradation, difficult soil-particle coating, low water absorption because
of the presence of salts, and high manufacture cost, has limited their applications [1]. Recently, the
use of “superhydrophobic sand” has been proposed, to realize the storage and transportation of the
surface water of sandy soils [7–12]. Various methods, such as the combustion of oil waste [13], crude
oil emulsion [14], paraffin wax [15], natural wax [16], and oil and fatty acids [17] have been proposed
for the development of hydrophobic coatings. The hydrophobic petroleum waxes were divided into
three principle groups—paraffin waxes, microcrystalline waxes, and petrolatum. The paraffin waxes
contained long-chain hydrocarbons that can be used to form a hydrophobic surface and exhibited

Coatings 2019, 9, 124 ; doi:10.3390/coatings9020124 www.mdpi.com/journal/coatings

Coatings 2019, 9, 124 2 of 13

water-repellency, on several substrates [15]. However, these coatings either did not adhere well to
the sand surface or were mechanically unstable. Recently, it has been proposed that the application
of nanomaterials on the sand surface, can combat desertification and encourage plant growth in arid
climates. Moreover, superhydrophobic sand prevents the diffusion of underground salt, which affects
the growth of plants. The application of the superhydrophobic property of certain nanomaterials for
mitigating environmental and resource issues, is a promising research topic of global significance.
The development of low-cost environmental-friendly superhydrophobic, thermally stable, and good
adhesion nanomaterials, is a challenge for desert greening.
Silica nanomaterials and silicon derivatives have gained immense attention for the development
of superhydrophobic sand because of their excellent adhesion with sand and glass surfaces [18–23].
Organic silicone derivatives, such as octadecyltrichlorosilane have also been used for coating sand
to produce hydrophobic sand [24]. Raw hydrophobic sand, contaminated with oil, can also be used
as a water repellent [25]. This work aims to modify new hydrophobic silane precursors to hydrolyze
with tetramethoxysilane (TMS), for the formation of superhydrophobic silica nanoparticles (SNPs). In
this respect, oleylamino- and oleylamide were prepared as hydrophobic silane precursors. The oleyl
groups can act as hydrophobic coats, after hydrolyzing the alkoxy silane group with tetraethoxysilane
(TEOS) in an alkaline-medium-based on sol–gel technique, to produce hydrophobic silica nanoparticles
(HSNP). Moreover, the oleyl groups can be interacted with paraffin waxes, during the hydrolysis
of silane precursors with TEOS, in the presence of paraffin wax emulsions, to produce hydrophobic
silica capped with paraffin waxes (HOSNP). Hydrophobically coating fine raw sand, with HSNP and
HOSNP, is another goal of the present work to increase the adhesion of paraffin waxes on the sand
surfaces, due to the presence of the silica nanoparticles, to produce superhydrophobic sand. The
water storage capacities of the superhydrophobic sand prepared and its blend with the unmodified
desert sand, were investigated, to evaluate its water storage and transportation properties. The
water-holding capacity, thermal stability, and anti-flow dragging performance of, both, the prepared
and the unmodified blend were also evaluated.

2. Materials and Methods

2.1. Materials
All chemicals used in the present work were analytical with high purity grades and were
supplied from Aldrich-Sigma Chemicals Co. (St. Louis, MO, USA). Vinyl trimethoxy silane (VTS),
tetraethoxysilane (TEOS), and γ-aminopropyltriethoxysilane (APS) were modified with oleic acid (OA)
and oleylamine (OAE), to synthesize hydrophobic silane precursors. Hexadecyltrimethylammonium
bromide (CTAB) was used as a cationic surfactant, to prepare the wax emulsion. El-Ameria light slack
wax (Alexanderia, Egypt) was subjected to fractional crystallization, using butyl acetate as the solvent,
at a fractionating temperature of 20 ◦ C, solvent feed ratio of 4/1, and washing ratio of 2/1, in order to
separate the paraffin waxes [25]. The fine raw desert sand obtained from the Saudi desert was only
cleaned with deionized water. The adhesive tape (3M) was obtained from a commercial source (3M
Science applied for life company, Minneapolis, MN, USA).

2.2. Techniques

2.2.1. Preparation of Hydrophobic Silane Precursors

Alkoxy silane oleylamide (SOA) was prepared by reacting OA (1 mol) with APS (1.1 mol), in a
reaction vessel, at 180 ◦ C, for 2 h, under a nitrogen atmosphere. SOA was also synthesized at a low
temperature, as follows: Equimolar ratios of OA and APS were evenly dispersed in an ethanol solution
(ethanol/water = 9:1) and the mixture was stirred at room temperature, for 1.5 h. The SOA yields at
high and low temperature were 92.1% and 83.5%, respectively.
Coatings 2019, 9, 124 3 of 13

Vinyltrimethoxy olylaminosilane (VOS) was prepared by reacting OAE (0.01 mol) with the vinyl
group of VTS (0.05 mol), in an 80 mL tetrahydrofuran (THF), while stirring at 65 ◦ C, for 4 h. THF was
removed using a rotary evaporator under pressure, to obtain OVA (yield 93.7%).

2.2.2. Preparation of the Paraffin Wax Emulsion

Paraffin waxes have a narrow melting temperature range of 51–54 ◦ C. The components of the
wax used in this study were mainly normal alkenes, with C18–C38 carbon atoms. The paraffin wax
emulsion was prepared by mixing the melted paraffin wax with the CTAB surfactant, by slowly adding
water, under gentle agitation, using a magnetic stirrer. The addition rate of water was kept constant, at
approximately 1.0 mL·min−1 . The emulsification temperature was varied from 50 to 80 ◦ C. The PWs
concentration of the emulsion was kept constant at 20.0 wt %, while the CTAB surfactant concentration
was 8.0 wt %.

2.2.3. Preparation of the Superhydrophobic Silica/Wax Capsules

Hydrophobic silica nanoparticles (HSNPs) were prepared as follows: TEOS (0.8 mL) was added
to methanol (100 mL) and kept in a sonication bath. After 10 min, a known volume of VOS (0.4 g),
and SOA (0.4 g) were added to it, while sonicating. After 20 min, 28% ammonium hydroxide (24 mL)
was added to the reaction mixture, as the catalyst to promote the condensation reaction. Sonication
was continued for a further 60 min, to obtain a white turbid suspension. The HSNPs were formed
by hydrolyzing the silicon precursors (VOS and SOA) with TEOS, in the presence of ammonia and
sonication. The obtained HSNPs suspension was dispersed in water/ethanol (50/50 vol %), under
gentle agitation, for 5 min, in order to stop the hydrolysis, separate, and purify the HSNPs. The
reaction mixture was then ultracentrifuged at 8000 rpm, for 30 min. This procedure was repeated five
times, to purify the HSNPs. The same procedure was used to prepare HOSNPs in the presence of the
PWs emulsion (2 g), which was added after its dispersion in methanol (100 mL).
In a typical procedure, the wax emulsion (2 g) was dissolved in 100 mL of deionized water, under
stirring. To this mixture, concentrated ammonia solution (7.0 mL; 28 wt %) was added to form a clear
solution. A mixture of n-hexane (20 mL), TEOS (3 mL), VOS (1 mL), and SOA (1 mL) was added,
dropwise, for over 30 min, under continuous stirring, to the obtained clear solution. As the reaction
proceeded at 35 ◦ C, a homogeneous milky colloidal solution was gradually formed, under continuous
stirring (200 rpm). This solution was dispersed in water/ethanol (50/50 vol %), under gentle agitation
for 5 min, and the resulting mixture was ultracentrifuged at 8000 rpm, for 30 min, to separate the
emulsified silica NPs (EOSNP1). This procedure was repeated five times to purify the EOSNP1. These
procedures were repeated by using different weight percentages of the PWs, ranged from 1 to 20 wt %,
related to the TEOS, the SOA, and the VOS, to prepare a series of EOSNP1 samples.
Emulsified silica NPs (EOSNP2) was prepared without using the n-hexane which was replaced by
chloroform. The paraffin wax emulsion (2 g) was mixed with distilled water (100 mL), under vigorous
magnetic stirring, for 1 h. The TEOS (2 g), the VOS (1 mL), and the SOA (1 mL) were dispersed in
chloroform (20 mL) and then added to the reaction mixture, which was stirred for another 30 min.
Emulsion was formed and stirred for a further 4 h, in the presence of APS (0.54 g and 1.5 mL of water).
The resulting solution was aged, overnight, to obtain the silica-coated wax nanoparticles (EOSNP2).

2.3. Characterization of the PWs/Hydrophobic Silica Nanocapsules

Thermogravimetric analysis (TGA; STA 449 C instrument, Netzsch Group, New Castle, DE, USA)
was carried out to determine the thermal stability and contents of the silica capsules. The samples
were heated at a heating rate of 283 K·min−1 , under a dynamic nitrogen flow of 45 mL·min−1 . The
morphology of the silica capsules was evaluated using a transmission electron microscope (TEM,
JEM-2100 F (JEOL, Tokyo, Japan) at an acceleration voltage of 200 KV). A scanning electron microscope
(SEM; JSM 6510LV, JEOL, Tokyo, Japan) was used to examine the surface morphology of the silica
capsules. Dynamic light scattering (DLS; Zetasizer Nano ZS, Malvern Instrument Ltd., Malvern, UK)
Coatings 2019, 9, 124 4 of 13

was used to investigate the particle size and the polydispersity indices (PDI) of the silica nanocapsules
in the n-hexane solutions at 25 ◦ C. The zeta potentials of the silica nanocapsules were determined
in ethanol/water dispersions. A drop shape analyzer (DSA-100, Krüss GmbH, Hamburg, Germany)
was used to determine the contact angles (with water) of the hydrophobic silica capsules using the
sessile drop method, at room temperature. The receding and advancing contact angles were measured
after polishing the glass plate, to produce a rough surface followed by washing with ethanol, 1 M HCl,
detergent, and acetone. The glass plate was dried and treated with ozone, before applying and casting
the dispersions of the HSNPs in the n-hexane (250 mg in 1 mL). The glass plate coated with the HSNPs
was air dried and then placed in a cleaned glass cell on a small support, which was partially filled
with HSNPs suspension. The glass cell was covered by the Parafilm through which a needle of the
DSA-100 was inserted to produce the liquid–vapor saturated air, inside the glass cell. The contact angle
measurements were repeated, five times, for reproducible and reliable contact angle measurements.

2.4. Coating of Sand with HSNPs

To obtain hydrophobic sand, 5 g of sand (diameter of 100–200 µm) was modified with 50 mL
(hexane/ethanol) of 0.5% HSNPs solution, under continuous stirring for 3 h, at room temperature. All
products were obtained after rinsing with ethanol, for three times, and drying at 60 ◦ C for 1 h. The
hydrophobic sand was mixed with the untreated sand (diameter of 1–3 mm), at various ratios, ranging
from 1:1 to 1:10 wt %. The water absorbing capacities of the untreated and the sand treated with the
HSNPs, were measured by pouring 5 mL of water into the simulated sand pits [8]. The water-holding
capacities of the modified desert sand were determined from the time used to pass water (10 mL), from
the 2 g of treated sand into the glass column (diameter 2 cm) [8].

3. Results and Discussion

The paraffin wax used in this study was extracted from a light slack wax, as discussed in the
experimental section, and had an average carbon number of C18–C38 (Table 1). The isolated paraffin
wax was also characterized by its high n-paraffin content (88.14 wt %), high iso- and cyclo-paraffin
content (18.76 wt %), and very low aromatic content (2.26 wt %) (Table 1). The isolated PWs were
utilized to prepare a stable PWs-in-water emulsion (PWs/W), in the presence of CTAB as a cationic
surfactant (emulsion droplet sizes 750 nm). The prepared PWs emulsion was dispersed in water or
methanol and was used as capping for the SNPs, as mentioned in the experimental section. The HSNPs
prepared in the presence of the PWs emulsion were obtained in double oil/water/oil emulsion, as
revealed by the optical microscope images shown in Figure 1a–c and the dropping test results. The
silane precursors (SOA and VOS) and the TEOS used as the oil phase—in bulk or in combination with
the n-hexane—were hydrolyzed in ammonia, at a reaction temperature of 35 ◦ C, to obtain hydrophobic
SNPs, in emulsion, as represented in Scheme 1. The silane and siloxane precursors were hydrolyzed
at 35 ◦ C, to prevent an increase in the size of the paraffin wax emulsion droplets. This facilitated the
penetration of the paraffin wax at the interfacial film, allowing the capping of the SNPs [26]. The
preparation of SNPs using this emulsion technique has been described elsewhere [27–29], where it
was found that the morphology, particle size, and porosity of SNPs are affected by the emulsion type
and the hydrolyzing conditions. Hydrophobic silica was prepared in the absence and presence of
PWs (HSNP and HOSNP, respectively) in a methanol solvent. The capping of hydrophobic silica
with EOSNP1 and EOSNP2, was carried out in water/hexane and water/chloroform emulsions,
respectively. The wax content of the emulsions was 40 wt %. The effect of the paraffin wax on the
morphology, particle size, surface charge, and thermal stability of the SNPs has been discussed in the
forthcoming section.
Coatings 2019, 9, x FOR PEER REVIEW 5 of 13

Table 1. Physical characteristics of the El-Ameria light slack wax according to American Society for
Coatings 2019, 9, 124 5 of 13
Testing and Materials (ASTM) standard methods.

Characteristics Light Slack Wax (Waste By-Product) Paraffin Waxes (PWs)

Table 1. Physical characteristics of the El-Ameria light slack wax according to American Society for
Yield 100 54.5
Testing and Materials (ASTM) standard methods.
Congealing point, °C 46 53
KinematicCharacteristics
viscosity, 98.9 °C, cSt 2.83
Light Slack Wax (Waste By-Product) 2.88
Paraffin Waxes (PWs)
Refractive Yield
index, 98.9 °C 1.4214
100 1.4187
54.5
Density, 70 °C,
Congealing point, ◦C 3
g/cm 0.7910
46 0.7750
53
Kinematic
Oil content, 98.9%◦ C, cSt
viscosity,wt 2.83
4.25 2.88
0.25
Refractive index, 98.9 ◦ C 1.4214 1.4187
Sulfur content, wt % 0.08 0.00
Density, 70 ◦ C, g/cm3 0.7910 0.7750
ConeOilpenetration,
content, wt %25 °C 23
4.25 –
0.25
Sulfur
Needle content, wt %
penetration, 25 °C 0.08
67 0.00
22
Cone penetration, 25 ◦ C 23 –
Color (ASTM-D 1500)
Needle penetration, 25 ◦ C
0.5
67
0.0
22
RefractiveColor
Index by TAPPI
(ASTM-D 1500)Equation –
0.5 1.4242
0.0
Refractive Index by TAPPI Equation Molecular Type Composition– 1.4242

Total saturates, wt % Molecular Type Composition

97.74 100
n-Paraffins content, wt %
Total saturates, wt % 78..98
97.74 88.14
100
n-Paraffins content,
Iso & cycloparaffins wt % wt %
content, 78..98
18.76 88.14
11.86
Iso & cycloparaffins content, wt % 18.76 11.86
Total
Totalaromatics, wt%%
aromatics, wt 2.26
2.26 0.00
0.00
Mono-aromatics,
Mono-aromatics, wt wt%% 0.64
0.64 0.00
0.00
Di-aromatics, wt
Di-aromatics, wt%% 1.62
1.62 0.00
0.00

Coatings 2019, 9, x FOR PEER1.REVIEW

Scheme Preparation scheme of the hydrophobic silica nanoparticles (SNP). 6 of 13
Scheme 1. Preparation scheme of the hydrophobic silica nanoparticles (SNP).

Figure 1. Optical microscope photos of (a) PWs emulsion and (b) silicon precursor
precursor PWs
PWs emulsion.
emulsion.

3.1. Characterization of the PWs/Silica Nanocapsules

The particle sizes and surface charges of the HSNPs, capped with the PWs, were determined by
DLS (Figure 2). The zeta potentials of the HSNPs were measured; shown in Figure 3a–d. Figure 2a–d
show the particle size (nm) and PDI of the HSNPs. The SNPs, capped with wax in the hexane/water
Coatings 2019, 9, 124 6 of 13
Figure 1. Optical microscope photos of (a) PWs emulsion and (b) silicon precursor PWs emulsion.

3.1. Characterization of the PWs/Silica Nanocapsules

3.1. Characterization of the PWs/Silica Nanocapsules
The particle sizes and surface charges of the HSNPs, capped with the PWs, were determined by
The particle sizes and surface charges of the HSNPs, capped with the PWs, were determined by
DLS (Figure 2). The zeta potentials of the HSNPs were measured; shown in Figure 3a–d. Figure 2a–d
DLS (Figure 2). The zeta potentials of the HSNPs were measured; shown in Figure 3a–d. Figure 2a–d
show the particle size (nm) and PDI of the HSNPs. The SNPs, capped with wax in the hexane/water
show the particle size (nm) and PDI of the HSNPs. The SNPs, capped with wax in the hexane/water
emulsion (EOSNP1; Figure 2c), showed monodispersed particles, with a size of 65 nm. Moreover, the
emulsion (EOSNP1; Figure 2c), showed monodispersed particles, with a size of 65 nm. Moreover, the
particle size of the HOSNPs (Figure 2b) was lower than that of the HSNPs (Figure 2a). This could
particle size of the HOSNPs (Figure 2b) was lower than that of the HSNPs (Figure 2a). This could be
be attributed to the accelerated hydrolysis of the alkoxy groups of SOA and VOS, in the presence of
attributed to the accelerated hydrolysis of the alkoxy groups of SOA and VOS, in the presence of the
the wax emulsion, because of the good compatibility between the wax and the oleyl groups of the
wax emulsion, because of the good compatibility between the wax and the oleyl groups of the SOA
SOA and the VOS, via a van der Waals interaction. The good compatibility between the reactants
and the VOS, via a van der Waals interaction. The good compatibility between the reactants reduced
reduced the particle size of the resulting nanoparticles, as shown in Figure 2a,b. Moreover, the use of
the particle size of the resulting nanoparticles, as shown in Figure 2a,b. Moreover, the use of CTAB
CTAB as the cationic surfactant as an emulsifier during the synthesis of HOSNPs, using oil-in-water
as the cationic surfactant as an emulsifier during the synthesis of HOSNPs, using oil-in-water
(EOSNP1) or oil-in-water-oil (EOSNP2) emulsions, facilitated the dispersion of the SOA and the VOS
(EOSNP1) or oil-in-water-oil (EOSNP2) emulsions, facilitated the dispersion of the SOA and the VOS
as the oil phase, in a continuous water phase. Chloroform was added to control the hydrophilicity
as the oil phase, in a continuous water phase. Chloroform was added to control the hydrophilicity
and particle size of the SNPs [27]. EOSNP2 showed a larger particle size than the EOSNP1 because of
and particle size of the SNPs [27]. EOSNP2 showed a larger particle size than the EOSNP1 because of
the use of chloroform during its synthesis, as illustrated in Figure 2c,d. This could be attributed to a
the use of chloroform during its synthesis, as illustrated in Figure 2c,d. This could be attributed to a
better compatibility of the n-PWs with hexane, than with chloroform, as the solvent that facilitated the
better compatibility of the n-PWs with hexane, than with chloroform, as the solvent that facilitated
capping of the SNPs with PWs [30–32].
the capping of the SNPs with PWs [30–32].

Figure
Figure 2.2. Dynamic
Dynamic light
light scattering
scattering (DLS)
(DLS) data
data ofof the
the hydrophobic
hydrophobic SNPs.
SNPs. (a)
(a) Hydrophobic
Hydrophobic silica
silica
nanoparticles
nanoparticles (HSNP),
(HSNP), (b)
(b) HOSNP,
HOSNP, (c)(c) Emulsified
Emulsified silica
silica NPs
NPs (EOSNP1),
(EOSNP1), and
and (d)
(d) EOSNP2
EOSNP2 in n-hexane,
in n-hexane,
at ◦ C.
at 25
25 °C.

The surface charges of the HSNPs prepared in the absence of wax (Figure 3a) were negative, with
an initial dispersion pH of about 5.4. This indicates that the absence of wax during the synthesis of the
HSNPs, increased the number of hydroxyl groups, negative charges, on their surface because of the
repulsive forces between the π electrons of the double bonds of the oleyl groups, in SOA and VOS [33].
The presence of wax during the preparation of the hydrophobic SNPs, changed their surface charges
to positive (Figure 3b–d). These data elucidate that the CTAB (positive charges) used to prepare wax
emulsion is responsible to neutralize the silica negative charges, in case of the HOSNP, EOSNP1, and
EOSNP 2, due to the electrostatic attraction forces [34]. Moreover, the positive charges that originated
from the amine and amide groups of the SOA and the VOS, can also add positive charges on the silica
surfaces. The high surface charges of the EOSNP1 (Figure 3c) and the EOSNP2 (Figure 3d), more than
of the repulsive forces between the π electrons of the double bonds of the oleyl groups, in SOA and
VOS [33]. The presence of wax during the preparation of the hydrophobic SNPs, changed their
surface charges to positive (Figure 3b–d). These data elucidate that the CTAB (positive charges) used
to prepare wax emulsion is responsible to neutralize the silica negative charges, in case of the HOSNP,
EOSNP1, and
Coatings 2019, EOSNP 2, due to the electrostatic attraction forces [34]. Moreover, the positive charges
9, 124 7 of 13
that originated from the amine and amide groups of the SOA and the VOS, can also add positive
charges on the silica surfaces. The high surface charges of the EOSNP1 (Figure 3c) and the EOSNP2
that of the
(Figure HOSNP
3d), more than(Figure 3b),
that ofelucidated
the HOSNP that(Figure
the formation of multiple
3b), elucidated emulsions
that by using
the formation of n-hexane
multiple
and chloroform is responsible for the dispersion–flocculation–redispersion of CTAB,
emulsions by using n-hexane and chloroform is responsible for the dispersion–flocculation– on the prepared
silica cappedof
redispersion with paraffin
CTAB, wax
on the [34]. silica capped with paraffin wax [34].
prepared

Zeta potential
Figure 3. Zeta potential data
data of
of the
the hydrophobic
hydrophobicSNP.
SNP. (a)
(a) HSNP,
HSNP, (b)
(b) HOSNP,
HOSNP, (c) EOSNP1,
EOSNP1, and
and (d)
(d)
ethanol/water, at
at 25 ◦ C.
25 °C.
EOSNP2 in ethanol/water,

The morphologies
The morphologies of of the
the HSNP,
HSNP, HOSNP,
HOSNP, EOSNP1,
EOSNP1, and and the
the EOSNP2
EOSNP2 samples
samples were
were examined
examined
from their TEM images (Figure 4a–d). The absence of the paraffin wax, resulted in the formation
from their TEM images (Figure 4a–d). The absence of the paraffin wax, resulted in the of
formation of
aggregates (Figure
aggregates (Figure 4a).
4a). Additionally,
Additionally, needle-like
needle-like (instead
(instead ofof spherical) HSNPs were
spherical) HSNPs were obtained when
obtained when
the PWs emulsion was used (Figure 4b). This could be attributed to the weaker interactions
the PWs emulsion was used (Figure 4b). This could be attributed to the weaker interactions of the of the
paraffin wax with the unsaturated groups of the oleyl groups of the silicone precursors
paraffin wax with the unsaturated groups of the oleyl groups of the silicone precursors (SOA and (SOA and
OVS), at
OVS), at the
the silica
silica surface.
surface. The
The presence
presence ofof hexane,
hexane, enhanced
enhanced the the stabilization
stabilization of
of the
the paraffin
paraffin wax,
wax, at
at
the surface of the SNPs, to prevent the aggregation of the hydrocarbon chains, to produce
the surface of the SNPs, to prevent the aggregation of the hydrocarbon chains, to produce spherical spherical
EOSNP1 (Figure
EOSNP1 (Figure 4c).
4c). The
The use
use of
of chloroform
chloroform resulted
resulted in
in the
the formation
formation ofof EOSNP2
EOSNP2 aggregates,
aggregates, because
because
of the poor solubility and dispersion of the paraffin wax in chloroform.
of the poor solubility and dispersion of the paraffin wax in chloroform.
Coatings 2019, 9, x FOR PEER REVIEW 8 of 13

Figure
Figure 4. TEM
4. TEM micrographsof
micrographs of(a)
(a) HSNP,
HSNP, (b)
(b)HOSNP,
HOSNP,(c)(c)EOSNP1,
EOSNP1,and (d) (d)
and EOSNP2.
EOSNP2.

3.2. Thermal and Wetting Characteristics of the PWs/HSNPs Microcapsules

Thermal stability is considered to be a crucial factor affecting the applicability of hydrophobic
silica capped with wax microcapsules, for coating desert sand. The thermal stabilities of the HSNP,
HOSNP, EOSNP1, and EOSNP2 samples were estimated by TGA and the results are summarized in
Coatings 2019, 9, 124 8 of 13

3.2. Thermal and Wetting Characteristics of the PWs/HSNPs Microcapsules

Thermal stability is considered to be a crucial factor affecting the applicability of hydrophobic
silica capped with wax microcapsules, for coating desert sand. The thermal stabilities of the HSNP,
HOSNP, EOSNP1, and EOSNP2 samples were estimated by TGA and the results are summarized in
Table 2. The initial decomposition temperatures, 10% loss temperatures, degradation steps, and residual
percentages (Y%) of the paraffin wax and the SNPs were determined. It should be noted that pure
paraffin wax exhibits a typical one-step thermal degradation at 180–270 ◦ C. The paraffin wax showed
almost no char, indicating that it experienced simple evaporation. The HSNP prepared in absence of
PWs had high silica contents of 38 wt % (as determined from their Y%). Except for the EOSNP2, all of
the hydrophobic SNPs showed only one degradation step, confirming their compatibility with the
paraffin wax [35]. The SNPs incorporated with paraffin wax (HOSNP) showed higher thermal stability,
as their degradation started at 250 ◦ C. The thermal stability of the hydrophobic SNPs decreased in
the order of: HOSNP > EOSNP1 > EOSNP2 > HSNP. These data elucidate that the incorporation of
paraffin wax into hydrophobic silica decreases the degradation of the ester and amine groups of the
silane precursors. The evaporation of the paraffin wax at 250–350 ◦ C, degraded the oleyl groups of
the EOSNP1 more than those of the EOSNP2 and the HOSNP. This could be attributed to the good
compatibility of the paraffin wax chain and the hydrophobic oleyl groups of silica, which acted as the
heat isolators for the nanocomposites [35]. A second weight loss was observed at 360–470 ◦ C, which
could be attributed to the decomposition of the hydrophobic oleyl shell.

Table 2. Thermogravimetric analysis (TGA) data of the SNPs coated with PWs.

Steps
Sample Weight Loss (%) IDT (◦ C) T 10 % (◦ C) Y (%)
Start Temp (◦ C) End Temp (◦ C)
0 250 5.5
HSNP 250 450 19.5 130 320 38
450 650 37
0 250 1.0
HOSNP 250 450 50.0 250 360 18
450 650 31.0
0 250 30.0
EOSNP1 250 450 25.0 150 170 20
450 650 25.0
0 250 10.0
EOSNP2 250 450 30.0 140 250 30
450 650 30.0

The wetting of the modified silica wax nano and microcapsules was evaluated by applying the
thin films (with a thickness of 2 µm) onto glass panels and measuring their water contact angles
(receding and advancing). The water contact angles of the treated and the untreated glass surfaces are
listed in Table 3. The results showed that the PWs emulsion could not form a hydrophobic surface on
the glass, leading to a low contact angle because of its poor adhesion to the glass and the formation of
cracked film surfaces on it. All HSNPs showed high contact angles, especially EOSNP1. This could be
attributed to the lower particle sizes of the HSNPs, and their positive surface charges, which attracted
the negative surface charges of the silicate glass, as discussed in the previous section. Compared to the
other hydrophobic SNPs, EOSNP1 formed a superhydrophobic film (contact angle > 150◦ ) because of
their good adhesion with glass and the combination of micro and nano roughness. This speculation
was validated by the high-resolution SEM images of the EOSNP1 film (shown in Figure 5), which
revealed the formation of the bridges between the EOSNP1 surface and its neighboring particles.
Moreover, the rough surface of the EOSNP1 (Figure 5a) produced air pockets between the top of the
microstructured silica capsules and the water droplets, which contributed to the highest contact angle
and superhydrophobicity of the EOSNP1 [36]. The presence of silica inside the wax spheres of the
EOSNP1 was confirmed by the SEM image (Figure 5b) of the crushed spheres after being soaked in
between the top of the microstructured silica capsules and the water droplets, which contributed to
the highest contact angle and superhydrophobicity of the EOSNP1 [36]. The presence of silica inside
the wax spheres of the EOSNP1 was confirmed by the SEM image (Figure 5b) of the crushed spheres
afterCoatings
being2019,
soaked
9, 124
in liquid nitrogen. The appearance of the smooth film (Figure 5b) on the surface
9 of 13
of the crushed EOSNP1 confirmed the wax layers formed on the surface of the spherical silica (present
inside the wax layer as spherical particles).
liquid nitrogen. The appearance of the smooth film (Figure 5b) on the surface of the crushed EOSNP1
confirmed the wax angle
Table 3. Contact layersofformed on the
the water surface
droplet on of
thethe spherical silica
hydrophobic SNP(present inside films,
microcapsule the wax layer
at 25 °C.as
spherical particles).
Contact Angle (degree)
Table 3. Contact angle ofSample
the waterCode
droplet on the hydrophobic SNP microcapsule films, at 25 ◦ C.
Receding Advancing
Glass
Sample Code 45 ± Contact
4 48(Degree)
Angle ±3
PWs Receding
55 ± 3 58 ±Advancing
2
Glass 45 ± 4 ±3
PWs
HSNP 110 ±1
55 ± 3
118 ± 148
58 ± 2
HOSNP
HSNP 120
110±±41 125 ± 1118 ± 1
HOSNP 120 ± 4 125 ± 1
EOSNP1
EOSNP1 165
165±±22 168 ± 2168 ± 2
EOSNP2
EOSNP2 118
118±±33 123 ± 1123 ± 1

Figure 5. SEM images of (a) EOSNP1 on the sand surface, and (b) the crushed EOSNP1 film.
Figure 5. SEM images of (a) EOSNP1 on the sand surface, and (b) the crushed EOSNP1 film.
3.3. Water Transportation of the Superhydrophobic Sand
3.3. Water Transportation of the Superhydrophobic Sand
It is well-known that desert sand particles (diameter of 100–200 µm) consist of hydrophilic silicates,
which have low surface
It is well-known thatroughness
desert sandand cannot
particlesabsorb water, and
(diameter hence, cannot
of 100–200 µm)store water
consist of[37]. This
hydrophilic
workwhich
silicates, aims tohave modify
lowthe surface
surface wetting characteristics
roughness of sandwater,
and cannot absorb by adhering with rough
and hence, cannotnanostructures
store water [37].
to produce superhydrophobic sands having high water contact
This work aims to modify the surface wetting characteristics of sand by adhering angles. In this study, we developed
with rougha
rough coating of EOSNP1 on the sand surfaces. EOSNP1 samples with different weight percentages
nanostructures
Coatings 2019, 9,tox FOR
produce superhydrophobic sands having high water contact angles. In 10
PEER REVIEW thisof study,
13
(1–20 wt %) of PWs were prepared. By dropping water onto the surfaces of the raw and treated sand,
we developed a rough coating of EOSNP1 on the sand surfaces. EOSNP1 samples with different
the wettability
rawpercentages
and treated was evaluated.
sand, the The water droplets quickly
Thepermeated the raw sand,permeated
indicating the
thatraw
the
weightwater contact
(1–20
angle of
wtwettability
the
%) of
raw
PWs
sand
was
was
wereevaluated.
prepared.
approximately 0
water
By
◦ . The
droplets
dropping quickly
water
photographs
onto
of the
the surfaces
water droplets
of the
sand, indicating that the water contact angle of the raw sand was approximately 0°. The photographs
on the EOSNP1-treated
of the water droplets onsand the surface are shownsand
EOSNP1-treated in Figure 6a–d.
surface are The water
shown in droplets showThe
Figure 6a–d. an oblate
water
shape
droplets show an oblate shape without wetting the sand surface, indicating the formationon
without wetting the sand surface, indicating the formation of a superhydrophobic film ofitsa
surface. The water-absorbing − 1
·g were
superhydrophobic film on its capacities of the
surface. The untreated sand
water-absorbing were found
capacities of theto be 0.553 mL
untreated sand and
5found
mL oftowater was completely absorbed by the raw sand.
be 0.553 mL·g and 5 mL of water was completely absorbed by the raw sand.
−1

Figure 6.
Figure 6. Photos
Photos of
of water
water on
on the
thetreated
treatedsand
sandwith
withEOSNP1
EOSNP1prepared
preparedininthe
thepresence
presenceofof different
different wtwt
%
% of PWs (a) 20 wt %, (b) 10 wt %, (c) 5 wt %, and (d) 1 wt
of PWs (a) 20 wt %, (b) 10 wt %, (c) 5 wt %, and (d) 1 wt %. %.

The surface morphologies of the EOSNP1-coated films with different PWs contents were
examined using the SEM images shown in Figure 7a–d. The SEM of the EOSNP1-coated films were
prepared by disperse-casting their dispersions in n-hexane on carbon grids. The roughness of the
EOSNP1-coated sand surfaces increased with an increase in the wax content up to a 15 wt % (Figure
 Figure
Coatings 2019, 9,6.124
Photos of water on the treated sand with EOSNP1 prepared in the presence of different wt
10 of 13
% of PWs (a) 20 wt %, (b) 10 wt %, (c) 5 wt %, and (d) 1 wt %.

The
Thesurface
surfacemorphologies
morphologies of the
of EOSNP1-coated
the EOSNP1-coated films with
filmsdifferent PWs contents
with different PWs were examined
contents were
using the SEM images shown in Figure 7a–d. The SEM of the EOSNP1-coated
examined using the SEM images shown in Figure 7a–d. The SEM of the EOSNP1-coated films were films were prepared by
disperse-casting their dispersions
prepared by disperse-casting theirin n-hexane
dispersions on in
carbon grids.on
n-hexane The roughness
carbon grids.ofThe
theroughness
EOSNP1-coatedof the
sand
EOSNP1-coated sand surfaces increased with an increase in the wax content up to a 15 wt7a–c),
surfaces increased with an increase in the wax content up to a 15 wt % (Figure and
% (Figure
decreased with a further increase in the wax content up to a 20 wt %
7a–c), and decreased with a further increase in the wax content up to a 20 wt % (Figure 7d). The (Figure 7d). The adhesion
of the superhydrophobic
adhesion EOSNP1 EOSNP1
of the superhydrophobic coatings coatings
on the desert
on thesand
desertwassand investigated by adhesion
was investigated tape
by adhesion
peeling. The modified superhydrophobic sand was adhered onto the glass
tape peeling. The modified superhydrophobic sand was adhered onto the glass surface by a suitable surface by a suitable glue,
to form
glue, to sand
form coating films films
sand coating with with
a thickness of 500
a thickness of µm.
500 µm.A double-sided
A double-sided adhesive tapetape
adhesive is pressed, at
is pressed,
approximately 10 kPa, onto the superhydrophobic coated surface [8,36].
at approximately 10 kPa, onto the superhydrophobic coated surface [8,36]. If the coating on the If the coating on the surface
readily
surfaceadheres to the adhesive
readily adheres tape without
to the adhesive sand then
tape without sanditthen
is said
it istosaid
have a poor
to have adhesion
a poor withwith
adhesion the
surface and and
the surface is considered to betoattached
is considered be attached to itto
only by van
it only der der
by van WaalsWaalsinteractions [8,36].
interactions TheThe
[8,36]. peel-off
peel-
adhesion
off adhesion data of the EOSNP1-coated sand revealed that the EOSNP1 coatings with a paraffinwax
data of the EOSNP1-coated sand revealed that the EOSNP1 coatings with a paraffin wax
content
content of
of up
up to
to 15
15 wt %, showed
wt %, showed good good adhesion,
adhesion,whilewhilethe thecoating
coatingwith withthe thePWs
PWscontent
contentofof2020
wtwt%
% showed poor adhesion. The adhesion data were consistent with the
showed poor adhesion. The adhesion data were consistent with the surface morphologies of the surface morphologies of the
EOSNP1
EOSNP1(Figure
(Figure7a–d).
7a–d).

Figure 7. SEM images of the EOSNP1 films, prepared using different percentages of PWs (a) 5, (b) 10,
(c) 15, and (d) 20 wt %.

The superhydrophobicity of the sand mixtures, produced from the blending of the sand with
the PWs emulsion and the EOSNP1 prepared in the presence of 10 wt % PWs, was inferred from
their low ability to pass water, as reported in the experimental section. The time taken by the sands
to pass 10 mL of water is shown in Table 4. The short duration taken by the untreated sand to pass
water (2 s), elucidates its lower water storage ability. Moreover, it is clear from Table 4 that the PWs
emulsion could not form superhydrophobic or hydrophobic sand. The ratio of the treated with the
untreated sand (1:10) was economically preferred than a ratio of 1:1, which contained lower contents
of the treated sand. The mixture of the untreated sand with the treated sand (containing EOSNP1
in the presence of 15 wt % of PWs) on the sand surface, at a, mixing ratio (wt %) of 1:10 (Table 4),
showed a good amount of time to pass water, after 17 min. Water was not absorbed by this sand but
steadily stayed and rolled on its surface. Such superhydrophobic sand has shown to have a great
water-holding and low-flow-dragging capacities, and hence is of great importance for desert water
storage and transportation.
Coatings 2019, 9, 124 11 of 13

Table 4. Efficiency of the mixed sand with the different ratios of sand treated with the EOSNP1, on the
preservation of water.

Time (s) for Water Sand Composition

Samples Preservation (Treated Sand: Untreated Sand wt %)
Untreated Sand 1:10 1:5 1:1
Blank (untreated Sand only) – – –
EOSNP1 in the presence of 10 wt % of PWs 2s 11 15 17
EOSNP1 in the presence of 15 wt % of PWs 17 19 25

4. Conclusions
The modification of desert sand with a well-adhered and thermally stable, rough
superhydrophobic coatings is a key challenge for achieving superhydrophobic sand. Superhydrophobic
PWs capsules containing hydrophobic silica nanoparticles (EOSNP1) were prepared using the emulsion
technique, in the presence of n-hexane, to produce highly dispersed spherical and thermally stable
nanoparticles. EOSNP1 coated onto the desert sand showed superhydrophobic characteristics with
water droplet contact angles of 165◦ . The water droplet rolled and was not absorb by the treated
sand with EOSNP1. The treatment of sand with the EOSNP1 achieved higher efficiencies to modify
the hydrophobicity of sand to convert it to a superhydrophobic sand, even when mixed with the
untreated sand with 1:10 wt %. The high thermal stability of the superhydrophobic sand treated with
the PWs/EOSNP1 capsules is also a breakthrough, which would allow the hydrophobic sand to be
applied in a wide range of harsh environments.

Author Contributions: Methodology, Investigation, Writing—Review and Editing, A.M.A; M.M.S.A; Supervision,
H.A.A.-L.; Revision and Resources; Data Curation, N.H.M.
Funding: This research was funded by Deanship of Scientific Research at King Saud University, grant
number RG-235.
Acknowledgments: The authors extend their appreciation to the Dean of Scientific Research at King Saud
University for funding this work through Research Group No. (RGP-235, Saudi Arabia).
Conflicts of Interest: The authors declare no conflict of interest.

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