Nanostructured silica from bagasse ash: the

effect of synthesis temperature and pH on

its properties

Muhammad Sholeh, Rochmadi

Rochmadi, Hary Sulistyo & Budhijanto
Budhijanto

Journal of Sol-Gel Science and

Technology

ISSN 0928-0707

J Sol-Gel Sci Technol

DOI 10.1007/s10971-020-05416-7

1 23
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 Author's personal copy
Journal of Sol-Gel Science and Technology
https://doi.org/10.1007/s10971-020-05416-7

ORIGINAL PAPER: NANO-STRUCTURED MATERIALS (PARTICLES, FIBERS,

COLLOIDS, COMPOSITES, ETC.)

Nanostructured silica from bagasse ash: the effect of synthesis

temperature and pH on its properties
1,2
Muhammad Sholeh ●
Rochmadi Rochmadi1 Hary Sulistyo1 Budhijanto Budhijanto1
● ●

Received: 7 June 2020 / Accepted: 14 September 2020

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Bagasse ash as one of the sugar mill wastes can create a serious environmental problem. Hence, we adopted a strategy to
reduce the waste by utilizing its silica content. Nanostructured silica was synthesized from bagasse ash via sodium silicate
route. The effect of synthesis temperature and pH on the morphology, primary particle size, pore size, thermal properties,
and agglomerate fragility were investigated. Electron microscopy analysis revealed the fractal structure of silica with the
appearance of mesopores and macropores. Higher synthesis temperature and pH resulted in greater primary particle size.
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Nitrogen physisorption analysis showed that the addition of secondary sodium silicate solution was able to prevent the
collapse of the aggregate/agglomerate structure at the drying stage. Lower bound water content and lower average diameter
of the nanostructured silica aggregate/agglomerates as determined from thermal analysis and particle size analysis,
respectively, were observed with increasing temperature from 60 to 90 °C and decreasing pH from 11 to 8 during the
synthesis protocol. The primary particle size of the silica was on a nanoscale and the agglomerate was easily destroyed,
therefore the material had the potential to be used in applications where well-dispersed particles are key, such as in rubber
compounding that utilizes silica as reinforcing filler.

Graphical Abstract

* Muhammad Sholeh
muhammad-sholeh@kemenperin.go.id
1
Department of Chemical Engineering, Faculty of Engineering,
Universitas Gadjah Mada, Yogyakarta, Indonesia
2
Center for Leather, Rubber and Plastics, Jl. Sokonandi No. 9,
Yogyakarta, Indonesia
 Author's personal copy
Keywords Bagasse ash Silica Aggregate Agglomerate Filler
● ● ● ●
Highlights
● Nanostructured silica was synthesized from bagasse ash by sol-precipitation method.
● Nanostructured silica was characterized using SEM, TEM, BET, TGA, FTIR, and PSA.
● The effects of synthesis temperature and pH on the properties of nanostructured silica were investigated.
● The material had the potential to be used as a rubber reinforcing filler.
1 Introduction
Bagasse ash is one of the sugar industry wastes that origi-
nates from around 1.5% of the mass of processed sugarcane.
We estimate that the production of bagasse ash in Indonesia
is 0.4 million tons/year. Disposal of this waste is a problem
because its utilization is limited to concrete brick and
landfills. On the other hand, the silica content in bagasse ash
is 50–78% [1–3]. There is then a high potential of this
material to be processed further into nanostructured silica
that may significantly increase the material value.
Nanostructured silica is in high demand due to its wide-
ranging applications. The preparation of nanostructured
silica from biomass via sodium silicate route has been
widely studied. Noushad et al. [4] examined the use of silica
from rice husk ash as a dental nanocomposite. Azizi et al.
[5] prepared nanostructured silica using bagasse ash as a
catalyst support. Durairaj et al. [6] reported the use of silica
from Bambusa vulgaris leaves ash as an adsorbent. Boon-
mee and Jarukumjorn [7] synthesized nanostructured silica
from bagasse ash with the sol-gel method followed by
freeze-drying and oven drying. The obtained nanosilica was
applied as a natural rubber filler. However, the silica content
in the rubber composite was limited to 5 parts per hundred
rubber (phr) due to the agglomeration of the silica particles.
This leads to insignificant improvement in the mechanical
properties of the composite.
Some researchers have reported the effect of synthesis
conditions on the characteristics of nanostructured silica.
Liou and Yang [8] showed that neutralizing sodium silicate
using hydrochloric acid resulted in a higher surface area
than sulfuric, oxalic, and citric acids. The surface area was
reduced in increasing aging temperature from 50 to 120 °C.
Gelation pH had the most influence on surface area com-
pared to other parameters. Salavati-Niasari and Javidi [9]
reported that a higher acid feeding rate resulted in greater
primary particle size. Particle size was reduced in increasing
sonication time from 10 to 20 min.
To obtain a well-dispersed composite, silica agglomer-
ates used as the reinforcing fillers must be easily broken
down and dispersed in the rubber matrix into colloidal-sized
aggregates during the compounding process [10]. To fulfill
this requirement, aggregate/agglomerate structures must not
Journal of Sol-Gel Science and Technology
collapse during drying. The high surface tension of water
causes the silica aggregate/agglomerate structure to collapse
during drying, resulting in hard silica chunks that need
grinding to obtain silica powder [8, 11, 12]. Agglomeration
can be overcome by adding alcohol [13], freeze-drying [14],
or adding secondary sodium silicate solution [10]. The
function of alcohol is to reduce surface tension during the
drying process while freeze-drying is to eliminate surface
tension because removal of water occurs by the sublimation
process. The function of secondary sodium silicate solution
is to reinforce the aggregate/agglomerate structure. While
both freeze-drying and alcohol addition techniques are not
economical, the strategy of adding secondary sodium sili-
cate solution is more promising.
Publications on the synthesis of nanostructured silica
using the addition of secondary sodium silicate solution are,
however, still scarce. Sholeh et al. [15] showed that pre-
cipitated silica from bagasse ash had an amorphous phase
and a nanostructure. The yield of silica recovered was found
to vary between 41.7 and 58.2% using the addition of
secondary sodium silicate solution. The effect of synthesis
condition on morphology, primary particle size, pore size,
agglomerate fragility, and thermal properties are still
unknown. Thus, this paper reports the extended work to
evaluate the properties of nanostructured silica as a rubber
reinforcing filler.
2 Materials and methods
2.1 Materials
Bagasse ash was collected from a sugar factory in Yogya-
karta, Indonesia. Our previous study showed the chemical
compositions of the bagasse ash [15]. Analytical grade
chemicals used in silica synthesis were sulfuric acid (Mal-
linckrodt) and sodium hydroxide (Merck). Natural rubber
(RSS) was purchased from PTPN IX Indonesia. Paraffinic
oil as a lubricant, zinc oxide and stearic acid as activators,
bis-(triethoxysilylpropyl) tetrasulfide (TESPT) as a coupling
agent, 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) as an
antioxidant, diphenyl guanidine (DPG) as a secondary
accelerator, N-cyclohexyl-2-benzothiazole sulfenamide
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Journal of Sol-Gel Science and Technology
Fig. 1 Steps of the synthesis of nanostructured silica from bagasse ash
(CBS) as a primary accelerator, and sulfur as a crosslinking
agent, were all purchased from local suppliers.
2.2 Synthesis of nanostructured silica
Figure 1 shows the flow diagram of the preparation proce-
dure of nanostructured silica. Organic components in
bagasse ash were firstly removed by heating at 600 °C for
6 h. The calcined bagasse ash was boiled with 15.5% (w/w)
sulfuric acid solution for 2 h to reduce metal contents. The
slurry was centrifuged and the acid-treated bagasse ash was
washed five times and dried in an oven overnight. The
cleaned bagasse ash was boiled with 13.3% (w/w) sodium
hydroxide solution for 2 h then filtered to give a clear
sodium silicate stock solution [15].
25 and 50 ml of sodium silicate stock solutions were
diluted to a final volume of 100 ml to give primary and
secondary sodium silicate solutions, respectively. The pri-
mary sodium silicate solution was partially neutralized
slowly with the sulfuric acid solution for 30 min to give
nanostructured silica. The reaction temperature and final pH
value were varied. Secondary sodium silicate solution and
4.4% (w/w) sulfuric acid solution were then added slowly
and simultaneously into the suspension for 2 h to reinforce
the aggregate. The precipitate was aged overnight at room
temperature. The slurry was centrifuged and the white solid
precipitate was washed with water three times to remove the
salt and then oven-dried [15].
2.3 Characterization of nanostructured silica
The surface morphology of bagasse ash and nanostructured
silica were characterized using scanning electron
microscopes (JEOL JSM-T300 and Phenom-World). A
transmission electron microscope (JEOL JEM-1400) was
used to determine the shape and size of the silica primary
particles. The particle size was measured using ImageJ
image processing software. A Brunauer–Emmett–Teller
(BET) surface area analyzer (QuadraSorb Station 1) was
used to reveal the surface area and pore size distribution of
the nanostructured silica. Adsorption-desorption isotherm
was collected at 77 K after outgassed at 300 °C for 12 h to
remove physically adsorbed water. A thermogravimetric
analyzer (Shimadzu DTG-60H) was used to determine the
character of silica mass reduction due to dehydration and
dehydroxylation processes. The test was carried out on a
nitrogen atmosphere with a temperature increase of 15°/min
from ambient temperature up to 1000 °C. The functional
groups of the nanostructured silica were investigated
through the FTIR spectrophotometer (Shimadzu IRPrestige-
21) employing the KBr pellet method. The FTIR spectrum
was recorded in the range of wave numbers 340–4700 cm
−1
. The nanostructured silica was subjected to particle size
analysis (PSA) to determine the size distribution of the
aggregate/agglomerate. After sonicated for 15 min, the
sample was analyzed by a dynamic light scattering particle
size analyzer (Horiba SZ-100). Diameter of the particle was
expressed by intensity weighted harmonic mean size (Z-
average).
2.4 Preparation of nanostructured silica/natural
rubber (NR) composite
The mixing of NR, paraffinic oil, zinc oxide, stearic acid,
TESPT, TMQ, and DPG was performed using an internal
mixer (Haake 3000 P) with 310 cc-volume, equipped with
roller rotors. A fill factor of 70% was chosen. Rotor speed
and initial temperature settings of the mixer were adjusted
to 60 rpm and 80 °C, respectively. The mixing process was
started with masticating 100 phr NR for 3 min, followed by
addition of 15 phr nanostructured silica and 1.35 phr
TESPT. Four minutes later, another 15 phr nanostructured
silica and 1.35 phr TESPT were fed into the mixer. Five
minutes later, 3 phr ZnO, 1 phr stearic acid, 1 phr TMQ, and
1 phr DPG were added. Total mixing time was 15 min. The
mixture of compounds were then collected from the internal
mixer. Next, 1.5 phr CBS and 1.5 phr sulfur were incor-
porated to the mixture using a two roll mill. In the final step,
vulcanization was done by a laboratory hydraulic press at a
temperature of 150 °C and a pressure of 14.7 MPa.
2.5 Characterization of nanostructured silica/NR
composite
The tensile strength and elongation at break were tested
using a universal testing machine (Tinius Olsen H25K)
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according to ASTM D412-06. Tear strength was tested
using the same machine with type C specimens according to
ASTM D624.
3 Results and discussions
3.1 Synthesis of nanostructured silica
The formation of nanostructured silica proceeded through
the following steps: first, primary sodium silicate solution
was reacted with sulfuric acid to form silicic acid and
sodium sulfate. Silicic acid monomers then formed oligo-
mers, and oligomers formed polymeric clusters. The poly-
meric clusters grew in size, became more compact, then
collapsed to form nuclei of nanosilica particles [16]. At pH
> 7, silanol groups on the silica surfaces were deprotonated
and thus become negatively-charged monomers. This
charge stimulated particle growth through the addition of
other monomers on the particle surface. Sodium sulfate as a
by-product of polymerization reaction played a role as a
coagulant of silica particles. At critical coagulation con-
centration, the sol became unstable and formed aggregates
of fractal structure. The colloidal solution became more
viscous as the concentration of aggregates increased and
finally, a gel formed [16].
Gelation time is the time interval between the start of
acid addition and the formation of a gel. Gelation time was
observed visually as the time when the slurry lost its fluidity
[17]. Table 1 shows the gelation time obtained in this study
at various synthesis temperatures from 60 to 90 °C. It is
seen that the gelation time decreases as the temperature
increases. The shorter gelation period is caused by the
increase in the polymerization rate [18]. The trend is in
agreement with the result obtained by other researchers
[17, 19].
Colby et al. [20] found that the gelation time (tgel) fol-
lows the Arrhenius equation:
 
1 E
¼ A exp  ; ð1Þ
tgel RT
where A is the Arrhenius constant and E is an apparent
activation energy. A plot of the natural log of 1/tgel vs 1/T
should give a straight line with a slope of E/R and an
Table 1 Gelation time as a function of synthesis temperature
Synthesis temperature, °C Gelation time, min
60 22.71
70 21.89
80 21.08
90 20.35
Journal of Sol-Gel Science and Technology
intercept of ln A. The calculated values obtained are E =
3.6861 kJ/mol, A = 0.1666 min−1, and R² = 0.9996.
The initial concentration of primary sodium silicate was
quite low so that the gel formed was quite weak. The gel
was easily destroyed by a faster stirring speed. The last
stage of the synthesis was the strengthening of silica
aggregate/agglomerate. The structure of the aggregate/
agglomerate must be strong enough to withstand the pres-
sure due to surface tension during the drying process so that
it did not collapse. The collapse of the aggregate/agglom-
erate structure produced hard silica granules that were dif-
ficult to disperse into the composite matrix. Aggregate/
agglomerate strengthening was done by slowly adding
secondary sodium silicate solution to the suspension formed
in the previous step. Silicic acid formed from the addition of
secondary sodium silicate attached to the surface of the
aggregate that has formed [10].
3.2 Electron microscopy analysis
The dried silica particles were collected and characterized
using SEM and TEM to obtain information on the particles
morphology and average diameter. Figure 2 shows SEM
images of bagasse ash and nanostructured silica. The mor-
phology of bagasse ash in Fig. 2a reveals heterogeneous
material with irregular shapes. Bagasse ash has rough and
hollow surfaces associated with the release of organic
material during the combustion process of bagasse to pro-
duce energy in the sugar industry. The micron-size primary
particles of bagasse ash greatly influence their ability as
reinforcement in rubber. These granules are difficult to
crush into nano-size during the compounding process.
Hence, the role of bagasse ash is only as a semi-reinforcing
filler [21].
Figure 2b shows the morphology of nanostructured silica
from bagasse ash and the elemental mapping from EDX
measurement that shows strong intensities of Si and O. It is
seen that silica primary particles with nano dimensions form
aggregate lumps. Aggregates then form fractal structures
into agglomerates. Aggregates (primary structures) are
formed with strong siloxane bonds, whereas agglomerates
(secondary structures) are formed with weaker Van der
Waals bonds [10]. A similar structure was found by other
researchers [19, 22, 23].
The TEM analysis (Fig. 3) further confirms the aggregate
structure as observed in the SEM images. A branched
structure made of connected clusters composed of small
silica primary particles is welded together into larger dense
areas [24]. The product contains semi-spherical primary
particles of <50 nm and micron-sized agglomerates with the
appearance of mesopores and macropores. The average
diameter of silica primary particles was calculated using
ImageJ software. The results are shown in Table 2. Higher
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Fig. 2 a SEM image of bagasse ash, b SEM image and elemental mapping of nanostructured silica (synthesized at pH = 8 and T = 80 °C)

Fig. 3 TEM image of

nanostructured silica with
synthesis condition: a pH = 8; T
= 60 °C, b pH = 8; T = 80 °C,
c pH = 8; T = 90 °C, d pH = 11;
T = 80 °C

pH results in greater primary particle size. At pH > 7, the particles for further growth, resulting in an increase in
formation of siloxane bonds in surface silanol groups cre- particle size by increasing pH [8]. A similar trend was
ates negative charges between silica particles and causes an observed by Witoon and Chareonpanich on the formation of
increase in electrostatic repulsion. The charge catalyzes silica nanoparticles using tetraethyl orthosilicate as a
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Table 2 The average diameter of silica primary particles Manipulation of Eq. (2) produced an equation to calcu-
Synthesis condition Daverage, nm late the diameter of silica primary particles as follows:
pH T, °C 6000
DBET ¼ ; ð3Þ
LBET  ρ
8 60 12.4
8 80 18.8 where: DBET: the diameter of silica primary particles, nm.
8 90 24.5 The parameter values as calculated from Eq. (3) are listed
11 80 21.9 in Table 3. It is seen that smaller BET test results corre-
spond to greater diameter of the silica primary particles. As
reinforcing fillers, the maximum diameter of silica primary
Table 3 Surface area and BET diameter at various synthesis particles is 30–40 nm [26]. All diameters values shown in
temperature and pH Table 3 thus fulfill this standard.
T, oC pH LBET, m2/ DBET, nm T, oC pH LBET, m2/ DBET, nm Interestingly, the values obtained from BET (Table 3) are
g g higher than the results from TEM (shown in Table 2). This
60 8 185.1 14.7 80 7 109.7 24.9 observed fact is due to surface joining between primary
70 8 137.6 19.8 80 8 111.4 24.5
particles into aggregates. This also proves that the pores
(shown in TEM images) were dominated by pores inside the
80 8 111.4 24.5 80 10 105.1 26.0
aggregate/agglomerate structure, and not by pores inside the
90 8 74.1 36.8 80 11 103.4 26.4
primary particle. As a comparison, Han et al. [27] synthe-
sized hollow silica with a hematite template. The authors
precursor [25]. Particle size was increased with an increase reported a hollow silica particle with 30 nm-diameter and
in the reaction temperature. This phenomenon indicates that 576.6 m2/g-BET surface area.
the nucleation rate decrease when the temperature increased Figure 4a–c shows that the isotherm curve of silica
and consequently, the particle size increased due to a high nanostructures follows Type IV according to the IUPAC
growth rate [10]. classification. This type is the adsorption characteristic of
mesoporous structures. Multilayer adsorption occurs at low
3.3 Nitrogen physisorption analysis relative pressure followed by capillary condensation at high
relative pressure [28]. The hysteresis cycle in Fig. 4a, b
BET analysis using nitrogen as adsorbate was performed to follows the H3-type which shows a pore network containing
obtain specific surface area, adsorption–desorption iso- macropores that cannot be fully filled by capillary con-
therm, and pore size distribution of the nanostructured densate [29, 30]. Figure 4a’, b’ further shows the distribu-
silica. The BET test results in Table 3 show that the surface tion of the pore size widened from ±2 to ±75 nm. The
area per unit mass of silica is influenced by the reaction higher the temperature, the smaller the pore volume, from
temperature and pH. At 80 °C, higher pH results in nanos- 1.37 cc/g at 60 °C to 0.29 cc/g at 90 °C. The pore volume
tructured silica with a lower specific area. Furthermore, increases from 0.32 cc/g at pH 7 to 0.81 cc/g at pH 10 then
higher reaction temperature results in smaller surface area drops to 0.46 cc/g at pH 11.
per unit mass of silica. The surface area of silica decreases Isotherm and pore size distribution of nanostructured
from 185.1 m2/g at a synthesis temperature of 60 °C to silica with and without the addition of secondary silica is
74.1 m2/g at 90 °C. shown in Fig. 4c-c’. The hysteresis loop without the addi-
If the primary particles are assumed to be spherical, solid tion of secondary silica (without reinforcement) follows the
(not porous), uniform in diameter, and the effect of adhe- H1 type isotherm which shows pore network containing
sion among primary particles due to aggregation is ignored, narrow range mesopores. According to IUPAC classifica-
then the surface area of the BET test is the total surface area tion, macropores are pores with widths exceeding 50 nm
of the silica primary particles. The diameter of primary [29]. Macropores of nanostructured silica with and without
particles can be calculated from the following equation [16]: the addition of secondary silica is 30 and 1% from total pore
volume, respectively. This indicates that without reinfor-
LT 4πr 2 N cement the aggregate/agglomerate structure collapsed dur-
LBET ¼ ¼4 3  1000; ð2Þ
MT 3 πr Nρ ing the drying step.

where: LBET: the specific surface area obtained with a BET 3.4 Thermal analysis
analyzer, m2/g. LT: the total area of all particles, m2. MT: the
total mass of all particles, g. r: primary particle radius, nm. Thermal analysis was performed to obtain information on
N: number of particles. ρ: silica density = 2.2 g/ml. the water content in nanostructured silica. The water content
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Fig. 4 Nitrogen
adsorption–desorption isotherm
and BJH pore size distribution of
the nanostructured silica a–a’
various synthesis temperature,
b-b’ various synthesis pH, c-c’
with and without secondary
sodium silicate reinforcement
(pH = 8; T = 80 °C)

consists of two types, namely free water and bound water.
Free water is water that adsorbed on the surface of silica
while bound water is water in the form of silanol (Si–OH)
groups [26]. There are three types of silanol groups found
on the surface of silica, namely (a) isolated silanols, (b)
germinals, and (c) vicinals.
The test was carried out from ambient temperature up to
1000 °C with a temperature increase of 15°/min on a
nitrogen atmosphere. The TGA test in Fig. 5a, b shows that
the reduction in mass of nanostructured silica is divided into
three stages. The first stage is relatively fast which occurs
due to the removal of free water (dehydration) on the sur-
face of silica (30–200 °C). The second and third steps are
slow which referred to the reaction of silanol condensation.
The weight loss at 200−600 °C occurs due to the removal
of geminal and vicinal silanols, and the weight loss at
600–1000 °C refers to the removal of isolated silanols [31].
The mechanism of water formation during silanol con-
densation follows Eq. (4) [32].
OH
SiO2 SiO2 O + H2O ð4Þ
OH
TGA data were evaluated to obtain the value of free and
bound water content summarized in Fig. 6. It can be seen in
Fig. 6a that higher synthesis temperature results in lower
free water content. This observed phenomenon is in
agreement with the smaller surface area of particles per unit
mass of silica shown by the BET test results in Table 3,
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Fig. 5 TG curves of
nanostructured silica at various
synthesis a temperature and
b pH

Fig. 6 The water content of

nanostructured silica at various
synthesis a temperature and
b pH

because smaller surface area of the particle contains less

silanol group per unit mass of silica. Moreover, Fig. 6b
shows that higher pH results in higher free water content.
This observed phenomenon demonstrates that higher
hydroxide ion levels in the suspension during synthesis
leads to higher number of silanol groups produced per unit
of surface area of silica. The increase in the number of
silanol groups is indicated by the higher levels of bound
water.

3.5 FTIR analysis

FTIR analysis was performed to validate the presence of

functional groups discussed in the previous sections.
The experiment was done in transmission mode
employing the KBr pellet method. According to the
nanostructured silica spectrum in Fig. 7a–e, variations in pH
and temperature of the synthesis did not appear to affect the
functional groups in silica. The most intense peaks are
observed at 1140 cm−1 because of the asymmetrical
stretching vibrations of the siloxane bond (Si–O–Si). This
peak appears together with two peaks at 830 and 500 cm−1
which are associated with symmetrical stretching vibrations
and rocking vibrations of Si–O bonds in a three-
dimensional SiO2 network. Absorption around 3450 cm−1
is caused by stretching vibration of silanol (Si–OH) and
adsorbed water. The peak at 1660 cm−1 is adsorbed water
Fig. 7 FTIR Spectra of nanostructured silica with synthesis conditions:
a pH = 8, T = 60 °C; b pH = 8, T = 80 °C; c pH = 8, T = 90 °C; d pH
= 7, T = 80 °C; e pH = 11, T = 80 °C; and f pH = 7, T = 80 °C fol-
lowed by heating at 1000 °C for 2 h
[33]. The absence of peaks in the range of 1700–2900 cm−1
indicates the absence of organic compounds because the
silica synthesis process does not use surfactants or templates
[34]. Figure 7f shows that the nanostructured silica calcined
at 1000 °C no longer has peaks at 1600 and 3400 cm−1.
This proves that the silanol bond has condensed into a
siloxane bond.
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3.6 Particle size analysis
In applications where well-dispersed silica particles is an
important aspect, such as in rubber compounding processes,
the primary particle size, the primary structure, and the level
of fragility of the agglomerate structure of the filler are key
parameters [10]. Thus, following the SEM and TEM ana-
lysis, PSA test was performed to evaluate the level of fra-
gility of the agglomerates.
The hydrodynamic diameter of nanostructured silica was
measured by a dynamic light scattering technique. Figure 8
(a) shows the effect of sonication time on the size of the
nanostructured silica agglomerates synthesized by the
addition of secondary sodium silicate as a reinforcement of
the aggregate/agglomerate structure. It showed that the
longer the sonication time the smaller the agglomerate size.
This level of fragility proves that the aggregate/agglomerate
structure does not collapse during drying. The aggregate/
agglomerate size after sonication for 15 min was 230 nm.
For comparison, nanostructured silica without the reinfor-
cement of aggregate/agglomerate structures had a mean
diameter of 6120 nm after sonication for 15 min (Figure not
shown). This is in line with the results of the pore size
distribution analysis (Fig. 4c’).
It can be seen from Fig. 8b that higher synthesis tem-
perature leads to smaller average diameter of the nanos-
tructured silica aggregate/agglomerate (this also means that
the agglomerate is more fragile). Whereas in Fig. 8c it is
seen that higher pH leads to greater average diameter of the
Fig. 8 PSA test results a z-
average of silica nanostructures
at various sonication times [T =
80 °C; pH = 8; secondary
sodium silicate = 120 min]; and
particle size distribution of silica
nanostructures at various
synthesis b temperatures and (c)
pH after sonication for 15 min
obtained by a dynamic light
scattering technique
nanostructured silica aggregate/agglomerate. Bound water
content (Fig. 6) seems to affect the fragility level of
agglomerates. The higher the bound water content (as
silanol), the stronger the van der Waals force that is
experienced between the aggregates during the drying
process. As a result, the agglomerates after drying become
denser in their porous structure. The closer the pore struc-
ture, the more difficult the agglomerates to be destroyed.
3.7 Mechanical properties of the composite
As discussed in the previous section, to be a reinforcing
filler, silica must have a primary particle diameter less than
40 nm and agglomerates that are easily crushed to a col-
loidal scale in the compounding process [10, 26]. The PSA
test (Fig. 8) shows that the addition of secondary sodium
silicate provides a good fragility of the agglomerate and
strongly overlapping agglomerate particle size distribution
in the synthesis temperature range of 60–90 °C and pH 7–9.
Meanwhile, the BET test (Table 3) shows that the primary
particle size is more influenced by the temperature than by
the pH of the synthesis. Therefore the practical application
of nanostructured silica into natural rubber is focused on the
effect of synthesis temperature on the reinforcing ability of
the silica.
Figure 9 shows mechanical properties in terms of tensile
strength, tear strength, and elongation at break for the gum
(unfilled NR) and the 30 phr nanostructured silica-filled NR
vulcanizates with various synthesis temperature. It is seen
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Fig. 9 a Tensile strength, b tear
strength, and c elongation at
break for the gum (unfilled) and
the nanostructured silica filled
NR vulcanizates with various
synthesis temperature
from Fig. 9a, b that all of the synthesized silica significantly
increased both the tensile strength and tear strength of the
NR-based composites. The composite filled with nanos-
tructured silica synthesized at 70 °C (Si 70 °C) exhibits the
highest mechanical properties among the nanostructured
silica filled NR composites. The tensile and tear strength of
the nanostructured silica/NR vulcanizate at nanostructured
silica concentration of 30 phr are up to ~1.5 and ~3.3-fold
higher than those of the gum vulcanizate. This result is
significantly better than that obtained by Boonme et al. [7],
in which the authors reported a negative effect on the
mechanical properties of the composites at 10 phr nanosilica
(90 nm) concentration. Hypothetically, the negative effect
was the consequence of filler-filler interaction. Filler
agglomeration was the main problem of the low optimum
silica concentration in their study. In our study, the nano-
scale silica primary particle diameter and good aggregate/
agglomerate structure enable the synthesized nanostructured
silica to become a highly promising reinforcing filler at a
high concentration.
The increase of tensile and tear strengths with decreasing
synthesis temperature from 90 to 70 °C was attributed to the
decreasing primary particle size of the silica as shown in
BET analysis. The smaller the primary particle size the
larger the silica surface area that interacts with the natural
rubber chain [35]. Interestingly, the tensile and tear
Journal of Sol-Gel Science and Technology
strengths of the vulcanizate filled with silica synthesized at
60 °C (Si 60 °C) were lower than those filled with Si 70 °C.
The detrimental effect on tensile strength at low synthesis
temperature may be attributed to the relatively high water
content as shown in thermal analysis (Fig. 6a). The higher
the silanol groups the more polar the nanostructured silica
and the higher the filler-filler interaction [35]. Figure 9c
shows that the elongation at break of the nanostructured
silica filled NR vulcanizate was lower than the gum vul-
canizate due to the presence of hard segments of filler which
made the rubber chain stiffer. The rigid silica particle
restricted the movement of the rubber chain [36].
4 Conclusions
In the quest of nanostructured silica for wide-ranging
applications from catalysis, medical applications, to rein-
forcing filler, we have synthesized the material from
bagasse ash and studied the effect of temperature and pH
during the synthesis. The resulting material was fully
characterized using various methods of different principles.
We found that the morphology, particle size, pore size, and
thermal properties of nanostructured silica from bagasse ash
were influenced by synthesis temperature and pH. The
gelation time of the synthesis of nanostructured silica
 Author's personal copy
Journal of Sol-Gel Science and Technology
decreased with increase in temperature. TEM and BET
results showed that the higher synthesis pH and temperature
leads to greater primary particle size. Reinforcement by
secondary sodium silicate solution prevented the silica
structure from collapsing during drying. The higher the
synthesis temperature and the lower the synthesis pH, the
more fragile the nanostructured silica aggregate/agglomer-
ates. Bound water content seems to affect the fragility level
of agglomerates. All characterization results showed that the
synthesized nanostructured silica in this study exhibits the
properties that are required in silica for rubber reinforcing
filler. To this end, we have shown the effect of the nanos-
tructured silica addition to natural rubber composites. It was
shown that the nanostructured silica that were synthesized at
various temperature between 60 and 90 °C significantly
increased the mechanical properties of the NR-based com-
posites. The highest mechanical properties were found at
NR filled with nanostructured silica synthesized at 70 °C.
Acknowledgements This research was financially supported by
Lembaga Pengelola Dana Pendidikan, Indonesia (Grant No.
201802210112406). MS would like to thank the staff members at
Rubber Research Laboratory, Center for Leather, Rubber and Plastics
(CLRP), Indonesia for the TGA analysis, compounding process, and
fruitful discussions. All the authors gratefully acknowledge the Head
of Metal Industries Development Center for use of the Haake
Rheomix.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
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