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Silica Nanoparticles From Waste Glass
Silica Nanoparticles From Waste Glass
Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
A R T I C LE I N FO A B S T R A C T
Keywords: Waste glass powder was used as a low cost precursor for production of colloidal nanosilica for the first time. The
Colloidal nanosilica process includes production of wet silica gel and thermal peptization of the wet gel. Purification of the glass
Peptization powder and wet gel production were initiated by acid washing. The obtained powder was reacted with sodium
Waste glass powder hydroxide to produce wet silica gel. Type of the applied acid was examined in one factor at a time route.
Taguchi design
Temperature of the alkaline step and concentrations of the applied acid and base were investigated using
Taguchi design of experiments. After finding the best combination of the investigated factor levels in production
of the wet gel, time of the stabilization in thermal peptization was studied. Characterizations of the wet gel and
colloidal silica were performed by XRF, DLS, FESEM, TEM, FTIR and N2 sorption evaluation. Accordingly pure
and stable colloidal nanosilica (98.50%) with average particle size of 21.9 nm was produced from the glass
powder successfully. Specific surface area of the dried porous optimum sample was 83.63 m2/g.
1. Introduction was proposed by Ahlberg and Simpson in order to obtain a more stable
colloid [15]. However, Rhee et al. [16] studied effects of some im-
Colloidal silica is dispersion of silica particles which are between portant experimental parameters such as concentration, pH of the gel-
1 nm and 1 µm in size showing specific deviations from true solutions ling and washing solutions, aging and duration of the peptization step.
[1]. Colloidal silica has growing and versatile applications. It can act as It has been reported that lower temperature differences between two
a mineral binder in cement and concrete [2], polishing slurry in pro- steps of the thermal peptization may lead to fabrication of colloids with
duction of mirrors and lenses [3], coating in textile and paints [4–6], lower average particle sizes [17].
carrier in drug delivery systems and precursor in production of catalysts Some minerals such as olivine, vermiculite and chrysotile have been
[7]. applied for production of nanosilica as inexpensive available Si sources
There are several processes for production of colloidal silica such as [18–21]. However, almost all of the mineral based synthetized nano-
ion exchange, acid-neutralization, peptization [8], direct oxidation, silica products reported in the literature are powder. In our previous
milling and dispersion [9], dialysis and electrodialysis [10]. Although work, perlite was used to obtain colloidal nanosilica [17]. Particle size
ion exchange is the most common process, but it has some dis- of the produced nanosilica was mostly about 8–74 nm. In this study,
advantages such as recycling of ion exchange resins and residual Na waste glass powder has been selected to produce colloidal nanosilica
which causes aggregation and lower stability of the colloid [9]. with smaller particle size for the first time. Glass powder is a chemically
Peptization is a simple, practical and environmental friendly neutral and abundant low cost source of silica. Reusing of waste glass
method for production of colloidal silica. Two distinct methods have has various advantages such as saving energy and materials, reduction
been proposed for peptization of a gel: Thermal and ultrasonic-assisted of the production costs, decrease of landfill space demands and so on
routs [11,12]. Thermal peptization has some benefits. Trail [13] con- [22,23]. Effective factors have been optimized using Taguchi design of
cluded that if there is no live steam, a tight 90% filled autoclave is more experiments. The utilized process had two steps: wet gel production and
effective for peptization. White and coworkers [14] investigated the thermal peptization. Studied factors of the thermal peptization were
impacts of temperature and pressure. According to their report, suitable type and concentration of the acid solution, concentration and tem-
temperature and pressure ranges for thermal silica gel peptization are perature of the alkaline solution and finally stabilization time which
80–200 °C and 7–225 psi, respectively. A two- step thermal peptization was considered as the second step of the thermal peptization. Wet pure
⁎
Corresponding author.
E-mail address: [email protected] (R. Norouzbeigi).
https://doi.org/10.1016/j.ceramint.2018.09.050
Received 5 August 2018; Received in revised form 5 September 2018; Accepted 6 September 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Please cite this article as: Asadi, Z., Ceramics International, https://doi.org/10.1016/j.ceramint.2018.09.050
Z. Asadi, R. Norouzbeigi Ceramics International xxx (xxxx) xxx–xxx
Table 1 silica gel and colloidal nanosilica with smaller particle sizes were se-
Wet gel production parameters and their levels. lected as targets of the experiments.
Symbol Wet gel production parameter Unit Level 1 Level 2
2. Materials and method
A Hydrochloric acid concentration M 2 4
B Alkaline step temperature °C 70 90
C Sodium hydroxide concentration M 2.5 4.5
2.1. Materials
Fig. 1. FESEM picture of glass powder particles (5KX magnification). Designed experimental runs were conducted according to Table 2.
Statistical analyses were performed to optimize the synthesis condition.
Consequently, the experiments were continued with thermal peptiza-
Table 4
tion of the obtained wet gel.
XRF elemental analysis for experiments with various acids.
Run SiO2 (%) Al2O3 (%) Na2O (%) SO3 (%) MgO (%) 2.2.2. Wet gel peptization
1 98.175 0.598 0.145 0.029 0.053
The wet gel was dispersed in a sodium hydroxide solution (0.1 M)
2 98.475 1.078 0.410 0.037 0 under vigorous stirring. Two distinct steps were performed. Duration of
3 97.773 0.722 1.463 0.042 0 the first thermal peptization step was 10 h and the temperature was
remained at 120 °C. The temperature was fixed at 160 °C and the
duration was set at four levels (1–4 h) in the second step.
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Z. Asadi, R. Norouzbeigi Ceramics International xxx (xxxx) xxx–xxx
Table 5
XRF elements analysis.
Experiment No. Al2O3(%) Na2O (%) SO3(%) MgO (%) K2O (%) Fe2O3(%)
Table 6 less than −30 mV [24]. Dynamic light scattering (DLS) and zeta po-
ANOVA table for Taguchi L4 designed experiments. tential analyses were performed using a Malvern light scattering unit
Source of Sum of DOF Mean of Contribution (ZEN 3600) with a 633 nm He–Ne laser.
variance square square percentage (%) For the other characterizations such as field emission scanning
electron microscopy (FESEM), Fourier transform infrared spectroscopy
A 46.649 1 46.649 79.56
(FTIR) and gas physisorption the samples were dried at 80 °C for 10 h.
B 3.803 1 3.803 6.49
C 8.180 1 8.180 13.95
FESEM (Zeiss, sigma) studies were operated at a 30 kV used for mor-
Error 0.000 0 – – phology assessment. Fourier Transform Infrared spectroscopy evalua-
Total 58.632 3 – – tion was carried out in the wavenumbers ranged from 450 to
4000 cm−1 (Perkin Elmer Spectrum, RX1) applied to analyze the sur-
face functional groups. Besides, the specific surface area of the opti-
mized sample was measured by N2 sorption method and the
Brunauer–Emmett–Teller (BET) model (NOVA® Station B). Finally, for
TEM analysis (Zeiss, EM10C, 100 kV), a drop of the optimized sample
was dried on a substrate.
XRF result and FESEM image of the initial glass powder are pre-
sented in Table 3 and Fig. 1, respectively. Elemental compositions of
Fig. 3. Wet gel production yield. the samples prepared under various acidic media are listed in Table 4.
Samples 1, 2 and 3 were obtained by hydrochloric, sulfuric and nitric
acids. Results show that using hydrochloric acid leads to a higher purity
resulted silica gels (Philips, PW 1800). Particle size distribution and (SiO2 content (%)) of the product.
zeta potential can be considered as two crucial features of the final H+ cations must diffuse through the solid phase to solve it in an
product. Average particle size and the polydisparity index (PDI) re- acidic solution [25]. As a result, more powerful acids like HCl can re-
present the quality and stability of colloids. PDI indicates the wideness lease more hydronium ions and subsequently remove the impurities. To
of the particle size distribution. As a result, lower PDI value shows improve the SiO2 content of the product, besides the temperature and
uniform particulate dispersion and is desired for high quality products. concentration of the alkaline step, the acidic concentration were in-
Another crucial property of practical colloids is stability. The measured vestigated according to the Taguchi experimental design. The Optimum
zeta potential values of the stable colloids are more than + 30 mV or experimental conditions and impact of the studied factors can be
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Z. Asadi, R. Norouzbeigi Ceramics International xxx (xxxx) xxx–xxx
Y3 + Y4 93.69% + 98.5%
A2̅ = = = 96.095%
2 2
EfA = A2̅ − A1̅ = 96.095% − 89.265% = 6.83% (4)
where PYi and mi are process yield and dried gel mass related to the ith
experiment, respectively. Indices i and 0 refer to the run numbers
(Table 2) and the raw waste glass. The process yield is defined by di-
vision of the dried silica gel and the initial raw glass waste mass (5 g).
According to Fig. 3, the production yield (%) of the first experiment
is more than 50%. For synthesis of this sample, temperature and con-
centration of the alkaline step were in the least level, so the sedi-
mentation of silica along with impurities was less than the other ex-
periments [28].
For investigation of the average particle size and particle size dis-
tribution, DLS analysis was carried out. The obtained results are illu-
strated in Fig. 4. The average particle sizes of the four prepared samples
Fig. 6. FTIR spectrum of dried obtained colloidal nano-silica.
were 23.3 nm, 21.9 nm, 35.9 nm and 37.9 nm respectively. Hence,
sample 2 made under 2 h stabilization duration had the smallest par-
estimated by factor main effect measurements (Ef) and analysis of ticle size.
variance (ANOVA) [26]. The weight percentage of silica in the dried gel PDI values of the obtained colloids are shown in Fig. 5. PDI of the
was considered as response of the experiments. XRF results and re- second experiment is less than the others. Particle size distribution
sponses are presented in Tables 2, 5, respectively. would be optimized when thermal stabilization is less than 2 h [12].
For calculation of Ef, the mean values of responses should be de- Smaller particles will sediment on the larger ones when higher silica sol
termined for each level. Accordingly, the factor effect can be computed temperature and alkaline conditions are applied (Ostwald ripening)
by subtracting the lowest mean value from the highest one [27]. Effect [29].
of the factor A (EfA) was calculated according to Eq. (4). In the second step of thermal peptization, functional groups existing
on the surface of nanosilica particles were eliminated, so the produced
Y + Y2 89.72% + 88.81%
A1̅ = 1 = = 89.265% colloid was more stable. On the other hand, Ostwald ripening was
2 2
happened in this step. As a result, the optimized time which balanced
two proposed phenomena was 2 h. Zeta potential of colloidal particles
can be considered a reliable criterion for stability assessment. The zeta
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Z. Asadi, R. Norouzbeigi Ceramics International xxx (xxxx) xxx–xxx
4. Conclusion
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