Construction and Building Materials 163 (2018) 875–879

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Construction and Building Materials

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Technical note

Addition of waste glass for improving the immobilization of heavy

metals during the use of electroplating sludge in the production of clay
bricks
Linqiang Mao ⇑, Huijuan Guo, Wenyi Zhang ⇑
School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, PR China

h i g h l i g h t s

 Waste glass addition reduces open porosity and surface area of bricks.
 Waste glass addition improves compressive strength of bricks.
 Brick matrix becomes more dense because glass phase filled in pores.
 Waste glass addition reduces the leachability of heavy metals significantly.

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

Article history: A novel strategy for improving the immobilization of heavy metals during the use of electroplating sludge
Received 27 September 2017 in the production of clay bricks, was proposed by the addition of waste glass. Waste glass addition
Received in revised form 30 November 2017 reduced open porosity and surface area, and enhanced compressive strength remarkably. With the add-
Accepted 27 December 2017
ing amount of waste glass powder up to 30 wt.%, surface area and open porosity declined from 0.84 to
Available online 4 January 2018
0.05 m2/g and from 10.69 to 1.16%, respectively. Compressive strength increased from 20 to 32.7 MPa.
Moreover, the leaching concentration of heavy metals decreased considerably and met the regulation
Keywords:
standard. Heavy metals, Cu and Zn, have been incorporated into stable spinels phase and adding waste
Waste glass
Electroplating sludge
glass was favored to the formation of spinel. It was regarded that waste glass and andesine melted
Immobilization and formed liquid phase during firing process, which improved the mass transfer and the reaction kinetic
Clay bricks of spinels formation. The liquid phase filled in the pores and densified bricks body, which also play a
important role in preventing heavy metals from releasing. Overall results suggested the addition of waste
glass powder was a promising method in improving immobilization of heavy metals during the use of
electroplating sludge in production of clay bricks.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction The substitution of electroplating sludge in the production of

The rapid development of electroplating industries have pro-
duced a great deal of electroplating sludge, which may pose serious
threat to human health and required special treatment prior to the
landfill, because this sludge usually contains a noticeable amount
of heavy metals. Solidification/stabilization technologies by
cementation were widely adopted approaches of eliminating the
hazards of heavy metals. However, the volume of cement solidifi-
cation matrix increases considerably comparing with electroplat-
ing sludge, which enhances the burden of the landfill [1].
⇑ Corresponding authors.
E-mail addresses: maolinqiang2008@126.com (L. Mao), 891545210@qq.com (W.
Zhang).
clay bricks has been successfully pursued since it can reduce both
the consumption of natural resources and the cost of waste dis-
posal [2]. For example, Pérez-Villarejo et al. [3] have investigated
the potential for the use of electroplating sludge in the production
of clay bricks. The leachability of heavy metals from the brick
matrix was reduced substantially, the maximum addition amount
was around 5 wt.%. While the leachability of heavy metals
exceeded the regulation value with addition amount over 5 wt%
[3]. The interaction of heavy metals with silicon, aluminum and
ferric resulting in the mineralization, were largely responsible for
the decreasing leachability of heavy metals from the bricks matrix
[4]. However, the reduction in the porosity and specific surface
area of fired bricks after firing process, also makes more contribu-
tion to preventing of heavy metals releasing. Therefore, decreasing

https://doi.org/10.1016/j.conbuildmat.2017.12.177
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
876 L. Mao et al. / Construction and Building Materials 163 (2018) 875–879

the porosity and specific surface area of fired bricks might improve
the immobilization of heavy metals. It is necessary to densify the
bricks body for decreasing the porosity and specific surface area.
The vitrification of the raw bricks by melting may be a good alter-
native, but vitrification was usually carried out above 1300°C [3].
Thus a traditional glass-forming technique may not be applied.
Waste glass powder would melt at relative low temperature
and produce some liquid phase [5]. It is assumed that the formed
liquid phase filled in the porosity and coat the surface of bricks
matrix, the porosity and specific surface area of fired bricks would
be decreased considerably, benefiting to prevent heavy metals
from releasing. To verify this hypothesis, in this study, waste glass
powder was employed to fill in porosity and densify bricks body
for examining its influence on enhancing the immobilization of
heavy metals.
Characteristic Leaching Procedure (HJ/T 300-2007) was used to
evaluate the immobilization of heavy metals after firing process,
the weight of every brick block was about 35 g and the whole fired
brick was steeped in sealed polyethylene bottles containing the
leaching solution of 700 mL (L/S = 20), and it was rotated end-
over-end at 60 rpm for same agitation periods. At the end of agita-
tion period, the leachates were filtered through a membrane (0.2
lm) and the concentration of heavy metals in leachates were
determined by flame atomic absorption spectrophotometer. In all
leaching tests, a pH 2.9 acetic acid solution was used as the leach-
ing fluid, and it was prepared by diluting 17.25 mL acetic acid to 1
L with deionized water [8].
3. Results and discussion

Table 1 presented Zn and Cu were main hazardous pollutants in

2. Materials and methods
the electroplating sludge, they were also the common heavy met-
als presented in electroplating sludge. The mass fraction of SiO2 in
The electroplating sludge and clay were collected from the elec-
clay and waste glass powder accounted for 56.19 and 70.49%,
troplating industry and a brick manufacturer respectively located
respectively. The mass fraction of Na and Ca oxides are 3.15 and
in Changhzou city, Jiangsu Province. Waste glass powder was
2.65 wt%, respectively. Which was lower than other sludge
obtained from milling broken glass bottles with ball crusher. All
obtained by lime neutralization and precipitation process, and this
raw materials were dried at 105 °C for 24 h and pass through a
sludge might be obtained by adding chemical complexing agent
74 lm sieve (200 mesh) for a homogeneous particle size. The
into effluent. Additionally, the loss on ignition at 900 °C of clay
chemical compositions of raw materials were analyzed by X-ray
and electroplating sludge were 9.26 and 34.54 wt%, respectively.
Fluorescence and results were shown in Table 1.
The main composition of waste glass used in this study was SiO2
Higher content of electroplating sludge of 10 wt% was added in
and accounted for 70.49 wt%, and no hazardous metals were
raw bricks for reflecting the increase in the immobilization of
detected.
heavy metals due to the substitution of waste glass. Different con-
Water absorption is an important factor for the durability of
tents (5, 10 15, 20, 25, 30 wt%) of waste glass powder were added,
clay bricks [9]. Fig. 1(a) showed both water absorption and open
the mixtures was milled in a ball mill for 300 min to obtain good
porosity declined with the increase in the addition of waste glass
homogenization. Solid bricks with 50 mm  35 mm  10 mm were
powder. With the adding content of waste glass powder up to
prepared with shape process under 40 MPa of pressure. The dry
30 wt.%, water absorption declined from 7.64 to 2.74%, and open
samples were then fired in a laboratory-type electrical furnace at
porosity decreased from 10.69 to 1.16%. It implied that the number
a rate of 5 °C/min to 950 °C for 3 h, and then the fired samples were
of pores decreased due to the addition of waste glass powder,
then cooled to room temperature [6].
which effectively prevented the leaching solution intruding into
The water absorption capacity, open porosity and compressive
bricks body and was favored to improve the immobilization of
strength were measured according to the standard procedure
heavy metals [10]. Additionally, the number of pores in clay body
(GB5101-2003). The morphology of samples was analyzed with
dropping greatly means a decrease in surface area of bricks body.
Scanning Electron Microscopy(SEM). The crystalline phase of the
Fig. 1(b) depicted that BET surface area of bricks declined remark-
raw materials was analyzed by the X-ray powder diffraction
ably from 0.84 to 0.05 m2/g with the adding amount of waste glass
(XRD). The surface area of bricks was detected by a N2 absorption
powder up to 30 wt.%. It was means that the contact area between
apparatus, adsorption-desorption isotherms of N2 at 77 K after out-
heavy metals and leaching solution would be cut down with the
gassing for 2 h at 150 °C, the BET surface area was calculated in a
addition of waste glass powder. SEM images in Fig. 2 showed the
Micrometritics equipment, following the BJH method [7]. Toxicity
fractures of bricks with various amount of waste glass powder
addition. It was observed that the quantity of pores reduced signif-
Table 1 icantly and the bricks matrix became more dense and homoge-
XRF analysis results of clay, electroplating sludge and waste glass powder. neous with the increase in waste glass contents, which was
Oxide content (%) Clay Electroplating sludge Waste glass powder agreed with the change in water absorption, open porosity and sur-
face area. These observations confirmed our assumption in which
SiO2 56.19 1.24 70.49
Al2O3 19.93 0.35 0.35 waste glass powder would fill in the pores at high process and den-
Fe2O3 6.02 27.54 2.80 sify bricks matrix. Open porosity, water absorption and surface
K2O 2.69 0.12 0.21 area of bricks are closely depended on the adding amount of waste
CaO 2.29 2.65 4.10 glass [10], and increasing waste glass addition was benefit to the
MgO 1.93 0.24 1.56
reduction in open porosity and surface area of bricks. The addition
TiO2 0.78 0.02 0.15
Na2O 0.52 3.15 20.30 of waste glass would produce liquid phase during firing process,
MnO 0.09 0.13 ndb these liquid phase might close the internal pores and reduce the
P 0.06 1.47 0.03 numbers and size of pores in fired brick body substantially [11,12].
S 0.04 0.29 nd
Fig. 3 presented the compressive strength of fired bricks, the
Cr2O3 0.02 nd nd
ZnO 0.16 14.24 nd
compressive strength increased with the introduction of waste
CuO nd 11.18 nd glass powder. According to the standard test (GB/T 2542, Chinese
Cl 0.01 2.80 nd standard), compressive strength of fired bricks must be higher than
LOIa 9.267 34.54 nd 10 MPa, the compressive strength of all prepared bricks in this
a
: Loss on ignition at 900 °C. study met regulation requirements. It is believed compressive
b
: not detected. strength is closely related with the porosity of bricks body, and
 L. Mao et al. / Construction and Building Materials 163 (2018) 875–879 877

10 15 1.0
(a) 0.9 (b)
Water absorption

Water absorption (%)

8 12 0.8

BET surface area (m2/g)

Open porosity

Open porosity (%)

0.7
6 9 0.6
0.5
4 6 0.4
0.3
2 3 0.2
0.1
0 0 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Waste glass powder content (%) Waste glass powder content (%)

Fig. 1. Effects of waste glass powder addition on (a): water absorption and open porosity, (b): BET surface area of prepared bricks.

Fig. 2. SEM images of bricks with different contents of waste glass. (a) 0, (b) 10%, (c) 20% and (d) 30%.

35 the evolution of compressive strength is consistent with open

porosity. The quantity of pores in clay bricks declined remarkably
30 with the increasing amount of waste glass powder in this study.
Compressive strength (MPa)

Thus, the addition of waste glass considerably contributed to

25 enhancing the strength development by densifying bricks matrix
[10]. Loryuenyong et al. [10] have reported that the compressive
20 strength declined dramatically when the adding amount of waste
glass over 45 wt%. This phenomenon was not observed in this case,
15 it was probably attributed to adding amount of waste glass in our
study below 45 wt%.
10 Fig. 4 depicted leaching behaviors of heavy metals from fired
bricks with different waste glass powder content. The leaching
5 concentration of heavy metals declined substantially with waste
glass addition up to 30 wt%, from 187 to 35 mg/L for Cu and from
0 217 to 31 mg/L for Zn. It is indicated that waste glass addition was
0 5 10 15 20 25 30
Waste glass powder content (%) beneficial to improve the immobilization of heavy metals. The reg-
ulation concentrations in Chinese standard (Identification stan-
Fig. 3. Effects of waste glass powder addition on compressive strength of bricks.
878 L. Mao et al. / Construction and Building Materials 163 (2018) 875–879

addition of waste glass powder. The addition of waste glass powder

200 has not changed the phase composition of clay bricks, while the
Cu
evolution in amount of mineral phase was not same. With the
Cu and Zn concentration (mg/L)

150
100
50
0 result indicated the introduction of waste glass has formed another
0 5 10 15
Waste glass powder content (%)
Fig. 4. Leaching concentration of heavy metals from bricks with various adding
amount of waste glass.
dards for hazardous wastes-Identification for extraction toxicity,
GB 5085.3-2007) for both Zn and Cu are 100 mg/L. When the add-
ing amount of waste glass over 20 wt.%, the leaching concentra-
tions of Zn and Cu from fired bricks are below 100 mg/L, met the
standard regulation requirement. It has been proved that waste
glass addition made bricks body more dense and reduced the
porosity volume and surface area. The reduction in the contact area
between bricks and leaching solution certainly lowered the leach-
ing risks of heavy metals [12]. Additionally, waste glass melted and
formed liquid phase during firing process, and the formed liquid
phase might incorporate heavy metals in glass phase, which pre-
vent heavy metals from releasing effectively [13].
Fig. 5 illuminated phase composition of fired bricks with vari-
ous amount of waste glass powder. Three minerals, quartz, ande-
sine and spinel, were detected in fired bricks without the
Zn
increasing amount of waste glass powder, it was observed the
characteristic peak intensity of quartz declined, however, for ande-
sine and spinel, its characteristic peak intensity increased signifi-
cantly. In this case, the decreasing peak intensity of quartz could
not be regarded the melting of quartz at higher temperature,
because the melting point of quartz was over 1700°C [14]. The liq-
uid glass phase may coat on the surface of quartz and impact the
penetration of X-ray. A broad diffraction peak between 20 and
35° was usually considered as amorphous glass phase [15], but
not detected in all fired bricks with addition of waste glass. This
20 25 30 minerals instead of glass phase, and the possible product might be
andesine. Andesine with relative low melting points (for example,
the melting points of Soda feldspar is around 1100°C), usually be
used to densify the ceramic body or coat on the surface of ceramic
as enamel layer [16]. The formed andesine may might also melt
and fill in the pores, play a important role in blocking pores and
desifying the brick body. Thus, the formation of andesine was
favourable to reducing surface area and porosity, and improving
the compressive strength of fired clay bricks. The formation of spi-
nel indicated heavy metals has been immobilized effectively [17–
19]. The chemical formula of spinel structure is usually AB2O4 (A
is a divalent metal, and B is a trivalent metal). Spinel structure pro-
vides advantages of high chemical resistibility and low thermal
conductibility, are widely employed as refractory materials used
in the glass and steel [20]. Using spinel structure to immobilize
heavy metals due to its excellent resistance against acid solution
have been reported widely [21,22]. It was detected that elevating
addition amount of waste glass was favored to the spinel forma-
tion, which could be attributed to the formation of liquid phase
resulted from fusing of waste glass. The formed liquid phase
reduced contact area and improved mass transfer between heavy
metals with Al2O3 or Fe2O3 at high temperature [23], benefited to
the formation of spinel.

1-Quartz 4. Conclusions
2-Andesine
In this work, waste glass was employed to improve the immo-
1 3 2
3-Spinel(Cu, Zn, Al) bilization of heavy metals during the use of electroplating sludge
12 22 3 3 3 30% in the production of bricks. The bricks with waste glass exhibited
1 3 2 excellent properties which had lower water absorption and higher
12 213 1 3 3 compressive strength. Cu and Zn have been incorporated into
25%
1 2 stable spinels phase and adding waste glass was favored to the for-
23 3
12 21 1 313 1 mation of spinels. Thus the leaching risk of heavy metals was
20% reduced substantially. This method may be a good way to reduce
1
Relative intensity

2 environmental risk during the use of hazardous waste in the pro-

3
12 2 2 1 3 1 3 13 1 15% duction of bricks or ceramics.
1
3 2 Acknowledgements
1
22 2 2 1 31 1
13 1 10%
1 This work was supported by National Natural Science Founda-
tion of China (21707011), Natural Science Fund of Jiangsu Province
1 2
(BK20170289), Natural Science Fund of Higher Colleges in Jiangsu
22 2 1 31 1 1 1 5%
1 Province (17KJB610001), Science-technology Support Plan Projects
of Changzhou city (CE20175009), and Changzhou University Scien-
tific Research Starting Foundation (ZMF17020046).
1 2 Without glass
2 2 1 31 1 1 1
10 20 30 40 50 60 70 80
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