Nuclear Instruments and Methods in Physics Research B 381 (2016) 11–15

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Nuclear Instruments and Methods in Physics Research B

journal homepage: www.elsevier.com/locate/nimb

Using of borosilicate glass waste as a cement additive

Weiwei Han a,b, Tao Sun a,c,⇑, Xinping Li c, Mian Sun d, Yani Lu e
a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, Hubei 430070, PR China
b
School of Civil Engineering and Architecture, Wuhan University of Technology, Wuhan, Hubei 430070, PR China
c
Key Laboratory of Roadway Bridge & Structure Engineering, Wuhan University of Technology, Wuhan, Hubei 430070, PR China
d
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, Hubei 430070, PR China
e
Urban Construction Institute, Hubei Engineering University, Xiaogan, Hubei 432000, PR China

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

Article history: Borosilicate glass waste is investigated as a cement additive in this paper to improve the properties of
Received 29 March 2016 cement and concrete, such as setting time, compressive strength and radiation shielding. The results
Received in revised form 15 May 2016 demonstrate that borosilicate glass is an effective additive, which not only improves the radiation
Accepted 17 May 2016
shielding properties of cement paste, but also shows the irradiation effect on the mechanical and optical
Available online 25 May 2016
properties: borosilicate glass can increase the compressive strength and at the same time it makes a
minor impact on the setting time and main mineralogical compositions of hydrated cement mixtures;
Keywords:
and when the natural river sand in the mortar is replaced by borosilicate glass sand (in amounts from
Borosilicate glass powder/sand
Cement paste
0% to 22.2%), the compressive strength and the linear attenuation coefficient firstly increase and then
Linear attenuation coefficient decrease. When the glass waste content is 14.8%, the compressive strength is 43.2 MPa after 28 d and
the linear attenuation coefficient is 0.2457 cm 1 after 28 d, which is beneficial for the preparation of
radiation shielding concrete with high performances.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction
With the increase of raw material demands and environmental
challenges, the nuclear power generation because of its cleanabil-
ity compared to other systems based on fossil fuels becomes more
and more popular. According to the International Energy Outlook-
2005 (Department of Energy, USA) report, about 15% of the world-
wide electrical power is generated by nuclear power. However, in
China, the percentage of nuclear power in electrical power is 1.19%
(2013), 2.29% (2014) and 3.01% (2015), respectively, which is far
less than the average of worldwide value at the same year. To
increase this percentage, a great amount of efforts have already
made in China. Based on the plan of China about the nuclear power
from 2016 to 2020, this fraction will increase to meet the growing
demands for power without releasing significant quantities of CO2
associated with fossil-fuel-fired power plants. However, there are a
few hazardous wastes and radiation leakage from unclear power
station, which make a huge casualties, financial and environmental
damages [1,2].
Vitrification is widely accepted as a safe process for treating
hazardous wastes and converting them into passively-safe
⇑ Corresponding author at: State Key Laboratory of Silicate Materials for
Architectures, Wuhan University of Technology, Wuhan, Hubei 430070, PR China.
E-mail address: sunt@whut.edu.cn (T. Sun).
leach-resistant materials. The glass can be designed for its good
chemical durability, sufficient mechanical properties, and superior
radiation than other waste forms [3], various special glasses have
been also claimed for different nuclear engineering applications
[4], and radiation shielding properties of various glasses are avail-
able in the literature [5–11]. Borosilicate glass, a one type of impor-
tant glass with the main glass-forming constituents’ silica and
boron oxide, is widely used in nuclear industry for its high absorp-
tion of neutrons. And, it is usually used as matrix for immobilizing
the radioactive ions present in the waste generated from the
nuclear [12–15].
However, glass is less suitable for low-level waste-forms but for
high-level waste-forms. Solidification is one of the most important
methods for the treatment and disposal of radioactive wastes. As
one kind of solidification, cementation has a high stability and
low cost, so that it is one of the most acceptable methods for
low- and intermediate-level wastes treatment. And radiation
shielding mortar or concrete is a kind of typical application exam-
ples of cementation. In order to obtain the mortar and concrete
with better shielding properties and make full use of wastes,
boron-containing wastes are used for the preparation of shielding
material [16,17]. Shiao and Tsai [18] point out that boron com-
pounds could decrease the radioactive permeability of concrete,
which is similar to the results obtained by other authors [19–21].
Özdemir et al. [22] show that boron-containing clay wastes could

http://dx.doi.org/10.1016/j.nimb.2016.05.016
0168-583X/Ó 2016 Elsevier B.V. All rights reserved.
12 W. Han et al. / Nuclear Instruments and Methods in Physics Research B 381 (2016) 11–15

be used as cement additives, and that mortar containing 1% of clay Table 2

wastes has higher compressive strength than Portland cement. Mix component of cement paste.

Although boron compounds modify and improve the shielding Component Unit Quantity
properties of cement and concrete, a few boron compounds bring A1 A2
some serious disadvantages such as retarding of cement hydration
Cement wt, % 71.4 64.3
[23], low mechanical strength [24,25], which cause a great nega- Borosilicate glass powder wt, % – 7.1
tive effects for the recycling of boron-containing wastes. Water wt, % 28.6 28.6
In order to expand the application of borosilicate glass, to effec-
tively solve the low- and intermediate-level unclear wastes, and
obtain a kind of cement-based material with good shielding radia-
tion, mechanics and set performances, the using of borosilicate Table 3
Mix component of cement mortar.
glass as a cement additive is investigated in this paper.
Component Unit Quantity

2. Experimental B1 B2 B3 B4
Cement wt, % 22.2 22.2 22.2 22.2
2.1. Materials Natural river sand wt, % 66.7 61.7 59.8 51.9
Borosilicate glass sand wt, % – 4.9 9.9 14.8
Water wt, % 11.1 11.1 11.1 11.1
Ordinary Portland cement (OPC) 42.5 used in this study is pro-
duced by Huaxin Cement Co. Ltd, Ezhou, Hubei, China. Borosilicate
glass waste is provided by I-boron Photoelectric Technology Co.
Ltd, Wuhan, China. The natural river sand in the experiments has
a fineness modulus [26] of 2.5. Ordinary drinking water is used water, after 2 h, testing the pH value of the supernatant slurry by
for the production of cement mixtures (see Table 1). the pH meter) and vice the loss on ignition. The radioactive perme-
ability of cement mortar is measured with the help of a FJ-47A X-c
2.2. Cement mixtures and methods detector (Shanghai Renri Radiation Protective Equipment Co. Ltd,
China) and 60Co (Wuxi Haizhou Protective Equipment Co. Ltd,
Borosilicate glass powder and borosilicate glass sand, China) as a radioactive source with activity of 1.41  1014 Bq.
respectively are obtained from borosilicate glass waste by sieving.
The size of the borosilicate glass ‘‘powder” (fine sand) is smaller
3. Results and discussions
than 1.18 mm, while the size of borosilicate glass ‘‘sand” (coarse
sand) is in the range of 1.18–4.75 mm. One type of cement mixture
3.1. Cement paste with borosilicate glass powder
is obtained by adding borosilicate glass powder to pure cement
paste (Table 2), and another type of cement mixture (mortar) is
From Tables 4 and 5, it is evident that the cement pastes with
obtained by adding borosilicate glass sand to cement mortar with
and without borosilicate glass powder do not exhibit significant
natural river sand in ratios of 0%, 7.4%, 14.8%, 22.2% (Table 3).
differences while the setting time or pH value are concerned. How-
Eighteen cube shaped samples (40 mm  40 mm  40 mm) are
ever, their chemically bound water content and compressive
cast in steel molds, and cured in standard conservation state (tem-
strength are slightly different.
perature 20 ± 1 °C, humidity P 95%). The samples are removed
Borosilicate glass is a one type of glass with the main glass-
from the molds after 1 d, and still cured in standard conservation
forming constituents’ silica and boron oxide. It is produced at a rel-
state for the tests: compressive strength is obtained by an auto-
atively high temperature (about 1300 °C) and it is a kind of frit.
mated breaking and compression resistance tester (WYA-300,
When the borosilicate glass powder is added to pure cement paste,
Wuxi Xiyi Building Materials Instrument Factory, China) with three
the chemical activity of its network former, B2O3, is greatly limited,
samples (40 mm  40 mm  40 mm) for each age and their mean
which is different from single boron oxide (B2O3), boric acid
value is treated as the compressive strength of this age. The miner-
(H3BO3) or borax (Na2B4O7). Accordingly, the hydration of the
alogical composition of the hydrated cement paste is investigated
cement paste with borosilicate glass powder is primarily con-
by X-ray diffraction (XRD) (D8 Advance, Bruker AXS Corporation,
trolled by the hydration process of cement phases. Based on the
Germany) with a scan rate of 1° per min and Fourier transforma-
crystallography theory of cement hydration, the setting and hard-
tion infrared spectrometer (FTIR) (Nicolet 6700, Thermo Electron
ening of cement are the processes of crystal formation and grow-
Scientific Instruments, USA) with a frequency range of 4000–
ing, the cement hydration will be improved for crystal nucleus
399 cm 1 is used. Its pH value and chemically bound water are
formation. Compared to the hydration of cement paste without
determined separately by a digital pH meter (putting 5 g hydrated
borosilicate glass, borosilicate glass may help to increase the crys-
cement paste powder (size 675 lm) into a cup with 50 ml distilled
tal nucleus formation with ‘‘micro-nucleation effect”, then the
hydration of cement paste with borosilicate glass can be improved.
Table 1 Finally, the compressive strength and amount of chemically bound
Chemical composition of OPC 42.5 and borosilicate glass waste in % by mass. water of the cement paste with borosilicate glass powder are
Composition OPC 42.5 Borosilicate glass waste
slightly higher than that of the cement paste without borosilicate
glass powder.
SiO2 21.04 77.0
Al2O3 6.94 2.0
Fe2O3 2.36 –
CaO 61.27 –
MgO 1.32 – Table 4
SO3 1.94 – Setting time.
B2O3 – 15.0
Properties A1 A2
Na2O – 4.5
PbO – 1.5 Initial setting time/min 220 215
Loss 3.76 – Final setting time/min 310 296
 W. Han et al. / Nuclear Instruments and Methods in Physics Research B 381 (2016) 11–15 13

Table 5 addition to hydration phases, diffraction peaks corresponding to

pH value, chemically bound water and compressive strength. phase of anhydrous cement, like C3S, b-C2S could also be observed.
Properties A1 A2 However, it can be seen that the intensity of most hydration phases
3d 7d 28 d 3d 7d 28 d of A1, especially Ca(OH)2 (2h, 18.04°, d = 4.91), are higher than that
of cement paste with borosilicate glass powder. This can be
pH value 12.46 12.61 12.85 12.43 12.57 12.81
Chemically bound water/% 9.84 12.59 15.15 10.12 12.63 15.28
explained by the fact that the pH value of the cement paste without
Compressive strength/MPa 31.4 40.2 46.4 34.7 42.8 53.7 borosilicate glass powder is higher than that of cement paste with
borosilicate glass powder (Table 5). Compared with the XRD pat-
terns of hydrated cement paste without borosilicate glass powder,
3.2. XRD and FTIR the intensity of CaSO4
2H2O and C2S of the hydrated cement paste
with borosilicate glass powder is lower, which means that the
In Fig. 1, the graph of cement paste with borosilicate glass hydration of cement with borosilicate glass powder is improved.
powder shows the presence of crystalline phases, which are the Based on the FTIR spectra (Fig. 2) of cement paste without
usual OPC hydration products (A1), such as ettringite, Ca(OH)2. In borosilicate glass powder and combined with the results of Feng

Fig. 1. XRD patterns of hydrated cement paste after 28 d.

Fig. 2. FTIR spectra of hydrated cement paste after 28 d.

14 W. Han et al. / Nuclear Instruments and Methods in Physics Research B 381 (2016) 11–15
Fig. 3. Compressive strength of cement paste with borosilicate glass sand.
and Wang [27], it is deduced that the Ca(OH)2 content of cement
paste with borosilicate glass powder is lower than that of the ref-
erence after 28 d, which confirms the result of pH value in Table 5
(the pH value of system is mainly provided by Ca(OH)2 in the solu-
tion). In addition, the bands of cement paste with borosilicate glass
powder both at 3430 cm 1 (OHfree from ettringite and C–S–H gel)
and at 1641 cm 1 (OH vibration of liquid water) moves to the left
compared with that of cement paste without borosilicate glass
powder, which means the ettringite structure of cement paste with
borosilicate glass powder is stronger than that of cement paste
without borosilicate glass powder. This also demonstrates that
cement paste with borosilicate glass powder has higher compres-
sive strength and chemical bound water.
3.3. Cement paste with borosilicate glass sand
A good additive should have high absorption cross-section for
radiation and at the same time irradiation effects on its mechanical
and optical properties should be small. In order to obtain a kind of
cement-based material with higher radiation shielding efficiency
and compressive strength, according to the literature [28] and
the Lambert Beer law, the compressive strength and linear attenu-
ation coefficient of cement paste with borosilicate glass sand are
investigated.
Fig. 4. Linear attenuation coefficient (l) of cement paste with borosilicate glass
sand after 28 d.
Fig. 3 shows that the compressive strength of cement paste with
borosilicate glass sand firstly increases and then decreases with the
content of boron-containing glass waste content in the cement
mixtures. When the borosilicate glass sand content is 14.8% of nat-
ural sand, the compressive strength of cement paste with borosil-
icate glass sand is the highest. As shown in Fig. 4, the linear
attenuation coefficient, l, increases firstly before this content
and then decreases at higher content. It is difficult to find a linear
relationship between the linear attenuation coefficient and borosil-
icate glass powder content, which agrees with the outcomes of
Demir and Keles [29]. Obviously, when the borosilicate glass sand
is 14.8%, l is 0.2457 cm 1, which is the best value. This can be
attributed to the total content of boron and other factors, like
structural characteristics of cement paste with borosilicate glass
sand.
4. Conclusions
Borosilicate glass waste is an effective additive for improving
the properties of cement-based cementitious materials, especially
setting time, compressive strength and radiation shielding effi-
ciency. Borosilicate glass can increase the compressive strength
and has a minor effect on the setting time, which causes that radi-
ation shielding concrete blended with boron compounds has
appropriate setting performance and good mechanical strength.
Further, when the natural river sand in cement mixtures is
replaced by boron-containing glass waste, the compressive
strength and linear attenuation coefficient firstly increase and then
decrease. When the glass waste content is 14.8% among natural
river sand, the compressive strength is 43.2 MPa after 28 d and
the linear attenuation coefficient is 0.2457 cm 1 after 28 d, which
are the best values in the cement mixtures proposed in this paper.
Acknowledgments
This work are financially supported by the National Natural
Science Foundation of China (Project 51204128), the National
‘‘Twelfth Five-Year” Plan for Science & Technology Support Devel-
opment Program of China (Project 2014BAB15B01), the YangFan
Innovative & Entrepreneurial Research Team Project (No.
201312C12), the State Key Laboratory of Silicate Materials for
Architectures (Wuhan University of Technology), the Hubei Key
Laboratory of Roadway Bridge and Structure Engineering (Wuhan
University of Technology) (No. DQJJ201510) and Nature Science
Foundation of Hubei Province (2014CFB575).
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