Construction and Building Materials: Ana Mafalda Matos, Joana Sousa-Coutinho
Construction and Building Materials: Ana Mafalda Matos, Joana Sousa-Coutinho
h i g h l i g h t s
" Glass powder is thoroughly analysed as a partial cement replacement material in mortar.
" Testing is carried out far beyond the usual mechanical testing and ASR by most authors.
" Chloride ingress, carbonation, sulphate attack and sorptivity are also considered for durability assessment.
" SEM demonstrated effect of ne glass particles well encapsulated into a dense matrix.
" This holistic study conrms that glass powder contributes to sustainability in construction.
a r t i c l e
i n f o
Article history:
Received 21 August 2011
Received in revised form 28 March 2012
Accepted 25 April 2012
Available online 23 June 2012
Keywords:
Waste
Glass powder
Mortar
Addition
Durability
Pozzolanic activity
a b s t r a c t
It is well known that Portland cement production is an energy-intensive industry, being responsible for
about 5% of the global anthropogenic carbon dioxide emissions worldwide. An important contribution to
sustainability of concrete and cement industries consists of using pozzolanic additions, especially if
obtained from waste such as waste glass.
Crushed waste glass was ground (WGP) and used in mortar as a partial cement replacement (0%, 10%
and 20%) material to ascertain applicability in concrete.
An extensive experimental program was carried out including pozzolanic activity, setting time, soundness, specic gravity, chemical analyses, laser particle size distribution, X-ray diffraction and scanning
electron microscopy (SEM) on WGP and resistance to alkali silica reaction (ASR), chloride ion penetration
resistance, absorption by capillarity, accelerated carbonation and external sulphate resistance on mortar
containing WGP.
Glass particles well encapsulated into dense and mature gel observed by SEM, may help explaining
enhanced durability results and thus conrming that waste glass powder can further contribute to sustainability in construction.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Concrete is the most commonly used construction material in
the world and it is the second most consumed product on the
planet after water [1].
Todays annual global cement production has reached 2.8 billion tons, and is expected to increase to some 4 billion tons per
year. At the same time, the cement industry is facing challenges
such as cost increases in energy supply, requirements to reduce
CO2 emissions and the supply of raw materials in sufcient qualities and amounts [2]. It is estimated that about 0.91.0 tons of CO2
are produced for a ton of clinker depending on the type of fuels
used [3].
Corresponding author. Address: Rua do Dr. Roberto Frias, 4200-465 Porto,
Portugal. Tel.: +351 225081936; fax: +351 225081441.
E-mail address: [email protected] (A.M. Matos).
0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.04.027
While cement production in its beginnings only focused on ordinary Portland cement, later cements with several main constituents were produced by replacing parts of the clinker content by
supplementary cementitious materials [3].
Ecological or environmental benets of alternative supplementary materials include (1) the diversion of non-recycled waste from
landlls for useful applications, (2) the reduction in the negative
effects of producing cement powder, namely the consumption of
non-renewable natural resources, (3) the reduction in the use of
energy for cement production and (4) the corresponding emission
of greenhouse gasses [4].
Solid industrial by-products, such as siliceous and aluminous
materials, as well as some natural pozzolanic materials are increasingly being used in the cement and concrete industry. The incorporation of these materials in concrete has been giving encouraging
results regarding the mechanical and durability properties of concrete [5].
206
2. Experimental program
2.1. Materials
Typical commercial Type I 42.5R Portland cement was used and commercial silica fume (SF) was employed as a reference pozzolanic material. Waste glass was obtained from a recycling glass industry in Portugal where waste glass such as car
windscreens is crushed and sold to the bottle industry. Fine waste glass from this
industry was ground during 48 h in a ball mill in the laboratory (WGP). Fig. 1 shows
particle size distribution of cement and WGP. X-ray diffraction on WGP showed that
no substantial crystalline phases were detected. Soundness and setting time tests
(NP EN 196-3 [36]) were carried out on pastes with 100% CEM I 42.5R (CTL) and
on paste with 10% (WGP10) and with 20% (WGP20) cement replacement with
WGP. Pozzolanicity test was carried out following NP EN 196-5 [37] on a sample
with 90% of cement and 10% of WGP. Chemical composition and physical characteristics of WGP and cement are given in Table 1. Scanning Electron Microscopy (SEM)
was carried out on CEM I 42.5R, silica fume and WGP samples shown in Fig 2.
3.16
0
WGP
Silica fume
0.92
70
1.2
0.65
8.7
3.7
16
0.35
17
<0.05
<0005
>99
Positive
Positive
2.68
0
2.20
0
207
p
RTL xd a xd
:
ZFU
t
r
RTL
e
ZFU
Dns
a2
e erf 1 1
2C d
C0
5
where Dns is the apparent diffusion coefcient obtained in a non-steady state migration test (cm2/s), R the gas constant R = 8.314 J/(mol K), T the absolute temperature
(K), L the thickness of specimen (cm), Z the ion valence, F the Faraday constant,
F = 9.648 104 J (V mol.), U the effective voltage applied (V), xd the depth of chloride
penetration measured by using a colorimetric method (cm), t the time of test duration (s), a the laboratory constant, e = 0.764 if external chloride concentration of
0.5 M. Cd the concentration of free chloride at which the colour changes when using
the colorimetric method to measure the chloride penetration depth (kg Cl/m3 solution) and C0 is the concentration of free chloride in the external solution.
Results can be seen in Fig. 7.
2 h, 20 m/2 h, 15 m
2 h, 30 m
3 h, 25 m/3 h, 25 m
3 h, 25 m
Several test specimens were produced. After demoulding the following day, test
specimens were cured in water at 20 C in a fog room until testing.
2.3. Strength
Flexural and compressive strength testing was undertaken at 7, 28, 90 and
180 days (and 562 days for CTL and WGP10) following the standard procedure in
NP EN 196-1 [35]. Results are presented in Fig. 3. The pozzolanic effect of glass powder may be assessed with the Activity Index (AI) (Fig. 4) which is the ratio between
strength of WGP containing mortar and strength of equivalent control mortar at the
same age.
Absorption by capillarity testing was undertaken on two months old cast test
specimens, approximately 50 mm diameter by 100 mm length generally following
standard procedure RILEM TC 116-PCD [45]. The samples were put to dry in a ventilated heater at 40 C until constant mass. For the test itself, test specimens were
placed moulded face downwards, in a shallow water bath. Water level was adjusted
automatically so that the formwork face was dipped to a depth of approximately
3 mm. During the test, water was drawn into the core by capillary forces and
weighed at time intervals up to 4.5 h from the start of the test [45].
The absorption of water into concrete under capillary action is dependent on
the square-root of time and may be modelled [24] by the following equation:
A A0 St 0;5
6
2
P4
Lx
i1 Li
Lx L0
100%
250
where A (mg/mm ) is the water absorption by unit area of concrete surface since the
moment the core was dipped in water, S is the sorptivity of the material, t is the
elapsed time and A0 (mg/mm2) is the water absorbed initially by pores in contact
with water. The above equation was found to provide a very good t to the data with
correlation coefcients of over 0.96 (Fig. 8). The average sorptivity value of each
mortar type is shown in Fig. 9.
2.7. Carbonation
Resistance to carbonation was assessed in accordance with the procedure described RILEM CPC-18 [44] where test specimens were exposed to 5 0.1% carbon
dioxide, relative humidity (RH) of 60 5% and temperature of 23 3 C, in an accelerated carbonation chamber.
Carbonation depth was evaluated on three test specimens for each mortar type,
water cured at 20 C followed by 2 and 4 months in the chamber. After splitting the
specimens, the surface was cleaned and sprayed with a phenolphthalein pH indicator. In the noncarbonated part of the specimen, where the mortar was still highly
alkaline, a purple-red colour was obtained. In the carbonated part of the specimen
where the alkalinity of mortar is reduced, no coloration occurred. Each value corresponds to the mean of twelve measurements taken around the four sides of the
freshly split and sprayed surface of each test specimen. Results can be seen in Fig. 10.
2.8. External sulphate attack
Resistance to external sulphate attack was evaluated according to the Portuguese standard E-462 [42], on six (1, 2, 3, 4, 5 and 6) mortar prisms of
16 16 160 mm. Test specimens were immersed in calcium hydroxide solution
during 28 days, measured along the 4 side faces of each specimen and taken as initial readings (L0). Test specimens 2, 4 and 6 were transferred to a sodium sulphate
solution and the others were maintained in calcium hydroxide saturated solution.
Readings were taken throughout 26 weeks and sulphate solution was renewed
every 2 weeks. The actual length increase of each specimen on day x is taken as:
ExpCaOH2 x
Lx L0
1600
The resistance to chloride permeability was evaluated by the CTH Rapid Method
according NT Build 492 [44] which is a non-steady state migration method based on
a theoretical relationship between diffusion and migration which enables the
ExpSO4 Na2 x
Lx L0
1600
208
Table 2
Mixture proportions and workability of mortar.
Materials/mortar
CTL
SF
WGP10
WGP20
450
0
0
1350
225
0
0.5
200
405
45
0
1350
225
0.34
0.5
198
405
0
45
1350
225
0
0.5
204
360
0
90
1350
225
0
0.5
206
3. Discussion
3.1. Chemical and physical properties of WGP
ExpCaOH2
ExpSO4 Na2
10
SEM was also carried out on samples CTL and WGP10 mortar samples cured in
water at 20 C for 562 days, as shown in Fig. 12, for 2500, 5000, 10,000 and 20,000
magnication in order to investigate changes in the cement hydrated micro
structure.
11
209
Table 3
Required grading requirements in ASTM C 1567 and grading for CEN sand used.
Grading requirements ASTM C 1567
CEN sand
Mass (%)
Mass (%)
2.36 mm
1.18 mm
0.60 mm
0.30 mm
0.15 mm
10
25
25
25
15
2,00 mm
1.60 mm
1.00 mm
0.50 mm
0.16 mm
0
7
26
34
20
(No.
(No.
(No.
(No.
(No.
8)
16)
30)
50)
100)
(17%), far above the limit (5%) imposed in the standard for y ash.
This corroborates Shao et al [12] who observed general accordance
with ASTM C 618 [33] but not meeting the optional requirement
for the alkali content, causing concern due to potential ASR.
Initial setting time (Table 1) was marginally shorter for WGP10
(10 and 20 min) for paste with 10% and 20% cement replacement
210
211
Fig. 8. Linear regression for absorption by capillarity during 4 h 30 min on test cores.
minerals and not available for the ASR which occurs in later stages.
With the presence of other chemicals the dissolved reactive silica
of glass powder will not be able to form ASR gel during the pozzolanic reaction, or even a gel having a swelling property likewise the
ASR gel. Otherwise, if there was any chance to form ASR gel during
the pozzolanic reaction from the reactive silica of glass powder one
can envisage that any existing ASR expansion would be noticeable.
If any ASR could occur during the pozzolanic reaction stage, the
produced expansion would vanish and accommodate within the
plasticity of fresh concrete. On the other hand, in the rst 4 weeks
of the pozzolanic reaction and hydration process, most of the alkalis would have been consumed in order to catalyse the pozzolanic
reaction and act as chemical activators to compensate for the lower
calcium content in the glass powder. Therefore, in later age, there
would not be enough free alkali to interact with the reactive silica
in the pore solution of the concrete to induce ASR, as illustrated in
Fig. 13.
212
Fig. 10. Carbonation depth results after 2 months curing followed by 4 months in the chamber.
[13] carried out the NT Build 492 [43] test as in the present study
and obtained similar improvement to WGP 20 at 56 days.
Absorption by capillarity and sorptivity proved to be similar for
WGP and CTL mortar and a little lower for SF mortar. This situation
may be explained by similar neness of both WGP and cement (see
Fig. 9). Much ner SF particles physically ll capillary pores reducing capillary absorption. Other authors, such as Taha and Nounu
[23] also showed similar results for concrete with cement replacement materials, but following BS 1881.
Carbonation depth for all blended cement mixtures was greater
than for the Portland cement mixture. It was found that carbonation increased along with the increase in WGP content, which is
consistent with the trend observed in concrete for various pozzolanic materials and probably due to CH reduction. WGP10 carbonated almost half of SF10 mortar, albeit pore renement due to
213
Pozzolanic reaction produces a secondary CSH that also decreases the capillary porosity of mortar and enhances signicantly
the pasteaggregate interface [28].
3.5. Scanning electron microscopy
Regarding SEM observations, glass particles seem to be thoroughly encapsulated and dispersed into to the hydrated products
of a dense and mature gel with needle shaped ettringite crystals
(see WGP10 10,000 and 20,000 times enlarged, Fig. 12). CH layered
crystals were observed in the CTL mortar (see CTL 5000 times enlarged, Fig. 12) and CSH gel lling the hydrated structure. CSH gel
in WGP10 was found to contain more calcium as well as more alkalis compared to CTL mortar. These ndings are in accordance with
Sobolev et al [30] who suggested that the main difference between
glass containing mortar and reference Portland cement is related to
the decrease in size and the amount of CH, caused by consumption
of CH as a result of the pozzolanic reaction involving glass grains.
More alkalis found in the gel of WGP10 compared to CTL also conrm ndings by Shayan and Xu [17] who proposed that the pozzolanic reaction of glass powder with cement causes the binding of
alkalis in the paste, making it unavailable for ASR [17] and therefore
in accordance with the mechanism proposed by Taha and Nounu
[22] explaining lower expansion due ASR when glass is used.
214
Table 4
Requirements in standards.
European Standards
Chemical requirements
Physical requirements
Silica fume
(NP EN
13263-1)
GP
Remarks
Cl
SO4
SO3
Free CaO
60.10%
63.0%
62.5%
60.3%
62.0%
61.0%
60.10%
62.5%
62.0%
<0005
<0.05
8.70%
OK
OK
Reactive CaO
SiO2
SiO2 + Al2O3 + Fe2O3
CaO + MgO + SiO2
NaO2eq
LOI
610%
P25%
P70%
P85%
P67.0%
Pozzolanicity
65.0%
Class A 6 5%
Class B 27%
Class C 49%
Activity index
P75% at 28 days
70%
71.82%
P85% at 90 days
6120 min plus start time of
the paste-setting reference
610 mm
64.0%
63.0%
17%
0.92%
P100% at
28 days old
Positive
OK
KO
OK
610 mm
Fig. 13. Model illustrates the consumption of alkali in the pozzolanic reaction in the
rst 4 weeks [22].
OK
4. Conclusions
5. Future developments
Acknowledgement
The authors would like to thank Mr. Oliveira from the glass
industry, LEMC, LABEST and to FCT under Project PTDC/ECM/
098117/2008.
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