Construction and Building Materials 127 (2016) 950–958

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Construction and Building Materials

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

Clay-based construction and demolition waste as a pozzolanic addition

in blended cements. Effect on sulfate resistance
Eloy Asensio de Lucas a,⇑, César Medina b, Moisés Frías a, María Isabel Sánchez de Rojas a
a
Eduardo Torroja Institute for Construction Science (CSIC), 28033 Madrid, Spain
b
School of Civil Engineering, UEX-CSIC Partnering Unit, University of Extremadura, 10071 Cáceres, Spain

h i g h l i g h t s

The influence of sulfates in blended cements based on construction and demolition waste as pozzolanic addition.

The influence of sulfate concentration in durability of cementitious matrices.

Changes in microstructure and morphology of cementitious matrices due to the incorporation of C&DW as pozzolanic material.

The influence that C&DW as pozzolanic addition has in corrosion indices.

Changes in porous network and its influence on behavior in the face of sulfate solution.

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

Article history: The significant structural implications of cement durability have given rise to substantial research on the
Received 29 January 2016 subject. This study explores the performance of new blended cements bearing pozzolanic construction
Received in revised form 21 September and demolition waste (C&DW) as an addition when exposed to sulfate attack. Durability is studied in
2016
cement pastes with and without C&DW, addressing the formation of new compounds, mechanical
Accepted 6 October 2016
Available online 17 October 2016
strength, outward appearance and porosity after soaking in two concentrations of sodium sulfate solution
for exposure times ranging from 14 to 56 days. The findings confirm that the inclusion of clay-based
C&DW improves blended cement durability.
Keywords:
Construction
Ó 2016 Elsevier Ltd. All rights reserved.
Demolition
Waste
Clay-based material
Pozzolanic additions
Cement
Sulfate attack

1. Introduction energies [1,2,5,6]. Another approach consists in reintroducing

materials that have reached the end of their service life in other
Governments worldwide are becoming increasingly sensitised realms into the production cycle for future constructions. Similarly,
to environmental issues and drafting policies accordingly. industrial waste and by-products such as kaolin, metakaolin, blast
One of the measures adopted is to encourage the recycling, furnace slag and fly ash can also be used as raw materials for
reuse and valorisation of materials with a heavy environmental cement manufacture [7–12].
impact. Such measures also help reduce the amounts of raw mate- In this vein, construction and demolition waste (C&DW) is also
rials extracted to generate new products and drive the replacement liable to reintroduction into the industry’s production cycle.
of fossil fuels with alternative sources of energy [1–4]. Earlier studies describing the successful use of clay-based
Recycling, reuse and valorisation are also avenues for reducing materials (tile, brick, sanitary ware) as pozzolanic additions in
the environmental footprint of an industry such as construction, cement have inspired further research on the introduction of
normally regarded as scantly sensitised to such concerns. Much C&DW in cement manufacture [13–19]. At present, such waste is
research has been conducted to improve industry sustainability, normally reused as an aggregate in recycled concrete, drainage
including the use of alternative raw materials and renewable material in roads or for aesthetic applications [20–30]. The suc-
cessful partial replacement of cement clinker (at different ratios)
⇑ Corresponding author. with pozzolanic clay-based C&DW from Spanish recycle plants
E-mail address: [email protected] (E. Asensio de Lucas). has given rise to two international patents [31,32].

http://dx.doi.org/10.1016/j.conbuildmat.2016.10.047
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958 951

This durability study explores the performance of conventional Table 2

and blended cement when exposed to 0.0, 0.5 or 1.0 M sodium Information about mineralogical compounds of the C&DW and cement pastes.

sulfate for different periods of time, comparing the post-attack Compound Chemical formula ICSD code
formation of compounds such as gypsum (Ca2SO42H2O), ettringite Illite K(Al4 Si2O9(OH)3) 090144
(3CaOAl 2 O 3 3CaSO 4 32H 2 O), thaumasite (Ca 3 Si(SO 4 )(CO 3 ) Quartz SiO2 067121
(OH)612H2O) and combinations of the three [33–41]. The expan- Orthoclase KSi3AlO8 010270
sive nature of such compounds renders their study particularly Anorthite CaAl2Si2O8 202710
Calcite CaCO3 040112
pertinent, given the cracking damage they may induce in cement Dolomite CaMg(CO3)2 202162
paste [33,35,42]. After exposure over lengthy periods, such crack- Hematite Fe2O3 082904
ing may lead to severe deterioration of the structures built with Ettringite Ca6(Al(OH)6)2(SO4)3(H2O)26 016045
such cements. Deterioration in specimens soaked in sodium sulfate Monocarboaluminate Ca4Al2(OH)2(CO3)(H2O)5 059327
Portlandite Ca(OH)2 064951
solutions at different concentrations worsens with time. This study
Belite Ca2SiO4 079551
quantifies the fluctuations in specimen weight, which are then Ferrite phase Ca2FeAlO5 009197
related to the formation of new products and changes in outward
appearance.
Prior studies have shown that three factors affect the durability
content of no >5%, as per European standard EN 197-1 [46]. Its
of blended cements containing pozzolanic additions: pore struc-
chemical composition, determined by X-ray fluorescence (XRF), is
ture refinement, low alkalinity and the low portlandite content in
given in Table 1.
the respective cement pastes [37,38,41,43,44]. This study focuses
Clay-based (tile and brick) construction and demolition waste
on the third factor. A number of instrumental techniques are used
(C&DW) was sourced from a Spanish recycle plant, where it was
to compare the pastes in terms of their portlandite content and the
ground to a particle size of under 63 lm. In addition to the
compounds formed.
majority component, SiO2, it contained other acidic oxides such
These new cements must be studied to determine the feasibility
as Al2O3 and Fe2O3 (Table 1) characteristic of pozzolanic materials
of their use and whether the replacement of clinker with C&DW
[8,11,13–17,46–54]. The XRD pattern for the C&DW reproduced in
materials enhances the properties of conventional cement.
Fig. 1 shows the mineralogical phases detected, where the majority
Of particular importance in this regard are durability-related
compound is quartz [19]. Table 2 includes the chemical formula
properties. This study compares durability between reference
and the ICSD (Inorganic Crystal Structure Database) code of all
cement and cement in which 30% of the clinker is replaced by
the compounds.
100% clay-based C&DW.
The blended cement (C&DWC) used in this study was prepared
A number of analytical techniques are deployed to establish
with 30 wt.% C&DW and 70 wt.% OPC.
cement composition and morphology and compare the differences
between the pastes with and without C&DW. Paste flexural
strength is also studied to determine sulfate-induced deterioration 2.2. Instrumental techniques
as per the Köch-Steinegger procedure [45].
The samples were chemically characterised via X-ray fluores-
cence (XRF) on a Philips PW1404 spectrometer fitted with a dual
2. Experimental anode Sc/Mo X-ray tube.
Sample mineralogy was determined on a Bruker AXS D8 X-ray
2.1. Materials powder diffractometer fitted with a 3-kW (Cu Ka1.2) copper anode
and a wolfram cathode X-ray generator. Scans were recorded
The CEM I 42.5 R ordinary Portland cement (OPC) used through- between 2h angles of 5–60° at a rate of 2°/min. The voltage gener-
out had a clinker content of at least 95% and a minority component ator tube operated at a standard 40 kV and 30 mA.

Table 1
Chemical composition of the starting materials (%) determined by XRF.

Oxides SiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O SO3 K2O TiO2 P2O5 LOIa
OPC 20.00 6.03 2.57 0.03 1.75 59.63 0.56 3.90 1.49 0.15 0.15 3.26
C&DW 59.63 18.51 5.92 0.09 3.12 4.78 0.73 0.42 3.59 0.84 0.15 2.15
a
LOI: Loss On Ignition.

Fig. 1. XRD patterns for recycled C&DW (I: illite, Q: quartz, O: orthoclase, A: anorthite, C: calcite, D: dolomite, H: hematite).
952 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958

The materials were characterised on a Thermo Scientific Nicolet to eliminate any excess salts and dried in a laboratory kiln at 40 °C
600 Fourier transform infrared spectrometer featuring a spectral to a constant weight.
resolution of 4 cm1 across a range of 4000–500 cm1.
Thermogravimetric (TG) and differential thermal analyses
3. Results and discussion
(DTA) were performed in an N2 atmosphere on a TA Instruments
SATQ600 analyser at temperatures of 25–1000 °C, heating at a rate
3.1. XRD analysis
of 10 °C min1.
The Hitachi S4800 electron microscope used to study the
The diffractograms for OPC and C&DWC in Fig. 2(a) and (b),
morphology of the C&DWC and OPC was coupled to a Bruker Nano
respectively, show the fluctuations in the hydrated phases with
XFlash 5030 silicon drift detector for EDX determination of the
rising sulfate concentration.
chemical composition of the samples.
XRD identified ettringite, monocarboaluminate, portlandite and
Porosity was quantified on a Micromeritics Autopore IV 9500
calcite as the main crystalline phases in the pastes, along with
mercury porosimeter designed to measure pore diameters
ferrite phase and belite from the anhydrous cement due to the
of 0.006–175 lm and operate at pressures of up to 33 000 psi
slow reaction kinetic of this calcium silicate [55]. Quartz, which
(227.5 MPa).
was identified in C&DWC only, was sourced from its 30% C&DW
Mechanical strength was found on an IBERTEST AUTOTEST
content [19,41] (see Table 1 and Fig. 1).
200/10-SW test frame fitted with an adapter for 1  1  6 cm
In OPC (Fig. 2(a)), the intensity of the reflection for ettringite
specimens.
rose while portlandite and monocarboaluminate line intensity
declined at higher sulfate concentrations. These findings were con-
2.3. Test methods sistent with research conducted by Goñi et al. [40] on ternary
cements, in which sulfate attack-induced ettringite was observed
Cement paste specimens measuring 1  1  6 cm were pre- to form from dissolved monocarboaluminate and portlandite.
pared with OPC and C&DWC at w/c ratios of 1:2. The absence of any diffraction line for gypsum suggested that
After room temperature-curing for 28 days, the specimens were due to the high sulfate content in the solution (0.5 and 1 M), port-
soaked in deionised water or 0.5 or 1.0 M sodium sulfate solutions landite reacted with these ions to form ettringite, the end product,
for 14, 21, 42 or 56 days. They were subsequently tested for rather than gypsum, the intermediate product observed by Hekal
mechanical strength to apply the Köch-Steinegger procedure. The et al. [56]. According to those authors’ findings, ettringite was gen-
solutions were not refreshed during soaking in the same way as erated when gypsum reacted with monosulfoaluminate or calcium
in the method used [45]. aluminate hydrate. Brown and Badger [57] reported that gypsum,
At each test age and prior to characterisation and mechanical in turn, formed as a result of the reaction between portlandite
testing, the specimens were washed three times in deionised water and the sulfates present in the solution.

Fig. 2. XRD patterns for (a) OPC and (b) C&DWC after soaking in Na2SO4 for 56 days (E: ettringite, P: portlandite, C: calcite, Q: quartz, M: monocarboaluminate, F: ferrite
phase, B: belite).
 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958 953

3.2. DTA analysis

Differential thermal analysis (Fig. 3) revealed that the port-

landite content was 37% lower in the 56 days C&DWC specimens
than in the samples soaked in deionised water. As that difference
was greater than the C&DW replacement ratio, ruling out the dilu-
tion effect as the sole explanation [37], a second factor must have

Fig. 6. FTIR spectrum showing ettringite band in (a) OPC and (b) C&DWC.

been present, associated with the reaction between portlandite

and the pozzolanic material and with the resulting hydration
products [37,38,42,46].
Further to the graph in Fig. 4, portlandite content fluctuated as
would be expected: the higher the sulfate concentration, the lower
the content of the hydration product in the OPC and C&DWC
Fig. 3. DTA analysis of OPC and C&DWC after soaking for 56 days in deionised pastes. The steeper decline in portlandite content in the unaddi-
water. tioned than in the additioned materials may have been related to
the formation of smaller amounts of sulfate-based compounds in
the latter.

3.3. FT-IR analysis

The infrared spectra for OPC and C&DWC at different sulfate

concentrations are reproduced in Fig. 5(a) and (b), respectively.
The bands at 1120, 3420 and 3635 cm1, associated with the asym-
metric stretching characteristic of the SAO bonds in SO2 4 groups,
denote the presence of ettringite [58]. The infrared spectrum range
between 1200 and 800 cm1, where the bands overlapped, was
enlarged as shown in Fig. 6 to better visualise the band at
1120 cm1 indicative of changes in ettringite formation. Ettringite
was clearly present in the 56 day OPC specimens (Fig. 6(a)). The
higher the Na2SO4 concentration, the more intense was the ettrin-
gite band. In contrast, while ettringite was present in the 56 day
C&DWC specimens, the pattern of its formation was somewhat
Fig. 4. Portlandite content (%) in OPC and C&DWC vs sulfate concentration. hazier in these pastes (Fig. 6(b)).

Fig. 5. FT-IR spectra for (a) OPC and (b) C&DWC after soaking in different concentrations of Na2SO4.
954 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958

3.4. SEM study of the cement pastes 3.5. Changes in specimens with soaking time

The differences in the size of the intra-pore portlandite plates in Specimens soaked in both sodium sulfate concentrations were
the two cement pastes after soaking in deionised water for 56 days weighed at each test time prior to the mechanical trials (see
are visible in the micrographs in Fig. 7. These images were Fig. 9). The OPC specimens exhibited greater weight gain than
consistent with the DTA findings, according to which the inclusion the C&DWC samples at both concentrations. This finding might
of C&DW favoured the pozzolanic reaction and hence the con- be attributable to the formation of more new compounds in
sumption of portlandite [59], reducing the size of the plates and the former than in the latter after exposure to sodium sulfate
generating hydration products. The ettringite forming in the two [59,60]. It is, moreover, consistent with the lower amounts of
56 days cements is depicted in Fig. 8. More ettringite was present portlandite in C&DWC determined with other techniques
in the pastes prepared with the reference cement (Fig. 8(a) and (b)) described above, inasmuch as portlandite is the hydration product
soaked in 0.5 and 1.0 M Na2SO4 than in the respective additioned that reacts to form the ettringite detected with XRD, FTIR and
pastes (Fig. 8(c) and (d)). SEM. Weight gain was greater in both cement pastes at the higher
Moreover, the intra-pore position of the ettringite needles and sulfate concentration due to the readier availability of these ions to
their proximity to the portlandite plates were consistent earlier react with the portlandite present in the paste, yielding reaction
findings on the mechanism governing the formation of this products with greater molecular weight [59]. In addition to the
hydration product [38,40]. steeper weight gain observed in the 56 days OPC, the specimens

Fig. 7. Portlandite plates in (a) OPC and (b) C&DWC.

Fig. 8. Ettringite needles filling pores in (a,b) OPC and (c,d) C&DWC.
 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958 955

Fig. 9. Weight of Na2SO4-soaked OPC and C&DWC vs time.

Fig. 11. Total porosity in 56 days cement pastes.

soaked at both concentrations exhibited visible edge and corner Pure and Applied Chemistry (IUPAC) defines micropores (<2 nm),
cracking and microcracking (Fig. 10(a)), whereas the C&DWC mesopores (2–50 nm) and macropores (>50 nm) [61]. Metha
specimens remained intact after 56 days of sulfate attack et al. distinguish between inter-laminar or gel pores, capillary
(Fig. 10(b)). pores (attributable to both high and low w/c ratios) and pores over
These macroscopic findings are an indication of how the expan- 50 lm [62]. Mindess et al. expand the classification to take account
sive products forming during the reaction between portlandite and of paste properties [63], while Frías and Goñi establish four groups
the sulfates present in the solution can affect the durability of of pore diameters: >1 lm; 1–0.1 lm; 0.1–0.01 lm and <0.01 lm
systems containing cements of this nature [33,35,42]. [64]. For the intents and purposes of this study, two pore size cat-
egories were established: <0.01 lm and >0.01 lm (see Fig. 12). The
3.6. Porosity mean pore diameters listed in Table 3 denote a refinement of the
pore network in the cement matrices, which was more accentuated
Fig. 11 plots the total porosity in 56 days OPC and C&DWC in the pastes containing the addition. Fig. 13 shows the pore size
against the sodium sulfate concentration in the soaking solution. distribution for OPC (Fig. 13(a)) and C&DWC (Fig. 13(b)) after
Total porosity was substantially lower in the sulfate- than in the 56 days of immersion in sodium sulfate solutions (0.5 and 1 M).
deionised water-soaked specimens. In contrast, no significant dif- A refinement of the pore structure is observed with the increase
ference was observed in the total porosity between the matrices of the concentration in the solution. Besides, the incorporation of
soaked in 0.5 and 1.0 M sulfate. Consequently, in terms of total C&DW to the cement as pozzolanic addition causes a displacement
porosity, in this study, pore refinement was regarded to take place in the distribution curves to smaller sizes in the same way that is
at 0.5 M. Irrespective of the sodium sulfate concentration, total shown in Table 3. That finding was consistent with reports by
porosity was higher in the pastes additioned with C&DW than in Goñi et al. on the durability of ternary cements prepared with
the reference OPC pastes (Fig. 11). That difference was associated paper sludge and fly ash [40] and by Sánchez de Rojas et al., who
with a higher content of smaller pores in the latter. A number of studied cements bearing waste generated by the Spanish clay-
pore size classifications are in place. The International Union of based materials industry [41].

Fig. 10. Specimens after soaking in Na2SO4 for 56 days: (a) OPC; (b) C&DCW.
956 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958

Fig. 12. Evolution of the percentage of pores with smaller sizes than 0.01 lm (a) and bigger than 0.01 lm (b).

Table 3 Table 4
Mean pore diameter (lm) in cement matrices after soaking in sodium sulfate for Flexural strength (MPa) values of specimens at 56 days.
56 days.
Sulfate concentration (M) 0.0 0.5 1.0
Sulfate concentration (M) 0.0 0.5 1.0
OPC 7.92 (0.73) 15.69 (1.49) 13.68 (0.71)
OPC 0.0486 0.0469 0.0376 CDWC 5.45 (1.10) 13.24 (1.08) 15.77 (0.84)
CDWC 0.0332 0.0305 0.0298

Fig. 14. Corrosion indices (Fss/Fsw) for 56 days OPC and C&DWC pastes.

F SS
CI ¼ ð1Þ
F SW
where CI is the corrosion index; FSS is the flexural strength after
immersion during 56 days in sulfate solution and FSW is the flexural
strength obtained at the same time after immersion in deionised
water (see Table 4).
The corrosion index for 56 days OPC and C&DWC at sodium sul-
fate concentrations of 0.0, 0.5 and 1.0 M are shown in Fig. 14. The
indices were higher for the specimens containing 30% C&DW than
for the unadditioned pastes at all concentrations.
The figure also shows that the corrosion indices were over 0.7,
the Köch-Steinegger threshold for sulfate-resistant cements [45].
This improvement in mechanical performance can be attributed
to the refinement of the cement matrix pore systems. In OPC, the
index was higher at 0.5 M than at 1.0 M, when flexural strength
began to decline. In the cement containing 30% C&DW, in contrast,
flexural strength remained unaffected. As a result, the corrosion
index was higher than in OPC. This finding was consistent with a
Fig. 13. Comparison of pore size distribution of OPC (a) and C&DWC (b) pastes after report by Sánchez de Rojas et al. [41], who observed that cement
56 days immersion in Na2SO4 (0.5 and 1 M).
pastes containing 20% clay-based waste had higher flexural
strength than OPC because the pozzolanic addition afforded the
3.7. Sulfate resistance pastes greater flexibility and elasticity [65]. An analysis of the flex-
ural strength and corrosion index values for the cements after
In this study, sulfate resistance was measured pursuant to the soaking in different concentrations of sodium sulfate revealed that
Köch-Steinegger procedure [45], i.e., in terms of a corrosion index replacing clinker with pozzolanic construction and demolition
based on flexural strength as Eq. (1) shows: waste improved paste durability.
 E. Asensio de Lucas et al. / Construction and Building Materials 127 (2016) 950–958 957

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