Construction and Building Materials 124 (2016) 219–227

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Construction and Building Materials

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

Use of industrial ceramic sludge in brick production: Effect on aesthetic

quality and physical properties
Chiara Coletti a,b,⇑, Lara Maritan a, Giuseppe Cultrone b, Claudio Mazzoli a
a
Department of Geosciences, University of Padova, Via G. Gradenigo 6, 35131 Padova, Italy
b
Department of Mineralogy and Petrology, Faculty of Science, University of Granada, Avda. Fuentenueva s/n, 18002 Granada, Spain

h i g h l i g h t s

Re-using sludge from the ceramic industry as an alternative eco-friendly additive.

Aesthetic quality and physical properties of traditional bricks and new mix design.

Economic and ecologic ways of developing bricks from recycled waste.

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

Article history: Most brick companies nowadays focus their research on the recycling of waste, in order to be able to mar-
Received 7 March 2016 ket new types of bricks. In this work, we explored the possibility of using ceramic sludge in brick produc-
Received in revised form 4 July 2016 tion, aiming to find an alternative eco-friendly additive to produce ‘‘eco-bricks” characterised by suitable
Accepted 17 July 2016
mechanical and aesthetic properties and durability. For this purpose, two types of bricks produced by an
Available online 25 July 2016
Italian factory (SanMarco-Terreal) were compared with a newly designed brick obtained from the same
starting clay, with the addition of ceramic sludge in place of the traditionally used siliceous sand. Bricks
Keywords:
and raw materials were investigated with a multivariate approach, consisting in the mineralogical and
Bricks
Sludge
chemical analysis, and the final products microstructurally investigated and their physical-mechanical
Mineralogy properties determined. Results show that bricks produced with added ceramic sludge can substitute tra-
Physical-mechanical properties ditional bricks well, fulfilling aesthetic requirements and maintaining sufficient mechanical properties.
Durability However, one drawback was that these new materials did not respond to freeze-thaw cycles, highlighting
Aesthetic quality their potential vulnerability in cold climates.
Porosity Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction plasticity, prevents shrinkage, and improves the mechanical resis-

tance of the finished product.
The raw material used in brick production is mostly composed Several researches have been carried out in the last few decades
of clay. The growing demand for high-quality final products, the on creating new types of bricks using additives, often consisting of
need to expand company production, and increasing attention to residual urban and industrial materials [2–9]. These works have
environmental problems (cfr. many regional, national and EC often demonstrated the potential of these materials, which have
norms) have led to the use of several additives in addition to nor- technical advantages and can reduce the environmental impact.
mal raw clay materials. Additives, both natural and synthetic, act The introduction of industrial waste in brick production is also a
as auxiliary ‘‘raw materials” and influence many properties of fired response to the problem of the disposal of large amounts of waste
products, such as colour, mechanical strength and durability [1]. In materials from various industrial activities. Storing these waste
ordinary brick production, quartz-rich sand is the additive mainly materials and the resulting global environmental hazard has
used as temper (10–20 wt%) since it is easily available, does not increased the demand and development of sustainable alterna-
release pollutants at any stage of the production process, reduces tives. For these reasons, industrial and academic attention has
focused on developing environmentally friendly, low-cost and
lightweight construction materials obtained from waste. Bricks
⇑ Corresponding author at: Department of Geosciences, University of Padova, Via mainly consist of clayey materials, can tolerate the addition of
G. Gradenigo 6, 35131 Padova, Italy. waste even in significant percentages, and are therefore suitable
E-mail address: [email protected] (C. Coletti). for this type of re-use [1].

http://dx.doi.org/10.1016/j.conbuildmat.2016.07.096
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
220 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227

One type of waste is sludge from ceramic production, consisting [11], and the NCSDC 74301 (GSMS-1) standard [12] was
mainly of silico-aluminous-based components (>50%), generally applied. Grain-size distribution in the size range between 0.02
with low contents of heavy metals [1]. Being compositionally sim- and 2000 lm of the sludge was determined using a Mastersizer
ilar to the raw clayey materials of bricks, this type of waste is 2000LF laser diffraction particle size analyser (Malvern
related to ceramic production and often inadequately disposed Instruments).
of, although it is an important source of additives in brick produc- The mineralogical composition of raw materials and bricks was
tion if properly designed new mixes are created. Nowadays, most determined by X-ray Powder Diffraction (XRPD) on a PANalytical
ceramic-producing companies have addressed their research and X’Pert diffractometer with Co-Ka radiation, operating at 40 kV
organisation of productive plants to recycle waste, save energy and 40 mA intensity; XRPD data were interpreted by X’Pert PRO
and re-use resources (mainly water) deriving from the production HighScore PlusÒ software (PANalytical). Semiquantitative phase
cycle, thus saving natural resources and resolving the waste dis- analysis was performed on the crystalline phases using the RIR
posal problem. All these aspects contribute much to the evaluation method. Since none internal standard was used during the XRPD
of company performance. Although re-using ceramic production acquisition, relative abundance of the amorphous phase was
waste (shards) is quite common, re-using sludge is more difficult, expressed only qualitatively, taking into consideration the pattern
due to its intrinsic nature. Sludge is very fine-grained and, accord- profile.
ing to the type of ceramic production from which it derives, does Colour of the raw materials and the fired bricks was determined
contain heavy metals in variable quantities, from few ppm as they on a Konica Minolta CM-700d spectrophotometer (10 measures
naturally occur in the base clay and possibly added temper, to per samples were performed). According to the CIE system, colour
some percent, as in the case of glazed and colour ware. Therefore, is described considering a parameter for luminescence (L⁄) and two
a sludge does not reflect environmental and human safety require- chromatic coordinates, a⁄ and b⁄, which reflect the amount of
ments, indicating that continual quality control of used materials is red-green (60: green,+60: red) and yellow-blue (60: blue,+60:
always important. yellow), respectively. Colorimetry was performed in dry and then
This work explores the possibility of using ceramic sludge in in wet conditions on the fired bricks, to determine all possible
brick production. Two types of commercial bricks produced by colour changes due to the presence of water or humidity. Colour
the Italian factory SanMarco-Terreal were analysed, and the results difference DE was calculated according to the following equation:
were compared with a newly designed brick obtained from the qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  2
ðL1  L2 Þ þ ða1  a2 Þ2 þ ðb1  b2 Þ
2
same starting clay tempered with ceramic sludge instead of the DE ¼
traditional siliceous sand. More in detail, the sludge here used
was obtained from the mechanical treatment (such as lapping or where subscript 1 refers to measurements on dry samples and sub-
scrapping) of a clay based highly-fired ceramic material. The min- script 2 on wet ones.
eralogical composition, texture, physical properties, water beha- Petrographic features, texture and degree of vitrification of the
viour and durability of both traditionally produced and newly bricks were studied on polished thin sections by Optical Micro-
designed bricks were analysed by a multi-analytical approach, scopy (OM) under polarized light with an Olympus DX–50
and the possibility of recycling ceramic sludge in brick production equipped with a Nikon D7000 digital microphotography system,
was critically evaluated. and on back-scattered electron (BSE) images obtained by Field
This research arose from definite interest on the part of the Emission Scanning Electron Microscopy (FESEM) with a LEO
company, which provided full technical support. GEMINI 1530, coupled to an INCA-200 Oxford microanalysis
system.
Water absorption [13] and drying [14] tests on fired bricks were
2. Materials and methods performed on cube-shaped samples (50-mm edge) on three sam-
ples of each brick type. Free and forced absorption (Al and Af), dry-
Three types of bricks (two (bricks 1 and 2) commercialized and ing index (Di), apparent and real density (Da and Dr), open porosity
industrially produced, and one (brick 3) experimentally produced (P) and degree of pore interconnection (Ax) were calculated.
in the SanMarco-Terreal laboratory, simulating the same prepara- Capillary rise (B) was studied on three prism-shaped samples
tion, forming and firing conditions used for the industrial ones) (25  25  120 mm) for each brick type, according to UNI EN
were prepared with the same carbonate-rich clay, quarried from 1925 [15]. The coefficient of capillarity (Ks) was calculated 9 min
the area of Marcon (Venice inland) and fired at 1050 °C. Any differ- after the test began.
ences among them were due to the additives used. Bricks were The distribution of pore access size (range 0.003–360 lm) was
formed by the soft-mud shaping method, in which the clay paste determined by Mercury Intrusion Porosimetry (MIP) on a model
is placed into 5  12  20 cm moulds, the walls of which are 9410 Micromeritics Autopore apparatus, which can generate a
spread with quartz sand to avoid clay from sticking and favour pressure of 414 MPa. Freshly cut samples of approximately 2 cm3
both water drainage while pressing and the separation from the were oven-dried for 24 h at 110 °C and then analysed. Nitrogen
mould. The colour of the commercial bricks was yellow (brick 1) adsorption was used to determine porosity in the range diameter
and black (brick 2), and both were prepared by tempering clay 2–3000 Å. Sorption isotherms were determined at 77 K on a
with 10 wt% of siliceous sand, but the black brick was obtained Micromeritics Tristar 3000 in continuous adsorption conditions.
adding to the clay paste and quartz sand also 15 wt% of the colour- Prior to measurement, samples were heated to 130 °C for 24 h
ing agent hausmannite (Mn2+Mn3+ 2 O4). Hausmannite is a secondary and out-gassed to 103 Torr on a Micromeritics Flowprep. The
waste product, approved according to valid environmental impact Barrett-Joyner-Halenda (BJH) method was used to obtain pore-
criteria [10] and derived from industrial sources, such as the produc- size distribution curves.
tion of ferroalloys and MnO2-based batteries. The newly designed Vp (compression pulse) and Vs (shear pulse) propagation veloc-
brick (brick 3) was prepared by tempering the same clay with ities were measured to check the elastic-mechanical characteristics
10 wt% of dried ceramic sludge provided by SanMarco-Terreal. and structural anisotropy of the fired bricks, and to detect com-
Raw materials (clay and sludge) and fired products were chem- pactness variations during and after ageing. Waves were transmit-
ically analysed by X-ray Fluorescence (XRF) using a S4 Pioneer ted in the three perpendicular directions of the cube-shaped
(Brucker AXS) spectrometer (estimated detection limit for major samples (50-mm edge) on a Panametrics HV Pulser/Receiver
elements: 0.01 wt%); ZAF correction was performed systematically 5058PR coupled to a Tektronix TDS 3012B oscilloscope.
 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227 221

Measurements were performed with Panametrics transducers of during the freeze-thaw test and every 3 cycles of salt crystallisa-
1 MHz on a contact surface 3 cm in diameter. Once wave velocities tion), sample compactness was also monitored by ultrasound.
(Vp and Vs) and apparent density (by MIP) were established, Pois-
son’s Coefficient (m), Young (E), shear (S) and bulk (K) modules
were calculated. 3. Results and discussion
Uniaxial mechanical tests were carried out on three cubic sam-
ples (40  40  40 mm) on an IPEMSA Model S-110 press with a 3.1. Clay and recycled materials
load force of 20 kg/s, according to UNI EN 1926 [16].
Accelerated ageing tests were carried out on three cubic samples According to mineralogical composition (Fig. 1; Table 1), the
(50 mm edge) for each brick type, to evaluate their resistance to clay material was an illitic-chloritic highly calcareous (carbonate-
frost and salt crystallisation. Freeze-thaw and salt crystallisation rich) clay. The abundance of carbonate was confirmed by the high
tests followed UNI EN 12371 [17] and UNI EN 12370 [18] norms, values of calcium and magnesium oxides, and loss of ignition
respectively. The former consists of 30 cycles each lasting 24 h, each (Table 2: CaO + MgO = 22.51 wt%; LOI = 19.65 wt%). The abundance
cycle including 8 h of freezing at 12 °C and 16 h of thawing at of carbonate conferred a yellow hue on the fired bricks, with a high
+20 °C under water. Samples were weighed at each cycle and care- b⁄ value (16.05) (Table 3).
fully observed visually to check their progressive decay. At the end Macroscopically, the powdered sludge was pale yellow in colour,
of the tests, samples were dried to measure their weight loss. The with a high value of lightness (L⁄ = 84.87) and low values of a⁄ and b⁄
salt crystallisation test consisted of 10 24-h cycles, during which coordinates (6.28 and 1.27, respectively) (Table 3). Its grain-size dis-
the samples were immersed for 4 h in a 14 wt% solution of NaSO4 tribution ranged between 0.25 and 1002 lm, with most of the parti-
10H2O at 20 °C, dried for 16 h in an electric oven at 100 °C, and cles (90%) smaller than 100 lm (Fig. 2). Chemically, sludge is highly
cooled for 4 h at 20 °C. They were weighed at each cycle and siliceous, and does not contain heavy metals (Table 1), i.e., it may be
observed by visual inspection. They were then washed in water, used safely in industrial production. From a mineralogical view-
to remove any salts trapped in pores, and dried to measure their point, this material is mainly composed of quartz, associated
weight loss. During both tests, at regular intervals (every 5 cycles with plagioclase, mullite, cristobalite and an amorphous phase

Counts Qz Raw materials Counts Fired Bricks

Qz
Clay 20000
Brick 1
20000 Fs
Cal

Gh

Ill Dol 10000

10000 Chl
Wo
Chl Qz Fs

Gh

Counts Counts

Hausmannite Brick 2
20000
15000

Qz
10000
Gh
10000
Bst
Qz Fs
5000

Counts Qz Counts Qz
Sludge Brick 3
30000
20000

20000

Gh
10000
Qz Fs
10000 Qz Di
Mul
Gh
Mul Crs Pl

0
10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
Position [°2Theta] Position [°2Theta]

Fig. 1. XRPD patterns of raw materials (clay, hausmannite, sludge) and fired bricks. Hausmannite and Brick 2 show a high background due to the Mn-fluorescence effect in the
powder sample produced by the cobalt anode incident radiation.
222 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227

Table 1
Semi-quantitative mineral composition determined by RIR method on XRPD data of raw clay material, hausmannite (Hsm), sludge and three fired bricks. Mineral abbreviations
after Whitney and Evans [40]: Qz = quartz; Ill = illite; Chl = chlorite; Kfs = K-feldspar; Pl = plagioclase; Cal = calcite; Dol = dolomite; Hem = hematite; Hsm = hausmannite;
Mul = mullite; Crs = cristobalite; Di = diopside; Gh = gehlenite; Wo = wollastonite; Bst = bustamite. Qualitative estimation of amorphous phase (Am): ⁄⁄⁄ = abundant; ⁄⁄ = -
medium; ⁄ = scarce; – = absent.

Raw Materials Qz Ill Chl Kfs Pl Cal Dol Hem Hsm Mul Crs Am
Clay 30 12 14 5 6 19 14 1 – – – –
Hsm – – – – – – – – 100 – – –
⁄⁄
Sludge 67 – – – 16 – – – – 16 2
Fired bricks Qz Kfs Pl Hem Wo Di Gh Bst Am
⁄⁄
1 28 11 19 1 12 11 18 –
⁄⁄⁄
2 21 20 18 1 – 12 16 11
⁄
3 28 17 21 1 7 13 13 –

Table 2
Chemical composition of major elements, expressed in wt% of oxides for clay material and sludge. LOI = Loss on Ignition.

SiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O TiO2 P2O5 LOI
Clay 39.81 10.63 3.87 0.08 4.75 17.76 0.54 2.37 0.43 0.11 19.65
Sludge 72.52 18.36 1.20 0.01 0.51 1.00 3.11 2.31 0.71 0.11 0.16

Table 3
Colour coordinates L⁄, a⁄ and b⁄ for raw clay material, hausmannite (Hsm), sludge and three fired bricks, measured in dry and wet conditions. DE: colour difference. Concerning
the brick with sludge (Brick 3), colour analysis was also performed after salt crystallisation (A.S.C.) test.

Raw materials
L⁄ SDL⁄ a⁄ SDa⁄ b⁄ SDb⁄
Clay 63.89 ±1.30 2.41 ±0.12 16.05 ±1.25
Hsm 35.67 ±1.03 10.85 ±0.87 8.70 ±2.77
Sludge 84.87 ±0.27 1.27 ±0.03 6.28 ±0.22
Fired bricks
Dry Wet
L⁄ SDL⁄ a⁄ SDa⁄ b⁄ SDb⁄ L⁄ SDL⁄ a⁄ SDa⁄ b⁄ SDb⁄ DE
Brick 1 71.95 ±1.35 6.63 ±0.49 23.62 ±1.02 58.78 ±1.12 9.61 ±0.46 26.86 ±1.03 13.88
Brick 2 37.05 ±0.72 4.48 ±0.11 7.32 ±0.27 26.22 ±0.56 3.72 ±0.09 5.30 ±0.20 11.04
Brick 3 72.20 ±0.77 6.39 ±0.56 18.98 ±1.00 57.90 ±0.55 10.00 ±0.41 23.22 ±0.80 15.34
Brick 3 A.F. 58.89 ±4.02 11.97 ±1.52 24.66 ±1.99 57.58 ±1.03 11.11 ±0.31 24.97 ±0.55 1.60

3.5
3.2. Fired bricks
3
Volume %

2.5 3.2.1. Colorimetry

2 Fired bricks are all characterised by a fine-grained paste, with
a yellow hue for bricks 1 and 3 and a dark grey one for brick 2.
1.5
Lightness (L⁄) was far higher for bricks 1 and 3 compared with
1
brick 2; chromatic coordinates a⁄ and b⁄ were very similar in bricks
0.5 1 and 3 but higher than those of brick 2 (Table 3). The colorimetric
0 results showed that sludge produces a brick (brick 3) with aes-
0.01 0.1 1 10 100 1000 thetic characteristics similar to those obtained with a siliceous
Particle Size (µm) sand temper (brick 1).
Changes in L⁄, a⁄ and b⁄ values were observed when the samples
Fig. 2. Grain-size distribution of sludge, expressed as volume percentage.
were wetted, although these changes did not affect all the samples
in the same way. All bricks became darker with the decrease of the
(Fig. 1; Table 1), indicating that the ceramic material from which the
L⁄ parameter.
sludge was obtained experienced high firing temperature.
Bricks 1 and 3 showed a very similar increment in the a⁄ and b⁄
Mullite is a common aluminium silicate found in ceramic prod-
values when wet (Table 3). Colour differences values between dry
ucts fired at temperatures exceeding 800 °C after kaolinite or
and wet conditions (DE values) are rather similar among all the
illite/muscovite breakdown [19,20]. The presence of amorphous
bricks. Nevertheless, the grey coloured brick (brick 2) recorded
phase also proves the high firing temperature at which the ceramic
the smallest change, while the yellow brick with sludge (brick 3)
body underwent partial melting. According to both its chemical
has the highest variability (Table 3).
and mineralogical composition, sludge used to produce brick 3,
did not undergo any further treatment.
The dye added to brick 2 turned out to be mineralogically com- 3.2.2. Mineralogical composition
posed only of hausmannite (Fig. 1; Table 1). It was dark brown in col- The mineral compositions of the bricks followed what was
our, with low values of lightness (L⁄ = 35.67), indicating a tendency expected from a typical ceramic material made of illitic-chloritic
to a grey hue, and a⁄ and b⁄ of 10.85 and 8.70, respectively (Table 3). carbonate-rich clay and fired at high temperature (1050 °C).
 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227 223

a b

5 mm 5 µm

c d

5 mm 5 µm

e f

5 mm 5 µm

Fig. 3. Photomicrographs (plain polars) of fired bricks: (a, b) brick 1; (c, d) brick 3; (e, f) brick 2.

Brick 1 was composed of predominant quartz, abundant gehlen- 3.2.3. Texture

ite, diopside and wollastonite, and associated anorthite, sanidine, Under the optical microscope, bricks 1 (Fig. 3a, b) and 3 (Fig. 3c,
hematite and an amorphous phase. It was very similar to brick 2, d) had a bright matrix (groundmass), whereas brick 2 (Fig. 3e, f)
which also contained bustamite (CaMnSi2O6), a Mn-rich high- had a dark groundmass, due to bustamite. All samples were very
temperature polymorph belonging to the wollastonite group, similar in terms of pore structure and grain-size distribution.
developed from the following reaction among hausmannite, Grains (about 20%) were sub-angular in shape, with non-selected
carbonate and quartz: distribution. Pores were mainly represented by ‘‘vesicles” and
‘‘vughs” [26] and were homogeneously distributed in the matrix.
2þ
CaCO3 þ 2SiO2 þ ðMn2þ Mn3þ 3þ
2 O4 Þ ! CaMn Si2 O6 þ Mn2 O3 þ CO2 : Reaction microstructures were better analysed by scanning
electron microscope. The decomposition of carbonates and the
Brick 3 had the same mineral composition as brick 1, but the migration of Ca2+ cations led to development of the sub-solidus
newly formed silicates and the amorphous phase were less devel- reaction with silicates and the growth of new mineral phases.
oped (Fig. 1). The characteristic peaks of mullite, detected in the In brick 1, feldspar and quartz grains showed reaction rims,
sludge, were absent in the XRPD diffractogram of the fired product, with a corona-like structure, composed of gehlenite and wollas-
probably because sludge represented only 10 wt% of the starting tonite (Fig. 4a). Micro-chemical analysis indicated a progressive
raw material, so that its concentration was too low to be detected. increase in Ca from core to rim, as also shown in Fig. 4b, in which
At 1050 °C, most of the minerals composing the clay material the corona structure forming round a grain of quartz displays
and the natural sand had already reacted, causing the disappear- various grey hues. In this case, wollastonite (CaSiO3) formed by
ance of illite, chlorite and carbonates (calcite and dolomite) reaction of carbonate in contact with the quartz grain:
[21,22], and contributing to the development of new silicates, such
as gehlenite, diopside and wollastonite (or bustamite). Decarbona-
CaCO3 þ SiO2 ! CaSiO3 þ CO2 :
tion of calcite takes place at 750–850 °C and plays an important
role in the development of new phases, due to the release and Brick 2 was characterised by the diffuse presence of bustamite
migration of Ca2+ cations, promoting reactions between minerals grains, randomly distributed in the matrix and at feldspar and
in the matrix. Gehlenite, for example, may derive from calcite quartz rims, also identified by XRPD analysis, abundant secondary
and illite (at 800–850 °C), and wollastonite can grow by reaction vesicles (Fig. 4c), and a high level of bonding between matrix and
between calcite and quartz (at 900–1000 °C) [23,24]. When dolo- grains. In this brick, hausmannite promoted melting. It was inter-
mite decarbonates between 700 °C and 800 °C, Mg2+ and Ca2+ esting to note that phyllosilicates, which underwent complete
cations are released, their reaction with quartz or silica derived dehydroxylation but maintained their sheet-like texture, were here
from the decomposition of clay minerals gives rise to the formation enriched in Mn derived from hausmannite decomposition (Fig. 4d).
of diopside at 900–1050 °C [25]. Orthoclase, initially present in the Secondary rounded pores and vesicles were also seen in brick 3
raw clay, is transformed into its high-temperature polymorph sani- (Fig. 4e), as well as fibrous Mn-enriched wollastonite crystals at
dine [25]; plagioclase is enriched in anorthite over 950 °C [23]. quartz-grain rims (Fig. 4f).
224 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227

a b
Qz Gh
Wo Ca 2+

Wo Qz
10 µm 1 µm

c bubble d
development Ill + Mn/Fe-bearing

Bst
10 µm 3 µm
Kfs
e f

bubble Wo
development

10 µm 10 µm

Fig. 4. FESEM-BSE images: (a) quartz and feldspar grains with reaction rims where gehlenite and wollastonite formed (brick 1); (b) Ca2+ enrichment at quartz rim with sub-
solidus reaction producing wollastonite (brick 1); (c) diffuse occurrence of bustamite (CaMnSi2O6) and considerable development of rounded pores forming bubbles by
reaction among minerals in groundmass (brick 2); (d) K-feldspar with formation of bustamite and phyllosilicate (Ill), with abundant Fe- and Mn-bearing oxides (brick 2); (e)
development of bubble-shaped pores and reaction rims (brick 3); (f) fibrous wollastonite crystals growing on quartz grains close to pores (brick 3). Abbreviations as in caption
of Table 1.

Table 4
Hydric parameters: Ab = free water absorption (%); Af = forced water absorption (%); Ax = degree of pore interconnection (%); Di = drying index; poHT = open porosity (%);
DbHT = apparent density (kg m3); DskHT = real skeletal density (kg m3); Ks = capillarity coefficient (g cm2 min½); B = capillarity rise (cm min½). MIP values: poMIP = open
porosity (%); DbMIP = apparent density (kg m3); DskMIP = real (skeletal) density (kg m3). N2 adsorption: BHJ des. V. = BHJ desorption Volume (cm3 g1).

1 DS1 2 DS2 3 DS3

Hydric test Free water absorption (Ab) 27.63 ±0.57 25.08 ±0.61 27.94 ±0.36
Forced water absorption (Af) 28.71 ±0.83 25.85 ±0.64 28.34 ±0.25
Degree of pore interconnection (Ax) 3.76 ±1.20 2.98 ±0.20 1.43 ±0.42
Drying index (Di) 1.35 ±0.00 1.36 ±0.00 0.39 ±0.00
Open porosity (poHT) 41.36 ±1.00 40.56 ±0.75 42.12 ±0.30
Apparent density (dbHT) 1.44 ±0.01 1.57 ±0.01 1.49 ±0.00
Real skeletal density (dskHT) 2.46 ±0.03 2.64 ±0.02 2.57 ±0.01
Capillarity coefficient (Ks) 0.43 ±0.04 0.33 ±0.07 0.41 ±0.04
Capillarity rise (B) 1.33 ±0.03 1.23 ±0.12 1.05 ±0.07
MIP Open porosity (poMIP) 47.45 – 46.87 – 49.57 –
Apparent density (dbMIP) 1.40 – 1.50 – 1.60 –
Real (skeletal) density (dskMIP) 2.68 – 2.87 – 3.10 –
N2 ads BHJ desorption Volume (BJH des.V.) 0.004450 – 0.009709 – 0.001566 –

3.2.4. Hydric behaviour and porosity the highest Ax value (3.76%), suggesting the difficulty of water
The hydric parameters (Table 4) indicated that the three bricks migrating within the brick. Brick 2 showed intermediate
differed in their water behaviour. Brick 3 was the sample with the characteristics.
highest free absorption value (Ab = 27.94%) and the best pore inter- Drying was very similar for bricks 1 and 2 (Di values: 1.35 and
connections (Ax = 1.43%), indicating pores favouring water access. 1.36, respectively), although brick 3 dried faster (Di = 0.39). Open
Brick 1 was the sample with the greatest difference between free porosity p0 was quite similar in all samples, the highest value being
and forced absorption (Ab = 27.63%; Af = 28.71%), as confirmed by recorded in brick 3 (p0 = 42.12%) and the lowest in brick 2
 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227 225

Table 5
(a) 3 Ultrasonic test. Propagation velocities of ultrasonic Vp and Vs pulses (m s1).
1.4 DM = total anisotropy (%); m = Poisson’s ratio; E = Young’s modulus (GPa); G = shear
modulus (GPa); K = bulk modulus (GPa). Uniaxial test: r = stress values (N mm2).
1.2
1 1 DS1 2 DS2 3 DS3
LogDV/Dr (ml/g)

1
0.8 2 Compression pulse (Vp) 2773 ±94 2804 ±75 2423 ±150
Shear pulse (Vs) 1299 ±71 1299 ±50 1326 ±100
0.6 Total anisotropy (DM) 12.26 ±4.88 10.73 ±1.24 12.30 ±4.86
0.4 Poisson’s ratio (m) 0.36 ±0.01 0.37 ±0.00 0.29 ±0.01
Young’s modulus (E) 64 ±3 63 ±3 72 ±3
0.2 Shear modulus (G) 11 ±2 12 ±1 15 ±1
0 Bulk modulus (K) 76 ±6 79 ±7 57 ±4
0.001 0.01 0.1 1 10 100 Stress values (r) 14.80 ±1.66 18.73 ±2.55 15.20 ±2.74
r (µm)

(b) in this pore-size interval (Fig. 5c). Conversely, the absence of these
0.35 micropores was the main cause, together with the best pore inter-
2
0.3 connections, of the faster drying velocities of brick 3 [19]. This evi-
dence indicates that the addition of sludge, probably because of its
Vads (cm3 g-1)

0.25
grain size and high degree of vitrification, determines lower micro-
0.2
1 porosity than the other two bricks; instead, the addition of man-
0.15 ganese oxide is responsible for increases in microporosity.
0.1
0.05 3.2.5. Physical-mechanical properties and durability
3 The highest average value of propagation velocities of brick 2
0
0 0.2 0.4 0.6 0.8 1 (Vp = 2773 m s1) (Table 5) was due to its high amorphous phase,
p/p0 which increased its compactness and made it more homogeneous.
This sample was in fact the brick with the lowest total anisotropy
(c) (DM = 10.73%) [19,29]. Bricks 1 and 3 showed very similar aniso-
0.02 tropy, although slightly higher (DM = 12.26% and 12.30%, respec-
tively), and the latter the lowest propagation velocity
0.015
Vads (cm3 g-1)

(Vp = 2423 m s1) due to its higher porosity, as attested by hydric

2 tests and MIP.
0.01 Brick 2 also had the highest values of Poisson’s ratio
(m = 0.37 GPa) and bulk modulus (K = 79 GPa), followed by bricks
1
0.005 1 (m = 0.36, K = 76 GPa) and 3 (m = 0.28, K = 56 GPa). The latter
3 clearly had the highest values for Young (E = 72 GPa) and shear
0 (G = 15 GPa) modules (Table 5), indicating that brick 2 was stiffer,
0 50 100 150 200 250 300
but brick 3 was softer.
d (Å)
Compressive strength values (r) measured with the uniaxial
Fig. 5. (a) Pore size distribution curves (log differential intruded volume (ml g1)) compressive test confirmed almost all the results obtained by
vs. pore radius (lm) of all bricks; (b) N2 isotherms of all bricks: volume adsorbed ultrasound, the highest r value being measured on brick 2
(cm3 g1) vs. differential pressure (p/po); (c) cumulative curves by BHJ method of all (r = 18.73 N mm2), followed by bricks 1 and 3, which showed
bricks: volume adsorbed (cm3 g1) vs. pore diameters (Å). very similar resistances (r = 14.80 N mm2 and 15.20 N mm2,
respectively). The apparent discordance of these two samples,
between bulk modulus (K) obtained by ultrasound and the com-
(p0 = 40.56%). Brick 1 showed the highest attitude to capillarity rise pressive test (r), was due to the higher porosity of brick 3 (accord-
(Ks = 0.43), followed by brick 3 (Ks = 0.41) and brick 2 (Ks = 0.33). ing to both hydric tests and MIP) which decreases the capacity of
All samples were characterised by similar porosimetric curves, wave transmission during ultrasound tests.
with predominant pore radius around 1 lm, and differences in Subjected to ageing tests, the three bricks showed different
the height of the main peak depending on porosity access to mer- behaviour. Although they behaved similarly during the first cycles,
cury (Fig. 5a). Open porosity obtained by MIP was always higher brick 3 started to fall apart after cycle 18 of the freeze-thaw test,
than that measured by water absorption, but followed the same with a consequent loss of fragments and weight (Fig. 6a) and a
trend, brick 3 showing the highest open porosity (p0 = 49.5%), fol- decrease in ultrasonic wave transmissions (Fig. 6b). From cycle
lowed by brick 1 (p0 = 47.45%), and brick 2 (p0 = 46.87%) (Table 4). 20 onwards, ultrasonic waves could not be measured in this brick,
Analysis of pores smaller than 0.03 lm in diameter by nitrogen which suffered progressive decay until its total disintegration after
adsorption indicated that brick 3, characterised by the highest cycle 30, with a weight loss of 95.62%. The behaviour of the other
open porosity, was the sample which contained fewer micropores two bricks was very different, weight losses being 3.50% in brick 1
(Fig. 5b). Instead, brick 2, with the lowest values of open porosity, and 0.30% in brick 2 after cycle 30 (Table 6).
showed adsorption-desorption isotherms with the highest values, The behaviour of samples submitted to salt crystallisation was
indicating the greatest number of micropores. very different to that after the freeze-thaw cycles. Bricks 1 and 2
All samples, according to the IUPAC classification, had nitrogen showed damaged edges at the end of the test, whereas brick 3
sorption isotherms type IV with H3 hysteresis loop [27,28], typical appeared to remain almost intact. Weight variations during the
of mesoporous materials. This phenomenon was particularly evi- test confirmed these different behaviours. Bricks 1 and 2 increased
dent in brick 2, which also had the greatest amount of gas volume their weight initially, due to crystallisation of salt in the pores;
intruded. BJH pore-size distribution for bricks 1 and 2 showed a they then maintained an oscillating trend caused by salt crystalli-
peak between 30 and 50 Å, indicating the occurrence of small pores sation within the pores and fissuring, with loss of fragments. At the
226 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227

(a) (b)
0.4 2 3000 2
0.2 1 2500 1
0 2000
0 5 10 15 20 25 30

Vp (m s-1)
ΔM/M

-0.2
cycles (day) 1500
-0.4
1000
-0.6 3
-0.8 500
3
-1 0
0 5 10 15 20 25 30
cycles (day)
(c) (d)
0.2
2800
2
0.15
3 2700

Vp (m s-1)
0.1
1
ΔM/M

2600
0.05
2 2500
3
0
0 2 4 6 8 10 2400
-0.05 cycles (day) 1 0 1 3 7 10
-0.1 cycles (day)

Fig. 6. (a) Weight variation (DM/M) vs. cycles (days) of all bricks subjected to 30 freeze-thaw cycles; (b) propagation velocities of ultrasonic Vp pulses (m s1) during freeze-
thaw tests; (c) weight variation (DM/M) vs. time (h) of bricks subjected to 10 salt crystallisation cycles; (d) propagation velocities of ultrasonic Vp pulses (m s1) during salt
crystallisation tests.

Table 6 stresses [19,30–32]. Indeed, the three different types of brick,

Weight loss (Wf  Wi)/Wi of dried samples after 10 cycles of salt crystallisation test obtained from the same clay and fired at the same temperature
and 30 cycles of freeze-thaw test.
(1050 °C) are very similar in the final properties, except for some
1 2 3 characteristics conferred by the use of the sludge instead of the
Salt crystallisation test 14.28 10.40 1.05 standard quartz sand for brick 3 and the dye addition to the brick
Freeze-Thaw test 3.50 0.30 95.62 2. The overall study, demonstrated the possibility of using ceramic
sludge in brick mixtures and highlighted changes in brick proper-
ties when manganese oxide is added as a dye. The brick with
end of the tests, they had lost up to 15% (brick 1) or 10% (brick 2) of sludge (brick 3) differs from the others for its porosity and frost
their weight (Fig. 6c). Instead, brick 3 showed a gradual weight behaviour probably due to the different grain size and grain
increase until the last cycle, due to constant accumulation of salt packing with respect to the brick obtained by using a standard
inside the pore system. This was also confirmed by ultrasound, temper. Colorimetric tests showed that bricks made with sludge
which showed a gradual increase in Vp values (Fig. 6d). At the have an aesthetic appearance similar to those of the commercial
end of the test, brick 3 recorded the lowest variation in weight, yellow bricks, that is, the colour of the former is compatible for fea-
with a small increase of  1% (Table 6) due to residual salt trapped sible substitution. As regards water behaviour, the sludge-made
in the pores after washing. The performance of the other two bricks brick has the best pore interconnections and slightly higher open
was clearly worse, with weight losses greater than 10% (Table 6). porosity, confirmed by mercury intrusion analysis and nitrogen
The aesthetic aspect of brick with sludge was inspected after salt adsorption. Uniaxial compression tests showed very similar stress
crystallisation test. Colorimetry results showed as bricks submitted values (r) for the commercial bricks, indicating that, despite the
to the salts crystallisation became darker, and the L⁄ parameter on change in temper, mechanical properties were also maintained.
dried samples decreased (L⁄ = 58.89) with respect to that of the Instead, the addition of hausmannite (Mn2+Mn3+ 2 O4) to the paste
same samples (brick 3) before the test (L⁄ = 71.95). Dried and wet- as a dye (brick 2) confers a different final aspect (grey, as attended)
ted bricks after salt crystallisation displayed rather similar values and causes an increase in mechanical strength: hausmannite does
(DE in Table 3), confirming little changes in the colour. not only act as a dye, but also changes brick texture, increasing vit-
rification and improving mechanical properties. These overall good
4. Conclusions mechanical features were also confirmed by ultrasound tests.
Contrasting behaviour was found as regards the durability of
The characterization of the commercial bricks and the optimiza- bricks. Commercial bricks 1 and 2 were particularly susceptible
tion of the new mix design obtained reusing a ceramic sludge con- to salt crystallisation, whereas the experimental sludge-made brick
firms the close relationships between mineralogy, porosity, was weaker after freeze-thaw cycles. These differences were due to
mechanical properties and durability under different environmental the different pore system of the three bricks and the aptitude of
 C. Coletti et al. / Construction and Building Materials 124 (2016) 219–227 227

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