Materials Letters 223 (2018) 166–169

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Red mud and electroplating sludge as coloring agents of distinct glazes:

The influence of heat treatment
J. Carneiro ⇑, M.N. Capela, D.M. Tobaldi, R.M. Novais, M.P. Seabra, J.A. Labrincha
University of Aveiro, CICECO, Department of Materials and Ceramic Engineering, 3810-193 Aveiro, Portugal

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

Article history: The use of red mud (RM) and Cr/Ni electroplating sludge (ES), two hazardous industrial wastes, was stud-
Received 3 February 2018 ied as possible coloring agents for commercial glazes: transparent (TR), bright white (BR) and matte (MT).
Received in revised form 22 March 2018 The influence that a heat treatment produced on the color development/stability was analyzed by com-
Accepted 2 April 2018
paring, separately, RM and ES non-calcined and calcined at 1200 °C. RM and ES yielded glazes with red/
Available online 7 April 2018
brown and grey/green hues, respectively. The calcination enhanced the powders coloring strength. ES
(non-calcined and calcined) provides a fairly stable coloration when added to BR and MT, and RM
Keywords:
(non-calcined and calcined) when added to TP and BR, upon firing at 1100 ± 15 °C. So, depending on
Red mud
Electroplating sludge
the type of glaze, when using RM and ES as coloring agents their previous heat treatment can be avoid
Waste valorization leading to meaningful environmental and economic benefits.
Ceramic glazes Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction separately to commercial glazes, comparing the coloring strength/

How to deal with industrial wastes? This is a question that can
have various answers and have been addressed continuously. The
neutralization and storage in landfills is the most common. Nowa-
days, the overpopulation, resources exhaustion, cost associated
issues and an overall awareness for ecological problems, induced
a paradigm shift towards the valorization of residues attempting
to create a self-sustained economy with minimal ecologic impact
[1].
The concept is fully embodied when a residue from an industry
is used as a raw material in a distinct one, as it is the actual situa-
tion. Hazardous wastes are here explored as coloring agents of
ceramic products, aiming to reach the desirable inertness [2,3].
Red mud (RM) or bauxite residue is a waste generated in the pro-
duction of alumina through the Bayer process. Is highly alkaline
and might contain significant concentrations of heavy metals,
which limits its recycling alternatives [4]. Additionally, the huge
generation rate worldwide imposes extra difficulties in its manage-
ment [4]. The electroplating sludge (ES) is generated from the
wastewater treatment of Cr/Ni electroplating process. Is also a haz-
ardous waste due to the high concentration of heavy metals [5].
The possibility of using each waste, alone or combined with
other components, as coloring agent of ceramic glazes was already
attempted [5–7]. In this work we studied the addition of ES and RM
⇑ Corresponding author.
E-mail address: jcarneiro@ua.pt (J. Carneiro).
stability of the powders without calcination and after calcination at
1200 °C. The color development and stability of the glazes is the
guide for answering the question: how relevant is the need of a
thermal treatment. The answer to this question can have a signif-
icant impact in industrial applications, since the resources
(e.g. time, energy, money, space) needed to pre-treat these materi-
als prior to application must be compensated by quality/properties
gains of the final products.
2. Experimental details
2.1. Materials
RM and ES were kindly provided by Alcoa Spain and Grohe
Portugal – Componentes Sanitários, Lda., respectively. The glazes
were kindly provided by Esmalglass - Itaca group.
2.2. Powders preparation
The residues prior to their addition to powder glazes were dried
(RM) and disaggregated (RM and ES) in a mortar, without sieving.
The thermal treatment consisted in the calcination of RM and
ES at 1200 °C for 3 hs in an electric furnace under a static air flow.
A rate of 5 °C/min was used for heating and cooling steps. In the
case of RM an additional step was added: 30 min dwell at 100 °C
to dry the sample. The calcined powders were then ball milled
(proportion of 1:4:1, sample: balls: water) for 1 h at 300 rpm.

https://doi.org/10.1016/j.matlet.2018.04.013
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 J. Carneiro et al. / Materials Letters 223 (2018) 166–169 167

Afterwards the powders were dried in a ventilated oven at 80 °C,

disaggregated and sieved (at 63 mm).

2.3. Test in glaze bodies

3 wt% of powders (calcined and non-calcined) were homoge-

nized with three different commercial powdered glazes,
(transparent = TP, bright white = BR and matte = MT) via wet ball
mixing for 30 min. Afterwards the mixtures were dried at 80 °C,
disaggregated and sieved (at 63 mm). The obtained powders were
pressed into Ø2.5 cm pellets and fired in an electric furnace in air
at 1100 ± 15 °C (30 min of dwell time and 10 °C/min heating/cool-
ing rate).

2.4. Sample characterization

Particle size distribution was determined by laser diffraction on

a Coulter LS particle size analyzer (LS230FM). The color coordinates
of the pellets were measured by a portable colorimeter – Konica
Minolta Chroma Meter CR-400 – using DC illuminant and 10° stan-
dard observer (Y: 94.0, x: 0.3130, y: 0.3191) according to the Com-
mission Internationale de l’Eclairage (CIE). CIEL*a*b* data are
expressed as brightness L*, changing from 0 (black) to 100 (white),
a*(+red, green), and b*(+yellow, blue) [8]. Color stability was
obtained using the DE2000 formula [9]. DE < 1 means that differ-
ences in color cannot be perceived by the standard observer; 1 <
DE < 2 only perceived by an experienced observer; 2 < DE < 3.5
an inexperienced observer can detect differences; 3.5 < DE < 5
everyone can see the differences; DE > 5 two distinct colour can
be seen [9].
3. Results and discussion
3.1. Powders characterization
RM is constituted mainly by iron oxide (52.25 wt%) and alu-
minum oxide (14.63 wt%). The detailed chemical characterization
have been presented elsewhere [6]. ES chemical composition is
more complex, but nickel oxide (25.10 wt%) and chromium oxide
(17.40 wt%) are the major components, followed by copper oxide
(15.18 wt%), calcium oxide (12.60 wt%), phosphorus pentoxide
(9.85 wt%) and a variety of compounds in minor percentages [10].
In Table 1 are listed the procedures used in each sample before
and after addition to powdered glazes. The residues arrived in two
forms, RM as a water-based slurry (31 wt% moisture) and ES as
dried agglomerates. However, ES is commonly available as slurry,
containing over 60% humidity [5]. Fig. 1 shows the particle size dis-
tribution for non-calcined (after drying and manual disaggrega-
tion) and calcined ES and RM. Non-calcined RM is composed by
smaller particles (mean value of 1.4 mm), whose size distribution
is also narrower. In contrast non-calcined ES is composed by larger
agglomerates, ranging from sub-micron sizes to values around 500
mm (mean value of 112.7 mm). Calcined samples tend to show a size
distribution more similar and uniform, due to processing condi-
tions (see Section 2.2), with mean particle size values of 3.5
(RM_1200C) and 2.6 (RM_1200C). Anyway, in all cases the
Fig. 1. Particle size distribution for non-calcined (after drying (RM) and manual
disaggregation (RM and ES)) and calcined (RM and ES at 1200 °C) powders.
waste-contained glazes were sieved (at 63 mm) without any resi-
due remaining.
3.2. Color development in glazes
The wastes coloring potential was tested in three distinct com-
mercial glazes, all fired at 1100 ± 15 °C. The resulting samples are
presented in Fig. 2. The use of RM originates distinct colors,
depending on the type of glaze: light brown for TP, reddish brown
in MT, and a light beige in BR. The calcination of the waste
improved its tinting strength, as observed visually in Fig. 2. Values
of color coordinates (Table 2) confirm this improvement, particu-
larly by the decrease (9%) of lightness values (L*). The only excep-
tion was observed with BR, where no significant changes were
noticed upon use of pre-calcined waste. The color stability was
tested by changing the maximum firing temperature in ±15 °C,
and then calculating DE values. TP glazes containing RM and
RM_1200C improved the stability of the coloring agent, providing
values of DE < 2. For MT the DE values for RM and RM_1200C are
slightly higher than that limit and color variations are visually per-
ceptible. Color changes of BR are negligible, probably due to lower
tinting strength of RM in this glaze.
The use of ES originates grey/green hues on the glazes: darker
for TP and lighter in BR and MT. The tinting strength of this waste
is much higher than RM, due to its chemical composition (presence
of Cr and Ni). The pre-calcination of the waste enhances its tinting
strength in BR and MT glazes, with L* values decreasing from 68.01
to 61.38 for BR and 63.77 to 54.72 for MT. At the same time, color
changes in these glazes are not perceptible towards temperature
changes around 1100 °C (DE < 1). This is a consequence of the for-
mation of a relatively stable spinel structure on the calcined ES
[10]. The behavior on TP glaze is substantially different; the color
seems to be rather similar independently of the addition of ES or
ES_1200C; but at the same time color changes are perceptible in
the two cases when firing temperature changes (±15 °C).

Table 1
Sample identification and treatment applied before and after addition to powder glazes.

Sample Received as Before addition to glazes After addition to glazes

RM Water-based slurry Dried/Disaggregated Wet ball mixing/Dried/Disaggregated/
ES Dry powder Disaggregated Sieved (at 63 mm)
RM_1200C – Calcined/Milled/Disaggregated/Sieved (at 63 mm)
ES_1200C – Calcined/Milled/Disaggregated/Sieved (at 63 mm)
168 J. Carneiro et al. / Materials Letters 223 (2018) 166–169

Fig. 2. Glazes: (a) bright transparent (TP), (b) bright white (BR) and (c) matte (MT), containing 3 wt% of non-calcined RM, RM_1200C, non-calcined ES and ES_1200C.

Table 2
CIEL*a*b* colorimetric coordinates of glazes (Fig. 2) TP, BR and MT loaded with 3 wt% of non-calcined RM, RM_1200C, non-calcined ES and ES_1200C. Color changes (DE) were
determined against temperature variations at 1100 ± 15 °C.

1085C DE 1100C DE 1115C

L*/a*/b* L*/a*/b* L*/a*/b*
TP RM 69.71/0.95/29.23 1.54 67.82/0.54/29.77 1.64 65.82/0.18/29.37
RM_1200C 63.43/2.13/30.52 1.38 61.84/1.76/30.46 1.16 60.56/1.42/29.98
ES 45.60/ 1.06/9.07 4.60 42.08/ 0.37/4.95 1.39 41.15/ 0.18/3.66
ES_1200C 43.90/ 1.35/7.53 2.27 42.17/ 0.68/5.71 4.14 41.66/ 0.77/1.01
BR RM 89.37/ 0.76/11.57 0.32 88.91/ 0.85/11.51 0.46 88.24/ 0.80/11.27
RM_1200C 88.04/ 1.49/11.62 0.33 87.78/ 1.52/12.06 0.23 87.59/ 1.47/11.76
ES 68.86/ 4.11/10.15 0.68 68.01/ 4.20/10.17 0.82 67.00/ 4.22/9.99
ES_1200C 61.28/ 2.95/6.72 0.19 61.38/ 3.07/6.87 0.63 60.68/ 3.22/6.95
MT RM 58.97/6.56/15.56 2.20 61.16/5.78/16.20 2.68 63.61/4.59/17.33
RM_1200C 53.96/4.61/11.80 2.13 55.89/4.05/12.79 2.97 58.59/3.27/14.51
ES 64.39/ 4.78/9.23 0.78 63.77/ 5.23/8.94 0.55 63.89/ 5.74/9.16
ES_1200C 54.83/ 3.91/5.95 0.60 54.72/ 4.41/5.91 0.67 55.10/ 4.89/6.22

The values of DE are in bold to highlight its significance since it represents the value of color stability of the glazes with pigments upon firing at different temperature. These
values represent an easy way for the reader to identify the most stable, and there for the best performing pigments.
 J. Carneiro et al. / Materials Letters 223 (2018) 166–169
4. Conclusions
Calcined and non-calcined RM and ES, two industrial residues,
were tested as coloring agents of distinct commercial glazes: trans-
parent, bright white and matte. RM and RM_1200C yielded glazes
with red/brown hues while ES and ES_1200C assures grey/green
hues.
From the results some conclusions can be drawn:
- RM and RM_1200C proved to be stable when added to TP and
BR glazes and fired at 1100 ± 15 °C.
- ES and ES_1200C proved stable when added to BR and MT (at
1100 ± 15 °C).
- ES-based powders provided higher tinting strength than RM
and RM_1200C, as denoted by the decrease in lightness (L*).
- Calcined powders provided higher tinting strength than non-
calcined ones.
To notice that the addition of residues directly to glazes did
not originate defects, such as pinholes and cracks. The heat-
treatment gave some advantages, namely an increase in tinting
strength. Nevertheless, the color stability remained close to
non-calcined based systems. If necessary the gain in tinting
strength can be circumvented by increasing the percentage of
powder in the glaze. Thus the application of an heat-treatment,
when using these industrial residues, seems avoidable in some
applications, allowing significant environmental and economic
benefits.
169
Acknowledgment
This work was developed within the scope of the project
CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-
007679 (FCT Ref. UID/CTM/50011/2013), financed by national
funds through the FCT/MEC and when appropriate co-financed
by FEDER under the PT2020 Partnership Agreement.
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