minerals

Article
Composition and Technological Properties of Clays
for Structural Ceramics in Limpopo (South Africa)
Lawrence Diko-Makia * and Rofhiwa Ligege
Department of Mining and Environmental Geology, University of Venda, Private Bag X5050,
Thohoyandou 0950, Limpopo Province, South Africa; rofhione@gmail.com
* Correspondence: dikom73@gmail.com or diko.makia@univen.ac.za; Tel.: +27-015-960-8595




Received: 9 June 2020; Accepted: 2 July 2020; Published: 7 August 2020


Abstract: This study evaluated the potential of raw clays from the Mukondeni region for structural
ceramics and pottery based on traditional firing techniques. Physical properties were identified by
particle size distribution, consistency limits, and clay activity. Mineralogical and chemical properties
were investigated by X-ray diffraction (XRD) and X-ray fluorescence (XRF). Extruded clay bodies
were fired at 900 ◦ C. Technological characteristics were measured by weight loss (WL), bulk density
(BD), dry linear shrinkage (DLS), fired linear shrinkage (FLS), water absorption (WA), and flexural
strength (FS). The clays were low in <2 µm fractions (≤19%) and of medium to high plasticity with a
clayey silt texture. Smectite was the dominant clay mineral while quartz and feldspar were major non
clay minerals. The most abundant oxides were SiO2 (63.57–68.73%), Al2 O3 (13.9–15.61%), and Fe2 O3
(4.86–6.18%), whereas K2 O, CaO, MgO, Na2 O, TiO2 , and P2 O5 were depleted. Characterization based
on the clay workability chart, Winkler’s diagram, and compositional ternary diagrams revealed
acceptable extrusion properties and suitability for structural ceramics and earthenware. The clays
showed acceptable WL, BD, LS, and WA, but unsatisfactory FS (≤1.08 MPa). Low mechanical strength
was attributed to presence of smectites and inert nature of feldspar at 900 ◦ C. Beneficiation through
mixing with carbonate-rich raw materials is recommended.

Keywords: structural ceramics; pottery; low firing temperature; fluxing agents; South Africa

1. Introduction
Natural clay (comprising clay minerals, silica, feldspar, and iron oxide) is the main raw material
in the manufacture of traditional ceramics [1–4]. According to Teixera et al. [5] and Serra et al. [2],
the exploitation of natural clays for various end-products, such as structural ceramics (bricks, roofing
tile and blocks), and earthenware (household ceramics), is based on their availability, accessibility,
and comparatively low to intermediate firing temperatures. The above attributes have been advanced
as the base for socioeconomic development and sustainability of small-scale and artisanal clay mining
sectors in developing economies [6]. The emphasis here is placed on lowering the cost of production,
especially with regard to energy consumption, and the assertion that traditional kilns seldom fire at
high temperatures above 900 ◦ C [7–9].
Nonetheless, final product quality has been correlated with mechanical strength and water
absorption capacity and shrinkage limits (volume and linear), which, in turn, depends on the sintering
temperature [3,9–19]. Sintering temperature is considered one of the most important processing
variables that influences final product costs [15]. During sintering, the clay body undergoes chemical
and structural modifications that deeply transform the inherent characteristics of raw ceramic material.
This process is accompanied by differential phase transformation and neo-mineral formation with
resultant effect on technological properties [4,6,17–26]. Therefore, for optimal exploitation of natural
clays, the sintering behavior needs to be fully appraised.

Minerals 2020, 10, 700 ; doi:10.3390/min10080700 www.mdpi.com/journal/minerals

Minerals 2020, 10, x FOR PEER REVIEW 2 of 11

mineral formation
Minerals 2020, 10, 700 with resultant effect on technological properties [4,6,17–26]. Therefore, for optimal 2 of 11
exploitation of natural clays, the sintering behavior needs to be fully appraised.
In this study, we investigated the technological properties of two natural clays from South Africa
In this study, we investigated
(Mukondeni–Limpopo Province) for the potential
technological properties
exploitation of of two natural
structural clays from
ceramics South Africa
and earthenware
(Mukondeni–Limpopo Province) for potential exploitation of structural ceramics
by artisanal clay miners. The temperature of 900 °C was selected as the suitable condition for the and earthenware by
artisanal clay ◦
beginning ofminers.
liquid The
phase temperature
sintering,ofincreased
900 C wasmaterial
selected densification,
as the suitable condition for the beginning
and mechanical strength
development in clay body (with exceptions at lower temperatures due to fluxing effect) [4,10,11]. in
of liquid phase sintering, increased material densification, and mechanical strength development It
clay
is body (with
anticipated exceptions
that findings at lower
from thistemperatures due to afluxing
study will provide basis to effect) [4,10,11].
advise on rawItmaterial
is anticipated that
suitability
findings
and from thiswhere
beneficiation study applicable.
will provide a basis to advise on raw material suitability and beneficiation
where applicable.
2. Materials and Methods
2. Materials and Methods
Mukondeni is situated in Limpopo Province of South Africa, approximately 130 km from the
Mukondeni
provincial capital is situated in Limpopo
(Polokwane). The clay mineProvince of South
and pottery Africa, approximately
production is situated along 130thekm from
main the
road,
provincial capital (Polokwane). The clay mine and pottery production is
about 300 m away from the settlement at coordinates 23°15′04″ N and 30°6′80″ E (Figure 1). Details situated along the main
road,
of its about
physical300geography
m away from and the settlementhave
stratigraphy at coordinates
been described23◦ 150elsewhere
04” N and[27]. 30◦ 6Geologically,
0 80” E (Figure 1).
the
Detailssite
study of its
liesphysical
within the geography
Southernand stratigraphy
Marginal have been
Zone (SMZ) of thedescribed
Limpopoelsewhere [27]. Geologically,
Belt. The approximately 60-
the wide
k- study ENE-WSW
site lies within the Southern
trending marginalof
SMZ consists Zone (SMZ) of
granulite the Limpopo
facies supracrustalBelt. gneisses
The approximately
of mafic,
60-k- wide and
ultramafic, ENE-WSW trending
metapelitic SMZ consists
composition, of granulite
intermixed facies supracrustal
with volumetrically dominantgneisses of mafic,
tonalitic grey
ultramafic, and metapelitic composition, intermixed with volumetrically dominant
gneiss. The metapelitic granulites consist of quartz, plagioclase, hypersthene, garnet, biotite tonalitic grey gneiss.
and
The metapelitic granulites consist of quartz, plagioclase, hypersthene, garnet,
cordierite, with less common perthitic K-feldspar, spinel, sillimanite, and late kyanite [27]. The biotite and cordierite,
with less common
formations perthitic
are largely K-feldspar,
described spinel, sillimanite,
as supracrustal and
gneisses that lateundergone
have kyanite [27]. The formations
a considerable are
degree
largely described as supracrustal gneisses that have undergone a considerable
of anatexis. Mineralogically, the grey gneisses comprise quartz, plagioclase, hornblende, and biotite degree of anatexis.
Mineralogically, the grey gneisses comprise quartz, plagioclase, hornblende, and biotite [27].
[27].

Figure
Figure1.1.Location
Locationofofstudy
studyarea;
area;inset,
inset,situation
situationofofLimpopo
LimpopoininSouth
SouthAfrica.
Africa.(Modified
(Modifiedfrom
from[27]).
[27]).

Composite samples of clay labelled MK 1 and MK 2 from the main excavation pits in the study
area were
were analyzed
analyzedforforparticle
particlesize
sizedistribution
distribution (PSD),
(PSD), Atterberg
Atterberg limits
limits (liquid
(liquid limit,
limit, plastic
plastic limit,limit,
and
and plasticity
plasticity index);
index); clay activity
clay activity (CA); mineralogy;
(CA); mineralogy; chemical chemical composition;
composition; and technological
and technological properties,
properties,
namely weightnamely weightbulk
loss (WL), lossdensity
(WL), bulk
(BD), density (BD), water
water absorption absorption
(WA), (WA), linear
linear shrinkage (DLSshrinkage
and FLS),
(DLS and FLS),
and flexural and flexural
strength (FS). strength (FS).
Particle size analysis by laser diffraction was performed with a Saturn DigiSizer 5200 (Council
for Geoscience, Pretoria, South Africa). The samples were dispersed in a water medium to form a
Minerals 2020, 10, 700 3 of 11

suspension of 0.00139 wt% solids and drawn into the size analyzer at a flow rate of 12.0 L/min and
circulation time of 120 s. An in-house standard was used to validate particle dispersion. Atterberg
limits were performed on the <63 µm fraction samples using the Casagrande apparatus [28]. For liquid
limit (LL) determination, 40 g of previously prepared fine mortar was spread in a cup (maximum
thickness = 1 cm) and divided by a standard axial groove. The LL was expressed as a percentage by
weight of the mortar after drying in an oven at 105 ◦ C, at which the groove closed over a length of 1
cm under the influence of 25 blows. The blows were produced by allowing the cup to drop from a
height of 1 cm onto a hard surface. In order to determine the limit of plasticity (PL), 10 g of the fine
mortar was used. Using the palm, the mortar was rolled on a flat surface until the tread of fine mortar
broke into sections of between 1 cm and 2 cm long, after being reduced to a diameter of 3 mm. The PL
was expressed as a percentage by weight after oven drying at 105 ◦ C. The plasticity index (PI) was
obtained from the arithmetic difference between LL and PL, whereas CA was calculated from the
following expression:
CA = PI/clay wt% (1)

X-ray diffractometry was used for mineral identification. Prior to analysis, the samples were
air-dried and gently ground with the aid of mortar and pestle into powdery form. Bulk and clay
fractions obtained through pipette method) were mounted as oriented aggregates onto glass slides
in a BRUKER D8 Advance diffractometer (Council for Geoscience, Pretoria, South Africa) equipped
with a LYNXEYE detector and a Ni-filter. Powder mounts were scanned from 2◦ 2θ CuK to 70◦
2θ CuK (λ = 1.54060) radiation at a speed of 0.05◦ 2θ steps size per second and generator settings
of 40 kV and 40 mA. An overnight glycolation (<24 h) test was performed on the clay fraction to
distinguish smectites from vermiculite [6]. Phase identification was based on BRUKER DIFFRAC
Plus-EVA evaluation program (Council for Geoscience, Pretoria, South Africa). Phase concentrations
were determined as semi quantitative estimates (with accuracy ±5%) using the Reference Intensity
Ratio (RIR) method and relative peak heights/areas proportions [29].
The chemical composition of the bulk samples was determined by X–ray fluorescence spectrometry
using a PANalytical Axios WDXRF spectrometer (Council for Geoscience, Pretoria, South Africa)
equipped with a 4-kW Rh tube in accordance with the method described by the authors of [26]. Milled
samples with grain size of <75 µm were heated at 1000 ◦ C for 3 h to oxidize Fe2+ and S and to determine
the loss on ignition (LOI). One gram of heated sample and 9 g of flux consisting of 34% LiBO2 and 66%
Li2 B4 O7 were fused at 1050 ◦ C to form stable glass disks. Each sample was analyzed three times, and
the mean was recorded. For quality control, an in-house amphibolite reference material (12/76) was
used to ensure accuracy of the data generated.
Technological tests were carried out at the Council for Mineral Technology (MINTEK, Johannesburg,
South Africa), as part of the ceramic evaluation process. Clay samples were dried at 110 ◦ C for 24 h
and ground to a fine powder. The materials were mixed in a pan mixer with minimum quantity of
water, suitable for extrusion in the Germatec Vacuum Extruder (Council for Geoscience, Pretoria, South
Africa). Test briquettes were extruded into a column with a cross section measuring 47 mm × 25 mm ×
150 mm. The briquettes were air-dried for five days, followed by drying in a ventilated oven at 110 ◦ C
for 24 h until two successive weighings at intervals of 2 h showed an increment of loss not greater than
0.2% of the previously determined weight of the specimen. After drying, the briquettes were cooled in
a drying room maintained at a temperature of 24 ± 8 ◦ C, with a relative humidity between 30% and
70%. The specimens were stored free from drafts, unstacked, with separate placement, for a period of
at least 4 h until the surface temperature was within 2.8 ◦ C of the drying room temperature. Specimens
which were noticeably warm to the touch were not used for any tests [6,16]. The specimens were stored
in the drying room at the required temperature and humidity until they were tested. The briquettes
were fired at 900 ◦ C using an electrically powered laboratory furnace at a heating rate of 80 ◦ C/h and
cooling time of 2 h. The fired specimens were tested for WL, BD, WA, LS, and FS. A total of five tests
were performed per mechanical property and the mean result was reported.
Minerals 2020, 10, 700 4 of 11

Weight loss (WL) was calculated between 105 ◦ C (Md) and peak firing temperatures (Mf) using
the following formula:
Md − Mf
 
WL (%) = × 100 (2)
Md
The bulk density (BD) of a specimen was obtained as the ratio of the fired specimen mass (Mf) to
the measured volume (V) of the specimen:
  Mf
BD g/cm3 = (3)
V
Water absorption (WA) was measured by weighing the dried briquette (M1) and the wet (M2)
after immersion in water for 24 h:
M2 − M1
WA (%) = × 100 (4)
M1
Dry and fired linear shrinkage (DLS and FLS) were determined across indentations made 100
mm apart by a digital Vernier caliper on the test briquettes. The dried/fired specimens were measured
at the indentations to determine its longitudinal shrinkage to the nearest millimeter. The measured
lengths were subtracted from the indentations, which were measured 100 mm, to obtain the shrinkage
in millimeters [6,16].
The flexural strength (FS) of briquettes was evaluated using the three-point bending test method [6]
using a Kingtest Auto 200 Press machine (Council for Geoscience, Pretoria, South Africa) at a loading
rate of 20 mm/min. The modulus of rupture values of each specimen was calculated and reported to
the nearest 0.01 MPa as follows:
3 FL
FS(MPa) = (5)
2bd2
where F = maximum load, L = distance between the supports (mm), b = net width of the specimen at
the plane of failure (mm), and d = depth of the specimen at the plane of failure (mm).

3. Results and Discussions

3.1. Physical Properties

The PSD is important for determining suitability for various ceramic applications. PSD could be
indicative of the drying and firing behavior of the raw material, as well as the mechanical strength
of the fired product [11,19,22] The results for PSD are summarized on Table 1. Mk 1 and Mk 2 were
low in clay fraction (18% and 19%), but high in 20–2 µm fraction (48% and 46%) respectively. The raw
materials were plotted on Winkler’s diagram (Figure 2) in order to evaluate their suitable for different
ceramic products [11,16,19]. Based on the PSD, MK 1 and Mk 2 were suitable raw materials for
common bricks. This observation is consistent with grain size classification of raw ceramic materials
from Cameroon [6,14,22], Morocco [16,30], and Turkey [4,31]. The predominance of silt-size fractions
(comprising quartz and feldspar grains) suggest that PSD may contribute positively toward clay body
skeleton, glass formation, and lowering of vitrification temperature [4,14].

Table 1. Physical properties of raw clay materials.

PSD (%) Atterberg Limits (mass%)

Sample
>20 µm 20–2 µm <2 µm LL PL PI CA
MK1 33 48 19 50.0 20.0 30.0 1.57
MK2 36 46 18 41.8 16.0 25.8 1.43
Table 1. Their consistency limits (PL, LL, and PI) were plotted on the Holtz and Kovacs diagram [33]
(Figure 3a) and the clay workability chart [34] (Figure 3b). The raw materials were of medium to high
plasticity (PI = 30 and 25.8 for Mk 1 and Mk 2, respectively), with montmorillonite (smectite) as the
major
Mineralsclay
2020, mineral.
10, 700 Mk 1 and Mk 2 plots were within the acceptable extrusion field, with MK 1
5 of 11
displaying a more sticky consistency than Mk 2. This observation is consistent with their PI values.

Minerals 2020, 10, x FOR PEER REVIEW 5 of 11

Table 1. Their consistency limits (PL, LL, and PI) were plotted on the Holtz and Kovacs diagram [33]
(Figure 3a) and the clay workability chart [34] (Figure 3b). The raw materials were of medium to high
plasticity (PI = 30 and 25.8 for Mk 1 and Mk 2, respectively), with montmorillonite (smectite) as the
major clay mineral. Mk 1 and Mk 2 plots were within the acceptable extrusion field, with MK 1
displaying a more sticky consistency than Mk 2. This observation is consistent with their PI values.

Figure
Figure 2. Grain
Grain size
size classification
classification of raw clay materials according to Winkler’s diagram [32]. Fields
Fields
indicate:
indicate: (A) Common bricks, (B) vertically perforated bricks, (C) roofing tiles and masonry bricks,
Common bricks, (B) vertically perforated bricks, (C) roofing tiles and masonry bricks, and
and (D) hollow
(D) hollow products.
products.

Plasticity
Based on PL is anandimportant
PI, the raw parameter
materials which
wereassists
suitablein determining
for pottery. However, the clay workability,
mixing them drying
with
behavior,
low plasticand ceramic
clays enables application
exploitation [1,6,13,14,19,22,32].
for bricks. The CA It is also
values an
of Mkindicator
1 and of
Mk the
2
Figure 2. Grain size classification of raw clay materials according to Winkler’s diagram [32]. Fields
major
(1.57 clay
and mineral
1.43) were
phase in theindicate:
significantly raw
lower material.
(A)than CA
Common TheforAtterberg
pure
bricks, limits
smectite
(B) vertically andbricks,
(7.2),
perforated clay activity
but close to of
(C) roofing the MK
tiles 1masonry
values
and andforMK 2 aresmectites
calcic
bricks, presented on
(1.5)
Table 1. Their
proposed and consistency
(D)
by Temga hollowet al. limits
products.
[22]. The (PL,CALL,values
and PI)werewerenonetheless
plotted on the Holtz and
comparable toKovacs diagram raw
other smectitic [33]
(Figure 3a)
materials andCameroon,
from the clay workability
which are chart [34]exploited
currently (Figure 3b). for The raw materials
structural ceramics were of medium to
[19].
Based on PL and PI, the raw materials were suitable for pottery. However, mixing them with
high plasticity
low plastic(PI = 30
clays and exploitation
enables 25.8 for Mk for 1bricks.
and The
MkCA 2, respectively),
values of Mk 1 and with
Mk 2montmorillonite
(1.57 and 1.43) were (smectite) as
the major clay mineral.
significantly MkCA
lower than 1 and Mksmectite
for pure 2 plots(7.2),
were butwithin
close tothe acceptable
the values extrusion
for calcic smectites field,
(1.5) with MK 1
proposed
displaying a more by Temga
stickyetconsistency
al. [22]. The CAthanvalues
Mkwere nonetheless
2. This comparable
observation to other smectitic
is consistent raw PI values.
with their
materials from Cameroon, which are currently exploited for structural ceramics [19].

Figure 3.
3. Consistency
Figure Figure
Consistency limits
3. Consistency
limits ofofraw
limits
of raw clay
rawclay materials:
clay materials:
materials: (a)According
(a)(a) According
According toto
to Holtz Holtz
and and
Kovacs
Holtz and Kovacs
diagram
Kovacs diagram
[33];
diagram [33];
[33]; (b)
(b) clay(b) clay workability
workability chart
chart [34].
[34].
clay workability chart [34].

Based on PL and PI, the raw materials were suitable for pottery. However, mixing them with low
plastic clays enables exploitation for bricks. The CA values of Mk 1 and Mk 2 (1.57 and 1.43) were
significantly lower than CA for pure smectite (7.2), but close to the values for calcic smectites (1.5)
proposed by Temga et al. [22]. The CA values were nonetheless comparable to other smectitic raw
materials from Cameroon, which are currently exploited for structural ceramics [19].
Minerals 2020, 10, x FOR PEER REVIEW 6 of 11

3.2. Mineralogical Composition

XRD patterns of bulk samples from ceramic raw materials are given in Figure 4. Table 2 presents
Minerals
a summary2020, 10,
of700
theresults of the mineral assemblages of the samples and the relative abundance 6 of 11
of
the respective minerals identified. The characteristic mineral assemblage comprised quartz, kaolinite,
smectite,
3.2. k-feldspar,
Mineralogical plagioclase, talc, and amphibole. Smectite, identified at 15 Å, was the dominant
Composition
clay mineral in both samples, accounting for 32% and 12% in MK 1 and Mk 2, respectively. Smectite
was XRD patterns of
distinguished bulkvermiculite
from samples from by ceramic
a notableraw materials
shift are given
in d-spacing in Figure
(17Å) 4. Table 2 presents
after glycolation. Quartz
a(31%
summary of the results of the mineral assemblages of the samples and
and 52%) and feldspar (28% and 24%) were the major nonclay minerals occurring the relative abundance
in Mk 1 and of
the respective minerals
2, respectively. The mostidentified.
prominent Thepeaks
characteristic mineraltoassemblage
were ascribed comprised
quartz at 3.34 Å due to quartz, kaolinite,
abundant free
smectite, k-feldspar, plagioclase, talc, and amphibole. Smectite, identified at 15 Å, was the
silica [6,35], while the associated minor clay mineral phases (kaolinite at 7.17 Å and talc at 9.31 Å) dominant
clay mineralcontributed
collectively in both samples,
6% and accounting
5% to MKfor 32%Mk
1 and and2,12% in MK 1 and Mk 2, respectively. Smectite
respectively.
was distinguished from vermiculite by a notable shift in d-spacing (17Å) after glycolation. Quartz
(31% and 52%) and feldspar (28%
Table 2. and 24%)composition
Mineralogical were the major
of rawnon clay
clay minerals
materials (%).occurring in Mk 1 and
2, respectively. The most prominent peaks were ascribed to quartz at 3.34 Å due to abundant free
Sample K-feldspar Plagioclase Quartz Talc Smectite Amphibole Kaolinite
silica [6,35], while the associated minor clay mineral phases (kaolinite at 7.17 Å and talc at 9.31 Å)
MK1 2 26 31 2 32 3 4
collectively
MK2
contributed
3
6% and 5%21
to MK 1 and52
Mk 2,3respectively.
12 7 2

Figure 4.
Figure 4. XRD patterns of raw clay materials.
materials.

Table 2. Mineralogical composition of raw clay materials (%).

The mineralogical constituents of ceramic pastes ranged from clay minerals as plastic and binder
components
Sample to siliceous sandPlagioclase
K-feldspar as skeletal components
Quartz and finally
Talc feldspars
Smectite and/or fineKaolinite
Amphibole carbonates as
fluxingMK1
agents. During 2
the firing26
process, 31
the main2 constituents
32
of raw clay
3
underwent
4
phase
transformations
MK2 through
3 decomposition
21 to produce
52 neo-mineralization,
3 12 like metakaolinite
7 and
2 spinel
at about 900 °C [11], as well as mullite, cristobalite, and wollastonite at higher temperatures [36,37].
The presence of smectite in the studied raw materials was expected to increase plasticity and impact
The mineralogical constituents of ceramic pastes ranged from clay minerals as plastic and binder
the drying and swelling behavior and fired strength of the finished product. The nonclay minerals,
components to siliceous sand as skeletal components and finally feldspars and/or fine carbonates
such as quartz and feldspar, enhance glass formation and densification at lower temperatures [22].
as fluxing agents. During the firing process, the main constituents of raw clay underwent phase
In order to determine the suitability of ceramic raw materials on the basis of mineralogical
transformations through decomposition to produce neo-mineralization, like metakaolinite and spinel
composition, the studied clays were plotted on the total clay–carbonate–quartz + feldspar ternary
at about 900 ◦ C [11], as well as mullite, cristobalite, and wollastonite at higher temperatures [36,37].
diagram (Figure 5a) proposed by Strazzera et al. [38] and applied to ceramic raw materials from
The presence of smectite in the studied raw materials was expected to increase plasticity and impact
southern Sardinia (Italy). The mineralogical compositions of Mk 1 and Mk 2 were equally compared
the drying and swelling behavior and fired strength of the finished product. The non clay minerals,
against three major deposits of brick clays from Veneto (Wurman deposit,), Central Piedmont
such as quartz and feldspar, enhance glass formation and densification at lower temperatures [22].
(Mindelian deposit), and Western Emilia-Ramagna (Rissian deposit) in Italy [39]. The latter three
In order to determine the suitability of ceramic raw materials on the basis of mineralogical composition,
the studied clays were plotted on the total clay–carbonate–quartz + feldspar ternary diagram (Figure 5a)
proposed by Strazzera et al. [38] and applied to ceramic raw materials from southern Sardinia (Italy).
Minerals 2020, 10, 700 7 of 11

The mineralogical compositions of Mk 1 and Mk 2 were equally compared against three major deposits
Minerals
of brick2020,
clays10,from
x FORVeneto
PEER REVIEW
(Wurman deposit,), Central Piedmont (Mindelian deposit), and Western 7 of 11
Emilia-Ramagna (Rissian deposit) in Italy [39]. The latter three deposits are eluvial clays (fluvio-glacial
deposits are
deposits) eluvial
enriched in clays
quartz(fluvio-glacial deposits)
and smectite but enriched
deficient in quartz
in dolomite and smectite
and calcite [39], like but deficient in
the Mukondeni
clays. Based on the comparison, Mk 1 was suitable for structural clay products, while suitable
dolomite and calcite [39], like the Mukondeni clays. Based on the comparison, Mk 1 was for
Mk 2 plots
structural
were clay(Figure
outliers products,
5a). while Mk 2 plots were
This observation outliers with
is consistent (Figure
clay5a). This observation
consistency and PSD is properties
consistent
with clay consistency
described earlier. and PSD properties described earlier.

Figure 5.5. Mineralogical

Figure Mineralogicaland
and geochemical
geochemical classification
classification of raw
of raw clay materials:
clay materials: (a)carbonate,
(a) Clay, Clay, carbonate,
quartz,
quartz, and feldspar ternary diagram [38]; (b) major oxide
and feldspar ternary diagram [38]; (b) major oxide content [40].content [40].

3.3. Chemical Composition

3.3. Chemical Composition
The
The chemical
chemical compositions
compositions ofof the
the bulk
bulk samples
samples are
are given
given in
in Table
Table 3.
3. Their
Their suitability
suitability as
as raw
raw
ceramic materials were assessed by comparing with the chemical compositions of Italian clays widely
ceramic materials were assessed by comparing with the chemical compositions of Italian clays widely
exploited
exploited for
for structural
structural ceramics
ceramics [39,40]. The most
[39,40]. The most abundant
abundant oxides
oxides in
in Mk
Mk 11 and
and MkMk 22 were
were SiO
SiO22
(63.57% and 68.73%), Al2O3 (15.61% and 13.9%), and Fe2O3 (6.18% and 4.86%), respectively, whereas
K2O, CaO, MgO, Na2O, TiO2, and P2O5 were present only in small quantities. The LOI values were
5.08 for Mk 1 and 3.29 for Mk 2. In general fluxing agents, such as alkali oxides (Na2O and K2O) and
alkaline earth oxides (CaO and MgO) are low (<3%), suggesting that it is unlikely that the
densification of these clays is at 900 °C. The presence of Fe2O3 and minor TiO2 corroborates
Minerals 2020, 10, 700 8 of 11

(63.57% and 68.73%), Al2 O3 (15.61% and 13.9%), and Fe2 O3 (6.18% and 4.86%), respectively, whereas
K2 O, CaO, MgO, Na2 O, TiO2 , and P2 O5 were present only in small quantities. The LOI values were 5.08
for Mk 1 and 3.29 for Mk 2. In general fluxing agents, such as alkali oxides (Na2 O and K2 O) and alkaline
earth oxides (CaO and MgO) are low (<3%), suggesting that it is unlikely that the densification of these
clays is at 900 ◦ C. The presence of Fe2 O3 and minor TiO2 corroborates classification of the studied
clays as reddish yellow ceramics [41]. Loss on ignition values were related to the dehydroxylation of
the clay minerals, organic matter oxidation, and decomposition of hydroxides [4,22]. The SiO2 /Al2 O3
ratios for Mk 1 (4.0) and Mk 2 (4.9) were significantly higher than the value generally found in pure
kaolinite (SiO2 /Al2 O3 : 1.18) and montmorillonite (SiO2 /Al2 O3 : 2.36), but comparable to those reported
in brick clays from Italy by Dondi et al. [39].

Table 3. Chemical composition (%) of Mokundeni clays versus brick clays from Italy.

Sample SiO2 Al2 O3 Fe2 O3 CaO K2 O MgO Na2 O TiO2 MnO P2 O5 LOI Total Si/Al
Mk 1 63.57 15.61 6.18 1.83 0.99 2.83 2.65 0.61 0.07 0.04 5.08 99.59 4.0
Mk 2 68.73 13.9 4.86 1.84 0.84 2.44 2.94 0.53 0.05 0.06 3.29 99.61 4.9
A (n = 5) 60.3 18.5 6.7 0.8 3.9 2.0 0.6 0.9 0.1 0.2 6.5 99.0 3.3
B (n = 5) 67.8 15.1 5.6 1.0 1.9 1.7 0.8 0.7 0.1 0.1 5.4 100.2 4.5
C (n = 3) 67.8 15.3 5.6 1.0 1.9 1.7 1.0 0.8 0.2 0.1 5.2 100.6 4.4
Italian brick clays: A (Veneto), B (Central Piedmont), and C (Western Emilia-Ramagna).

Further comparison with major oxide content used to classify ceramic raw materials from Sardinia
(Figure 5b) by Fiori et al. [40] showed that Mk 1 and Mk 2 are very close outliers for earthenware and
red clay body production. A 10% to 15% increase in Al2 O3, alkali and alkali earth oxide contents would
render the studied clays suitable for red bodies and earthenware (Figure 5b).

3.4. Technological Properties

A summary of the drying behavior (DLS) and firing characteristics (WL, BD, WA, FLS, and FS) of
the studied clays after heat treatment at 900 ◦ C is presented on Table 4. The mean values of test results
(n = 5) for Mk 1 and Mk 2, respectively, were: DLS (5.67% and 5.0%), WL (11.37% and 8.65%), Bd
(1.72 g/cm3 and 1.77 g/cm3 ), WA (12.58% and 11.70%), LS (7.0% and 5.72%), and FS (1.08 and 0.87 MPa).

Table 4. Firing characteristics of raw clay materials.

Sample Characteristics T1 T2 T3 T4 T5 Mean

WL (%) 16.06 12.40 8.34 8.33 11.71 11.37
BD (g/cm3 ) 1.72 1.71 1.72 1.72 1.72 1.72
WA (%) 12.75 12.73 11.99 12.59 12.82 12.58
MK 1
FLS (%) 7.50 7.74 5.79 7.08 6.90 7.00
FS (MPa) 1 1.09 1.11 1.1 1.11 1.08
DLS (%) 5.02 5.84 5.33 6.5 5.67 5.67
WL (%) 10.87 8.36 9.07 7.94 7.03 8.65
BD (g/cm3 ) 1.78 1.77 1.78 1.77 1.78 1.77
WA (%) 11.55 11.88 11.54 11.51 12.02 11.70
MK 2
LS (%) 6.00 5.65 5.59 5.33 6.01 5.72
FS (MPa) 0.77 0.94 0.87 0.88 0.89 0.87
DLS (%) 4.93 4.85 4.76 4.83 5.63 5.00
Weight loss (WL), Bulk density (BD), Water absorption (WA), Fired linear shrinkage (FLS), Flexural strength (FS),
Dry linear shrinkage (DLS), and T (number of tests).

In order to appraise the technological performance of Mk 1 and Mk 2 after firing, we compared

them against ceramic specifications based on WL [5], LS [4], FS, and WA [5,42]. According to
Yongue-Fouateu et al. [6], values for LS (2–10%), WA (8.03–24.27%), and FS (1.2–11.8 MPa) have
frequently been used as quality and process control parameters in the development and manufacturing
Minerals 2020, 10, 700 9 of 11

stages to produce structural ceramics. The studied clays registered WL below the 14% threshold [5],
suggesting low organic matter content. LS for Mk 1 (7%) and Mk 2 (5.72%) fell within the range
suggested by Yongue-Fouateu et al. [6], but Mk 2 was lower than the 7–10% range prescribed by
Manukaji [36] and Semiz [4]. Ceramic specifications according to FS and WA are presented on Table 5.
The WA of the studied clays were suitable for massive bricks, ceramic blocks, and even roof tiles,
whereas FS were significantly lower than values reported for Italian brick clays by Dondi et al. [43].
Based on FS, Mk 1 and Mk 2 were unsuitable for any ceramic piece at the current firing temperature.

Table 5. Ceramic specifications based on flexural strength and water absorption [5,42,43].

Flexural Strength (MPa) Water Absorption (%)

Ceramic Piece Indicated A B C Mk 1 Mk 2 Indicated Mk 1 Mk 2
Values (n = 5) (n, =; 5) (n = 3) (1.08) (0.87) Values (12.58) (11.70)
√ √
Not classified <1.96 – – – –
√ √
Massive bricks ≥1.96 6±2 6±2 8±2 – – ≤25
√ √
Ceramic blocks ≥5.39 6±2 6±2 8±2 – – ≤25
√ √
Roof tiles ≥6.37 12 ± 2 14 ± 2 – – – ≤20
Italian brick clays: A (Veneto), B (Central Piedmont), and C (Western Emilia-Ramagna).

4. Conclusions
This study investigated the suitability of two raw clay materials from the Mukondeni region
(South Africa) for structural ceramics and earthenware, after firing at 900 ◦ C. The following conclusions
can be deduced from the physical, mineralogical, chemical, and technological characteristics of the raw
materials:
• The predominance of smectite contributes to the high DLS and FLS observed. This also
resulted in the development of cracks on ceramic bodies after dry processing and the increase in
apparent porosity.
• Mechanically, the raw clays showed acceptable WL (11.37% and 8.65%), BD (1.72 and 1.77 g/cm3 ),
and WA (12.58% and 11.70%), but unsatisfactory FS (≤1.08 MPa). Low mechanical strength was
attributed to the fact that feldspars (though in high percentage) remained substantially inert at
900 ◦ C.
• Beneficiation through mixing with carbonate-rich raw materials may enhance fluxing effects
and improve mechanical strength of clay bodies at 900 ◦ C. Mixture with low plasticity clays is
also recommended.

Author Contributions: Conceptualization, L.D.-M.; methodology, L.D.-M.; formal analysis, L.D.-M. and R.L.;
investigation, R.L.; writing—original draft preparation, R.L.; writing—review and editing, L.D.-M.; supervision,
L.D.-M.; funding acquisition, L.D.-M. All authors have read and agree to the published version of the manuscript.
Funding: Incentive Funding for Rated Researchers by National Research Foundation (NRF), South Africa
(UID109316) is acknowledge.
Conflicts of Interest: The authors declare no conflict of interest.

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