materials

Article
A Study on Tannery Sludge as a Raw Material for
Cement Mortar
Jurgita Malaiškienė *, Olga Kizinievič and Viktor Kizinievič
Laboratory of Composite Materials, Institute of Building Materials, Vilnius Gediminas Technical University,
Linkmenu˛ St. 28, LT 08217 Vilnius, Lithuania; olga.kizinievic@vgtu.lt (O.K.); viktor.kizinievic@vgtu.lt (V.K.)
* Correspondence: jurgita.malaiskiene@vgtu.lt; Tel.: +370-5-2512329




Received: 12 April 2019; Accepted: 8 May 2019; Published: 13 May 2019


Abstract: The paper analyses the properties (chemical and mineral composition, microstructure,
density, etc.) of recycled tannery sludge (TS) and the possibilities for using it in cement mortar
mixture. Mortar specimens containing 3–12% of tannery sludge by weight of cement and 3–9% of
tannery sludge by weight of sand were tested. Flowability, density, ultrasonic pulse velocity (UPV),
flexural and compressive strength, water absorption and sorptivity of the mortar were analysed.
X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis of tannery sludge and
mortar are presented. The tests revealed that replacement of 6% of cement with tannery sludge in
the mix increased flexural and compressive strength and UPV values, whereas water absorption
decreased. SEM and XRD analysis revealed that specimens with tannery sludge contained lower
amounts of ettringite and higher amounts of portlandite; the obtained structure was denser and
contained more calcium hydrosilicates (C-S-H). Chromium leaching values in cement mortars were
found not to exceed the limit values set forth in Directive 2003/33/EC.

Keywords: tannery sludge; waste; recycling; cement mortars; compressive strength; leaching

1. Introduction
Rational use of industrial waste is a major challenge in implementing the provisions of the
Circular Economy Documentation and realising the concept of Cleaner Production when it comes to
increasing production efficiency and reducing the risk to humans and the environment. Therefore,
rational recycling of industrial waste is becoming a major challenge. As part of waste recycling
and recovery programs, some natural materials will have to be replaced with waste in the future,
including in the construction sector.
Volumes of tannery sludge (TS) are increasing all over the world. The sludge from leather
processing consists of organic and inorganic substances. The chemical composition of inorganic
substances commonly presented in tannery sludge includes the following elements and their chemical
compounds: nitrogen, ammonia, sulphides, calcium compounds, chromium (III) salts (especially
sulphates) as well as high chromium content [1–7]. The most toxic chemical element formed during
leather tanning is chromium (VI) which is oxidized from chromium (III). Chromium (VI) is carcinogenic,
mutagenic and can cause allergy. According to the current legislation [8,9], the permissible level of
chromium in tannery sludge is 3 mg/kg.
Scientists [10–13] claim that leather processing waste consists of 23% organic carbon, 9% calcium,
9% chromium and chlorides, sulphates and carbonates and the main component is calcite. Authors [14]
additionally state that it can be made up of microorganisms that are hazardous to health. According to
some research data [5], the sludge produced in the leather processing industry consists of chromium
oxide, sodium chromium oxide, quartz, gypsum and chromium sulphate hydroxide. Experimental tests
revealed [15,16] that when tannery sludge is added to cement, chromium oxide reacts with calcium ions

Materials 2019, 12, 1562; doi:10.3390/ma12091562 www.mdpi.com/journal/materials

Materials 2019, 12, 1562 2 of 14

and inhibits the formation of portlandite and C3 S. In specimens with TS, more intense ettringite peaks
and high levels of calcite are obtained. In addition, the leaching of chromium in cement specimens is
very low. Research [17] has also shown that after mixing tannery sludge with different types of cement,
the leaching of chromium does not exceed the maximum allowable limits specified in the relevant
hygiene standards.
As has already been mentioned, one of the most harmful substances in leather processing is
chromium, which is necessary to protect leather from water penetration and rotting. However,
only 60–80% of the chromium is consumed in leather processing, the residual amount, when allowed
by ecological standards, is removed through the sewer [18].
Harmful sludge in Europe normally cannot be disposed to landfills due to the high content
of chromium that drains away from the materials and enters the soil and groundwater. Therefore,
research is being carried out and attempts are being made to prepare this waste for proper use in
the production of building materials. The results of research [19] show that the harmful effects of
chromium are neutralized using TS waste in geopolymers. The addition of TS waste improves the
compressive strength of the specimens. Reference [20] describes that the leaching of chromium is
significantly reduced and bonded by the ladle furnace slag.
There are studies [21–23] which propose to neutralize chromium with activated carbon.
Reference [24] discussed the possibility of removing 99% of chromium (III) from tannery sludge
by using nanosized polymeric materials that have great potential to remove heavy metal cations
from wastewater. Reference [24] presents the mineral composition of the sludge produced during
leather processing. The investigated dried waste consisted of calcite (CaCO3 ) and quartz (SiO2 ) and at
1000 ◦ C it also contained chromium (III) oxide and NaSO4 . When used as an additive in cement mixes,
this waste additive changes cement hydration, accelerates the initial and final setting time. A properly
selected amount of waste can increase the compressive strength of cement. Some research proves
an improvement in the strength of concrete if CaCO3 is added to concrete mixes. Other authors [25]
report a healing of concrete cracks as a result of calcium instability in wet air. This phenomenon is
beneficial for concrete structures. It is supposed that the said effect would be more useful in dry air
conditions [26]. Scientists [27] have found that tannery sludge added at 0.7% by weight of cement
does not change the chemical composition of cement but slightly reduces its flexural and compressive
strength after 28 days. The waste investigated by these authors was made up of approximately 60% of
organic combustible substances, which could have caused the strength to decrease. Researchers [28]
have found that it would be possible to use such dried waste in cementitious materials to reduce the
thermal conductivity of walls; however, the thermal conductivity starts increasing when the waste
is moistened.
The purpose of our work is to investigate the properties of dried TS waste and to determine its
effect on the performance of cement mortars.

2. Materials and Methods

The following materials were used for the specimens: cement CEM I 42.5 R (its chemical
composition is presented in Table 1 and physical-mechanical properties in Table 2), sand as a
fine aggregate (fraction 0/2), plasticising admixtures (superplasticizer Master Glenium sky 628),
TS and water.
Mineral composition of the cement: C3 S—56.6%, C2 S—16.7%, C3 A—9.0%, C4 AF—10.6% and
7.1% others (alkaline sulphates and CaO).

Table 1. Chemical composition of cement.

CaO SiO2 Al2 O3 Fe2 O3 MgO K2 O Na2 O SO3 Cl L.O.I.

63.2 20.4 4.0 3.6 2.4 0.9 0.2 3.1 0.05 2.15
Materials 2019, 12, 1562 3 of 14

Table 2. Physical-mechanical properties of cement.

Compressive Compressive
Particle Soundness “Le Passing 32 Vicat Initial,
Strength after 2 Strength after H2 O, %
Density, g/cm3 Chatelier”, mm µm, % min
Days, MPa 28 Days, MPa
3.1 1.0 78.5 30 55 180 27.5

The apparent density of sand established by applying the pycnometer method with isopropyl
alcohol is equal to 2.64 g/cm3 ; the bulk density established by EN 1097-3:1998 is equal to 1.67 g/cm3 ,
whereas the water absorption measured by EN 1097-6:2000 is equal to 0.65%.
The amount of heavy metals in the eluate from cement specimens was determined by an atomic
absorption spectral analysis method using a Buck Scientific 2010 VGP spectrometer (East Norwalk, CT,
USA) with air-acetylene flame. The eluate was prepared according to standard LST EN 12457-2:2003,
L/S equals to 0.1 l/kg; 3 samples of batch were tested.
Table 3 presents the results of the eluate test and extractable metals detected in the solid residue
as well as other properties of the sludge. The results show that TS waste contains chlorides, sulphates,
fluorides, and heavy metals. TS humidity reaches 78.4%, pH is 7.9, and total organic carbon is 0.66%.
TS had a bulk density of 0.47 g/cm3 , particle density of 1.67 g/cm3 . Heavy metals present in TS do not
exceed the limits specified in 2003/33/EC; however, chromium content is very close to the allowable
limit values.

Table 3. Analysis of extractable metals in the solid residue and other properties of tannery sludge.

Parameter Results
pH 7.9
Dry matter, % 78.4
Chlorides, mg/kg 3688
Sulphates, mg/kg 6288
Fluorides, mg/kg 0.80
Cadmium, mg/kg <0.001
Lead, mg/kg <0.001
Chromium, mg/kg 0.416
Nickel, mg/kg <0.052
Copper, mg/kg 0.208
Zinc, mg/kg 0.544
Barium, mg/kg 0.152
Selenium, mg/kg <0.001
Stibium, mg/kg <0.001
Arsenic, mg/kg 0.024
Mercury, mg/kg 0.001
Dry residue, mg/kg 15728
Molybdenum, mg/kg 0.024
Dissolved organic carbon, mg/kg 42.4
Total organic carbon, % 0.66

Mineral composition tests of TS revealed that the TS mainly contains calcite and quartz minerals
and a large amount of amorphous phase. Traces of chromium oxide and calcium sulphite hydrate
were also detected (Figure 1).
TS microstructural analysis revealed that the TS is amorphous and contains particles of different
sizes and shapes. The particles are round, have a loose structure and an uneven surface. Smaller particles
stick to larger particles, thus forming larger aggregates of particles (individual grains are clearly seen).
The size of particle aggregates is ~0.10 µm (Figure 2).
databases.
identification was carried out by decoding the XRD patterns according to ICDD diffraction
The water absorption rate of cement mortars was determined by cutting the prisms (mortar
databases.
specimens 160 mm
The water × 40 mmrate
absorption × 40ofmm, 6 specimens)
cement mortars into
was two equal parts,
determined drying the
by cutting them to a constant
prisms (mortar
mass and then
specimens 160weighting.
mm × 40 mm Afterwards,
× 40 mm,the specimens into
6 specimens) weretwo
immersed in water
equal parts, andthem
drying weighted after 10
to a constant
min,
mass30 andmin,
then60 weighting.
min, 300 min, 24 h and 96
Afterwards, theh.specimens were immersed in water and weighted after 10
Materials 2019, 12, 1562 4 of 14
min, 30 min, 60 min, 300 min, 24 h and 96 h.
500
500
450
450
400
400
350
a.u.a.u. 350
300
300 C
250
Intensity,

Q C
250
200 C Q
Intensity,

Q C
200
150 C Q
Q C
150
100 Q
100
50
50
0
04 14 24 34 44 54
4 14 24 2 Ɵ, 34
degrees 44 54
2 Ɵ, degrees
Figure 1.
Figure 1. X-ray
X-ray diffraction patterns of
diffraction patterns of tannery
tannery sludge:
sludge: C—calcite,
C—calcite, Q—quartz.
Q—quartz.
Figure 1. X-ray diffraction patterns of tannery sludge: C—calcite, Q—quartz.

Figure 2. Scanning electron microscopy (SEM) image of tannery sludge (TS).

Figure 2. Scanning electron microscopy (SEM) image of tannery sludge (TS).
The superplasticizer complied with provisions of LST EN 934-2 and the water complied with the
provisions of LST EN 1008:2003. The consistency of prepared mortars was determined according to
LST EN 1015-3. The specimens were formed, cured and hardened in accordance with the standard LST
EN 1015-11:2007. The compressive strength after 28 days (6 specimens) was measured by hydraulic
press ALPHA3-3000S in accordance with the standard LST EN 1015-11:2007, sorptivity (6 specimens)
was measured according to LST EN 1015-18.
The microstructures of TS and mortars were observed with a scanning electron microscopy (SEM)
device—JEOL JSM-7600F (Tokyo, Japan). The parameters of electron microscopy were as follows:
voltage of 10 kV; distance to the surface of the specimen, from 7 to 10 mm. Prior to the test, the specimen
surface was covered with a thin golden layer by gold electron vacuum evaporation.
X-ray diffraction (XRD) analysis of the phase composition of the materials was accomplished by
diffractometer DRON-7 (Burevestnik, ST Petersburg, Russia). The following parameters were used for
the tests: voltage—30 kV; current—12 mA; the range of the diffraction angle—from 4 to 60◦ , the detector
movement step—0.02◦ ; the duration of the intensity measuring in a step—0.5 s. Phase identification
was carried out by decoding the XRD patterns according to ICDD diffraction databases.
The water absorption rate of cement mortars was determined by cutting the prisms (mortar
specimens 160 mm × 40 mm × 40 mm, 6 specimens) into two equal parts, drying them to a constant
Materials 2019, 12, 1562 5 of 14

mass and then weighting. Afterwards, the specimens were immersed in water and weighted after
10 min, 30 min, 60 min, 300 min, 24 h and 96 h.
The ultrasonic pulse velocity (UPV) of mortar prisms (3 specimens) was measured with the
instrument Pundit 7 (transducer frequency 54 kHz, Proseq SA, Switzerland) and the velocity (V, m/s)
was calculated from the equation:
V = l/τ (1)

where l is specimen length, m; τ is the time of transfer of ultrasonic signal through the specimen, s.
Ultrasonic pulse velocity is the characteristic of a material according to which changes of porosity
and strength of materials can be estimated.
Two compositions of cement mortars were prepared: in composition C, a portion of the cement
was replaced with chromium-rich tannery sludge; in composition S, a portion of sand was replaced
with tannery sludge. Compositions were formulated, taking into consideration the findings of other
researchers and previous work with similar waste [29,30] and thus using the maximum waste content
up to 15%. Compositions of cement mortar mixes are presented in Table 4. Test compositions
were prepared by mixing dry raw materials (powdered dry tannery sludge (dried at 105 ◦ C ± 5 ◦ C
temperature was used) at first and then, adding water mixed with superplasticizer. 40 mm × 40 mm ×
160 mm prisms were moulded from the compositions specified below.

Table 4. Compositions of cement mortar mixes.

Compositions of Cement Mortar Mixes Per One Cubic Meter

Designation: Tannery Tannery Cement Water Superplas-Ticizer,
Sand 0/2, g
Sludge, % Sludge, g Content, g Content, g g
K 0 0 500 250 5 1500
Replacing a Part of Cement
CD3 3 15 485 250 5 1500
CD6 6 30 470 250 5 1500
CD9 9 45 455 250 5 1500
CD12 12 60 440 250 5 1500
Replacing a Part of Sand
SD3 3 45 500 250 5 1455
SD6 6 90 500 250 5 1410
SD9 9 135 600 300 5 1365

The analysis of extractable metals was done in accordance with LST EN 12457-2:2003, TS humidity
was determined in accordance with LST EN 15934:2012. Cr3+ amount in the eluate was determined
with an atomic absorption spectral analysis method using a Buck Scientific 2010 VGP spectrometer
with air-acetylene flame. Eluate for chromium leaching tests was prepared in accordance with LST EN
12457-2:2003. Cr3+ leaching values were evaluated against the limit values specified in 2003/33/EC
(2003/33/EC 2002) [9].

3. Results and Discussion

At first, the flowability of the mortars was tested. The flowability was found to decrease with a
higher TS content in the mix (Figure 3). A sharper decrease in flowability was observed when part of the
sand was replaced with TS. This effect can be explained by a higher content of TS in the mix compared
to the replacement of the part of the cement. The higher porosity of the structure and significantly
higher TS particle surface area, which requires more water to wet the particle, influenced the flowability
decrease. It is not feasible to replace more than 9% of sand with TS because the workability of the mix
Materials 2019, 12, 1562 6 of 14

deteriorates.
Materials 2019, 12,When 9% ofREVIEW
x FOR PEER sand was replaced with TS, the moulding of specimens was aggravated,
6 of 14
Materials
so 2019, 12, x of
the amounts FOR PEER and
water cement were increased and a constant ratio V/C = 0.5 was
REVIEW 6 of 14
maintained.
of the cement was replaced with TS. With the maximum content of TS (12%), the flowability
Nevertheless, the flowability was only 10 cm or 50% compared to the reference specimen. A less of the
of
mixthe cement
reduced was
by replaced
~20%. with TS. With the maximum content of TS (12%), the flowability of
significant flowability decrease was observed when part of the cement was replaced with TS. With thethe
mix reduced by ~20%.
maximum content of TS (12%), the flowability of the mix reduced by ~20%.
Changing sand Changing cement
12 Changing sand Changing cement
12

9
%%
of TS,

9
of TS,

6
Content

6
Content

3
3

0
0
0 5 10 15 20 25
0 5 10 15
Flow diameter, mm 20 25
Flow diameter, mm
Figure 3. Relationship between mortar slump and TS content in the mix.
Figure 3. Relationship between mortar slump and TS content in the mix.
Figure 4 illustrates how the density of the mix depends on the amount of TS that replaces a part
Figure
Figure 4 illustrates how
howthe
thedensity
densityofofthe
themix
mixdepends
dependsononthe amount ofof
TSTS
that replaces a part of
of sand or a 4part
illustrates
of the cement. the amount that replaces a part
sand or a part of the cement.
of sand or a part of the cement.
2250
2250 Density, changing cement
Density, changing
Density, changing sand
cement
2200 Density, changing sand
2200

2150
2150
3 3
kg/m
kg/m

2100
2100
Density,
Density,

2050
2050

2000
2000

1950
1950

1900
1900 0 3 6 9 12
0 3 6 9 12
Content of TS
Content of TS
Figure 4. The impact of TS content in the mix on mortar density.
Figure 4. The impact of TS content in the mix on mortar density.
Figure 4. The impact of TS content in the mix on mortar density.
The density of hardened mortar increases when up to 6% of the fine aggregate (sand) is replaced
The density of hardened mortar increases when up to 6% of the fine aggregate (sand) is
with TS (the density of a specimen containing 6% of TS increased by 7%); however, with further
The with
replaced density of hardened
TS (the density ofmortar increases
a specimen when 6%
containing up ofto TS
6%increased
of the fine aggregate
by 7%); (sand)
however, with is
increase of TS content, the density of the hardened mortar starts decreasing. The increase in initial
replaced with TS (the density of a specimen containing 6% of TS increased by 7%); however,
further increase of TS content, the density of the hardened mortar starts decreasing. The increase in with
density is caused by the consumption of finer TS particles in the mix. These particles fill in the pores
furtherdensity
initial increase of TS content,
is caused the density ofofthe
by the consumption hardened
finer mortar
TS particles starts
in the decreasing.
mix. The increase
These particles in
fill in the
and act as crystallisation centres. During visual inspection, no pores were observed on the surface of
initial density is caused by the consumption of finer TS particles in the mix. These particles
pores and act as crystallisation centres. During visual inspection, no pores were observed on the fill in the
pores and
surface act as crystallisation
of specimens containingcentres. During
6% of TS. visual inspection,
The surface no pores
of the specimen wereand
is even observed on the
has a darker
surface(Figure
colour of specimens containing
5). The change 6% ofcan
in colour TS.beThe surfaceby
explained of the
thefineness
specimen is even
of TS and The
addition. has finer
a darker
the
colour (Figure 5). The change in colour can be explained by the fineness of TS addition.
addition, the more intensive the colour of the specimen. Similar changes in cement mortar colour The finer the
addition, the more intensive the colour of the specimen. Similar changes in cement mortar colour
were found by other researchers [31,32], who used waste materials in cement mixes. A decrease in
the density of specimens containing TS > 7% occurs because higher TS content absorbs more water
and reduces the water content required for the cement hydration process. Therefore, the mortar has
more pores and capillaries, which in turn reduce the mortar density and subsequently the strength.
Materials 2019, 12, 1562with higher TS content, pores up to 1 mm in size were seen, as with the reference
In specimens 7 of 14

specimen. When up to 6% of cement is replaced with TS, a stable growth of ~4% in specimen density
is observed. The bigger differences between density result when TS is used to replace a part of the
specimens containing 6% of TS. The surface of the specimen is even and has a darker colour (Figure 5).
cement or a part of the sand are explained by higher TS content in the mix calculated by the weight
The change in colour can be explained by the fineness of TS addition. The finer the addition, the more
of the sand.
intensive the colour of the specimen. Similar changes in cement mortar colour were found by other
The change in density and structure of the specimens with higher TS content in the mix can be
researchers [31,32], who used waste materials in cement mixes. A decrease in the density of specimens
evaluated to some extent from the change of the ultrasonic pulse velocity (UPV) along the entire
containing TS > 7% occurs because higher TS content absorbs more water and reduces the water content
length of the specimen. The changes in UPV, depending on TS content in the mix, are presented in
required for the cement hydration process. Therefore, the mortar has more pores and capillaries,
Figure 5.
which in turn reduce the mortar density and subsequently the strength.

Changing sand Changing cement

12
Content of TS, %

3200 3300 3400 3500 3600 3700 3800

Ultrasound pulse velocity, m/s

Figure 5. The impact of TS content on ultrasound pulse velocity (UPV).

Figure 5. The impact of TS content on ultrasound pulse velocity (UPV).
In specimens with higher TS content, pores up to 1 mm in size were seen, as with the reference
specimen.
FigureWhen up to 6%
5 illustrates of cement
that is replaced
the highest with TS,
UPV values area stable
recordedgrowth of ~4% in specimen
in specimens where 6%densityof both is
observed.
sand The bigger
and cement are differences
replaced with between
TS. UPVdensity result
values when TS
increase is used
with to replaceofaTS
the increase part of the cement
amount in the
or a up
mix parttoof6%.
theUPVsand values
are explained
decrease byinhigher
mixesTSwithcontent
a TSinamount
the mixofcalculated
above 6%. byThese
the weight of the have
specimens sand.
moreThe voidschange in density
of different formsandwith
structure of theair.
entrained specimens with higher
UPV increased ~4% in TSspecimens
content in withthe mix6% can be
of TS
evaluated atopart
replacing someofextent
cementfromandthe in
change of the ultrasonic
specimens with 6% of pulse
TS velocity
replacing (UPV) along
a part of the entire
sand, thelength
UPV
of the specimen.
increased by ~2%.The changes pulse
Ultrasonic in UPV, depending
velocity values onmake
TS content in thetomix,
it possible are presented
predict that cement in Figure
mortars 5.
with 6% Figure 5 illustrates
TS will have thethat the highest
highest strength.UPV values are recorded in specimens where 6% of both sand
and Higher
cement are replaced
flexural with TS.
strength wasUPV valuesin
observed increase with the containing
all specimens increase of up TS amount
to 12% in of the
TS mix up
in the
to 6%. UPV
cement values decrease
mix compared in mixes specimen
to the reference with a TS without
amountTS of (Figure
above 6%. These
6). The specimens
highest flexuralhave more
strength
voids
was of different
observed forms withcontaining
in specimens entrained air.6% UPV
of TS.increased ~4%the
In this case, in specimens with 6% of
strength increased TS Almost
26%. replacing noa
part of cement
changes and strength
in flexural in specimenswerewith 6% ofin
observed TSspecimens
replacing where
a part of
upsand,
to 6%theof UPV
the sandincreased by ~2%.
was replaced
Ultrasonic
with pulse velocity
TS; a reduction values
tolerance ofmake
2% was it possible
observed. to predict that cement mortars with 6% TS will have
the highest
Figure 7strength.
illustrates the compressive strength results. The best compressive strength results were
obtainedHigher flexural strength
in specimens where was3% of observed
sand was in replaced
all specimens
with containing up to 12% of
TS. The compressive TS in the
strength cement
increased
mix26%.
by compared
With atohigher
the reference
contentspecimen
of TS inwithout
the mix,TSthe (Figure 6). The highest
compressive strengthflexural
startedstrength was
decreasing;
observed in specimens containing 6% of TS. In this case, the strength increased
however, it remained higher, as compared to the reference specimen. In specimens where a part of 26%. Almost no changes
in flexural
the cement strength
was replacedwere with
observed in best
TS, the specimens
resultswhere up to 6%in
were obtained ofspecimens
the sand was replaced6%
containing with TS;
of TS.
a reduction
In tolerance
such specimens, theofcompressive
2% was observed.
strength increased by 10%.
Figure
The 7 illustrates
increase the compressive
of strength was influenced strength
by theresults. The best
pozzolanic compressive
properties of TS.strength resultsofwere
The strength the
obtained inincreased
specimens specimenseven where 3% lower
with of sandcement
was replaced
contentwith TS. The
because TS compressive
particles acted strength increased by
as crystallisation
26%. With a higher content of TS in the mix, the compressive strength started decreasing; however,
it remained higher, as compared to the reference specimen. In specimens where a part of the cement was
replaced with TS, the best results were obtained in specimens containing 6% of TS. In such specimens,
the compressive strength increased by 10%.
 increase
chromium cement
content hydration
in tannery because
sludge.ofChromium
decreasedpresent
viscosity
in of the gels
tannery formed
sludge and subsequently
is known to significantlya
greater
increasediffusion rate due tobecause
cement hydration the formation of nucleation
of decreased points
viscosity of thefrom
gelswhich
formed hydrate crystals growa
and subsequently
up. Thisdiffusion
greater phenomenon is ato function
rate due of TSofpercentage
the formation nucleation added. Authors
points from found
which similar
hydrate trends
crystals growof
compressive strength changes
up. This phenomenon after 28 days
is a function of TSofpercentage
curing. Compressive strengthfound
added. Authors gradually increased
similar trends up
of
to a certain amount
compressive strengthof changes
TS in theafter
mix 28
and started
days decreasing
of curing. after a certain
Compressive limit
strength was reached.
gradually increased up
Materials 2019, 12, 1562 8 of 14
to a certain amount of TS in the mix and started decreasing after a certain limit was reached.

Figure 6. The effect of TS content in the mix on flexural strength.

Figure 6. The effect of TS content in the mix on flexural strength.
Figure 6. The effect of TS content in the mix on flexural strength.
55
Compressive strength, changing cement
55
Compressive
Compressive strength,
strength, changing
changing sand
cement
50 Compressive strength, changing sand
50
MPa

45
MPa
strength,

45
strength,

40
40
Compressive

35
Compressive

35

30
30

25
25

20
0 3 6 9 12
20
0 3 6 of
Content TS 9 12

Figure 7. The effect of TS content in the mixTS

Content of on compressive strength.

The increase of strength was influenced by the pozzolanic properties of TS. The strength of the
specimens increased even with lower cement content because TS particles acted as crystallisation
centres. At first, they absorbed the majority of water, which was later released into the system and thus
promoted hydration. Researchers [17] found that cement hydration rate depended on the chromium
content in tannery sludge. Chromium present in tannery sludge is known to significantly increase
cement hydration because of decreased viscosity of the gels formed and subsequently a greater diffusion
rate due to the formation of nucleation points from which hydrate crystals grow up. This phenomenon
is a function of TS percentage added. Authors found similar trends of compressive strength changes
was
andreplaced
thawing with TS.The
cycles. In this case,water
lowest waterabsorption
absorptionwas decreased
observed ~17% after 96 h of
in specimens soaking.
where 6% of With the
cement
increase of TS content up to 12%, water absorption remained the same as in specimens
was replaced with TS. In this case, water absorption decreased ~17% after 96 h of soaking. With the with 6% of
TS.
increase of TS content up to 12%, water absorption remained the same as in specimens with 6% of
TS. The trends of water absorption over time were similar in all cases: the specimens absorbed the
greatest
Materials
The amount
2019, of
12, 1562
trends water absorption
of water during the over
first 300
timemin;
wereafterwards, thecases:
similar in all specimen became saturated
the specimens absorbed 9and
of 14
the
stopped absorbing water. In specimens where part of the sand was replaced with
greatest amount of water during the first 300 min; afterwards, the specimen became saturated and TS, the best water
absorption
stopped results were
absorbing observed
water. in specimens
In specimens containing
wheregradually
part of the 6% was
sand of TS. After 24 h, water
TS, theabsorption
after 28 days of curing. Compressive strength increased upreplaced with
to a certain amount ofbest water
TS in the
reduced
absorption by results
37% and werebyobserved
28% after in 96 h. Specimens
specimens containing
containing 6% of TS After
TS. absorbed
24 h,water
water slower,
absorptionas
mix and started decreasing after a certain limit was reached.
compared
reduced to specimens
by 37%the and without
by 28% TS. This test
after mortar also confirmed
96 h. Specimens the
containingobservation that
TS absorbed it is not
water feasible
slower, to as
Afterwards, ability of cement to absorb water was tested in two ways: by immersing
replace
compared more to than 6%
specimensof sand with
without TS
TS. because
This test of
alsochanges in
confirmed the
thestructure.
observation that it is not feasible to
the specimens completely in water (Figures 8 and 9) and by immersing the cut edge of the specimen in
replace
water tomore
a depththan
of 6% ofmm
5–10 sand(Figures
with TS10because
and 11). of changes in the structure.
8

78
% %
absorption,

67
absorption,

56

45
Water

34
Water

23 0% 3% 6% 9% 12%
12 0% 3% 6% 9% 12%
10 500 1000 1500 2000
0 500 Duration,
1000 min 1500 2000
Duration, min
Figure 8. Water absorption when a part of cement is replaced with TS.
Figure 8. Water absorption when a part of cement is replaced with TS.
Figure 8. Water absorption when a part of cement is replaced with TS.
8
78
% %
absorption,

67
absorption,

56
45
34
Water

23
Water

12 0% 3% 6% 9%

01 0% 3% 6% 9%

00 500 1000 1500 2000

Duration, min
0 500 1000 1500 2000
Materials 2019, 12, x FOR PEER REVIEW 10 of 14
Figure 9. Water absorption Duration,
when a part of min is replaced with TS.
sand
Figure 9. Water absorption when a part of sand is replaced with TS.
0.35 Figure 9. Water absorption when a part of sand is replaced with TS.
The sorptivity values are presented in Figures 10 andChanging
11. cement Changing sand
Sorptivity, kg/(m2min0,5)

0.3 values are presented in Figures 10 and 11.

The sorptivity
0.25

0.2

0.15

0.1

0.05

0
0 3 6 9 12
TS content, %
Figure 10.The
Figure10. Theimpact
impactofofTS
TScontent
contenton
onsorptivity.
sorptivity.

9
Changing cement Changing sand
8
7
 0.05

0
0 3 6 9 12
TS content, %
Materials 2019, 12, 1562 10 of 14
Figure 10. The impact of TS content on sorptivity.

9
Changing cement Changing sand
8

Sorptivity, kg/m2 7
6
5
4
3
2
1
0
0 3 6 9 12
TS content, %
Figure 11. The
Figure11. The impact
impact of
of TS
TS on
on the
the sorptivity
sorptivity in
in mortars
mortarsused
usedfor
forrenovation
renovationapplication.
application.

Figure 8 illustrates
The values that the
of sorptivity water absorption
presented in Figure 10ofwere the mix decreases
determined forwith a higher
ordinary content
mortars when of the
TS
in the mix. In all batches, the standard deviation of water absorption
results were recorded 10 and 90 min after the specimens had been saturated with water due to was from 0.01% till 0.15%.
Water absorption
capillary action. characteristics are usable
The average standard for evaluating
deviation of all the frost was
batches resistance of mortars
0.01 kg/m 2min0.5.inValues
external of
applications. Mortars with lower water absorption tend to decompose less
sorptivity presented in Figure 11 were determined by measuring the initial mass of the specimen when exposed to freezing
and
and thawing
the masscycles. The lowest
after saturation duewater absorption
to capillary action was observed
after 24 h. The in average
specimens wheredeviation
standard 6% of cement of all
was replaced with TS. In this case, water absorption decreased ~17% after
batches was 0.14 kg/m . The results obtained in both tests were very similar. The lowest sorptivity
2 96 h of soaking. With the
increase of TS content up to 12%, water absorption remained the same as
was obtained in mortars containing 6% of TS. Sorptivity in specimens where 6% of the cement was in specimens with 6% of TS.
The trends
replaced with TS ofreduced
water absorption
by ~30%, as over time were
compared to similar in all cases:
the reference specimenthe specimens absorbed
and in specimens the
where
greatest amount of water during the first 300 min; afterwards, the
6% of the sand was replaced with TS, sorptivity reduced by 50%. Besides, those specimens specimen became saturated and
stopped absorbing
containing 6% of TSwater.
had theIn lowest
specimens where
surface part ofItthe
porosity. cansand was replaced
be explained by thewith TS, the
optimal best water
amount of TS
absorption results were observed in specimens containing 6% of TS. After
and the water amount used. TS has a rather large specific surface area through which water required 24 h, water absorption
reduced by 37%
for cement and by is
hydration 28% afterabsorbed.
easily 96 h. Specimens
Fine TS containing
particles TS absorbedwith
saturated water slower,
water fill as
in compared
the voids
to specimens without TS. This test also confirmed the observation that it is
between cement particles and thus promote a faster release of water to C3S crystals where C-S-H not feasible to replace more
than 6% of starts.
formation sand with TS because
A cement matrix ofwith
changes in the
a dense structure.
structure is formed. When the TS amount in the mix
The sorptivity values are presented in Figures
is increased, there is not enough water to wet TS particles 10 and 11. and thus cement binding decelerates and
The values
the porosity of sorptivity
of the presented in Figure 10 were determined for ordinary mortars when the
mortar increases.
results were
The recorded
best results 10wereandobtained
90 min afterwiththe specimensinhad
specimens been6%
which saturated withwas
of the sand water due to capillary
replaced with TS;
action. The average standard deviation of all batches was 0.01 kg/m 2 min0.5 . Values of sorptivity
therefore, SEM analysis of these specimens and reference specimens was performed. The SEM
presented
images areinpresented
Figure 11in were determined
Figure 12. by measuring the initial mass of the specimen and the mass
after saturation due to capillary action after 24 h. The average standard deviation of all batches was
0.14 kg/m2 . The results obtained in both tests were very similar. The lowest sorptivity was obtained in
mortars containing 6% of TS. Sorptivity in specimens where 6% of the cement was replaced with TS
reduced by ~30%, as compared to the reference specimen and in specimens where 6% of the sand was
replaced with TS, sorptivity reduced by 50%. Besides, those specimens containing 6% of TS had the
lowest surface porosity. It can be explained by the optimal amount of TS and the water amount used.
TS has a rather large specific surface area through which water required for cement hydration is easily
absorbed. Fine TS particles saturated with water fill in the voids between cement particles and thus
promote a faster release of water to C3 S crystals where C-S-H formation starts. A cement matrix with a
dense structure is formed. When the TS amount in the mix is increased, there is not enough water to
wet TS particles and thus cement binding decelerates and the porosity of the mortar increases.
The best results were obtained with specimens in which 6% of the sand was replaced with TS;
therefore, SEM analysis of these specimens and reference specimens was performed. The SEM images
are presented in Figure 12.
Materials 2019, 12, 1562 11 of 14
Materials 2019, 12, x FOR PEER REVIEW 11 of 14

Materials 2019, 12, x FOR PEER REVIEW 11 of 14

(a) (b)
Figure
Figure 12. Microstructure
12. Microstructure imagesofof(a)
(a) images (a) specimen
specimen without
withoutTS,
TS,and (b)(b)
and specimen
(b) withwith
specimen 6% of
6%sand
of sand
replaced with TS (magnification: ×7000).
replaced with TS (magnification: ×7000).
Figure 12. Microstructure images of (a) specimen without TS, and (b) specimen with 6% of sand
replaced with TS (magnification: ×7000).
BothBoth images images illustrate
illustrate portlandite
portlandite plates (CH)
plates (CH) growing
growingasaswell wellas as
needle-shaped
needle-shaped ettringite (E) (E)
ettringite
growing in the voids. In addition, they show calcium silicate hydrate (C-S-H) in the form of comb
growing in theimages
Both voids. illustrate
In addition, they show
portlandite platescalcium silicate hydrate (C-S-H) in the form of comb (E) and
and lattice framework and AFm in the form of (CH) growing
fine plates as well as
developing in needle-shaped
cavities when there ettringite
is much
latticegrowing
framework in theand AFm
voids. in the form
In matrix.
addition, theyofshow
fine calcium
plates developing
silicate hydratein cavities whenin theinthere is comb
much CH
CH and ettringite in the According to Reference [33], tiny AFm(C-S-H)
plates grow form of
larger pores
and ettringite
and lattice in the
framework matrix. and According
AFm in the to
formReference
of fine [33],
plates tiny
developing
and divide large pores into small pores as a frame, which causes the most probable aperture to
AFm plates
in cavitiesgrow
when in larger
there is pores
much and
divide CH and
large ettringite
pores intoin the
small matrix.
pores According
as a frame, to Reference
which [33],
causes tiny
the
become small. On the other hand, the thin plates promote the formation of C-S-H, the size of which AFm
most plates
probablegrow in larger
aperture pores
to become
and
Ondivide
small.decreases the other
duelarge pores
tohand,
the into
the
limited small
thin plates
growth pores as The
promote
space. a frame, which
the formation
C-S-H fills thecauses thebetween
of C-S-H,
space mosttheprobable
size aperture
of which
the thin to
platesdecreases
and
due to become
creates small.
the limited
a network On
growth the other hand,
space.toThe
structure the
C-S-H
reduce thin plates
the fills promote
the space
porosity. the
between
Specimens formation
the batch
of this of C-S-H,
thin plates
had the the
and size of
creates
lowest which
a network
porosity
decreases
and one of due
the to the limited
highest strengths growth
(Figurespace.
12b). The
The C-S-H
images fills
also the space between
illustrate that the the thin plates
structure of and
mortar
structure to reduce the porosity. Specimens of this batch had the lowest porosity and one of the highest
creates
containing a network
6% 12b). structure
of TS is denser to reduce
thanalso the porosity.
the structure ofthat Specimens
the reference of this
specimen. batch had
No open the lowest porosity
pores are visible,
strengths (Figure The images illustrate the structure of mortar containing 6% of TS is
andaverage
the one of the pore highest
size is strengths
~2 µm, (Figure
crystals are12b). The images
smaller; there is also
a illustrate
higher amount thatofthe structure
C-S-H and aof mortar
very lowsize is
denser than
containing the structure
6% of TS isThe of the
denser reference specimen.
than the structure No
of thethat open
reference pores are visible, the average pore
amount of ettringite. experimental results show a finer specimen.
TS leads toNo open
faster pores are
cement visible,
hydration,
~2 µm, thecrystals
average are
pore smaller;
is ~2there is a higher amount of C-S-H and a veryoflow amount of ettringite.
lower amounts ofsize
ettringite µm,
andcrystals
higher are smaller;
amounts of there
C-S-Hiscreatea higher amount
a higher C-S-H
strength and a very
of mortar. low
Calcite
The experimental
amount of resultsThe
ettringite. show that a finer
experimental TS show
results leadsthat to faster
a finer cement
TS leads hydration,
to faster lower
cement amounts of
hydration,
(C) is visible more clearly in specimens with TS.
ettringite
lower and
X-ray higher
amounts of amounts
diffractionettringite
analysis of C-S-H
and higher
was create
amounts
performed a higher
of C-S-H
for strength
specimens aofhigher
mortar.
createcontaining Calcite
strength
6% (C)
andisreference
of mortar.
of TS visible
Calcitemore
clearly(C)inisspecimens
specimens visibleto more
findwith clearly
what TS.
type in of
specimens
mineralswith TS.
had formed in the cement mortar. X-ray diffraction patterns
X-ray X-ray diffraction
diffraction
are presented in Figure 13. analysis
analysis waswas performed
performed for specimens
for specimenscontaining containing 6%6% of TS andand
of TS reference
reference
specimens to find what type of minerals had formed in the cement
specimens to find what type of minerals had formed in the cement mortar. X-ray diffraction patterns mortar. X-ray diffraction patterns
are presented in Figure 13.
are presented in Figure 13.
Q

Q
SD6 C A Q
E E DP Q Q D C Q EP Q Q
Q DE C P E A AC Q Q C P P A
SD6 C A Q
CD6 E E D P Q Q D P Q
DE C P E A AC Q QC Q E C P Q
P A
CD6
K

K
4 14 24 34 44 54
2Ɵ, degrees
4 14 24 34 44 54
2Ɵ, degrees

Figure 13. X-ray diffraction (XRD) patterns (E—ettringite, Q—quartz, D—dolomite, C—calcite,
P—portlandite, A—alite).
Materials 2019, 12, 1562 12 of 14

X-ray diffraction patterns revealed the same minerals, only in different amounts, in all
mixes—portlandite (Ca(OH)2 ), quartz (SiO2 ), ettringite (3CaO·Al2 O3 ·3CaSO4 ·31H2 O), calcite (CaCO3 )
dolomite (CaMg(CO3 )2 , and alite (3CaO·SiO2 ). Figure 13 illustrates that the specimen with 6% TS
contained lower amounts of ettringite and alite and higher amounts of portlandite. Portlandite does
not have a significant effect on the strength of the structure, however a higher content of the mineral
creates a pH of 12.5–13 necessary for smooth cement hydration [34,35]. This means that the amount of
hydration had increased in specimens with TS, thus leading to the increase in specimen strength and
cement hydration acceleration.
It must be ensured that the leaching of chromium will not exceed the limit values in order to use
tannery sludge in cement mortar manufacture. According to Directive 2003/33/EC, chromium leaching
from non-hazardous waste may not exceed 2.5 mg/L.
Tests of chromium leaching from cement mortars revealed that even with the highest tannery sludge
addition of 9%, the amount of leached chromium does not exceed the limit values of non-hazardous
waste (2.5 mg/L) according to the normative document (Table 5).

Table 5. Tests in chromium leaching from cement mortars.

Cement Mortars
Parameters
K SD3 SD6 SD9
Cr, mg/L 0.12 0.14 0.17 0.19

The average standard deviation of chromium leaching in all batches was 0.01 mg/l. Therefore, it can
be stated that tannery sludge can be safely recycled in cement mortar manufacture. However, chromium
leaching increases in mortar when the content of TS increases. After adding 9% TS, the chromium
leaching, compared to the control sample, increases by 58% and it is close to the requirements (<0.2 mg/L).
We recommend using a composition with 6% TS, the chromium leaching of which is 0.17.

4. Conclusions
It was found that it is feasible to use TS in construction mortars by replacing 6% of cement or
natural aggregate—sand—with TS. Up to a 6% addition of TS reduced porosity and water absorption
of the mortar, increased the strength up to 26% and increased density and ultrasonic pulse velocity by
~4%. In this way, the expensive binding material—cement—can be saved.
XRD analysis showed that all analysed mortars contained similar standard minerals—portlandite,
quartz, ettringite, calcite, dolomite, and alite. Specimens modified with TS contained a higher amount
of portlandite, C-S-H and a lower amount of ettringite, as well as a lower amount of non-hydrated
cement minerals. XRD analysis results were confirmed by SEM tests.
The values of chromium leaching from cement mortars met the requirements for non-hazardous
waste prescribed in 2003/33/EC and in the normative documents of other countries.

Author Contributions: Conceptualization, J.M., O.K. and V.K.; methodology, O.K. and V.K.; software, J.M.;
validation, J.M., O.K. and V.K.; formal analysis, J.M.; investigation, J.M., O.K. and V.K.; resources, V.K.; data curation,
J.M.; writing—original draft preparation, J.M. and O.K.; writing—review and editing, J.M.; visualization, J.M.;
supervision, J.M.; project administration, J.M.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

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