buildings

Article
Application of the Hazardous Waste Vitreous Enamel
Generated in the Production Process of Heating Devices as a
Partial Replacement for Cement
Milan Kragović 1, * , Marija Stojmenović 1 , Nenad Ristić 2 , Sonja Milićević 3 , Sanja Živković 1 ,
Shanke Liu 4 and Jelena Gulicovski 1

1 “Vinča” Institute of Nuclear Sciences, National Institute of the Republic of Serbia, University of Belgrade,
11351 Belgrade, Serbia
2 Faculty of Civil Engineering and Architecture, University of Niš, Aleksandra Medvedeva 14, 18106 Niš, Serbia
3 Institute for Technology of Nuclear and Other Mineral Raw Materials, Franše d’Eperea 86,
11000 Belgrade, Serbia
4 Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences,
Beijing 100029, China
* Correspondence: [email protected]

Abstract: Solving problems with hazardous waste materials is of crucial importance today. In the
presented study, the application of waste vitreous enamel as a cement replacement up to 30% in mortar
and concrete production was investigated. The chemical and physical-chemical characterization of the
starting material was performed, as well as a leaching test and physical-mechanical characterization
of mortar and concrete mixes. Obtained results showed that, due to its chemical composition,
the vitreous enamel used must be classified as hazardous waste. At the same time, it possesses
pozzolanic properties and satisfies minimal criteria for use as a cement replacement. Testing mortars
Citation: Kragović, M.; Stojmenović, and concrete mixes indicate that waste vitreous enamel can be applied as a construction material for
M.; Ristić, N.; Milićević, S.; Živković, cement replacement in the maximal amount of 20%. The leaching test was performed in accordance
S.; Liu, S.; Gulicovski, J. Application with international standard EN 12457-2 on hardened mortar with a maximal cement replacement of
of the Hazardous Waste Vitreous
20%. The results showed that there was no significant release of toxic elements, i.e., that the practical
Enamel Generated in the Production
application of hazardous waste vitreous enamel in the construction industry may be fully in line with
Process of Heating Devices as a
environmental standards.
Partial Replacement for Cement.
Buildings 2022, 12, 1287. https://
doi.org/10.3390/buildings12081287
Keywords: hazardous waste; vitreous enamel; mortar; concrete; cement replacement; building industry

Academic Editor: Rita Bento

Received: 21 July 2022

Accepted: 17 August 2022 1. Introduction
Published: 22 August 2022 The rapid development of industry as well as a constant need for new and more
Publisher’s Note: MDPI stays neutral
advanced products has resulted in the generation of large quantities of waste, and its
with regard to jurisdictional claims in
quantities can be measured in millions and billions of tons. Depending on the country, such
published maps and institutional affil- waste is disposed of at legal (commonly in developed and middle developed countries)
iations. and/or insufficiently secured illegal landfills (mainly characteristic of underdeveloped
countries where it has a great negative impact on the environment and human health).
Depending on the nature of the waste, its properties, and its origin, different methods
of disposal are used, i.e., different types of secured landfills, such as open, controlled,
Copyright: © 2022 by the authors. and closed. In order to avoid problems of treatment and disposal, it is necessary to work
Licensee MDPI, Basel, Switzerland. on the requests for the input of technology on waste minimization [1–4]. In the case of
This article is an open access article non-hazardous waste, it can be returned to the production process using appropriate
distributed under the terms and technologies with reasonable investments, which is followed with low-cost production of
conditions of the Creative Commons end products, so that, besides environmental gains, economic benefits may be achieved, too.
Attribution (CC BY) license (https://
The environmental benefits are visible in the removal of the waste from the environment
creativecommons.org/licenses/by/
as well as by reducing consumption of natural resources. This is the practice in almost all
4.0/).

Buildings 2022, 12, 1287. https://doi.org/10.3390/buildings12081287 https://www.mdpi.com/journal/buildings

Buildings 2022, 12, 1287 2 of 17

highly developed countries, and to a lesser extent in middle-developed countries, with a

tendency to apply more in underdeveloped countries.
However, a significant problem is waste, which is hazardous for the environment
due to its composition and characteristics. Manipulation of such waste is much more
complex and expensive. For such waste it is difficult to obtain useful value and removal
from the environment without large investments. For that reason, there are considerably
smaller numbers of plants in the world where such waste may be treated, so the transport
and management of this kind of waste is very expensive, and it represents a significant
individual economic burden for each country. At the same time, hazardous waste at landfills
located in the environment, regardless of whether they are legal or illegal, are a constant
threat and danger, both, to nature and to human and animal health. For these reasons, it
is very important to find a way to treat such waste, remove it from nature, and give it a
useful value and a safe applicability in practice. Chen et al. [5] developed supercritical
water oxidation technology in order to treat oil-based drill cuttings (OBDC) from a shale
gas field and high-nickel-content electroplating sludge (Ni-EPS) obtained as a hazardous
waste in an electroplating factory. The authors pointed out that the applied technology is
expensive but effective in solving problems with the mentioned hazardous waste. Haji
Ali et al. [6] showed that application of nickel foam as an electrode may be used for the
electrochemical treatment of liquid hazardous wastes generated during COD (Chemical
Oxygen Demand) tests, which contain mercury, silver, and chromium (VI). However, the
authors pointed out that the disadvantage of the application of the proposed method is
the large-scale production of nickel foam. Gupt et al. [7] used a naturally occurring raw
mineral material, bentonite, from a deposit in India in order to ensure that hazardous waste
contaminated with heavy metals does not further harm the environment. The authors have
shown that bentonite is effective in preserving natural resources from hazardous waste
of this type. However, in this way, natural resources are consumed while the amount of
waste is not reduced, so that only in the short time can the problem be mitigated or solved.
Some authors [8,9] examined various methods by which it is possible to monitor the impact
of hazardous waste from landfills on the environment, while other authors [10,11] examined
the possibility of legislation to solve the problem of illegal landfills or to find ways for
more efficient networking between hazardous waste producers and plants that deal with
its processing. Additionally, the problem of hazardous waste, such as bottom ash [12] or
fly ash [13–15], can be solved by applying it in the construction industry, as a substitute for
cement in the production of mortar and concrete.
Immobilization of hazardous waste by its application in the construction industry
(cement or mortar and concrete production industry), where it is used as a substitute for
natural raw materials, can be particularly interesting from the aspect of solving environ-
mental and economic problems caused by hazardous waste. The significant benefits of
such an approach are the application is very simple and significant amounts of waste can
be consumed. Immobilization of hazardous waste materials of different origins in the
construction industry is well described in the literature [16–22]. However, comprehensive
research must be carried out prior to application as wastes of different origins, deposits,
lots, or treatment may have completely opposite properties. For these reasons, each waste
must be monitored separately, and complete research must be done. Furthermore, applied
materials must meet criteria prescribed by the relevant standards in terms of physical-
mechanical and physical-chemical properties (“Rulebook on restrictions and prohibitions
on the production, placing on the market and use of chemicals”, “Rulebook on the cate-
gories, testing and classification of waste”, EN 450-1:2012). It is also important that after
application, there is no leaching of hazardous components and there is no possibility of
their flushing and returning to nature, i.e., meeting the criteria prescribed by the relevant
national directives, applicable in the country where the waste material is used (“Rulebook
on permitted quantities of hazardous and harmful materials in agricultural land and water
for irrigation and methods for testing”—applicable in Serbia).
Buildings 2022, 11, x FOR PEER REVIEW 3 of 17

Buildings 2022, 12, 1287

on permitted quantities of hazardous and harmful materials in agricultural land and3 of wa-17

ter for irrigation and methods for testing”—applicable in Serbia).

Production of heating devices on solid, liquid, and gaseous fuels generated a signifi-
cant Production of heating
amount of waste devices
material, which on solid, liquid,
is mostly and gaseous
vitreous enamels.fuels From generated
the aspect a signif-
of en-
icant amountprotection,
vironmental of waste material,
reducingwhich is mostly
the deposit of thisvitreous
waste andenamels.
finding From the aspect
its useful valueof is
environmental protection,
a challenge. Namely, reducing
vitreous enamel theisdeposit of this or
a transparent waste and mass,
opaque finding its useful
colorless or value
coloredis
awith
challenge. Namely,which
metal oxides, vitreous enamel by
is applied is amelting
transparent or opaque
to metal plates,mass, colorless
ceramic, or colored
or glass objects
with metal oxides, which is applied by melting to metal plates, ceramic,
for decoration and protection. The corrosion protection properties of enamel coatings are or glass objects for
decoration and protection. The corrosion protection properties of
one of the main reasons for vitreous enamel’s broad application in the industry to coat enamel coatings are one
of the main
various reasonsproducts
electrical for vitreousand enamel’s
household broad application
appliances, in the
dishes, industry
panels, to coatchemical
devices, various
electrical products for
reactors, pipelines andgases,
household appliances,
and various liquids dishes, panels,
and steel devices,
products. The chemical
vitreousreactors,
enamel
pipelines for gases, and various liquids and steel products. The
coating matrix possesses a glassy nature and because of that it shows excellent imperme-vitreous enamel coating
matrix
ability, possesses
washability, a glassy nature and because
and high-temperature of resistance
(fire) that it shows excellent
as well. impermeability,
In addition, it is not
washability, and high-temperature (fire) resistance as well.
affected by UV exposure, so its surface aspect remains unchanged in time, In addition, it is notwhich
affected by
is the
UV exposure, so its surface aspect remains unchanged
main advance in comparison with organic paints and polymers [23,24]. in time, which is the main advance
in comparison
In order to with organicthe
improve paints and polymers
properties [23,24].
of vitreous enamel, certain additives are often
In order to improve the properties of vitreous
added to it [24–27], which may contain ingredients that may enamel, certain
be additives
harmful for arethe
often added
environ-
to
ment. After the enameling process, a part of such a matrix remains as waste, which asAfter
it [24–27], which may contain ingredients that may be harmful for the environment. such
the enameling process, a part of such a matrix remains as waste, which as such cannot be
cannot be reused for coating but must be disposed of in a landfill, where it can affect the
reused for coating but must be disposed of in a landfill, where it can affect the environment,
environment, and thus human and animal health. For that reason, it is important to find
and thus human and animal health. For that reason, it is important to find useful value for
useful value for it. To our knowledge, finding the useful value of waste vitreous enamel
it. To our knowledge, finding the useful value of waste vitreous enamel and its potential
and its potential practical application is not well described in the literature and studies on
practical application is not well described in the literature and studies on this topic are
this topic are very rare [28].
very rare [28].
In this paper, the application of waste vitreous enamel generated in a plant for the
In this paper, the application of waste vitreous enamel generated in a plant for the
production of heating devices will be tested to our knowledge for the first time in an area,
production of heating devices will be tested to our knowledge for the first time in an area,
which are realistic bases for the consumption of large quantities of this waste material, i.e.,
which are realistic bases for the consumption of large quantities of this waste material,
in building and construction industries. For that purpose, testing of vitreous enamel as a
i.e., in building and construction industries. For that purpose, testing of vitreous enamel
potential replacement for cement in the production of mortar and concrete will be per-
as a potential replacement for cement in the production of mortar and concrete will be
formed. TheThe
performed. mainmainemphasis
emphasis in in
thethepaper
paperisison
onpractical
practicalapplication,
application, but but waste vitreous
waste vitreous
enamel was also characterized by physical-chemical and physical-mechanical
enamel was also characterized by physical-chemical and physical-mechanical methods and methods
and then
then testedtested as a replacement
as a replacement for cement
for cement in accordance
in accordance with adequate
with adequate standards standards
by using by
using prescribed
prescribed physical-mechanical
physical-mechanical methods. methods.

2. Materials and Methods

2.1. Sampling
The waste vitreous
vitreous enamel
enamel (Figure 1) was was taken
taken from
from aa heating
heating devices
devices production
production
plant
plant in
in Serbia,
Serbia, one
one of
of the
the largest
largest factories
factories in
in Southeast
Southeast Europe,
Europe, which
which generates
generates approxi-
approx-
mately
imately40 40tons
tonsofofwaste
wastevitreous
vitreousenamel
enamelevery
everyyear.
year.

Figure 1.
Figure 1. Raw
Raw waste
waste vitreous
vitreous enamel
enamel sample.
sample.

For this research, the samples were taken from the production plant in a time period of
4 months (October 2019–January 2020). In this time period, a total of 60 samples were taken
(15 each month). Then, all samples were mixed and homogenized, and one representative
Buildings 2022, 12, 1287 4 of 17

was prepared and taken for analysis. The representative sample was 100% with size <63 µm,
and with a specific mass of 2.5 g/cm3 .
Ordinary Portland cement CEM I 42.5R was used from the company Moravacem
Popovac, Serbia. The chemical and mineralogical composition of the used cement are given
in Table 1 [17].

Table 1. Chemical and mineralogical composition of CEM I 42.5R.

Chemical Composition
SiO2 Fe2 O3 Al2 O3 CaO MgO SO3 Na2 O K2 O LOI
21.62 2.60 7.00 60.16 2.34 2.55 0.33 0.66 2.68
Mineral properties
brownmillerite; calcium-silicate-oxide; calcite; larnite; magnesium-silicate; calcium-hydroxide

2.2. Physical-Chemical Analyses

Chemical analysis and determination of the content of heavy metals in the repre-
sentative waste vitreous enamel sample and after a leaching test were performed using
inductively coupled plasma optical emission spectrometry (ICP-OES) on an ICP spectrome-
ter Spectroflame (Spectro Analytical Instruments, Kleve, Germany). Arsenic concentrations
were determined by microwave digestion according to EPA 3051A procedure.
X-ray powder diffraction (XRD) was applied to analyze phase composition of samples.
XRD pattern of the waste vitreous enamel sample was collected using a SIEMENS D500
diffractometer, with CuKα radiation at 40 kV and 40 mA, a 0.02◦ step size over a 2θ range
of 20–75◦ . Using Diffracplus software, the diffractogram was analyzed for identifying
phase of samples in terms of the Powder Diffraction File (PDF) cards published by the Joint
Committee on Powder Diffraction Standards (JCPDS)—International Centre for Diffraction
Data (ICDD).
A Micromeritics ASAP 2020 instrument was used to measure the textural properties
of the waste vitreous enamel samples. The nitrogen adsorption–desorption isotherms were
obtained by adsorption at −196 ◦ C. Firstly, the sample was degassed at room temperature
for 1 h and then, under the same residual pressure, for 24 h at 120 ◦ C. The Brunauer–
Emmett–Teller (BET) method was used for determination of the specific surface area (SBET )
of the investigated sample [29]. The Dubinin–Radushkevich (DR) equation was applied to
the nitrogen adsorption isotherms to obtain the micropore volume (Vmic ) [30]. Mesopore
volume (Vmeso ) was determined by the Dollimore and Heal (DH) method [31].

2.3. Testing of the Pozzolanic Activity of Waste Vitreous Enamel

In order to determine the potential for application of waste vitreous enamel as the type
II addition in production of concrete in accordance with standard EN 206, the following
determinations were performed: pozzolanic class, activity index, water requirement, and
initial and final setting time. The pozzolanic class was determined in accordance with
standard SRPS B.C1.018 and the activity index was determined according to standard
EN 450-1. The water requirement was determined according to standard EN 450-1 Annex
B, while initial setting time and final setting time and soundness were determined according
to standard EN 196-3.

2.4. Mortar and Concrete Preparation

For mortar preparation, fine river sand (fraction 0/2 mm) was used with specific
gravity and water absorption of 2610 kg/m3 and 1.52%, respectively. For making concrete, a
crushed gabbro with fractions 4/8 mm and 8/16 mm was used as the coarse aggregates with
a specific gravity of 2890 kg/m3 and a water absorption of 0.58%. As the fine aggregates,
river sand with a fraction of 0/4 mm, a specific gravity of 2620 kg/m3 , and a water
absorption of 1.42% was used.
Buildings 2022, 12, 1287 5 of 17

Preparation of mortar mixtures and production and curing of specimens was performed
according to the standard EN 196-1. A total of 5 different mortar mixes were made: a
reference mixture (M-E) and 4 mixtures (M-7.5, M-15, M-22.5, and M-30) in which cement
was replaced with 7.5, 15, 22.5, and 30% of waste vitreous enamel. The mass ratio 1:3 and 1:2
was used in all mixtures for quantify binder and sand, i.e., both water and binder, respectively.
For improving workability of the mortar mixtures, the superplasticizer was used in the same
amount in all mixtures. Table 2 shows quantities of materials for making one series of
mortar specimens (3 prisms with dimensions 40 × 40 × 160 mm) in the laboratory mixer
“Hobart N-50”. Quantities of materials are given in mass and volume ratio.

Table 2. Mix proportion of mortar for one series of samples.

Component M-E M-7.5 M-15 M-22.5 M-30

Cement [g (cm3 )] 450.00 (142.86) 416.25 (132.15) 382.5 (121.43) 348.75 (110.71) 331.96 (100.00)
Waste enamel [g (cm3 )] - 33.75 (11.63) 67.5 (23.28) 101.25 (34.91) 135.00 (46.55)
River sand 0/2 mm [g (cm3 )] 1350.00 (517.24) 1350 (517.24) 1350 (517.24) 1350 (517.24) 1350 (517.24)
Water [g] 225.00 (225.00) 225 (225) 225 (225) 225 (225) 225 (225)
Superplasticizer [g (cm3 )] 1.00 (0.92) 1.00 (0.92) 1.00 (0.92) 1.00 (0.92) 1.00 (0.92)
SUM [g (cm3 )] 2026.00 (886.02) 2026.0 (886.94) 2026.0 (887.87) 2026.0 (888.78) 2026.0 (889.71)

Preparation of concrete mixtures, production, and curing of specimens was performed

according to the standard EN 12390-2. A total of 4 different mixtures were used in which
cement was replaced with waste vitreous enamel in the 0, 10, 20, and 30% (labels C-E, C-10,
C-20, and C-30). A superplasticizer on the base carboxylates was added to all concrete
mixtures. Quantities of materials in mass and volume ratio for 1 m3 of concrete mixtures
are given in Table 3.

Table 3. Mix proportion of concrete mixtures for 1 m3 . Assumed air content for all samples was ~2%.

Component C-E C-10 C-20 C-30

Cement [kg (m3 )] 380.00 (0.121) 342.00 (0.109) 304.00 (0.097) 266.00 (0.084)
Waste enamel [kg (m3 )] - 38.00 (0.013) 76.00 (0.026) 114.00 (0.039)
River sand 0/4 mm [kg (m3 )] 808.00 (0.308) 808.00 (0.308) 808.00 (0.308) 808.00 (0.308)
Crushed aggr. (4/8 mm) [kg (m3 )] 376.00 (0.130) 376.00 (0.130) 376.00 (0.130) 376.00 (0.130)
Crushed aggr. (8/16 mm) [kg (m3 )] 696.00 (0.240) 696.00 (0.240) 696.00 (0.240) 696.00 (0.240)
Water [kg (m3 )] 180.00 (0.180) 180.00 (0.180) 180.00 (0.180) 180.00 (0.180)
Superplasticizer [kg (m3 )] 3.04 (0.002) 3.04 (0.002) 3.04 (0.002) 3.04 (0.002)
SUM 2443.04 (0.981) 2443.04 (0.982) 2443.04 (0.983) 2443.04 (0.983)

2.5. Physical-Mechanical Characterization of Mortar and Concrete Samples

For determination of the physical-mechanical properties of the mortar samples, the
following tests according to appropriate standards were used: Consistency—by flow table
(EN 1015-3); Bulk density of fresh mortar (EN 1015-3); Bulk density of hardened mortar
(EN 1015-10); Flexural strength and Compressive strength, (EN 196-1); Water absorption
at atmospheric pressure (EN 13755); Water absorption coefficient due to capillary action
of hardened mortar (EN 1015-18); Drying shrinkage (SRPS B.C8.029:1979 (ASTM C 596));
Adhesion between mortar and a concrete substrate (EN 1015-12).
For determination of the physical-mechanical properties of the concrete samples, the
following tests were done in accordance with adequate standards: Consistency—slump
test (EN 12350-2); Density of fresh concrete (EN 12350-6); Air content in fresh concrete
(EN 12350-7); Density of hardened concrete (water saturated) (EN 12390-7); Flexural
strength (EN 12390-5); Compressive strength (EN 12390-3); Tensile splitting strength
(EN 12390-6); Secant modulus of elasticity (EN 12390-13); Depth of penetration of wa-
ter under pressure (EN 12390-8); Freeze-thaw resistance with de-icing salts—Scaling
(CEN-TS_12390-9); Determination of ultrasonic pulse velocity (EN 12504-4).
Buildings 2022, 12, 1287 6 of 17

The leaching test was carried out in accordance with the EN 12457-2 standard. The test
was performed on the mortar mixture, where a maximal amount of cement was replaced
with waste material. The test was not carried out on concrete because the percentage
content of waste material in concrete is lower compared to mortar. The testing procedure
was as follows: samples of dry mortar prisms were crushed mechanically and sieved
through a 4 mm sieve. Then, 100 g of material finer than 4 mm was poured into a metal
grid located inside the glass vessel of the laboratory shaker. 1000 mL of distilled water
with a temperature of 200 ◦ C was poured into the glass container, after which the mixer
with a vertical rotary propeller was started. The speed of rotation of the propeller was
150 rpm, and the time of water flow around the sample was 24 h. The mortar sample was
then filtered through filter paper, and the concentration of heavy metals was determined
on the obtained eluate.

3. Results and Discussion

3.1. Physical-Chemical Characterization of the Waste Vitreous Enamel Samples
3.1.1. Determination of Chemical Composition and Heavy Metal Content
Results of the determination of chemical composition and heavy metal content in the
waste vitreous enamel samples are presented in Table 4. According to Standard “Službeni
Glasnik 56/2010” as well as EN 12457/EN 16192: 2011 applicable in the Republic of Serbia,
in the investigated representative waste vitreous enamel sample, the contents of Sb, Se,
Zn, Cu, Ni, Cd, Mo, and Pb were higher in comparison with the maximal values for non-
hazardous waste prescribed by standards and, because of that, the waste vitreous enamel
must be classified as a hazardous waste. For that reason, the disposal of this type of waste
in landfills is very dangerous and finding a useful application for it should be a priority.

Table 4. The content of elements in representative waste vitreous enamel sample.

Content, mg/kg
Determined Limits for Disposal of Limits for Disposal of
Element
Amount Non-Hazardous Waste Hazardous Waste
Mo 15.0 10 30
Hg <0.15 0.2 2.0
Sb 9.5 0.7 5.0
Se 4.5 0.5 7.0
Sr 222.0 - -
Ba 35.5 100 300
Ca 6854.0 - -
Mg 234.0 - -
Ti 620.0 - -
V 18.5 - -
Mn 7353.0 - -
Fe 10,153.0 - -
Co 2872.0 - -
Cu 2463.0 50 100
Zn 312.0 50 200
Ni 68.5 10 40
Cd 4.0 1 5.0
Al 622.0 - -
Si 53,380.0 - -
Pb 14.0 10 50
As <0.5 2 25
Be <0.05 - -
Cr 59.0 10 70
Tl 48.0 - -
Sn <1.0 - -
Limited values are prescribed by “Službeni Glasnik 56/2010”. Dashes mean that the standard does not prescribe limits.
 Be <0.05 - -
Cr 59.0 10 70
Tl 48.0 - -
Sn <1.0 - -
Buildings 2022, 12, 1287 Limited values are prescribed by “Službeni Glasnik 56/2010”. Dashes mean that the standard7does
of 17
not prescribe limits.

For the
For the Republic
Republicof ofSerbia,
Serbia,the
theapplication
applicationofof waste
wastematerials
materials in the
in thebuilding
building andand
ce-
ment industry is prescribed by the “Rulebook on restrictions and prohibitions
cement industry is prescribed by the “Rulebook on restrictions and prohibitions on the on the pro-
duction, placing
production, on the
placing onmarket and use
the market andofuse
chemicals” as wellasaswell
of chemicals” “Rulebook on the catego-
as “Rulebook on the
ries, testing and classification of waste”, which do not restrict the use of materials
categories, testing and classification of waste”, which do not restrict the use of materials on the
on
basis of the content of heavy metals in raw materials. Thus, although the
the basis of the content of heavy metals in raw materials. Thus, although the investigated investigated
sample isishazardous,
sample hazardous,ititcan
can
bebe used
used in the
in the building
building and and cement
cement industry.
industry. It isimportant
It is only only im-
portant that there is no release of heavy metals after the leaching test on
that there is no release of heavy metals after the leaching test on the mortar mixture the mortar mix-
is
ture is carried out in accordance with the EN 12457-2
carried out in accordance with the EN 12457-2 standard. standard.

3.1.2. X-ray Powder Diffraction Analysis (XRD)

diffraction analysis
The results of the X-ray powder diffraction analysis are
are given
given in
in Figure
Figure 2.
2.

Figure 2.
Figure 2. XRD
XRD diagram
diagram of the waste
of the waste vitreous
vitreous enamel.
enamel.

As can
can be
beseen
seenininFigure
Figure2,2,the waste
the wastevitreous
vitreousenamel
enamelis composed
is composedfrom the crystal
from and
the crystal
amorphous
and amorphousphases. The main
phases. composition
The main of the crystal
composition phase includes
of the crystal quartz, hematite,
phase includes and
quartz, hem-
hedenbergite. The amorphous
atite, and hedenbergite. components
The amorphous are indicated
components byindicated
are a big bumpby background
a big bump in the
back-
2θ range of 15–35 ◦ . The amorphous phase originates from glass matrix of vitreous enamel,
ground in the 2θ range of 15–35°. The amorphous phase originates from glass matrix of
which
vitreousmainly contains
enamel, whichSi and Al. A
mainly high content
contains Si andofAl.
Fe in
A the vitreous
high enamel
content of Fe isinproved by the
the vitreous
results presented in Table 4, and it mainly exists as the form of hematite and hedenbergite.
enamel is proved by the results presented in Table 4, and it mainly exists as the form of
hematite and hedenbergite.
3.1.3. Textural Properties
The values of textural properties of the waste vitreous enamel are presented in Table 5.

Table 5. Textural properties of the waste vitreous enamel sample.

Sample SBET, m2 /g Vtotal , cm3 /g Vmeso , cm3 /g Vmicro , cm3 /g

Vitreous enamel 15.3 0.0794 0.0654 0.0140

As can be seen from Table 5, the specific surface area of the waste vitreous enamel
sample was 15.3 m2 /g. The standard “EN 197-1-Cement—Part 1 Composition, specifica-
tions and conformity criteria for common cements”, which is applicable in the Republic of
Serbia and the EU, prescribes that additions, such as silica fume, should have a SBET of at
least 15 m2 /g, which means that the investigated sample satisfied the required criteria and
can be used as a cement replacement, from the point of textural properties.

3.2. Testing of the Pozzolanic Activity of Waste Vitreous Enamel

Pozzolanic activity is one of the most important parameters on which largely depends
whether the material can be used in concrete production or not. From that point, pozzolanic
Buildings 2022, 12, 1287 8 of 17

activity and the activity index of the waste vitreous enamel were firstly determined in
accordance with appropriate standards, and the results are presented in Table 6.

Table 6. Results of testing pozzolanic activity and parameters of cement paste with addition of the
waste vitreous enamel from an enamel plant.

Property Standard Parameters/Results Requirement Conclusion

Flexural strength: 2.02 MPa >2.0 MPa class 5 of pozzolanic

Class of pozzolanic materials SRPS B.C1.018
Compressive strength: 5.50 MPa >5.0 MPa materials

After 28 days: 79.42% >75% satisfies

Activity index EN 450-1
After 90 days—94.75% >85% satisfies

Water requirement EN 450-1 Annex B 94% <95% satisfies

Initial setting time 135 min <230 min satisfies

EN 196-3
Final setting time 165 min not prescribed -

Soundness EN 196-3 1.0 mm <10 mm satisfies

The obtained results showed that the investigated sample possesses pozzolanic activity
and belongs to class 5 of pozzolanic materials due to values of the flexural and compressive
strengths. The water requirement, initial setting time, final setting time and soundness also
possess values that completely satisfied standard requirements, which means it is possible
to use it as a type II admixture for the production of concrete in accordance with EN 206.

3.3. Effects of Waste Vitreous Enamel on Mortar Properties

Test results of physical and mechanical properties of mortar mixtures based on Port-
land cement, natural sand, and addition of waste vitreous enamel are given in Tables 7 and 8
and Figures 3–6.

Table 7. Test results of physical properties of mortar mixtures.

Property Unit M-E M-7.5 M-15 M-22.5 M-30

Consistency—by flow table mm 135 ± 2.0 144 ± 2.5 147 ± 3.0 153 ± 2.5 164 ± 3.0

Bulk density of fresh mortar kg/m3 2299 ± 8 2294 ± 6 2289 ± 7 2281 ± 9 2275 ± 8

Bulk density of hardened mortar kg/m3 2294 ± 7 2290 ± 8 2285 ± 6 2278 ± 8 2270 ± 9

Water abs. at atm. pressure % 7.54 ± 0.12 7.45 ± 0.10 7.36 ± 0.09 7.25 ± 0.11 7.16 ± 0.08

Water abs. due to capillary action

of hardened mortar: for mortars m2 × min−0.5 0.24 ± 0.02 0.23 ± 0.01 0.23 ± 0.02 0.22 ± 0.01 0.21 ± 02
other than renovation mortars

Water absorption due to capillary

action of hardened mortar: for kg/m2 5.50 ± 0.03 5.53 ± 0.04 5.57 ± 0.05 5.62 ± 0.04 5.65 ± 0.03
renovation mortars
 mortar. At
mortar. At 1414 days,
days, all
all mortar
mortar mixtures
mixtures had had almost
almost the the same
same shrinkage
shrinkage values,
values, while
while inin
the later curing phase (days 21 to 90), the reference sample
the later curing phase (days 21 to 90), the reference sample had less shrinkage compared had less shrinkage compared
to the
to the mortars
mortars in in which
which partial
partial replacement
replacement of of cement
cement by by waste
waste vitreous
vitreous enamel
enamel waswas per-
per-
formed. This
formed. This is is logical,
logical, given
given thethe fact
fact that
that the
the pozzolanic
pozzolanic reaction
reaction occurs
occurs later
later after
after the
the
Buildings 2022, 12, 1287 formation of
formation of portlandite
portlandite (calcium
(calcium hydroxide)
hydroxide) in in the
the hydration
hydration process
process of of the
the cement,
cement,
9 of 17
which is
which is necessary
necessary for for its
its initiation.
initiation. The
The pozzolanic
pozzolanic reaction
reaction results
results inin the
the contraction
contraction of of
hydration products, which caused increased shrinkage of
hydration products, which caused increased shrinkage of the mortar with the addition ofthe mortar with the addition of
waste
waste
Table 8. materials
materials [32,33].
[32,33]. of the mortar mixtures.
Drying shrinkage
Mechanical strength,
Mechanical strength, and and especially
especially compressive
compressive strength,
strength, areare very
very important
important pa- pa-
rameters
Designation
rameters for cement
for cement
of Mortarcomposites.
composites. M-ETheThe flexural
flexural
M-7.5andand compressive
compressive
M-15 strength tests were
M-22.5 tests
strength were per-
M-30per-
formed at
formed at the
Age the mortar specimen
mortar
[days] specimen age age of
of 2,
2, 7,
7, 28,
28, and
and 90ε90 days.
days.
sm,sr A
[mm/m]A graphical
graphical representation
representation of of
the results is shown in
the results is3shown in Figures0.00 Figures 3 and
3 and 4. 4.
0.00 0.00 0.00 0.00
ItItcan
canbebe4observed
observedthat that0.25
with
with increasing
±increasing
0.02 cement
0.23cement replacement
± 0.03 replacement
0.20 ± 0.03 by by waste
waste
0.18 vitreous
vitreous
± 0.02 enamel,
0.16enamel,
± 0.03
thestrength
the strengthof 7ofmortar
mortarspecimens
specimens decreased
0.38 ± decreased
0.03 atearly
0.36 at
± earlyages
0.02 ages
0.33(2(2 and77days).
± and
0.01 days).
0.30 ±OnOn theother
0.03the other
0.28 hand,
±hand,
0.02
with increasing
with increasing
14 age age (28
(28 and
and 90±days)
0.59
90 days) the
0.01 the strength
0.59 ± 0.02 of
strength of0.58
mortar
± 0.02
mortar with0.57
with waste
waste vitreous
± 0.02
vitreous enamel
± 0.02
0.56enamel
approached21
approached thevalues
the valuesof ofthe
the0.69 ± 0.03 mortar.
reference
reference 0.70 ± 0.03
mortar. Thisis
This is0.70 ± 0.03 to
attributed
attributed the±
to0.71
the 0.03
pozzolanic
pozzolanic 0.72 ± 0.03
reaction
reaction
of waste 28
vitreous enamel, 0.91 ± 0.02
which 0.90 ±itself
manifests 0.03 at0.88a ± 0.02
later stage 0.85
of ± 0.02 0.84For
hardening. ± 0.02
that
of waste vitreous enamel, which manifests itself at a later stage of hardening. For that
56 0.93 ± 0.02 0.92 ± 0.02 0.90 ± 0.02 0.87 ± 0.01 0.86 ± 0.01
reason, the
reason, the percentage
percentage of of possible
possible replacement
replacementof of cement with with waste vitreous
vitreous enamel was was
90 0.94 ± 0.03 0.93 ± 0.01cement 0.92 ± 0.01waste 0.89 ± 0.02 enamel0.88 ± 0.02
estimated on
estimated on the
the basis
basis ofof strength
strength at at 90
90 days.
days.

Figure
Figure 3.
Figure3. Flexural
3.Flexural strength
Flexuralstrength of
strengthof mortar
ofmortar samples.
mortarsamples.
samples.

Buildings 2022, 11, x FOR PEER REVIEW 11 of 17

Figure
Figure 4.
Figure4. Compressive
4.Compressive strength
Compressivestrength of
strengthof mortar
ofmortar samples.
mortarsamples.
samples.

In Figure
In Figure 5, 5, the
the percentages
percentages of of flexural
flexural and
and compressive
compressive strength
strength of
of the
the mortar
mortar pre-
pre-
pared with partial replacement of cement by waste vitreous
pared with partial replacement of cement by waste vitreous enamel and the referenceenamel and the reference
mortar at
mortar at 90
90 days
days of of age
age are
are presented.
presented.
Figure 55 shows
Figure shows thatthat the
the decrease
decrease in in flexural
flexural strength
strength that
that occurs
occurs with
with the
the increase
increase in
in
the percentage
the percentage of of cement
cement replacement
replacement by by waste
waste vitreous
vitreous enamel
enamel waswas very
very low,
low, whereas
whereas
inthe
in thecase
caseofof15%
15%replacement
replacementthere
therewaswasno nodecrease.
decrease.The
Thecompressive
compressivestrength
strengthdecreased
decreased
slightly with an increase in the percentage of replacement, with
slightly with an increase in the percentage of replacement, with a maximum decrease ofa maximum decrease of
13%. If 15 % is the acceptable level of strength decrease, then it can be
13%. If 15 % is the acceptable level of strength decrease, then it can be concluded that in concluded that in
the production
the production of of mortar,
mortar, upup to
to 30%
30% of of cement
cement cancan be
be replaced
replaced by by waste
waste vitreous
vitreous enamel.
enamel.

5. Percentage ratio of flexural (left) and compressive strength (right) of mortar

Figure 5. mortar with waste
vitreous enamel
vitreous enamel and
and reference
reference mortar
mortar at
at 90
90 days.
days.

The testing results of adhesion between mortar and a concrete substrate are shown
in Figure 6.
 Figure 5. Percentage ratio of flexural (left) and compressive strength (right) of mortar with waste
vitreous enamel and reference mortar at 90 days.

Buildings 2022, 12, 1287 10 of 17

The testing results of adhesion between mortar and a concrete substrate are shown
in Figure 6.

Figure
Figure 6. Adhesion between
6. Adhesion between mortar
mortar and
and aa concrete
concrete substrate.
substrate.

Based on the consistency test results presented in Table 7, it can be concluded that with
The replacement of cement with waste vitreous enamel resulted in a reduction in the
the increase in the percentage of cement replacement by waste vitreous enamel, the flow
adhesion of the mortar in comparison with concrete substrate, with an exception for ce-
of mortar on the flow table also increased. The highest flow was achieved on the mortar
ment replacement of 7.5%, when an adhesion strength increased 10% and 15%, where the
made with 30% replacement of cement by waste vitreous enamel, which is 21% higher
adhesion is equal to that of M-E. With an increase in the percentage of cement replacement
than the reference mortar. The main reason is the lower water requirement of vitreous
in an amount higher than 15%, the adhesive strength decreased with a maximum reduc-
enamel compared to cement, as a result of which the amount of free water in the mortar
tion of 15% for the M-30 sample. The lower limit of adhesive strength for repair mortars
mixture increases. In general, the addition of waste vitreous enamel contributed to the
is 1.5 MPa, thus,
improvement all tested
of mortar mortar mixtures meet this condition. It should be noted that in
workability.
all samples the fracture
The replacement of cementwas at the junction
with waste between
vitreous the mortar
enamel and the substrate.
contributed to a slight reduc-
tion in the bulk density of mortar in the fresh and hardened state. This reduction is up to
3.4.kg/m
24 Effect3 of
forWaste Vitreous
the fresh andEnamel
up to 25 onkg/m
Concrete
3 forProperties
the hardened state.
Test replacement
The results of physical
of cementandwith
mechanical properties
waste vitreous of concrete
enamel did not mixtures based
significantly on
affect
Portland
the watercement,
absorptionnatural sand,
values, coarse crushed
regardless aggregate,
of the test method.and addition
Water of waste
absorption vitreous
of reference
enamelat
mortar are given in Tables
atmospheric 9–11was
pressure andthe
Figures
lowest, 7 and
while 8.with the increase in the percentage of
cement replacement with waste vitreous enamel, the absorption value slightly decreased. A
Table 9.trend
similar Test results of physical
was observed properties
for of concrete
determination mixtures.
of the absorption coefficient due to capillary
absorption of water. In the case of a 90-min test (test for non-repair mortars), the lowest
Property Unit C-E C-10 C-20 C-30
absorption coefficient was recorded for mortars marked “M-30”, while in the case of a
Consistency—slump test mm 200 ± 10 210 ± 12 220 ± 9 240 ± 11
24-h test (test for repair mortars), the lowest absorption coefficient was recorded at reference
Density of fresh concrete kg/m3 2466 ± 12 2495 ± 9 2488 ± 10 2481 ± 12
mortar. Results of shrinkage measurements are given in Table 8.
Air content in fresh concrete %
Dry shrinkage was performed 2.6mortar
on ± 0.19 prisms 1.9with
± 0.16 1.5 ±of0.18
dimensions 160 × 401.3 ×±400.15
mm.
Density of hardened concreteShrinkage
(water saturated)
is expressed kg/m
as the ratio 2455
3
of the± change
10 2490
of the ±length
12 and2485 ±8
the length of2477 ± 11
the prism
Determination of ultrasonic pulse
(ε = velocity
∆l/l). Based on the km/s
shrinkage5.21measurement
± 0.022 5.23results,
± 0.020due5.20 ± 0.018
to the drying5.18of ± 0.015
cement
mortars it can be observed that mortar mixtures with the addition of waste vitreous enamel
had lower shrinkage values in the initial curing phase (first 7 days) than the reference
mortar. At 14 days, all mortar mixtures had almost the same shrinkage values, while in the
later curing phase (days 21 to 90), the reference sample had less shrinkage compared to the
mortars in which partial replacement of cement by waste vitreous enamel was performed.
This is logical, given the fact that the pozzolanic reaction occurs later after the formation of
portlandite (calcium hydroxide) in the hydration process of the cement, which is necessary
for its initiation. The pozzolanic reaction results in the contraction of hydration products,
which caused increased shrinkage of the mortar with the addition of waste materials [32,33].
Mechanical strength, and especially compressive strength, are very important parame-
ters for cement composites. The flexural and compressive strength tests were performed at
the mortar specimen age of 2, 7, 28, and 90 days. A graphical representation of the results
is shown in Figures 3 and 4.
It can be observed that with increasing cement replacement by waste vitreous enamel,
the strength of mortar specimens decreased at early ages (2 and 7 days). On the other hand,
with increasing age (28 and 90 days) the strength of mortar with waste vitreous enamel
approached the values of the reference mortar. This is attributed to the pozzolanic reaction
Buildings 2022, 12, 1287 11 of 17

of waste vitreous enamel, which manifests itself at a later stage of hardening. For that
reason, the percentage of possible replacement of cement with waste vitreous enamel was
estimated on the basis of strength at 90 days.
In Figure 5, the percentages of flexural and compressive strength of the mortar pre-
pared with partial replacement of cement by waste vitreous enamel and the reference
mortar at 90 days of age are presented.
Figure 5 shows that the decrease in flexural strength that occurs with the increase in
the percentage of cement replacement by waste vitreous enamel was very low, whereas in
the case of 15% replacement there was no decrease. The compressive strength decreased
slightly with an increase in the percentage of replacement, with a maximum decrease of
13%. If 15 % is the acceptable level of strength decrease, then it can be concluded that in the
production of mortar, up to 30% of cement can be replaced by waste vitreous enamel.
The testing results of adhesion between mortar and a concrete substrate are shown
in Figure 6.
The replacement of cement with waste vitreous enamel resulted in a reduction in
the adhesion of the mortar in comparison with concrete substrate, with an exception for
cement replacement of 7.5%, when an adhesion strength increased 10% and 15%, where the
adhesion is equal to that of M-E. With an increase in the percentage of cement replacement
in an amount higher than 15%, the adhesive strength decreased with a maximum reduction
of 15% for the M-30 sample. The lower limit of adhesive strength for repair mortars is
1.5 MPa, thus, all tested mortar mixtures meet this condition. It should be noted that in all
samples the fracture was at the junction between the mortar and the substrate.

3.4. Effect of Waste Vitreous Enamel on Concrete Properties

Test results of physical and mechanical properties of concrete mixtures based on
Portland cement, natural sand, coarse crushed aggregate, and addition of waste vitreous
enamel are given in Tables 9–11 and Figures 7 and 8.

Table 9. Test results of physical properties of concrete mixtures.

Property Unit C-E C-10 C-20 C-30

Consistency—slump test mm 200 ± 10 210 ± 12 220 ± 9 240 ± 11

Density of fresh concrete kg/m3 2466 ± 12 2495 ± 9 2488 ± 10 2481 ± 12
Air content in fresh concrete % 2.6 ± 0.19 1.9 ± 0.16 1.5 ± 0.18 1.3 ± 0.15
Density of hardened concrete (water saturated) kg/m3 2455 ± 10 2490 ± 12 2485 ± 8 2477 ± 11
Determination of ultrasonic pulse velocity km/s 5.21 ± 0.022 5.23 ± 0.020 5.20 ± 0.018 5.18 ± 0.015

Table 10. Test results of mechanical properties of concrete mixtures.

Property Unit C-E C-10 C-20 C-30

Flexural strength MPa 28 days: 7.0 ± 0.2 28 days: 6.4 ± 0.3 28 days: 5.9 ± 0.1 28 days: 5.6 ± 0.3

Compressive strength MPa 90 days: 7.4 ± 0.3 90 days: 6.8 ± 0.2 90 days: 6.4 ± 0.2 90 days: 6.1 ± 0.2

See Figure 6

Tensile splitting strength MPa 28 days: 3.9 ± 0.2 28 days: 3.5 ± 0.2 28 days: 3.0 ± 0.3 28 days: 2.8 ± 0.2

Secant modulus of elasticity GPa 28 days: 33.0 ± 0.3 28 days: 33.5 ± 0.2 28 days: 33.2 ± 0.2 28 days: 33.0 ± 0.3
 Table 10. Test results of mechanical properties of concrete mixtures.
Table 10. Test results of mechanical properties of concrete mixtures.
Property
Property Unit
Unit C-E
C-E C-10
C-10 C-20
C-20 C-30
C-30
Flexuralstrength
Flexural strength MPa 2828days:
MPa days:7.0
7.0± ±0.2
0.2 2828days:
days:6.4
6.4± ±0.3
0.3 2828days:
days:5.9
5.9± ±0.1
0.1 2828days:
days:5.6
5.6± ±0.3
0.3
Compressive strength
Compressive strength MPa 90 days: 7.4 ± 0.3 90 days: 6.8 ± 0.2 90
MPa 90 days: 7.4 ± 0.3 90 days: 6.8 ± 0.2 90 days: 6.4 ± 0.2days: 6.4 ± 0.2 90 days: 6.1 ±
90 days: 6.1 ± 0.2 0.2
Buildings 2022, 12, 1287 SeeFigure
Figure6 6 12 of 17
See
Tensile splitting strength
Tensile splitting strength MPa 28 days: 3.9 ± 0.2 28 days: 3.5 ± 0.2 2828days:
MPa 28 days: 3.9 ± 0.2 28 days: 3.5 ± 0.2 days:3.0
3.0± ±0.3
0.3 2828days:
days:2.8
2.8± ±0.2
0.2
Secantmodulus
Secant modulusofofelasticity
elasticity GPa
GPa 2828days:
days:33.0
33.0± ±0.3
0.32828days:
days:33.5
33.5± ±0.2
0.2 2828days:
days:33.2
33.2± ±0.2
0.2 2828days:
days:33.0
33.0± ±0.3
0.3
Table 11. Depth of penetration of water under pressure and freeze/thaw resistance with de-icing salt
ofTable
concrete
11. mixtures.
Depth of penetration of water under pressure and freeze/thaw resistance with de-icing
Table 11. Depth of penetration of water under pressure and freeze/thaw resistance with de-icing
salt of concrete mixtures.
salt of concrete mixtures.
Property Unit C-E C-10 C-20 C-30
Property
Property Unit C-E C-10 C-20 C-30
Depth of penetration of water under pressure mm Unit 12 C-E 10 C-10 C-20
14 C-30
16
Depthofofpenetration
Depth penetration ofwater
waterunder
underpressure
pressure mm 12 10 14 1616
Freeze-thaw resistanceofwith de-icing salts—Scaling kg/m2 mm 2 0.14 12 0.11 10 0.1514 0.19
Freeze-thaw resistance with de-icing salts—Scaling
Freeze-thaw resistance with de-icing salts—Scaling kg/m
kg/m2 0.14
0.14 0.11
0.11 0.15
0.15 0.19
0.19

Figure7.7.Compressive
Figure Compressivestrength
strengthofofconcrete
concretesamples.
samples.
Figure 7. Compressive strength of concrete samples.

Figure 8. The percentage ratio of compressive strength of concrete with waste vitreous enamel and
Figure 8.
Figure Thepercentage
8. The percentageratio
ratioof
ofcompressive
compressivestrength
strength of
of concrete
concrete with
with waste
waste vitreous
vitreous enamel
enamel and
and
reference concrete at 90 days.
reference
reference concrete
concrete at
at 90
90 days.

Basedon
Based
Based ononthe
theresults
the resultsof
results ofofconcrete
concreteconsistency
concrete consistencytesting,
consistency testing,itititcan
testing, canbe
can bebeconcluded
concludedthat
concluded thatby
that byin-
by in-
in-
creasing
creasing the
the content
content of of waste
waste vitreous
vitreous enamel,
enamel, the the
size size
of of
the the
slump
creasing the content of waste vitreous enamel, the size of the slump increased. A maxi- slump increased.
increased. A A
maximummaxi-
mumslump
slump
mum slump
of of240
240ofmm 240was
mmmm wasrecorded
recorded
was recorded
for the for
for theconcrete
concrete
the concrete
mixture, mixture,
C-30,C-30,
mixture, C-30,which
which which washigher
was higher
was higher
than
than
than the
the referencereference
mixture
the reference mixture
by 20%.
mixture by 20%.
As inAs
by 20%. As
the in
incasethe case of
of mortar
the case mortar
mixtures,
of mortar mixtures,
mixtures,the mainthe main
reason
the main reason for
for this
reason for
this
this phenomenon
phenomenon
phenomenon is the is the
is lower lower
water
the lower water requirement
requirement
water requirement of vitreous
of vitreous enamel
of vitreous enamel
enamel compared
compared
compared to
to cement. cement.
to cement.
The
The content
content of of
airair entrained
entrained into
into fresh
fresh concrete
concrete decreased
decreased
The content of air entrained into fresh concrete decreased with the increasing with with
the the increasing
increasing per-
percent-
per-
centage
age of of
cement cement replacement.
replacement. The The reference
reference mixture mixture
had thehad
highest the
centage of cement replacement. The reference mixture had the highest percentage of en- highest
percentagepercentage
of of
entrained en-
trained air (2.6%), while the C-30 mixture had the lowest (1.3%). This can be attributed toto
trained
air (2.6%),air (2.6%),
while the while
C-30 the C-30
mixture mixture
had the had
lowest the lowest
(1.3%). This(1.3%).
can beThis can
attributedbe attributed
to the better
thebetter
placing
the better placingofof
ofplacing
concrete concrete
mixed
concretewith mixed with
wastewith
mixed wastematerial.
material.
waste material.
The replacement of cement with waste vitreous enamel contributed to the slight
increase in the concrete bulk densities in the fresh and hardened state, which was primarily
a consequence of the lower content of air entrained.
The concrete porosity, aggregate type and interfacial transition zone (ITZ) are the most
important factors that affect the ultrasonic velocity values of concrete. Based on the results
presented in Table 9, it can be seen that all concrete mixtures had values of ultrasonic velocity
that was higher than 4.5 km/s, which is a limit for strong concrete [32]. The differences in
the values of the ultrasonic velocities were insignificant, which indicates that all concrete
mixtures had a uniform quality in terms of physical and mechanical characteristics.
Buildings 2022, 12, 1287 13 of 17

The flexural strength test for the samples was performed at 28 and 90 days. Based on
results presented in Table 10, it can be observed that the flexural strength decreased with
the increase of cement replacement, and ranges between 9 and 20% at 28 days’ age and
between 8 and 18% at 90 days’ age, in comparison to the C-E.
Compressive strength is the most significant characteristic of concrete, and it was
determined at the age of 2, 7, 28, and 90 days. The results are shown at Figure 7. From
presented results, it can be seen that the C-10 concrete mixture had a higher value of
compressive strength relative to the reference concrete for all ages. On the other hand,
with the increase of cement replacement by waste vitreous enamel by more than 10%, the
strengths of concrete specimens decreased for all ages. In the first 7 days, the concrete
strengths of mixtures C-E and C-10 had the highest increase, while after increasing ages,
the compressive strength of concrete made with waste vitreous enamel was higher than the
reference one due to the delayed pozzolanic reaction. A similar conclusion was reached by
authors [32,34,35] in the study of durability of concrete supplemented with recycled CRT
glass as cementitious material.
Figure 8 shows the percentages of compressive strengths of concrete samples prepared
with partial replacement of cement by waste vitreous enamel and reference concrete for 90 days.
The diagram shows a slight decrease in compressive strength with an increase in the
percentage of cement replacement for more than 10%, while in the concrete mixture, C-10,
there was a slight increase in strength in some cases. The acceptable level of compressive
strength decrease is 15%, so that it can be concluded that up to 20% of cement can be
replaced by waste vitreous enamel in concrete production.
Based on the test results from Table 10, it can be seen that the tensile splitting strength
slightly decreased with the increase in the percentage of cement replacement by waste
vitreous enamel. The reference concrete had the highest strength value (3.9 MPa), while the
concrete mixture with 30% cement replacement had 28% lower tensile splitting strength.
The secant modulus of elasticity of concrete was tested at a sample age of 28 days. As
can be seen from Table 10, the modulus of elasticity of concrete increased with the increase
in the percentage of cement replacement by waste vitreous enamel up to 10%, when it
reaches the maximum value (33.5 GPa). With the further increase of cement replacement,
the modulus of elasticity slowly decreased and reached a minimum for concrete, with
30% cement replacement (33.0 GPa).
The depth of penetration of water under pressure in hardened concrete and freeze/thaw
resistance with de-icing salt of concrete are shown in Table 11. The results of depth pen-
etration of water under pressure showed that the C-10 mixture had the lowest value of
penetration (10 mm), which is slightly less than for reference mixture (12 mm). When the
content of waste vitreous enamel in concrete was greater than 10%, the depth of water
penetration through concrete increased moderately. According to Neville and Brooks [36],
all concrete mixtures can be considered as waterproof as none of them has a penetration
greater than 30 mm. It can be concluded that waste vitreous enamel does not have a
negative effect on the resistance of concrete mixtures to the pressurized water action.
After 56 freezing-thaw cycles with de-icing salt, the least scaling of concrete surface
was achieved for concrete mixture with 10% replacement of cement (C-10). In Table 11 it
can be seen that with a further increase of waste vitreous enamel content, the freeze/thaw
resistance of concrete reduces. The C-10 mixture had decreased scaling in comparison
to the reference mixture (E), while the C-20 and the C-30 mixtures had slightly higher
damage compared to sample E. A possible reason for such a result is the consequence of
the formation of hydration phases during the pozzolanic reaction of waste vitreous enamel,
which caused a reduction in permeability to fluids. A similar conclusion was reached by
Jihwan et al. [37], who tested the durability of concrete with recycled glass as a partial
replacement for cement.
Buildings 2022, 12, 1287 14 of 17

3.5. Leaching Test

The leaching test was performed on the mortar mixture with maximal allowed cement
replacement, where 20% of cement was replaced with waste vitreous enamel. The leaching
test was carried out in accordance with the standard EN 12457-2, and the results are shown
in Table 12.
Table 12. Concentration of the released elements after the leaching test.

Released Element Concentration, µg/dm3 * Allowed Values, µg/dm3

Cu 4 <100
Zn 17 <1000
Ni 20 <100
Cd 2 <10
Pb 30 <100
Cr 3 <500
Hg <0.1 <1
As <5 <50
Mg 5 -
Fe 27 -
Co 8 -
Al 47,500 -
Sn <10 -
Si 665 -
Mo <1 -
Sr <1 -
Ca 140 -
Mn <1 -
V <10 -
* According to the Rulebook on permitted quantities of hazardous and harmful substances in soil and irrigation
water and methods of their testing, “Službeni glasnik RS 23/1994“—is applicable in Serbia. Dashes mean that the
Rulebook does not prescribe limits.

From the results presented in Table 12, it can be seen that according to the rulebook,
which is applicable in Serbia, after a leaching test during 24 h, the concentrations of the
released elements from a mortar sample with 20% cement replacement with waste vitreous
enamel were much lower than allowed.
In order to fully confirm that the application of waste vitreous enamel is safe for
the environment, the leaching test was continued and performed for the next 60 days.
For the whole examined time interval, the concentration of released elements did not
deviate significantly in relation to those shown in Table 12. Thus, it may be concluded
that application of the waste vitreous enamel as a replacement for cement in mortar and
concrete productions is completely acceptable from ecological as well as human health
safety aspects.

4. Conclusions
Based on the results of testing the pozzolanic activity of waste vitreous enamel, as
well as its effect on the properties of cement paste, mortar, and concrete, the following can
be concluded:
1. The waste vitreous enamel possesses pozzolanic activity and belongs to class 5 of
pozzolanic materials. Additionally, the activity index, water requirement, setting
time, and soundness possess values that completely satisfied standard requirements,
which means it is possible to use a type II admixture for the production of concrete in
accordance with EN 206;
2. Replacing cement with waste material contributed to a reduction in compressive
strength of up to 12% and flexural strength of up to 7%, and also contributed to a
reduction in shrinkage due to drying and water absorption. Due to its glassy structure,
waste enamel has a positive effect on the consistency of the mortar by increasing its
workability by approximately 20%. Generally, replacement of cement with waste
Buildings 2022, 12, 1287 15 of 17

vitreous enamel in the amount of up to 20% in mortar does not greatly reduce its
physical and mechanical characteristics compared to the characteristics of the reference
mortar made with 100% cement;
3. The use of waste vitreous enamel in concrete, as a partial replacement of cement,
contributes to a slight decrease in mechanical properties, while on the other hand it
does not compromise the durability of the concrete. Replacement of cement with waste
vitreous enamel contributes to the improvement of concrete consistency (increases
settlement by 10–30 mm) and reduction of entrained air content by 20–50% compared
to reference concrete. Compressive strength decreases by 6% at 20% replacement of
cement, i.e., 22% at 30% replacement, while flexural strength decreases by a maximum
of 13%. The depth of penetration of water under pressure in hardened concrete and
freeze/thaw resistance with de-icing salt of concrete with waste material are in range
of reference concrete for replacement of cement to 20%. Generally, the physical and
mechanical properties of concrete mixed with up to 20% of cement replacement with
waste vitreous enamel do not significantly differ from the reference concrete;
4. Bearing in mind that the use of waste vitreous enamel solves the problem of its dis-
posal, and it can be used as a replacement for cement, it can be used in the production
of mortar and concrete whose quality is slightly lower than cement composites made
only with cement as a binder;
5. The application of the hazardous waste vitreous enamel as a replacement for cement
in mortar and concrete productions is completely acceptable from ecological as well
as human health safety aspects;
6. Further research should be focused on the study of the effect of pozzolanic reaction of
waste vitreous enamel on the characteristics of the interfacial transition zone and the
porous system of concrete composites in general.

Author Contributions: M.K. and M.S. conceived and designed the experiments, wrote the paper,
and contributed to all experiments and the analysis of the obtained results. N.R. performed physical-
mechanical measurements and contributed to analyzing the results. J.G., S.Ž. and S.M. participated
in leaching test measurements and analysis of the obtained results. S.L. contributed in the work with
XRD measurements. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: These investigations were supported by the Ministry of Education, Science, and
Technological Development of the Republic of Serbia (Contract numbers 451-03-68/2022-14/200017)
through the realization of research themes 1702203 and 1702205.
Conflicts of Interest: The authors declare no conflict of interest.

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