recycling

Article
Tire Recycled Rubber for More Eco-Sustainable
Advanced Cementitious Aggregate
Matteo Sambucci 1,2 , Danilo Marini 2 and Marco Valente 1,2, *
1 Department of Chemical and Material Engineering, Sapienza University of Rome, 000184 Rome, Italy;
matteo.sambucci@uniroma1.it
2 INSTM Reference Laboratory for Engineering of Surface Treatments, Department of Chemical and Material
Engineering, Sapienza University of Rome, 000184 Rome, Italy; danilo.marini@uniroma1.it
* Correspondence: marco.valente@uniroma1.it; Tel.: +39-06-4458-5582




Received: 1 April 2020; Accepted: 3 May 2020; Published: 11 May 2020


Abstract: This research focused on using ground tire rubber (GTR) with different grain sizes as a
replacement for the mineral aggregates used in a cement-based mixture suitable for extrusion-based
Additive Manufacturing. The use of two types of GTR particles and the possibility to apply rubberized
mixtures in advanced manufacturing technologies are the innovative aspects of this work. At the
base of this strategy is the possibility of achieving cementitious aggregates, which would potentially
be improved regarding some technological-engineering requirements (lightness, thermal-acoustic
insulation, energy dissipation capacity, durability) and environmentally sustainable. The integration
of waste tires into cement-based materials is a promising solution for the reuse and recycling of
such industrial waste. In addition, this approach may involve a considerable reduction in the use
of natural resources (sand, water, coarse mineral aggregates) needed for the building materials
production. The purpose of the research was to investigate the effect of sand-GTR replacement on
certain chemical-physical properties of mixtures (permeable porosity, surface wetness, and water
sorptivity), closely related to material durability. Besides, the role of rubber on the printability
properties of the fresh material was evaluated. GTR fillers do not alter the rheological properties
of the cement material, which was properly extruded with better print quality than the reference
mixture. Concerning chemical-physical characterization, the GTR powder-granules synergy promotes
good compaction of the mixture, hinders the cracks propagation in the cement matrix, decreases the
permeable porosity, improves the surface hydrophobicity and preserves optimal water permeability.

Keywords: additive manufacturing; cement-rubber mixtures; tire recycling; permeable porosity;

wetting properties; water sorptivity; cement material durability

1. Introduction
Thanks to the development of Additive Manufacturing (AM) in the construction sector, concrete
technology has considerably advanced in engineering, architectural and environmental terms. The main
benefits of additive processes, compared to standard manufacturing, are summarized in the following
aspects: higher fabrication speed, lower waste materials production, ease of prototyping and high
freedom in terms of the design of shapes [1]. The combination of digital fabrication and cement-based
materials promoted the development of innovative manufacturing processes for both small-scale
production (building components, urban furnishings) and large-scale fabrication (infrastructures,
housing modules). A detailed overview of additive technologies with building materials is reported
in [2]. Among the technologies currently in operation, the extrusion-based method is the most
widespread in academic and industrial sectors [1]. The deposition apparatus is very similar to the
common Fused Deposition Modeling (FDM) printers for polymers: the cement-based material is

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Recycling 2020, 5, 11 2 of 13

extruded by a digitally controlled nozzle, through layer-upon-layer deposition, until the pre-designed
object is built. In this context, the composition of the material plays a key role in the quality of
the final product. The rheology of the cement mixture must be properly studied to obtain the best
printability properties, such as extrudability, workability, buildability and inter-layer adhesion. The
correct balance of these parameters ensures a fresh material that can maintain its shape during
deposition, able to support the successive layers immediately after extrusion and provide the bond
between the adjacent layers avoiding the formation of voids and structural defects. These aspects
are fundamental to the structural integrity and mechanical strength of the hardened material [3].
The scientific literature highlights several studies related to the optimization of mixtures with metal
fillers [4] or reinforcement fibers (carbon, glass, basalt, polypropylene fibers) [5,6] mainly to improve
the workability and mechanical strength of the material.
This research work is based on the modification of “printable” cement mortar by the total
replacement of fine mineral aggregates with rubber fillers deriving from waste tires. In traditional
manufacturing, the use of ground tire rubber (GTR) as aggregate in the cement matrix is a widely
used strategy both to improve some physical and engineering properties of the building material
(deformability, vibro-acoustic damping, thermal insulation, lightness) and to achieve interesting effects
from an environmental point of view (disposal of waste tires and reduction in the use of natural
resources) [7]. Generally, researchers in this field focused their attention on incorporating a single
type of polymer aggregate (generally, 0.5–5 mm crumb rubber) as a partial substitute for fine mineral
aggregate (20%/25% by volume replacement) [8,9].
The innovative aspect of this work is the use of two different GTR particle grains (0–1 mm rubber
powder and 2–4 mm rubber granules) in cement compound for additive construction and evaluate how
their synergy affected the several chemical-physical performances of the material. For this purpose,
two rubberized mixtures have been designed and developed:

• Singly-sized rubber filler mixture (SSM) was obtained for total sand replacement with GTR powder
• Combined-sized rubber filler mixture (CSM) was obtained for total sand replacement with
specific GTR granules/powder ratio (25% by volume of rubber powder—75% by volume of
rubber granules)

In addition, a reference mortar (Ref.) containing 100% sand was also prepared to compare its
properties with those of the rubber-cement samples. Specifically, in the CSM mix production, a larger
amount of polymer coarse aggregate was selected than the powder. The fine aggregate encourages
material compaction and ensures a better voids-filling ability. Rubber coarse aggregate, on the other
hand, performs greater engineering functionality in terms of workability improvements, ductility,
micro-cracks reduction, acoustic and thermal inertia [10,11].
The paper describes an experimental program that examines the effect of GTR/sand replacement on
the print quality of the cement material, linked to the fresh mix rheology. Later, the research investigated
how the two types of GTR fillers affect the chemical-physical performances of the cement compound
in terms of morphological properties, surface wetness, and water permeability. These properties
are closely related to the durability performances of cement-based material, one of the fundamental
requirements for applications in the building and architectural fields.

2. Results and Discussion

2.1. Print Quality Investigation

The additive manufacturing of the slabs made it possible to evaluate the correct rheology of
cement mixtures and the structural characteristics of hardened materials. The presence of GTR fillers,
replacing the mineral aggregate, preserves suitable printability properties of the fresh compounds,
which were extruded without interruptions or collapse phenomena. Besides, the printed objects
showed good surface finish and dimensional conformity with reference to 3D CAD design.
Recycling 2020, 5, x 3 of 13
Recycling 2020, 5, x 3 of 13

Recycling
printed2020, 5, 11showed
objects good surface finish and dimensional conformity with reference to 3D 3CAD of 13
printed objects showed good surface finish and dimensional conformity with reference to 3D CAD
design.
design.
The visual
The visual inspectionofofthe the internal morphology of the specimens revealed better compaction
The visualinspection
inspection of theinternal morphology
internal morphology of the specimens
of the specimensrevealed better
revealed compaction
better compactionand
and uniformity
uniformity of
of the of the
rubberizedrubberized mixtures
mixturesmixtures
compared compared to
to the Ref.tomix the Ref. mix (see Figure 1a). The good
and uniformity the rubberized compared the(see Figure
Ref. mix 1a).
(see The
Figuregood1a).
homogeneity
The good
homogeneity
of GTR modified of GTR modifiedresulted
compounds compounds resulted instructure
in a defect-free a defect-free structure
while, while, inmix,
in the standard the standard
it can be
homogeneity of GTR modified compounds resulted in a defect-free structure while, in the standard
mix,
seen it can be seen the presence of inter-layer voids (see Figure 1b). The non-polar character of the
mix, the presence
it can be seen ofthe
inter-layer
presence voids (see Figurevoids
of inter-layer 1b). The
(see non-polar
Figure 1b).character of the rubber
The non-polar additives
character of the
rubber
could additives
changes the could
overall changes
surface the overall
tension of surface
the tension
mixtures (lowerof the mixtures
rubber-cement (lower rubber-cement
additives interfacial
rubber additives could changes the overall surface tension of the mixtures (lower rubber-cement
additives interfacial
interactions) interactions)
with consequent withfluidity
greater consequent
than thegreater
“neat” fluidity thanThis
mixture. the “neat” mixture. This
additives interfacial interactions) with consequent greater fluidity than the effect
“neat”results in easier
mixture. This
effect
flow results in easier flow that promotes the filling of gaps before hardening and minimizes the
effectthat promotes
results the flow
in easier fillingthat
of gaps beforethe
promotes hardening
filling ofand gaps minimizes the formation
before hardening and of voids in the
minimizes the
formation
interstices of voids in the interstices between the filaments. Our hypothesis is in good agreement
formation between
of voids the filaments.
in the Ourbetween
interstices hypothesis the isfilaments.
in good agreement with the
Our hypothesis results
is in goodreported
agreement by
with the studies
previous results reported
[12,13]. For by instance,
previous studies [12,13]. For instance, Aiello
that and Leuzzi [12]behaviour
observed
with the results reported by previousAiello
studiesand Leuzzi
[12,13]. [12]
For observed
instance, Aiello the
andrheological
Leuzzi [12] observed
that
of theconcrete
fresh rheological behaviour
changes of freshtoconcrete
from “fluid” “hyper-fluid”changes when fromthe“fluid”
mineralto “hyper-fluid”werewhen the
that the rheological behaviour of fresh concrete changes from “fluid” toaggregates
“hyper-fluid” replaced
when the
mineral
with aggregates
rubber were
aggregates. replaced with rubber aggregates.
mineral aggregates were replaced with rubber aggregates.

(a) (b)
(a) (b)
Figure 1. Inter-layer adhesion evaluation in cementitious samples (a) and investigation of structural
Figure 1. Inter-layer
Figure 1. Inter-layer adhesion
adhesion evaluation
evaluation in
in cementitious
cementitious samples
samples (a)
(a) and
and investigation
investigation of
of structural
structural
defects (b).
defects (b).
defects (b).

2.2. Porosity Measurements

2.2. Porosity Measurements
The results of
of the
the vacuum
vacuum saturation
saturation method
method areare shown
shown in in Figure
Figure 2.2. Modified mixtures with
The results of the vacuum saturation method are shown in Figure 2. Modified mixtures with
GTR aggregates exhibited
exhibited aa lower
lower permeable
permeable porosity
porosity than
than the
the standard
standard mix.mix. This behaviour is
GTR aggregates exhibited a lower permeable porosity than the standard mix. This behaviour is
closely related to three reasons [14]: (a) Ref. sample porosity is high
to three reasons [14]: a) Ref. sample porosity is high because of because of the use of porous
closely related to three reasons [14]: a) Ref. sample porosity is high because of the use of porous
mineral
mineral aggregates;
aggregates;(b)b)rubberized
rubberized mixtures were
mixtures developed
were with with
developed less water
less than
waterthethan
standard mixture,
the standard
mineral aggregates; b) rubberized mixtures were developed with less water than the standard
so duringsothe
mixture, aging
during theprocess the formation
aging process of air bubbles
the formation and voids
of air bubbles is lessis relevant;
and voids (c) thanks
less relevant; to
c) thanks
mixture, so during the aging process the formation of air bubbles and voids is less relevant; c) thanks
their viscoelastic
to their properties,
viscoelastic properties, rubber
rubber particles
particlesmore
moreeffectively
effectivelyhinder
hinderthethecracks
cracks propagation
propagation (due
(due
to their viscoelastic properties, rubber particles more effectively hinder the cracks propagation (due
hygrometric
hygrometric shrinkage)
shrinkage) in in the
the cement
cement matrix
matrix than
than stiff
stiffmineral
mineralaggregates.
aggregates.
hygrometric shrinkage) in the cement matrix than stiff mineral aggregates.

Permeable porosity (%)

Permeable porosity (%)
40.0%
40.0%
30.0%
30.0%
20.0%
20.0%
33.3% 22.0%
10.0% 33.3% 22.0% 25.7%
10.0% 25.7%

0.0%
0.0%
Ref SSM CSM
Ref SSM CSM

Figure 2. Permeable porosity (%) experimental results.

Figure 2. Permeable porosity (%) experimental results.
Comparing SSM and CSM mixtures, it is possible to observe that the presence of GTR granules
lightly increases the voids percentage than the mixture with only GTR powder. Coarse rubber
Recycling 2020, 5, x 4 of 13
Recycling 2020, 5, 11 4 of 13
Comparing SSM and CSM mixtures, it is possible to observe that the presence of GTR granules
lightly increases the voids percentage than the mixture with only GTR powder. Coarse rubber
aggregates provide better
aggregates provide better performance
performance on on cracking
cracking blocking
blocking but
but have
have poor
poor adherence
adherence toto the
the matrix.
matrix.
This effect produces interface voids that affect the open porosity of the material. On the
This effect produces interface voids that affect the open porosity of the material. On the other, other, powder
particles have a larger
powder particles havespecific surface
a larger area
specific than granules,
surface area thansogranules,
they ensure betterensure
so they adhesion with
better cement
adhesion
resulting in a more compact microstructure [10].
with cement resulting in a more compact microstructure [10].
Optical
Optical micrographs, acquired with
micrographs, acquired with 16× magnification, confirm
16× magnification, confirm the
the trend
trend determined
determined by by the
the
experimental permeable porosity results. For microscopy analysis, Ref. sample was
experimental permeable porosity results. For microscopy analysis, Ref. sample was compared with compared with
CSM
CSM sample
sample (containing
(containing both
both GTR
GTR fillers). The concentration
fillers). The concentration and
and size
size of
of voids
voids (labeled
(labeled in
in yellow)
yellow) in
in
the
the rubberized
rubberized sample
sample (Figure
(Figure 3b)
3b) are
are much
much lower
lower than
than in
in the
the “neat”
“neat” material
material (Figure
(Figure 3a).
3a).

(a) (b)
Figure 3. Optical microscopy analysis on cement-based samples: porosity distribution in Ref. (a) and
CSM (b).

2.3. Water Contact

2.3. Water Contact Angles
Angles (WCAs)
(WCAs) Test
Test
WCAs
WCAs test results (see
test results (see Table
Table 1)
1) show
show that
that GTR
GTR fillers
fillers reduce
reduce the
the wettability
wettability of
of the
the cementitious
cementitious
surface (increase in WCA value).
surface (increase in WCA value).
Table 1. Average WCA values for each cement-based mixture.
Table 1. Average WCA values for each cement-based mixture.
Mixture Type Average WCA
Mixture Type Average WCA
Ref. 54 ◦ ± 15◦
Ref. 54°◦ ± 15°◦
SSM 80 ± 14
SSM 80°◦± 14°◦
CSM 111 ± 38
CSM 111° ± 38°

A
A comparison
comparison among
among the the Ref. sample and
Ref. sample and the
the rubberized
rubberized mixtures
mixtures isis reported
reported inin Figure
Figure 4,
4, with
with
the high-resolution images of the respective surfaces captured during the
the high-resolution images of the respective surfaces captured during the WCA experiment. SSM WCA experiment. SSM and
CSM
and CSM test surfaces (Figure 4b,c, respectively) appear rougher than Ref. surface (Figure 4a) duethe
test surfaces (Figure 4b,c, respectively) appear rougher than Ref. surface (Figure 4a) due to to
distribution of polymer
the distribution aggregates
of polymer incorporated
aggregates in the cement
incorporated in thepaste. A very
cement different
paste. surface-water
A very different
droplet interaction
surface-water is observed
droplet interactionon the samples: on
is observed “neat” cement matrix
the samples: “neat”promotes faster water
cement matrix absorption
promotes faster
and
watergreater drop spreads
absorption over the
and greater drop surface compared
spreads over the tosurface
the rubberized
compared surfaces.
to the The GTR particles
rubberized act
surfaces.
as hydrophobic sites, preventing the deposition of the liquid on the cement
The GTR particles act as hydrophobic sites, preventing the deposition of the liquid on the cement matrix and its potential
permeation
matrix and itsin the material.
potential The size of
permeation in polymer particles
the material. The plays
size ofa polymer
key role in this water-repellent
particles effect.
plays a key role in
The
this presence of GTReffect.
water-repellent granules The(CSM)
presence decreases
of GTRthe wetting(CSM)
granules properties, as thethe
decreases probability of water drop
wetting properties, as
settles on the hydrophobic
the probability of water drop site is higher
settles on thethan the presence
hydrophobic siteof
is only GTR
higher thanpowder (SSM).ofThe
the presence coarse
only GTR
rubber
powder (SSM). The coarse rubber aggregates expose a greater contact surface for the water stable
aggregates expose a greater contact surface for the water drop, which tends to remain drop,
and
whichundeformed after deposition
tends to remain stable and(see Figure 4c).after
undeformed Thedeposition
wetting behavior of the4c).
(see Figure CSMThecan be classified
wetting behavioras
hydrophobic (WCA > 90 ◦ ). Thus, filler hydrophobicity prevails over the absorbent behavior of the
of the CSM can be classified as hydrophobic (WCA > 90°). Thus, filler hydrophobicity prevails over
hydrophilic
the absorbent cement
behaviormatrix [15].
of the hydrophilic cement matrix [15].
Recycling 2020,
Recycling 5, 5,
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xx 5 of513
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(a) (b) (c)

(a) (b) (c)
Figure
Figure 4.4.Water
Waterdrop—cement
drop—cementsurface
surface interaction:
interaction: Ref.
Ref.(a),
(a),SSM
SSM(b)
(b)and
andCSM
CSM(c)(c)
samples.
samples.
Figure 4. Water drop—cement surface interaction: Ref. (a), SSM (b) and CSM (c) samples.
2.4.2.4.
Water
WaterSorptivity
SorptivityTest
Test
2.4. Water Sorptivity Test
For this
For experimental
this experimentalstudy, twotwo
study, specimens of each
specimens mixture
of each werewere
mixture tested, and the
tested, andaverage S-index
the average
was For
S-index this
determined. experimental
was determined. study,
The qualityThe
of the two
cement
quality specimens
mixtures
of the of
cementwaseach mixture
evaluated
mixtures were tested,
wasbyevaluated
considering and
by the the average
recommended
considering the
S-index
sorptivity was
recommended determined.
values sorptivity
proposed byThe
valuesquality of
andthe
proposed
Papworth by cement
[16]. mixtures
Papworth
Grace was
and Grace
These evaluated
[16].
reference by considering
These reference
sorptivity sorptivity
performance the
classes
recommended
areperformance sorptivity
classes
listed in Table valuesinproposed
2. are listed Table 2. by Papworth and Grace [16]. These reference sorptivity
performance classes are listed in Table 2.
Table2.2.Sorptivity
Table Sorptivityperformance classes proposed
performance classes proposedby
byPapworth
Papworthand
andGrace.
Grace.
Table 2. Sorptivity performance classes proposed by Papworth and Grace.
Sorptivity
Sorptivity(mm/min 0.5)) Performance
(mm/min0.5 Classes
Performance Classes
Sorptivity
Poor
Poor (mm/min
Acceptable0.5) Performance
Acceptable Very Classes
VeryGood
Good
>0.2
Poor 0.1 to 0.2
Acceptable Very<0.1
Good
>0.2 0.1 to 0.2 <0.1
>0.2 0.1 to 0.2 <0.1
The water sorptivity index results are plotted in Figure 5.
The water sorptivity
The water sorptivity index
index results
results are
are plotted
plotted in in Figure
Figure 5.
5.
Water Sorptivity Index (mm/√min)
8.0 × 10−3 Water Sorptivity Index (mm/√min)
8.0 × 10−3−3
6.0 × 10
−3
4.0××10
6.0 10−3 5.9 × 10−3 6.5 × 10−3
5.7 × 10−3
−
2.0××10
4.0 103−3 5.7 × 10−3 5.9 × 10−3 6.5 × 10−3

2.0 × 10−03
Ref SSM CSM
0
Figure 5. Water sorptivityRef
of Ref. mix and rubber-cement
SSM mixturesCSM
(SSM and CSM).

All cement-based
Figure 5. WaterWatermixtures
sorptivitycanofbe
Ref.classified
mix and as
mix and “very good”mixtures
rubber-cement
rubber-cement since the S-index
(SSM values are less
and CSM).
than 0.1 mm/min0.5. In rubberized mixtures, a slight increase in sorptivity is observed compared to
theAll cement-based
standard material.mixtures
cement-based This trend
mixtures can
can bebeclassified
may be related
classifiedasto“very
as the
“verygood”
weak since
adhesion
good” thebetween
since S-index
the values
the
S-index GTR are
values less
are than
particlesless
0.1and 0.5
themm/min
cement . Inmatrix, which mixtures,
can mixtures,
generate additional access
in ducts for liquid
than mm/min
0.1 0.5rubberized
. In rubberized a slight increase
a slight increase sorptivity
in sorptivity ispenetration.
is observed
observedcompared
compared to the
to
standard
the Asmaterial.
standard highlighted
material.ThisbyThis
the SEM
trend may(MIRA
trend be
may 3 FEG-Scanning
related
be to the to
related weaktheElectron
adhesion Microscope)
between
weak adhesion themicrograph
between GTRthe in Figure
particles
GTR and the
particles
and6a,the
cement thematrix,
weak rubber-cement
cement which
matrix,can interface
generate
which is more
additional
can generate relevant
access
additional in the
ducts
access presence
forducts
liquidfor of GTRpenetration.
penetration.
liquid granules. This effect
implies a greater
As highlighted
highlighted by water
by the penetration
theSEMSEM(MIRA in the CSM
(MIRA33FEG-Scanning sample than
FEG-ScanningElectron other
Electron cement
Microscope)
Microscope) mixtures, confirming
micrograph
micrograph the 6a,
in Figure
in Figure
6a,trend
the the
weak of water
rubber-cement
weak sorptivity
rubber-cement previously
interface is more
interface analyzed.
is relevant On the other
in the presence
more relevant hand, in the
of GTR granules.
in the presence SSM mix, the
This effect
of GTR granules. GTR
implies
This effecta
powder-cementitious
greater water
implies penetration
a greater matrix
water penetration adhesion
in the CSM in sample appears
the CSMthansample more
other cement cohesive (Figure
mixtures,
than other cement 6b),
confirming
mixtures, confirming
theconfirming the
trend of water the
functionality
sorptivity of the fine
previously fillers toOn
analyzed. ensure betterhand,
theanalyzed.
other material compaction and toGTR
minimize interface voids
trend of water sorptivity previously Oninthe
the SSM mix,
other hand,the in thepowder-cementitious
SSM mix, the GTR
[10].
matrix adhesion appears
powder-cementitious more cohesive
matrix adhesion(Figure appears6b), more
confirming the functionality
cohesive (Figure 6b),of the fine fillersthe
confirming to
ensure better of
functionality material
the fine compaction and tobetter
fillers to ensure minimize interface
material voids [10].
compaction and to minimize interface voids
[10].
Recycling 2020, 5, 11
x 6 of 13

(a) (b)
SEM micrograph
Figure 6. SEM micrograph of rubber fillers-cement matrix interface: rubber granule–cement adhesion
(a) and rubber powder-cement
powder-cement adhesion
adhesion (b).
(b).

3. Materials and
3. Materials and Methods
Methods

3.1. Experimental Extrusion System for Cement-Based Mixtures

3.1. Experimental Extrusion System for Cement-Based Mixtures
The laboratory testing of fresh printing mixtures and the additive manufacturing of the samples
The laboratory testing of fresh printing mixtures and the additive manufacturing of the samples
were performed at the Mechanical Engineering Department of the Marche Polytechnic University
were performed at the Mechanical Engineering Department of the Marche Polytechnic University
(Ancona, Italy). In general, the extrusion system comprises a COMAU 3-axis robotic-arm equipped with
(Ancona, Italy). In general, the extrusion system comprises a COMAU 3-axis robotic-arm equipped
a PVC deposition nozzle (Ø = 10 mm), a pumping system, an aluminum tank with piston, a vibrating
with a PVC deposition nozzle (Ø = 10 mm), a pumping system, an aluminum tank with piston, a
platform and a printing surface. The pumping system applies 4 bar pressure to the cylindrical tank
vibrating platform and a printing surface. The pumping system applies 4 bar pressure to the
containing the fresh cement mortar. This process drives the piston, which promotes the entry of the
cylindrical tank containing the fresh cement mortar. This process drives the piston, which promotes
mixture into the deposition nozzle. The nozzle is connected to the robotic arm that moves according to
the entry of the mixture into the deposition nozzle. The nozzle is connected to the robotic arm that
the instructions imposed by the control software. CURA® control software (Utrecht, Netherlands)
moves according to the instructions imposed by the control software. CURA® control software
elaborates the 3D CAD file of the object to be made and allows to select the manufacturing parameters
(Utrecht, Netherlands) elaborates the 3D CAD file of the object to be made and allows to select the
(printing speed, infill, layer thickness, print path). The 3D design is completed in a layer by layer
manufacturing parameters (printing speed, infill, layer thickness, print path). The 3D design is
process through a combined motion of the robotic arm in X, Y, and Z direction.
completed in a layer by layer process through a combined motion of the robotic arm in X, Y,and Z
direction.
3.2. Materials Preparation
In this work,
3.2. Materials the rubberized mixtures (labeled as SSM and CSM respectively) were developed from
Preparation
a standard printable cement mortar (labeled as Ref.). Ref. mix (provided by INNOVAcrete® , Ancona,
Italy)In this work,
consists theI rubberized
of Type mixtures
Portland cement, 0–0.4(labeled as SSMsand,
mm limestone and CSM respectively)
0.35 w/c were developed
ratio and chemical additives
from a standard printable cement mortar (labeled as Ref.). Ref. mix (provided by
(Silica fume, Calcium oxide, superfluidifyng agent and reducer additive) in proper proportions. INNOVAcrete GTR,
®

Ancona, (Figure
powder Italy) consists
7a) andofgranules
Type I (Figure
Portland7b) cement, 0–0.4 mmby
were provided limestone sand, 0.35Tyre
ETRA (European w/c Recycling
ratio and
chemical additives (Silica fume, Calcium oxide, superfluidifyng
Association) and were obtained by ambient mechanical grinding of scrap tires. agent and reducer additive) in
proper proportions. GTR powder (Figure 7a) and granules (Figure 7b) were provided by
Fillers size was evaluated by optical microscope analysis (Leica MS5 device): powder has 0.5–1.1 mm ETRA
size, while Tyre
(European Recycling
granules Association)
have 2.5–3.7 and The
mm size. wereaverage
obtained by ambient
density of GTR mechanical
aggregatesgrinding of scrap
(determined by
tires.
Micromeritics AccuPyc 1330 He-pycnometer, Norcross, GA, USA.) is 1202 kg/m . 3
Fillers size was evaluated by optical microscope analysis (Leica MS5 device): powder has 0.5–
1.1 mm size, while granules have 2.5–3.7 mm size. The average density of GTR aggregates
(determined by Micromeritics AccuPyc 1330 He-pycnometer, Norcross, GA, USA.) is 1202 kg/m3.
Recycling 2020, 5, x 7 of 13

Recycling 2020, 5, 11
x 7 of 13

(a) (b)
Figure 7. Size and shape of GTR powder (a) and granules (b) used in the research work.
(a) (b)
Starting with the reference formulation, the following sand-GTR volume replacements were
Figure 7. Size and shape of GTR powder (a) and granules (b) used in the research work.
performed: in SSM, sand was totally replaced with rubber powder; in CSM, sand was replaced by 25
vol.%Starting
rubber with
Starting powder
with the and
the 75 vol.%
reference
reference rubber granules.
formulation,
formulation, the As mentioned
the following
following sand-GTR
sand-GTR earlier,
volume
volumethe fresh mix rheology
replacements
replacements were
were
and the
performed:raw materials balance must be optimized according to the extrusion system
performed: in SSM, sand was totally replaced with rubber powder; in CSM, sand was replaced by by
in SSM, sand was totally replaced with rubber powder; in CSM, sand features
was (nozzle
replaced 25
design,
25 vol.%
vol.% pumping
rubber
rubber system,
powder
powder andprinting
and 75 vol.% process
75 vol.% rubber parameters)
rubbergranules.
granules. As and proper
Asmentioned
mentioned printability
earlier, thethe
earlier, fresh requirements.
mixmix
fresh rheology To
and
rheology
establish
the
andraw thematerials
the materials
raw appropriate
balance mixture
must
balance proportions,
be optimized
must aaccording
qualitative
according
be optimized to investigation
to the extrusion was
systemsystem
the extrusion performed
features on the
(nozzle(nozzle
features design,
flowability,
pumping extrudability,
system, printing
design, pumping and buildability
process parameters)
system, printing of the fresh
and proper
process parameters) mixtures. For
andprintability this purpose,
requirements.
proper printability six-layer slabs
To establish
requirements. To
with
the dimensions
appropriate 220 mm
mixture × 160 mm
proportions, × 55
a mm were
qualitativeprinted with
investigation a linear
was extrusion
performed
establish the appropriate mixture proportions, a qualitative investigation was performed on the speed
on the of 33 mm/s.
flowability,
Below is a extrudability,
extrudability,
flowability, description of
and buildability
and the test procedure
ofbuildability
the fresh of the to
mixtures. Forevaluate
fresh this theFor
purpose,
mixtures. optimal
six-layer mix
slabs design
this purpose, with for slabs
each
dimensions
six-layer
cement-based
220
withmmdimensions compound:
× 160 mm 220×mm55 mm
× 160were
mm ×printed
55 mmwith
wereaprinted
linear extrusion speed
with a linear of 33 mm/s.
extrusion speed ofBelow is a
33 mm/s.
•description
Below is aofdescription
the it
Flowability: test procedure
of tothe
defines totest
the evaluate thewhich
with optimal
easeprocedure to themix design
evaluate
fresh thefor
mix each
optimal
flow cement-based
out mix
of thedesigncompound:
nozzle for each
without
cement-based compound:
obstruction. This printing criteria was evaluated by visual inspection of the deposition process.
• Flowability: it defines to the ease with which the fresh mix flow out of the nozzle without
• Flowability: This
obstruction.
Extrudability:it itdefines
printing
refers easewas
to criteria
the fresh with which
evaluated
material the fresh
by visual
ability to mix flow out
be inspection
continuously of deposition
of the the nozzle
deposited without
process.
through the
• obstruction.
Extrudability:Thisit printing
refers to criteria
the was
fresh evaluated
material by
ability visual
to be inspection
continuously
extrusion nozzle with good dimensional conformity/consistency and without defects. of the deposition
deposited process.
through the
extrusion nozzlewas
Extrudability withqualified
good dimensional conformity/consistency
as “correct” if the to printed and without
object defects.
wasdeposited Extrudability
completely free the
of
• Extrudability: it refers to the fresh material ability be continuously through
was qualified as
discontinuity and “correct”
voids. if the printed object was completely free of discontinuity and voids.
extrusion nozzle with good dimensional conformity/consistency and without defects.
• Buildability:
Extrudabilityititcan bequalified
evaluatedas by “correct”
the numberifofthelayer of the sample that
wascanthat
be printed without
• Buildability: was
can be evaluated by the number of printed
layer of object
the sample completely free of
can be printed
collapse or relevant
discontinuity and deformation.
voids. In this study, 6 layers was adopted as the target requirement to
without collapse or relevant deformation. In this study, 6 layers was adopted as the target
accept the mixture as “printable”.
• requirement
Buildability: to
it accept
can bethe mixture by
evaluated as “printable”.
the number of layer of the sample that can be printed
Figure 8 shows
without8 shows
Figure collapse some steps
or relevant
some of the
steps of the printability
printabilityIntest.
deformation. this study, 6 layers was adopted as the target
test.
requirement to accept the mixture as “printable”.
Figure 8 shows some steps of the printability test.

(a) (b)
slab extrusion
Figure 8. Printability test: slab extrusion process
process (a)
(a) and consistency of the optimum fresh mix (b).
(a) (b)
Figure 8. Printability test: slab extrusion process (a) and consistency of the optimum fresh mix (b).
Recycling 2020,
Recycling 2020, 5,
5, 11
x 88 of
of 13
13

For each rubberized formulation, the water content has been gradually varied in order to obtain
similar
Forprintability properties
each rubberized as Ref. mix.
formulation, Tablecontent
the water 3 belowhas
shows
beenthe printable
gradually mix designs,
varied referring
in order to obtain
to 1 m3,printability
similar for each compound.
properties as Ref. mix. Table 3 below shows the printable mix designs, referring to
1 m3 , for each compound.
Table 3. Mix proportions of cementitious aggregates.
Table 3. Mix proportions of cementitious aggregates.
Mix Design Ref. SSM CSM
Mixw/c ratio
Design 0.375
Ref. 0.325
SSM 0.287
CSM
Sand (kg/m3)
w/c ratio 1100
0.375 0
0.325 0
0.287
GTR
Sandpwd. 3)
(kg/m(kg/m 3) 0
1100 300
0 750
3) 3 00 300
GTR
GTRpwd. (kg/m
gran. (kg/m ) 0 24075
GTR gran. (kg/m 3) 0 0 240
Additives (kg/m3
3) 152 152 152
Additives (kg/m ) 152 152 152

As shown in Table 3, the water-to-cement ratio (w/c ratio) is lower in the rubberized compounds
than As Ref.shown in Tablethis
mix. Besides, 3, the water-to-cement
decrease ratio (w/c
is more relevant ratio)mix
in CSM is lower in the rubberized
containing compounds
the coarse rubber filler.
than Ref. mix. Besides,
The aforementioned effectthis
is decrease
related toisthe
more relevant
greater sizeinand
CSM mix containing
hydrophobic theofcoarse
nature rubber
the polymer
filler.
particlesThecompared
aforementioned effect is
to limestone related
sand. to the greater
According to Lyse‘ssizerule
and[17],
hydrophobic nature of
as the aggregate theincreases,
size polymer
particles
the watercompared
required to limestone sand.workability
reach specific According of to the
Lyse‘s rule
fresh [17], as decreases.
material the aggregate
Thesize
lowerincreases,
use of
the
waterwater required
for the to reach
production specific workability
of rubberized of the freshtomaterial
mortars, compared decreases.
the standard The lower
cement-based use of
material,
water
can be considered a beneficial aspect with regard to optimization in the use of natural resources can
for the production of rubberized mortars, compared to the standard cement-based material, for
be
theconsidered
construction a beneficial
industry. aspect with regard to optimization in the use of natural resources for the
construction industry.
3.3. Samples Manufacturing
3.3. Samples Manufacturing
After air-dry hardening, a preliminary observation on the printed slabs (see Figure 9) was
performed air-dry
After hardening,
to evaluate a preliminary
the print quality ofobservation
the mixtures on (presence
the printedofslabs (see surface
defects, Figure 9) was
finish,
performed to evaluate the print quality of the mixtures (presence of defects,
inter-layer adhesion). Then, 48 mm × 42 mm × 22 mm specimens (four samples for each mixture) andsurface finish, inter-layer
adhesion).
70 mm × 40 mm Then,
× 4048mmmm × 42 mm
specimens × samples
(two 22 mm specimens (four samples
for each mixture) for each
were extracted from mixture)
the slabsand
by
70 mm × 40 mm × 40 mm specimens (two samples for each mixture) were
cutting with a diamond circular saw. The first samples were used for porosity test, optical extracted from the slabs by
cutting with a diamond circular saw. The first samples were used for porosity
microscopy analysis, and water contact angle test. The second ones were characterized by water test, optical microscopy
analysis,
sorptivityand test.water contact angle test. The second ones were characterized by water sorptivity test.

(a) (b)
Top-view (a) and front-view (b) of a printed slab (SSM mix).
Figure 9. Top-view

3.4. Porosity Measurements

3.4. Porosity Measurements
The
The pore
poresystem
systemofof cement-based
cement-basedmaterials can adversely
materials affectaffect
can adversely both mechanical behaviour
both mechanical (failure
behaviour
strength and creep
(failure strength strain)
and creepand transport
strain) properties.properties.
and transport TransportTransport
propertiesproperties
are intimately related to
are intimately
the durability of the material: higher porosity promotes the permeation
related to the durability of the material: higher porosity promotes the permeationof physical-chemical agents
of
(liquids, gasses, various aggressive ions, pollutant agents) resulting in material degradation
physical-chemical agents (liquids, gasses, various aggressive ions, pollutant agents) resulting in [18].
Vacuum
material saturation
degradation method (ASTM C1202) [19] was used to determine the permeable porosity
[18].
of cement-based mixtures.
Vacuum saturation method The specimens were dried
(ASTM C1202) in the
[19] was oven
used at 110 ◦ C for
to determine the2permeable
h to determine the
porosity
oven-dry mass (W
of cement-based dry ). Subsequently,
mixtures. the specimens
The specimens were driedwere
in theplaced
oven inside
at 110 a°Cdesiccator
for 2 h toconnected
determineto a
the
Recycling 2020, 5, 11 9 of 13

vacuum pump. The pump was started and run for 4 h at a pressure of 0.3 bar to evacuate all air from
the open pores. After the process, the samples were weighed and the saturated surface-dry mass of the
specimen in air (Wsat ) was evaluated. Then, bidistilled water was gradually fed into the desiccator,
until the blocks were fully covered. 24 h later samples were taken out of the liquid and weighed (Wwat ).
The permeable porosity (P% ) was calculated based on Equation (1).

Wsat − Wdry
P% = (1)
Wsat − Wwat

Optical microscope (OM) images, acquired with Leica MS5 device, were analyzed by ImageJ
software (Bethesda, DC, USA.) to evaluate the distribution of open porosity and surface defects in
each sample.

3.5. Water Contact Angles (WCAs) Test

Water contact angles (WCAs) on the reference and rubber-cement composites surfaces were
measured using an OCA15 Pro analyzer (DataPhysics Instruments, Filderstadt, Germany). Analyses
were performed by the sessile drop method and using ultrapure water as testing liquid. Twelve drops
with a fixed volume of 3 µL were deposited (dosing rate = 1 µL/s) and analyzed for each cement-based
formulation. WCA measurements were determined ten seconds after the water drop deposition. From
the twelve depositions made, an average WCA value was calculated. The study was performed to
evaluate the effect of hydrophobic rubber fillers on cement matrix wettability.
As confirmed by several studies [20,21], reducing the wetting properties of concrete can be an
interesting strategy to improve resistance to moisture and corrosive liquid permeation, one of the
main factors of building materials deterioration. Besides, the development of a hydrophobic cement
matrix can imply other interesting benefits such as icephobicity, self-cleaning behavior, and resistance
to paints and graffiti [15].

3.6. Water Sorptivity Test

According to Elawady et al.’s definition, sorptivity is the tendency of a cement-based material to
absorb and transmit water and other liquids by capillarity [22]. It was recognized as an important
chemical-physical index of durability performance because the experimental method used for its
evaluation reflects the way that most building materials will be penetrated by water and other corrosive
agents [23]. Capillary absorption depends on two factors: (a) porous structure of the material (porosity
degree, tortuosity, pore size); (b) physical-rheological properties of permeating fluid (surface tension,
density, viscosity) [15].
Sorptivity index (S) was evaluated in accordance with ASTM C1585 [24]. The test is based on
determining the water absorption rate by measuring the mass increase of the sample as a function
of time and in the unidirectional flow condition. The samples were placed in a Pyrex glass pan on
Aluminum rods. The function of the rods is to avoid contact between the test surfaces and the bottom of
the pan and thus ensure correct material-liquid exposure. Bidistilled water in the pan was maintained
at about 1 cm above the base of the specimens throughout the experiment. The test was performed for
40 days during which, at regular time intervals of 24 h, the mass of the samples (Wn ) was determined.
A total of 15 mass measures were recorded. In each detection, the temperature of the water (T) was also
measured in order to obtain an accurate density value of the liquid (%). Prior to the test, the sides of the
specimens were coated by silicone rubber to ensure unidirectional water absorption and minimize the
liquid side evaporation during the test. Dry samples were weighed (Wi ) before starting the experiment.
Figure 10 shows sorptivity specimens during the test.
Recycling 2020, 5, 11 10 of 13
Recycling 2020, 5, x 10 of 13

Figure 10. Cementitious specimens during water sorptivity test.

Sorptivity index (S) was obtained by using Equation (2):

((Wn −−W ))
i = ×√ √ (2)
( ) × = S× t (2)
ρ(T) × A
where A = the test surface of the specimen that was in contact with water (mm2); t = time (min). To
where A = Sthe
determine test surface
index, of the specimen
the cumulative volumethat was inabsorbed
of water contact with water
per unit of(mm
2 t = time (min). To
area );(1st member of the
determine S index,
equation) was the against
plotted cumulative
t1/2. Svolume
(mm/min of 0.5
water absorbed
) is the slope ofper
theunit
bestoffit
area
line(1st
to member of the
the absorption
equation) was plotted against t1/2 . S (mm/min0.5 ) is the slope of the best fit line to the absorption curve.
curve.
4. Rubberized Cementitious Aggregates: Cost-Benefit Analysis
4. Rubberized Cementitious Aggregates: Cost-Benefit Analysis
Concrete and mortar have become very expensive materials because the high price of aggregates
Concrete and mortar have become very expensive materials because the high price of
which constitute three-quarters of the mixture volume [25]. Incorporation of waste tire rubber fillers as
aggregates which constitute three-quarters of the mixture volume [25]. Incorporation of waste tire
mineral aggregates replacement in cement-based compounds could be beneficial not only in engineering
rubber fillers as mineral aggregates replacement in cement-based compounds could be beneficial not
and environmental terms but also in manufacturing costs of the aforesaid building materials. Table 4
only in engineering and environmental terms but also in manufacturing costs of the aforesaid
below lists the average costs of the mineral and rubber aggregates used for the development of the
building materials. Table 4 below lists the average costs of the mineral and rubber aggregates used
three mixtures investigated in this work.
for the development of the three mixtures investigated in this work.
Table 4. Average cost (per ton.) of aggregates used in the production of cement mixtures.
Table 4. Average cost (per ton.) of aggregates used in the production of cement mixtures.
Aggregate Type EUR/ton Source
Aggregate Type EUR/ton Source
Limestone sand
Limestone sand (0–0.4
(0–0.4mm)
mm) 120
120 [26]
[26]
GTR powder (0–1 mm) 140 ETRA
GTR powder (0–1 mm) 140 ETRA
GTR granules (2–4 mm) 170 ETRA
GTR granules (2–4 mm) 170 ETRA

The
The lightly
lightly higher
higher (but
(but not
not prohibitive)
prohibitive) cost
cost of
of polymer
polymer raw
raw materials, compared to
materials, compared to the
the stone
stone
aggregate
aggregate commonly used as a constituent of the cement mixture, can be compensated by
commonly used as a constituent of the cement mixture, can be compensated by some
some
interesting
interesting economic
economic and
and production
production factors
factors [27,28]:
[27,28]:
•
• Indirect costs
costs savings. Replacing traditional
savings. Replacing traditional aggregates
aggregates with
with recycled raw materials implies
savings related to landfill
landfill tax, landfill gate fee and aggregates levy.
tax, landfill gate fee and aggregates levy. The indirect costs rate
depending on the socio-economic
socio-economic policy of the country,
country, but
but an
an average
average saving
saving of
of EUR
EUR 15
15 per m33
per m
of recycled-based cement
cement material
material produced
produced isis estimated.
estimated.
• Indirect benefits. Despite its initial higher unit cost, the low density of GTR fillers compared to
• Indirect benefits. Despite its initial higher unit cost, the low density of GTR fillers compared to
that of limestone sand (~2600 kg/m33 ) could also result in cost savings when the replacement is
that of limestone sand (~2600 kg/m ) could also result in cost savings when the replacement is
performed in terms of volume rather than weight. The use of lighter raw materials would result
performed in terms of volume rather than weight. The use of lighter raw materials would result
in reduced quantities of aggregates required. Referring to Table 3, about 300 kg of tire rubber
in reduced quantities of aggregates required. Referring to Table 3, about 300 kg of tire rubber
filler instead of 1100 kg of sand is needed to obtain 1 m33 of cement mixture suitable for AM. In
filler instead of 1100 kg of sand is needed to obtain 1 m of cement mixture suitable for AM. In
this context, an additional savings source concerns the smaller amount of water needed for the
this context, an additional savings source concerns the smaller amount of water needed for the
production of rubberized mixtures.
production of rubberized mixtures.
• Tax incentives. In several countries, relevant economic incentives have been provided for
• Tax incentives.
companies usingIn several and
recycling countries,
reuse rawrelevant economic
materials. incentives
For example, havethe
in Italy, been provided
“Green Economyfor
companies using recycling and reuse raw materials. For example, in Italy, the “Green Economy
law” aims to financially support companies that invest in low-environmental manufacturing
Recycling 2020, 5, 11 11 of 13

law” aims to financially support companies that invest in low-environmental manufacturing

approaches. Under this legislation, companies can take advantage of a 10% tax credit on
investments made.

5. Conclusions
This paper examines the usage of two types of GTR fillers (rubber powder and rubber granules)
as substitutes for fine mineral aggregates in a cement-based mixture suitable for AM. The aim of the
research was to investigate the synergistic effect of the different rubber aggregate grain size on material
printability and certain physical-chemical properties related to performance durability. Based on the
experiments performed, subsequent conclusions are reported:

1. The greater deformability of fillers compared to fine mineral aggregates implies less rigidity of
the deposed filaments and therefore better inter-layer adhesion. The internal morphology of
the hardened rubberized materials is homogeneous and free of structural defects, while the Ref.
samples show voids and cavities due to poor layers bonding.
2. Permeable porosity of cement mixtures modified with rubber fillers is lower than the Ref. mixture.
The lower w/c ratio required for the realization of rubberized mixtures compared to the standard
formulation minimizes the formation of pores related to the aging process. Besides, fillers synergy
plays a key role in the microstructural properties of the material: rubber powder ensures the
mixture compaction, while rubber granules hinder the crack propagations in the matrix.
3. The presence of rubber aggregates increases material hydrophobicity. This aspect is crucial
regarding the material’s inertia to moisture and damaging agents.
4. Water sorptivity test showed very good permeability performances for all the mixtures developed
in this research work. In the CSM mix, the water capillary absorption is slightly higher due to the
effect of interface cavities acting as conduits for liquid penetration.

Hence, the use of GTR fillers as aggregates in cement mortar has eco-sustainable credentials, in
that it uses a waste product to optimize several performances and provide a material that will be
potentially more durable than a plain mixture with subsequent lower life cycle costs due to reduced
maintenance requirements. In addition, the use of recycled materials in the construction industry can
bring significant benefits in terms of production costs and financial support.
In future research works, the experimental testing on the material will be completed (static and
dynamic mechanical characterization, thermal and acoustic testing). Subsequently, according to the
performances determined by the experimental characterization, the most suitable type of building and
architectural application will be evaluated. The high freedom of design offered by AM can be used to
perform topology optimization studies in order to improve technological properties by operating on
prototype shapes and geometries.

Author Contributions: Experiments were designed by M.V. and M.S.; M.S. and D.M. carried out the experiments,
which were also supervised by M.V.; M.S. written and D.M. and M.V. contributed to the discussion of the results
and to the revision of paper. All authors have read and agreed to the published version of the manuscript.
Funding: This research was also performed thanks to “Sapienza” University direct financing, for PhD student
Matteo Sambucci, called “Avvio alla Ricerca”.
Acknowledgments: The authors express their sincere gratitude to Valeria Corinaldesi and Glauco Merlonetti
(Marche Polytechnic University) for their support in the additive manufacturing process. Besides, the authors
would like to thank MariaGabriella Santonicola and Elisa Toto (Sapienza University of Rome) for their technical
assistance in water contact angle measurement.
Conflicts of Interest: The authors declare no conflict of interest.
Recycling 2020, 5, 11 12 of 13

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