Waste Management 85 (2019) 574–584

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Carbon black recovery from waste tire pyrolysis by demineralization:

Production and application in rubber compounding
Juan Daniel Martínez a,⇑, Natalia Cardona-Uribe a, Ramón Murillo b, Tomás García b, José Manuel López b
a
Grupo de Investigaciones Ambientales (GIA), Universidad Pontificia Bolivariana (UPB), Circular 1 N° 74-50, Medellín, Colombia
b
Instituto de Carboquímica (ICB-CSIC), Miguel Luesma Castán 4, 50018 Zaragoza, Spain

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

Article history: Pyrolysis offers the possibility to convert waste tires into liquid and gaseous fractions as well as a carbon-
Received 28 August 2018 rich solid (CBp), which contains the original carbon black (CB) and the inorganic compounds used in tire
Revised 17 December 2018 manufacture. Whilst both liquid and gaseous fractions can be valorized without further processing, there
Accepted 11 January 2019
is a general consensus that CBp needs to be improved before it can be considered a commercial product,
Available online 24 January 2019
seriously penalizing the pyrolysis process profitability. In this work, the CBp produced in a continuous
pyrolysis process was demineralized (chemical leaching) with the aim of recovering the CB trapped into
Keywords:
the CBp and thus, producing a standardized CB product for commercial purposes. The demineralization
Carbon black
Carbon black recovery
process was conducted by using cheap and common reagents (HCl and NaOH). In this sense, the acid
Demineralization treatment removed most of the mineral matter contained in the CBp and concentration was the main
Pyrolysis parameter controlling the demineralization process. An ash content of 4.9 wt% was obtained by using
Waste tire 60 min of soaking time, 60 °C of temperature, 10 mL/g of reagent/CBp ratio and HCl 4 M. The demineral-
ized CBp (dCBp) showed a carbon content of 92.9 wt%, while the FRX analysis indicated that SiO2 is the
major component into the ash. The BET surface area was 76.3 m2/g, and textural characterizations (SEM/
EDX and TEM) revealed that dCBp is composed by primary particles lower than 100 nm. Although dCBp
showed a low structure, the surface chemistry was rich in surface acidic groups. Finally, dCBp was used in
Styrene Butadiene Rubber (SBR) compounding, probing its technical feasibility as substitute of commer-
cial CB N550.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction In a good pyrolysis process, the liquid yield should be higher

than 40% of the waste tire weight. This liquid shows the best pos-
Waste tires are considered a continuously growing environ- sibilities for commercialization among the pyrolysis products,
mental problem with negative impacts on economy and health since it can be added to petroleum refinery feedstock, or to be used
matters (Zabaniotou et al., 2014). About 1.5 billion tires are sold as: (i) a source of value-added products (for instance limonene
worldwide each year, and 50% of that amount is estimated to be (Danon et al., 2015), or as an alternative liquid fuel given its higher
discarded without any treatment (Thomas and Gupta, 2016). Pyrol- heating value (>40 MJ/kg (Martínez et al., 2013a)). On the other
ysis is an energy and material recovery process and could form part hand, the solid yield should match the contents of fixed carbon
of the solution to this global issue, and is currently considered an and ash of the waste tire (approximately 35–40% of the waste tire
effective and sustainable process able to deal with the waste tire weight). This carbonaceous material contains the carbon black (CB,
disposal problem (Antoniou and Zabaniotou, 2013; Martínez between 80 and 90 wt%) and the inorganic substances (between 10
et al., 2013c; Williams, 2013). However, one of the major issues and 20 wt%) used in tire manufacture (Martínez et al., 2013c; Sagar
behind this practice is the process economy and the value of the et al., 2018) and for this reason, is commonly referred as pyrolytic
resulting products. Specifically, the profitability of the waste tire carbon black (CBp). In addition, it can also contain extra carbona-
pyrolysis at industrial or semi-industrial scale depends on the mar- ceous residues onto the CBp surface as consequence of repolymer-
ket/application for the major products obtained, i.e. the liquid and ization reactions among the polymer-derivates, mainly depending
the solid fraction. on the pyrolysis severity (Chaala et al., 1996; Murillo et al., 2006;
Roy et al., 2005).
CB is essentially an amorphous carbon material of quasi-
⇑ Corresponding author.
graphitic structure commonly used as reinforcing filler and pig-
E-mail address: juand.martinez@upb.edu.co (J.D. Martínez).

https://doi.org/10.1016/j.wasman.2019.01.016
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
 J.D. Martínez et al. / Waste Management 85 (2019) 574–584 575

ment in rubber and plastic products and coatings. In rubber man- demineralization of waste tire and lignocellulosic wastes as well
ufacture, CB is used to strengthen the rubber and aid abrasion as their respective pyrolysis chars were highlighted. However, nei-
resistance, being the major reinforcing filler in the rubber industry. ther of them has showed a robust experience at semi pilot-scale as
The most popular CB by far for rubber manufacture is the one made showed in this work.
by the furnace process, with grades ranging from N100 through Herein, the CBp produced in a continuous pyrolysis process was
N700 series (Liang, 2004). Given the high cost of CB, which can vary demineralized (chemical leaching) in order to recover the CB
between 600 and 1000 €/ton (depending mainly of the CB grade trapped into the CBp. The demineralization process was performed
and market fluctuations), the most straightforward CBp application by using cheap and common reagents commonly used in the
is as substitute of commercial CB, i.e. to be used in rubber formu- chemical industry (HCl and NaOH). To the best of authors’ knowl-
lations. Besides the environmental advantages of this application, edge, this is a promising study investigating the recovery of the CB
for instance that of CO2 reduction, this market positively affects trapped in the CBp considering an easy and scalable process which
the economy feasibility of pyrolysis since this application forms a has been operated with higher sample (150 g) than those reported
recycling loop for the CB recovered from waste tires. in literature. Likewise, this is one of the first studies showing how a
CBp properties seem to be strongly dependent on both the demineralization process improves the CBp for Styrene Butadiene
pyrolysis conditions and technology. In addition, tire manufacture Rubber (SBR) compounding, in order to assess its technical feasibil-
uses various grades of commercial CB depending on the end-use ity as a concept proof. From this work, the barriers regarding the
properties and the tire component (inner liner, sidewall, belt pack- recovery of CB from waste tires are expected to be reduced in order
age, tread, cushion gum). Therefore, the CBp notably differs from a to improve the economic feasibility of the waste tire pyrolysis
unique CB and for this reason does not show the same reinforce- process.
ment properties than a commercial CB (Mastral et al., 1999). A
compendium of CBp yields as well as some physical-chemical
2. Materials and methods
properties from different results reported in literature are shown
elsewhere (Antoniou and Zabaniotou, 2013; Martínez et al.,
2.1. CBp production
2013c; Williams, 2013).
Physical properties such as surface area and structure are con-
The demineralization process was studied in a semi pilot-scale
sidered key factors in the CB industry. In fact, two ASTM standards
system. The CBp used in this work was produced in long-term
are addressing these issues (D6556-17 and D2414-17, respec-
pyrolysis experiments (more than 500 kg of shredded waste tires
tively). Besides these properties, surface activity is also an impor-
were pyrolyzed in 100 h of operation) by using a continuous auger
tant aspect for the application of CB as reinforcing filler. This
reactor at 550 °C, as showed elsewhere (Martínez et al., 2013b).
property is defined by both surface area and surface chemistry
Liquid and gas yields were 42.6 ± 0.1 and 16.9 ± 0.3 wt%, respec-
(related to the chemical reactivity of chemical groups onto CB sur-
tively. The CBp yield was 40.5 ± 0.3 wt%, which was slightly higher
face), since they determine the level of physical and chemical
than the resulting sum between the ash and the fixed carbon
interaction, respectively, during compounding (Donnet, 1993).
contents present in the waste tire (35 wt%). Before being dem-
Although there are no standards involving surface activity (linked
ineralizated, the CBp was submitted to an extra-heating at 700 °C
to oxygen-containing functional groups) and chemical composition
under inert atmosphere (N2) by using the same pyrolyzer reactor
(particularly ash content) to classify CBs and much less CBp; these
in order to decrease residual carbonaceous deposits as well as to
two parameters seem to be the most important barriers to the CBp
reduce the strong unpleasant odor.
application in rubber compounding.
Among others, rubber formulations using CB needs suitable sur-
face activity since these properties determine the strength of the 2.2. Semi pilot-scale facility for demineralization
CB–rubber interaction (Chaala et al., 1996; Darmstadt et al.,
2002; Roy et al., 2005). Some oxygenated functional groups, such The semi pilot-scale facility is depicted in Fig. 1 and consisted of
as carboxyls, phenols and ketones (acidic functional groups) have (1) a 2 L jacketed glass reactor AFORA 110 with (2) one mechanical
been identified onto the CB surface, and they strengthen surface stirrer. The reactor also incorporated a (3) thermocouple sensor
activity (Rodgers and Waddell, 2005). Likewise, ash content has and also a (4) reflux condenser to prevent possible water evapora-
been considered a major barrier for the CBp incorporation in rub- tion and changes in reagents concentration. Two heater/chiller
ber’s market (Chaala et al., 1996; Roy et al., 2005). The inorganic units provide hot and cold water to both reactor and condenser.
matter presence into CBp represents an inert load and hence, does This experimental set-up was designed, assembly and operated
not contribute to the surface area. Consequently, it can cover active for the dCBp production and allowed identifying the main variables
sites hindering the interaction between the CBp and the polymer. involved in the demineralization process.
Therefore, a post-treatment process able to reduce mineral mat-
ter, improving surface activity in the CBp during compounding is 2.3. Experimental procedure for demineralization
investigated in this work. Demineralization from acid and basic
reagents has been extensively studied for coal deashing to obtain Once concentration and volume of reagent were prepared and
environmentally acceptable clean fuels (Önal and Ceylan, 1995; 150 g of CBp placed into the reactor, the temperature was settled
Bolat et al., 1998; Alam et al., 2009). It is well-known that mineral at the value chosen to conduct the experiment. The liquid-solid
matter in coals has a marked and undesired effect on most coal uti- mixture was mechanically stirred by the mechanical agitator. Dif-
lization processes. Likewise, this process has been explored by sev- ferent rotation velocities were tested in order to achieve a proper
eral authors in order to assess gasification/activation and stirring process. In all cases, the rotation velocity of the mechanical
combustion processes using demineralized CBp (dCBp) as a raw stirrer was fixed at 400 rpm since this value showed to be the best
material (Ariyadejwanich et al., 2003; Ucar et al., 2005; Suuberg condition to reach an intimate mix between the reagent and the
and Aarna, 2009; Alexandre-Franco et al., 2010). In addition, there CBp. Regardless of the experimental conditions, the residual solid
are some works dealing with CBp demineralization as those con- obtained after conducting the demineralization process was suc-
ducted by Chaala et al. (1996); Roy et al. (2005) and Zhang et al. cessively washed with distillated water until the filtrate pH was
(2018). Iraola-Arregui et al. (2018) have been recently neutral. Later, the washed solid was dried using an electric oven
reviewed some of these works, where operating conditions for at 120 °C during 5 h. The variables studied in this work are listed
576 J.D. Martínez et al. / Waste Management 85 (2019) 574–584

SBET was determined by multi-point N2 adsorption at 196 °C in a

Micromeritics ASAP-2020 apparatus, whereas particle density and
porosity were obtained from a Micromeritics AccuPyc II 1340
helium picnometer and from a Quantachrome PoreMaster 33 mer-
cury porosymeter, respectively.
SEM/EDX analyses were conducted using a Hitachi S-3400 N
instrument. This equipment was coupled to Röntec XFlash de Si
(Li) for energy-dispersive X-ray (EDX) analysis, in order to deter-
mine the elemental microanalysis. The incident electron beam
energy used was 15 keV. TEM images were acquired using a FEI
Technai G2 microscope operated at 200 kV. The samples were trea-
ted by sonicating in absolute ethanol for several minutes, and a few
drops of the resulting suspension were deposited onto a holey-
carbon film supported on a copper grid, which was subsequently
dried.
TPD was also performed in order to quantify both CO and CO2
concentration released when samples were submitted to a pro-
gressive heating in an inert atmosphere. Thus, 100 mg of sample
was heated at 20 °C/min from 25 to 900 °C in a 20 cm3/min Ar flow
to carry the desorbed gases during the reaction. A conventional
flow-through reactor connected to a mass spectrometer Omnistar
GSD30102 registered the m/z fragments 28 and 44 for CO and
CO2, respectively. Both CO and CO2 concentrations were related
to the presence of basic and acid functional groups, respectively.

2.5. Rubber processing

Fig. 1. General scheme of the semi pilot-scale facility. In order to test the practical ability of the upgraded CBp and
identify the importance of the demineralization process, both
CBp and dCBp were used in SBR formulations. Vulcanization
curve, Mooney viscosity and some physical properties of the SBR
in Table 1. The experimental campaign associated with the
vulcanizates such as tensile stress at 300% elongation (also known
demineralization process started with a reproducibility study fol-
as modulus at 300%), tensile stress at break, elongation at break,
lowed by the optimization of the process variables, as shown later.
tear resistance, hardness and abrasion loss were determined and
Demineralization experiments were conducted aimed at finding a
compared with those obtained when using a commercial CB
CBp with the lowest ash content without remarkable losses of
(N550).
carbon.
Table 2 shows the components and the proportions used in each
rubber formulation. All samples were based on parts per hundred
(phr) of SBR. Firstly, activating agents (ZnO and stearic acid) were
2.4. Characterization techniques
added into the rubber and then, after dispersion, fillers under study
were included. At last, TBBS (n-tert-butyl-2-benzothiazolesulfena
Both CBp and dCBp were subjected to ultimate and proximate
mide) and sulfur were added as vulcanization accelerators.
analyses, ash chemical composition, BET surface area (SBET), Hg
All blends were prepared in a mixing cylinder at 40 °C and fix-
porosimetry, He picnometry, scanning electron microscopy/energy
ing a gear friction of 1:1.2 following the standard ASTM D-3182-16.
dispersive using X-ray (SEM/EDX), transmission electron micro-
After 24 h, both viscosity and vulcanization curves were obtained
scopy (TEM) and temperature-programmed desorption (TPD) anal-
according to the standards ASTM D-2084-17 and ASTM D-5289-
yses. In addition, relevant properties of some commercial CBs
17, respectively. Thus, some rheological parameters involved in
(N234, N375, N550 and N772) were also determined for compar-
the reaction and the Mooney viscosity (ML1+4), were determined.
ison purposes.
The curing degree measurements were conducted in a Moving
The ultimate analysis was carried out in a Carlo Erba-1108
Rheometer, Model MDR 2000E, (Alpha Technologies) whereas the
instrument, the moisture and the ash contents were measured
viscosity was determined from a viscometer MV 2000E (Alpha
according to EN 14774-3 and EN 14775, respectively; while the
Technologies).
volatile matter was determined according to EN 15148. Fixed car-
bon was calculated by difference. The ash composition was deter-
mined by inductively coupled plasma-optical emission Table 2
spectroscopy using an ICP-OES JY 2000 Ultrace equipment. Formulations for rubber processing using CBp, dCBp and CB N550.

Component Vulcanized
(phr)
CBp dCBp N550
Table 1 SBR 1500 100 100 100
Parameters studied for CBp demineralization. CBp 50 0 0
dCBp 0 50 0
Parameter Values
N550 0 0 50
Temperature (T, °C) 50, 60 and 70 ZnO 5 5 5
Reagent/CBp ratio (R, mL/g) 5, 10 and 15 Stearic acid 1.2 1.2 1.2
Soaking time (t, min) 15, 30 and 60 TBBS 1 1 1
Reagent concentration (HCl and NaOH, M) 2, 4, 6 and 8 Sulfur 1.7 1.7 1.7
 J.D. Martínez et al. / Waste Management 85 (2019) 574–584 577

3. Results and discussion experimental facility scale and the experimental error associated,
the results found suggest that demineralization shows a reason-
3.1. Post-heating treatment of CBp able reproducibility.
Furthermore, it was found a notably S reduction mainly due to
The formation of carbonaceous deposits during waste tire sulfides solubilization with no apparent carbon reduction (see
pyrolysis onto the CBp surface affects the surface activity and mor- Table 3 for comparison). This behavior is in agreement with results
phology. These carbonaceous deposits are likely located in the void reported by Chaala et al. (1996) regarding the use of H2SO4 for CBp
space between the primary particles of the CB aggregate, blocking demineralization as well as those found by Alam et al. (2009) for
a portion of their surface (Pantea et al., 2003). Therefore, the orig- coal de-ashing using HNO3 and HCl. According to Loadman
inal CB is trapped into the CBp and therefore, the reinforcement (1998), the S content in CBp does not play any part in the curing
properties of CBp could not be the same than those of commercial of vulcanizates and can be considered as inactive. The S content
CB. As showed in Table 3, the post-heating treatment decreased the in commercial CBs mainly depends on the feedstock and contents
volatile matter (from 4.7 to 2.4 wt%,) and led to an increase of the around 0.6 wt% are common in those obtained from furnace pro-
SBET (from 65.7 to 72.4 m2/g), as expected. Volatile matter in CBp cess (Donnet, 1993).
produces agglomerated particles that are difficult to break. Similar results have been reported by using other chemical
Similarly, the strong odor was diminished leading to more prac- reagents in CBp demineralization, as showed in Table 4. As
tical handling of the CBp. Surface area is a very important property inferred, the demineralization conditions used in the present work
for CB utilization in rubber manufacturing since it is one of the are less severe than those reported in Table 4. In addition, the ash
parameters that determine the degree of interaction of the rubber content reduction is remarkable taking into account the higher
within the CB (Tricás et al., 2002; Liang, 2004; Norris et al., 2014) amount of sample processed (150 g) as compared to those
and consequently, its reinforcement capacity. In fact, an increase observed in literature. Table 5 shows the ash composition analysis
of surface area suggests an increase in the concentration of active of both CBp and dCBp as well as the reduction ratio of each com-
sites in the edges of graphite-like regions, which could provide pound. As expected, the acid treatment favored the removal of
higher interaction between the CB filler and the rubber matrix Al, Ca, Fe Na and Zn, whereas Si was highly enriched.
(Darmstadt et al., 2000).
3.2.2. Soaking time influence
3.2. Semi pilot-scale tests: demineralization process The soaking time influence was studied at 15, 30 and 60 min.
Temperature, reagent/CBp ratio and reagent concentration were
As commented above, the CBp virtually contains all of the inor- kept constant (60 °C, 5 mL/g and HCl 1 M, respectively). These
ganic matter used in tire manufacture since they are not devolati- experimental conditions were more demanding since they consid-
lized at typical pyrolysis temperatures. Consequently, the ash ered a very low reagent concentration and also a low reagent/CBp
concentration in CBp is considerably higher (15 wt%) as com- ratio. As seen in Table 6, the higher the soaking time, the lower the
pared to that of commercial CBs (<0.5 wt%) (Roy et al., 2005). This ash and the volatile matter contents. For this reason, 60 min has
section shows a reproducibility study and the effect of soaking been chosen for performing the rest of the experiments. Even so,
time (t), temperature (T), reagent/CBp ratio (R), reagent concentra- it is worth to point out that the demineralization results are not
tion and sequential treatment acid/base on the demineralization as good as those shown in Table 3. It seems that higher reagent
process, according to levels showed in Table 1. concentration must be used.

3.2.1. dCBp production: repeatability tests 3.2.3. Temperature influence

In order to assess the reproducibility of the demineralization The reaction temperature is a key variable in solubilization pro-
process, seven independent runs at equal conditions were con- cesses. However, high temperatures lead to significant energy
ducted. The experimental conditions were 60 min, 60 °C, 3 mL/g penalties and possible reagent losses by evaporation. Three reac-
and HCl 3 M. As observed in Table 3, the demineralization condi- tion temperatures (50, 60 and 70 °C) were tested while keeping
tions led to C, H, N and S contents of 91.5 ± 0.2, 0.6 ± 0.0, 0.3 ± 0.0 constant the other process conditions (soaking time of 60 min,
and 0.9 ± 0.0 wt%, respectively. The demineralization process reagent/CBp ratio of 10 mL/g, and HCl 2 M). As observed in Table 6,
greatly increased the C content at expense of the ash content, indi- around 60% of ash reduction was achieved for all the samples,
cating an ash reduction ratio around 50%. Taking into account the while the C content increased between 7 and 9 points (see Table 3

Table 3
Ultimate and proximate analyses of the CBp before and after post-heating treatment and for the repeatability tests.

Sample/ Ultimate analysis wt.% (a.r) Proximate analysis wt.% (d.b) SBET
run (m2/g)
C H N S A VM FC
CBp before treatment 88.0 1.5 0.4 2.5 13.2 4.7 82.1 65.7
CBp after treatment 83.0 0.5 0.3 2.7 15.0 2.4 82.6 72.4
1 90.3 0.6 0.3 0.9 7.1 2.9 90.0 –
2 91.7 0.6 0.3 0.9 8.2 2.1 89.6 –
3 92.0 0.6 0.3 0.9 6.7 1.9 91.3 –
4 92.1 0.5 0.3 1.0 7.1 2.3 90.6 –
5 91.4 0.6 0.3 1.0 9.1 2.6 88.3 –
6 90.9 0.5 0.3 0.8 9.0 2.7 88.3 –
7 91.8 0.5 0.3 0.9 6.6 2.5 90.9 –
Mean value 91.5 0.6 0.3 0.9 7.7 2.4 89.9 –
Std. desv. 0.7 0.0 0.0 0.0 1.0 0.3 1.2 –
Abs. error ± 0.2 0.0 0.0 0.0 0.4 0.1 0.5 –

(a.r): as received; (d.b): dry basis; C: carbon; H: hydrogen; N: nitrogen; S: sulfur; A: ash; VM: volatile matter; FC: fixed carbon; SBET: BET surface area.
578 J.D. Martínez et al. / Waste Management 85 (2019) 574–584

Table 4
Demineralization conditions and results found in literature.

CBp ash content Demineralization conditions

Initial (wt.%) Final (wt.%) Reagent and concentration Time (min) Temp. (°C) CBp (g) R (mL/g) Ref.
14.8 6.8 H2SO4 1 N 30 60 5 10 Chaala et al. (1996)
14.7 6.2 HCl 1 M 1440 25a 2 40 Ariyadejwanich et al. (2003)
14.0–15.0b 4.0–5.0 HCl 10 wt% 120 100 43–46 n.r Ucar et al. (2005)
15.0 5.6 HCl 12 Mc 270c 25a n.r n.r Suuberg and Aarna (2009)
14.0 1.2 HCl 4 Md 360 60 11 10 Zhang et al. (2018)

n.r: not reported.

a
Room temperature.
b
CBp from truck tire.
c
Four washing cycles using fresh acid, the time showed here included that took it in the four cycles.
d
Demineralization using ultrasonic conditions.

Table 5 observed, HCl concentrations lower than 4 M produced a minor

Ash composition analysis of CBp and dCBp. solubilization degree, whereas higher concentrations led to higher
Compound CBp (wt.%) dCBp a
(wt.%) Reduction ratio (%) ash removal. However, it seems that HCl concentrations higher
Al2O3 1.9 0.2 89.9
than 4 M start to affect the organic matter because both C and
CaO 4.9 0.3 93.1 VM showed a trend to decrease. Hence, the optimal HCl concentra-
Fe2O3 1.2 0.2 80.7 tion was fixed at 4 M. At this concentration, the S content was
K2O 1.0 1.5 – reduced around 57% whereas the SBET increased respect to the ini-
MgO 1.3 1.7 –
tial CBp.
Na2O 0.7 0.3 49.1
SiO2 39.0 85.8 –
TiO2 0.1 0.4 –
ZnO 31.7 5.4 83.1 3.2.5. Reagent/CBp ratio influence
Total 81.7 96.0 – The reagent/CBp ratio is an important variable because it is
a
A mixture of all runs (HCl 3 M, 60 min, 3 mL/g and 60 °C). associated with the reagent consumption to carry out the deminer-
alization process. Generally speaking, the higher the reagent vol-
ume and concentration, the higher the demineralization extent.
However, it could affect the C content. From this point of view,
for comparison). Also, these temperature levels did not seem to the goal to be achieved is to find a minimum reagent/CBp ratio
have a strong influence on the demineralization process since both in order to: (i) reduce operating costs and (ii) minimize the C
the ash content and the SBET differences were minimal and were reduction. Thus, three different reagent/CBp ratios (5, 10 and
within the experimental error found in Section 3.2.1. The interme- 15 mL/g) were tested while keeping the other process parameter
diate temperature of 60 °C was chosen for conducting the rest of constant (60 min of soaking time, 60 °C of temperature and HCl
experiments. concentration of 4 M). As shown in Table 6, the higher ash content
was achieved using 5 mL/g in contrast to those obtained at 10 and
3.2.4. Reagent concentration influence 15 mL/g. However, 15 mL/g seems to attack the organic matter
This experimental campaign was performed by varying four dif- given the reduction of C, H and VM in comparison to the values
ferent HCl concentrations, as follows: 2, 4, 6 and 8 M. The soaking found using 10 mL/g. Hence, 10 mL/g showed the most favorable
time was fixed at 60 min, while temperature and reagent/CBp ratio value for conducting the demineralization process, even though
were 60 °C and 10 mL/g, respectively. Table 6 also shows the SBET was slightly lower than those obtained at 5 and 15 mL/g. At
results obtained for the different concentrations tested. As this condition a reduction ratio around 67% was reached.

Table 6
Variables effect on the demineralization process.

Ultimate analysis wt.% (d.b) Proximate analysis wt.% (d.b) SBET

(m2/g)
Parameter C H N S A VM FC
Soaking time (min)
15 88.2 0.6 0.3 2.0 9.1 2.2 88.7 74.5
30 88.2 0.6 0.3 1.8 8.9 2.5 88.6 77.1
60 89.8 0.6 0.3 2.0 8.1 2.3 89.6 76.0
Temperature (°C)
50 90.6 0.6 0.3 1.3 6.1 2.2 91.7 77.8
60 91.8 0.6 0.3 1.1 6.1 2.2 91.7 76.5
70 92.0 0.6 0.3 1.2 6.0 2.4 91.7 77.4
HCl concentration (M)
2 91.8 0.6 0.3 1.1 6.1 2.2 91.7 76.5
4 92.9 0.6 0.3 1.1 4.9 2.5 92.6 76.3
6 92.0 0.7 0.3 1.3 5.3 2.4 92.3 75.4
8 92.0 0.7 0.3 1.2 5.6 2.1 92.1 79.1
Reagent/CBp ratio (mL/g)
5 91.6 0.6 0.3 1.0 5.9 2.6 91.5 78.4
10 92.9 0.6 0.3 1.1 4.9 2.5 92.6 76.3
15 92.0 0.5 0.3 1.1 5.5 2.3 92.2 78.1

(d.b): dry basis; C: carbon; H: hydrogen; N: nitrogen; S: sulfur; A: ash; VM: volatile matter; FC: fixed carbon; SBET: BET surface area.
 J.D. Martínez et al. / Waste Management 85 (2019) 574–584 579

3.2.6. Sequential acid/base treatment the agglomerates of the former were less homogenous and much
Sequential treatment with HCl and NaOH was carried out in larger than that of N550. In this way, the N550 agglomerates seem
batch and alternately, i.e. the solid obtained in the first treatment to be finer and more homogenous than those of dCBp, which at first
(that obtained at 60 min of soaking time, 60 °C of temperature, glance exhibit quasi-spherical and elongated shape. In addition,
10 mL/g of reagent/CBp ratio and HCl 4 M) was used as raw mate- this commercial CB showed a smoother surface composed by a
rial for the second one. From this sequence, removal of both acidic finer grain structure in contrast to the dCBp, although this fact
and basic compounds is expected. The experimental conditions did not seem to affect the surface area.
used for the base treatment (NaOH) were the same utilized for Size and bulkiness of both aggregates and agglomerates are
the acid treatment but using a concentration of 5 M. As seen in described by the term structure. High structure indicates that there
Table 7, the ash content decreased from 4.9 to 3.1 wt% ascribed is a large number of primary particles per aggregate, whereas low
to the SiO2 solubilization. Chaala et al. (1996) also found and ash structure is related to a weak level of aggregation (Donnet, 1993).
content around 3.0 wt% after submitting the CBp to an acid-base Comparing Figs. 2 and 3, the structure of dCBp was lower than that
treatment (H2SO4 1 N and NaOH 10 N) by using 5 g of CBp. of N550, which was rather moderate. This is not surprising since
The acid treatment removes most of the mineral matter con- tire manufacturing uses different CBs grades and hence, the result-
tained into the CBp, and excepting by the reagent concentration, ing CBp is a mixture of different CBs. In addition, the presence of
no major effects of the process variables studied were found. Gen- both mineral matter and carbonaceous deposits, which were not
erally speaking, an ash content of 4.9 wt% was obtained by using removed after both the post-pyrolysis heating treatment and the
60 min of soaking time, 60 °C of temperature, 10 mL/g of reagent/ demineralization process, could also contribute to the lower struc-
CBp ratio and HCl 4 M. Although the sequential acid/base treat- ture of dCBp. Structure plays an important role in the reinforce-
ment led to an ash content close to 3 wt%, its implementation at ment properties of any CB (Chaala et al., 1996). Low structure
industrial scale is environmentally unfriendly, costly and time con- CBs pack much more tightly than high structure ones and are more
suming, and consequently unattractive. Looking for the industrial difficult to disperse during the mixing stage (Boonstra, 1967;
sector interest, only the acid treatment is proposed in this work Wijayarathna et al., 1978).
to produce a dCBp aiming the substitution of commercial CBs. EDX characterization carried out at both CBp and N550 (Fig. 2a
and b, respectively), is showed in Table 9 (area analyzed is marked
3.3. dCBp characterization: comparison with commercial CBs in these Figs.). In contrast to the dCBp surface, the N550 surface
showed the predominant presence of C, S and O and the absence
3.3.1. Surface area, porosity and real density of mineral matter, as expected. Si, Al, Mg, K, Na and Cl were more
Table 8 shows the ultimate analysis, SBET, porosimetry and real relevant than C onto the dCBp surface. This observation was also
density of dCBp (produced at 60 min of soaking time, 60 °C of tem- indicated by Chaala et al. (1996). The authors advised that after
perature, 10 mL/g of reagent/CBp ratio and HCl 4 M) and different demineralization, salts and non-soluble oxides remain fixed onto
types of commercial CBs (N550, N772, N375 and N234). Firstly, it is the surface of the CBp aggregates.
worth to point out the slightly higher SBET of dCBp (76.3 m2/g)
respect to that found before demineralization (72.4 m2/g). This 3.3.3. TEM analysis
increase was expected taking into account the partial removal of TEM micrographs showed that dCBp is mainly composed by
mineral elements which were blocking the CBp porosity. Likewise, nearly nano-size spherical particles lower than 100 nm, but with
SBET of dCBp is higher than those of N550 (44.8 m2/g) and N772 a wide range particle size distribution (Fig. 4a, b), in contrast to
(26.8 m2/g) and lower than those of N234 (120.4 m2/g) and N375 the high homogeneity found to the N550 (between 35 and
(89.6 m2/g). This first comparison suggests that the dCBp could 60 nm) (Fig. 4c, d). The mean primary particle size of commercial
serve as substitute of medium/low-grade CBs such as N375 and CBs is mostly in the nanometer range (from 8 to 100 nm) with par-
N550, being closer to N550. The CB N550 is typically used in tire ticles often aggregating in grape-like clusters up to 500 nm (Rodat
inner-liners, carcass, inner tubes, hoses, extruded goods and ‘‘V” et al., 2011). Sometimes the term agglomerate is confused with
belts whereas the CB N300 series are often used for standard tire aggregate. An agglomerate comprises of a large number of aggre-
treads, rail pads, solid wheels, mats, tire belts, sidewall, bushing, gates, which are physically held together as opposed to the contin-
weather strips and hoses among others (Liang, 2004). uous graphitic structure, which strongly links the particles in
Although results shown in Table 8 are on a.r basis, the C content aggregates (Donnet, 1993). The ability to break up these agglomer-
for dCBp (92.9 wt%) was lower than all commercial CBs at expense ates into aggregates in order to ensure an adequate dispersion is
of the higher ash content, whereas H (0.6 wt%) and S (1.1 wt%) con- crucial for achieving a desirable CB performance. Although signifi-
tents were higher. N content (0.3 wt%) compared well with all cant literature has been developed on the CB dispersion in various
commercial CBs. Likewise, real density and porosity were also in medium (Pomchaitaward et al., 2003; Hanada et al., 2013); its
the range between those of N375 and N550, as seen for the SBET. practical application remains in experience practitioners who have
the expertise, the technique and the trade secrets. However, high
3.3.2. SEM/EDX analysis shear mixing in polymeric systems causes significant aggregate
SEM micrographs revealed some morphological characteristics breakdown relative to the dry state (Donnet, 1993).
of N550 (Fig. 2) and dCBp (Fig. 3). Although the appearance of dCBp The pattern found for the dCBp is ascribed to the several types
(Fig. 3d) showed some similarities respect to that of N550 (Fig. 2b), and brands of waste tires pyrolyzed, which are incorporating dif-

Table 7
Sequential acid/base treatment effect on the demineralization process.

R T t Ultimate analysis wt.% (d.b) Proximate analysis wt.% (d.b)

(mL/g) (°C) (min)
Treatment C H N S A VM FC
HCl 4 M 10 60 60 92.9 0.6 0.3 1.1 4.9 2.5 92.6
NaOH 5 M 10 60 60 95.1 0.7 0.3 0.8 3.1 2.7 94.2

(d.b): dry basis; C: carbon; H: hydrogen; N: nitrogen; S: sulfur; A: ash; VM: volatile matter; FC: fixed carbon; SBET: BET surface area.
580 J.D. Martínez et al. / Waste Management 85 (2019) 574–584

Table 8
Properties of dCBp and commercial CBs.

Ultimate analysis wt.% (a.r) SBET qreal Interparticle Intraparticle

(m2/g) (g/cm3) porosity (%) porosity (%)
Sample C H N S
dCBp 92.9 0.6 0.3 1.1 76.3 1.92 21.4 62.5
N234 95.2 0.3 0.3 1.1 120.4 1.97 13.4 65.3
N375 97.3 0.3 0.3 0.6 89.6 1.96 13.8 61.5
N550 98.7 0.3 0.3 0.6 44.8 1.92 16.8 63.7
N772 98.5 0.3 0.3 0.9 26.8 1.90 10.7 49.9

(a.r): as received; C: carbon; H: hydrogen; N: nitrogen; S: sulfur; SBET: BET surface area; qreal: real density.

Fig. 2. SEM micrographs of CB N550. (a) magnification 1000; (b) magnification 10,000.

Fig. 3. SEM micrographs of dCBp. (a) magnification 500 (backscattering); (b) magnification 1500; (c) magnification 2500 (backscattering); (d) magnification 10,000.

ferent CBs grades, as previously stated. In this sense, Helleur et al. for commercial CBs. This heterogeneity reduces the space availabil-
(2001) showed similar TEM micrographs for the CBp produced in ity for a proper filler-rubber interaction. Roughly speaking, the lar-
an ablative pyrolysis process. Huang and Tang (2009) also found ger the particle size, the lower the surface area and the poorer the
a wider CBp particle size distribution in comparison to that found reinforcement potential (Liang, 2004). The loss of reinforcement is
 J.D. Martínez et al. / Waste Management 85 (2019) 574–584 581

Table 9
EDX characterization of both N550 CB and dCBp.

Element (wt.%)

Sample C O S Si Al Mg K Na Cl
N550 93.8 5.5 0.6 0 0 0 0 0 0
dCBp 17.5 41.4 0.5 25.5 10.5 2.2 1.3 0.5 0.5

Fig. 4. TEM images of dCBp (a, b) and CB N550 (c, d).

translated by a reduction in modulus, tensile strength, abrasion tant sites with respect to rubber filler and filler–filler interaction,
resistance and other mechanical properties (Barlow, 1993) since the acidic functional groups are preferably located at the
edges of the graphitic basal planes or at the crystallite edges. These
3.3.4. TPD analysis acidic functional groups are altered when the CB is submitted to
Besides porosity, surface functional groups also affect the inter- heat treatment under vacuum or inert atmosphere in the temper-
facial adhesion characteristics of the CB with the rubber polymer ature range 300–800 °C, and are linked to the evolved CO2 (Donnet,
(Boonstra, 1967; Darmstadt et al., 2000). According to Chaala 1993; Shen et al., 2008). These acidic functional groups have been
et al. (1996), the surface effect is a key CB parameter to be consid- suggested to be carboxylic, anhydride, lactonic and phenolic
ered more than just a filler. The surface chemistry is a very impor- among others (Donnet, 1993; Burg and Cagniant, 2008).
tant property which influence some physico-chemical properties of Fig. 5 shows the TPD for both dCBp and N550. Functional groups
CB such as wettability, catalytic, electrical and chemical reactivity. can be quantified according to the decomposition temperature and
Hence, the presence of oxygen-containing acidic functional groups type of gas released (CO2 and CO). In this sense, carboxyl groups
on the CB surface determines their practical application in the rub- decompose between 200 and 400 °C, whereas phenolic or quinone
ber and plastic sector (Donnet, 1993). As stated by Mathew et al. groups decompose at higher temperatures (Shen et al., 2008). As
(2009), the CB surface consists of graphitic planes, amorphous car- seen in Fig. 5, the CO2 evolved by dCBp (0.074 mmol/g) was higher
bon, crystallite edges and slit shaped cavities. Particularly, the than that obtained by N550 (0.035 mmol/g) while the CO was neg-
crystallite edges and the slit shaped cavities are the most impor- ligible for both samples and for this reason was not shown.
582 J.D. Martínez et al. / Waste Management 85 (2019) 574–584

Fig. 5. TPD results for dCBp and CB N550.

Fig. 6. Viscosity curve of the rubber fillers used.

Therefore, the surface of dCBp is covered with higher acidic

groups than that of N550, which could be related to the HCl treat- Table 10
ment since it favors the formation of acidic functional groups in Rheological parameters obtained in rubber processing.
demineralization processes (Önal and Ceylan, 1995; Lou et al.,
Vulcanized
2011). Treatments with oxidizing agents are common procedures
in CB technology in order to increase the concentration of acidic Parameter CBp dCBp N550

functional groups considerably (Donnet, 1993). The interaction Mooney viscosity at 100 °C 98.0 91.8 80.6
between rubber and filler is mainly determined by the polymer ML (dN.m) 3.21 3.04 2.61
MH (dN.m) 20.22 28.81 19.64
molecules adsorption onto the filler surface either chemically or MS (dN.m) 17.01 17.71 17.03
physically (Donnet, 1993; Fröhlich et al., 2005). This adsorption DM = MH ML (dN m) 17.01 25.77 17.03
is governed by many properties such as structure, surface area ts1 (min) 3.35 1.87 4.25
and surface chemistry, being the last two gathered by the term sur- ts2 (min) 5.17 3.89 6.96
tc10 (min) 4.81 3.52 6.45
face activity (Fröhlich et al., 2005; Tricàs Rosell, 2007). Even so,
tc50 (min) 10.07 8.64 11.63
surface chemistry seems to play an important role in rubber- tc90 (min) 22.08 17.81 21.53
filler interaction since it exerts a notable influence in the adhesion tc97 (min) 30.84 24.56 28.97
ability and physical contact (Gessler, 1969; Dannenberg, 1986).
Because of the higher CO2 evolved, dCBp has much higher acidic
surface groups than N550; and hence, a good polymer-filler inter- of the dCBp was not as good as that of the N550, it is worth noting
action is expected, which could balance the detriment role of other that is better than that found using the CBp. The higher Mooney vis-
factors such as ash content. According to Bhadra et al. (2003), CBs cosity for the vulcanizate with both CBp and dCBp in comparison to
with high amount of surface acidic functional groups influence that N550 is ascribed, besides the mineral matter, to the influence
positively the rubber-filler interaction. of both surface area and rubber-filler interaction (given the surface
activity) since it has been reported that these parameters increase
3.4. Rubber compounding the viscosity (Sae-Oui et al., 2002). Likewise, it is not ruled out
the possible worst dispersion of these fillers. Both CBp and dCBp
Rubber formulations were carried out by using (i) the CBp after showed a wider size distribution, in terms of aggregates, which
post-pyrolysis heating-treatment, (ii) the dCBp obtained at 60 min negatively influences the dispersion ability (Donnet, 1993).
of soaking time, 60 °C of temperature, 10 mL/g of reagent/CBp ratio Furthermore, no major differences were found for ML and MS
and HCl 4 M, i.e. that with 4.9 wt% of ash content and 76.3 m2/g of and hence, the vulcanization reaction must follow the same pat-
surface area, and (iii) the commercial CB N550. The aim of these tern regardless the filler used. ML gives information on the process-
tests was to identify the effect of replacing CB N550 with both ing ability of the rubber (Nabil et al., 2013). This result indicated
CBp and dCBp on SBR processing, as well as to observe the response that both CBp and dCBp have a little negative impact on the rubber
on some mechanical properties. processability (Dick, 2003). On the other hand, MH increased
Fig. 6 shows the Mooney viscosity and the Mooney relaxation slightly for CBp and notably for dCBp respect to the value found
curve according to the formulations prepared (see Table 2). Like- to the N550. This parameter relates to the ultimate reticulation
wise, Table 10 shows the rheological parameters involved in the density that results from the vulcanization process (Dick, 2003).
rubber compounding such as Mooney viscosity at 100 °C, mini- Thus, dCBp seems to contribute favorably with the vulcanizate net-
mum torque (ML), highest torque (MH), scorch torque (MS) and tor- work. The increase of the crosslink density could be ascribed to the
que increment (DM). Also, different cure times (tc) and scorch acidic chemical surface and surface area which favor the chemical
times (ts) are showed. Mooney viscosity gives information just links formation between polymer chains and the filler according to
for one point of the flow curve and is the most used property for the results found by Rajeev and De (2002). These functional groups
rubber characterization since it determines the mechanical pro- should increase the polarity on the dCBp surface, and consequently
cessing ability. The higher the viscosity, the higher the shearing increase the final reinforcement (Yehia et al., 2004). In addition, the
force during mixing and therefore, a higher frictional heat and mix- higher the DM, the higher the chemical cross-linking due to the
ing temperature. mobility reduction of the rubber chains (Sagar et al., 2018). Hence,
As seen in Fig. 6, the SBR vulcanizate with N550 led to the lowest the dCBp seems to show a great interaction with the SBR.
Mooney viscosity (80.6 MU) followed by that one with dCBp (91.8 On the other hand, Fig. 7 shows the vulcanization curve at
MU) and CBp (98.0 MU). Although the resulting Mooney viscosity 160 °C for all SBR formulations. As observed, three different regions
 J.D. Martínez et al. / Waste Management 85 (2019) 574–584 583

can be identified (Sui et al., 2008). The first region is the scorch Table 11
time or induction period that provided a safe processing time. Mechanical properties obtained in rubber compounding.

The second region is the curing or vulcanization reaction period, Vulcanized

during this stage the crosslinking network is formed in the SBR Parameter CBp dCBp N550
and the stiffness of rubber is increased. In the third period, the
Modulus at 300% (MPa) 13 13 15.5
crosslinking network in the SBR is mature and some over-curing Tensile strength (MPa) 14.1 17.5 16.8
reversion, equilibrium, or additional but slower crosslinking may Elongation at break (%) 319 350 320
occur for the different rubber materials (Sui et al., 2008). The Tear strength (kN/m) 61 68 78
scorch time at different torque levels (ts1 and ts2) and all the vul- Hardness (Shore A) 68 69 69
Abrasion loss (mm3) 58 68 55
canization times (tc10, tc50, tc90 and tc97) were determined from
Density (g/cm3) 1.15 1.15 1.15
Fig. 7 and are also listed in Table 10. tsi means the time required
for the increase of 1 (ts1) or 2 (ts2) points from ML. These parame-
This randomness in the mechanical properties is ascribed to the
ters are indicators of the time required for the beginning of the
combined effect of mineral matter presence, structure, specific sur-
crosslinking process. Likewise, tci means the time taken to achieve
face area and chemical surface which play an important role in
different vulcanization levels. These parameters, specifically ts2
reinforcement (Boonstra, 1967; Donnet, 1993). There are trade-
and tc90, are indicators of the time at which vulcanization begins
offs in rubber compounding regarding some properties of the
and reaches completion, respectively (Nabil et al., 2013).
resulting material. The use of a particular reinforcement to
All these reference times were shortened when dCBp is used in
improve a particular property may have a negative effect on other
comparison to both CBp and N550, indicating that the vulcaniza-
properties (Donnet, 1993; Donnet and Custodero, 2005). Despite
tion reaction was completed earlier. Thus, dCBp seems to behave
these facts, dCBp proved to have reinforcing effects on SBR formu-
as an effective catalyst agent for rubber compounding. However,
lations comparable with medium-grade CB such as N550 and
if the tS is not sufficient to enable for instance, a proper mixing
therefore, it could be used for rubber compounding.
before the beginning of vulcanization, different inhibitors can be
used (Kruželák et al., 2015). Generally speaking, the filler addition
in rubber compounding reduces both the scorch and the vulcaniza- 4. Conclusions
tion time. The higher the filler loading, the lower the curing time
(Sae-Oui et al., 2002). However, given the mineral matter presence Reagent concentration showed the major effect on demineral-
in both CBp and dCBp their respective load contributions as net CB ization. The optimal conditions using only one step of demineral-
were lower than that of N550. The decrease in both scorch and vul- ization are 60 min, 60 °C, 10 mL/g and HCl 4 M. After
canization time may be attributed again to the higher surface acid- demineralization, the ash content in CBp was reduced in 67% since
ity of dCBp. Accelerators used in rubber formulation are generally the ash content decreased from 15.0 wt% to 4.9 wt%.
basic compounds and hence, their activity is faster in presence of The SBET of the dCBp slightly increased (76.3 m2/g) respect to the
acidic groups decreasing these rheological parameters (Bhadra CBp (72.4 m2/g) and is higher than that for N550 (44.8 m2/g). dCBp
et al., 2003). Also, it is worth to point out that the presence of is mainly composed by primary particles lower than 100 nm with a
ZnO and SiO2, as well as other minor metal oxides, can cause an wide range particle size distribution. This behavior is related to the
increase in the rate of the early reactions (Coran, 2005). presence of several tires (types and brands) and CB grades used in
Some key mechanical properties of the SBR vulcanizates are the different parts of the pyrolyzed tires. Additionally, dCBp
shown in Table 11. As seen, the incorporation of dCBp only led to showed a low structure whereas the N550 presented a moderate
a reduction of both the modulus at 300% and the tear strength at structure. The surface chemistry of dCBp showed a higher amount
break, in comparison to the vulcanizate with N550. Conversely, of surface acidic groups than N550.
tensile strength, elongation at break, and abrasion loss were higher Although the SBR vulcanized with dCBp showed a reduction in
for dCBp than those for N550, while hardness remained practically both the tensile modulus at 300% and the tear strength in compar-
unaltered. Likewise, it is worth to highlight that all properties were ison to the vulcanized with N550, some other important mechan-
enhanced by using dCBp instead of CBp and so, the demineraliza- ical properties were comparable and even better. This randomness
tion process proved to be a useful treatment for improving the in the evolution of the mechanical properties is ascribed to the
CBp properties as a reinforcement filler. counterbalance effect of a higher mineral matter presence and
poorer structure versus a higher specific surface area and richer
chemical surface. Despite these negative properties, it was demon-
strated that dCBp shows relevant reinforcing effects and can be
25 used for rubber formulations.

20 Acknowledgements

Authors would like to express all his gratitude to Integrated

Torque (dNm)

15 CBp Center for the Development of Research (CIDI) at Pontificia Bolivar-

dCBp
Period III
N550
iana University (UPB) for the financial support given by the
Period research project (629B-0616-24). N. Cardona-Uribe is also in debt
10 I
with CIDI at UPB and its program ‘‘Formación Investigativa” for
the MSc scholarship.
5
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