Progress on recovered Carbon Black from Waste Tire Pyrolysis
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Recovered carbon black from waste tire
Progress on recovered Carbon
pyrolysis · technology · reinforcement
Black from Waste Tire Pyrolysis
The use of recovered carbon black from
waste tire pyrolysis is not progressing .
The potential reasons for this stagnation
are discussed considering the latest in- Present status and potential improve- major morphological characteristics. The
vestigations in this domain. What can be ments of their performance in rubber variations we observe represent most
expected from the present achieve- Tire recycling is considered today as a probably mainly the difference in the
ments of the pyrolysis technology? The must and waste tire pyrolysis is certainly waste tyre compositions used as raw
availability of active sites on the carbon for the time being one of the main tech- material and also to some extent the
black surface might be one of the major nologies considered to achieve this goal. difference in pyrolysis equipment and
causes of the lack of performance in re- Many different research teams are wor- operating conditions. Pieter ter Haar [4]
inforcement of the recovered material. king on this technology and in the mean- in a presentation of investigations exe-
The indications in the carbon black lite- time several plants have been construc- cuted at Pyrolux, reports the differences
rature are listed and discussed in view of ted around the world, covering however in analytical data and compounded per-
potential new ways to improve the per- only a very small fraction of the world formance of rCB from ASTM 3191 SBR
formance of the recovered material and waste tire recycling. The reason for this compounds. It is quite interesting to
close to some extend the carbon black stagnation is the fact that recovered car- notice the difference between lower and
cycle in the rubber industry. bon black is not a valid candidate for medium reinforcing carbon blacks like
Two technologies are pointed out. The first carbon black replacement in order to N-660 and N-330 on one hand and high
one is the use of low temperature plasma . close the product cycle. Recovered car- reinforcing N-110. In the first case the
The second one, looking more promising is bon black is practically not suitable for drop in performance between virgin and
the use of thermal plasma generating ful- high quality use and only in a limited recovered carbon black is visible in the
lerenes and fullerene-like species on the number of applications. It is also quite stress strain value which could be due to
surface. interesting to notice that no established a lower structure of the recovered mate-
carbon black producer has apparently rial, while for N-110 the drop in perfor-
shown any interest or need in investing mance between virgin and recovered car-
Fortschritte in der Entwick- in the, in principle, competitive product bon black is mainly visible in tensile
lung von Rußen aus Altreifen - candidate and an ecological way to vali- strength, which is partially due to the
Stand und neue Wege zur date carbon black production. higher modulus, but could be mainly due
We realize that since 2011, when we to poorer dispersion.
Verbesserung der Leistung in published the paper “Pyrolysis Carbon
Elastomeren Black, an opportunity for the rubber in- The results obtained by ter Haar on
dustry [1] no significant progress in the the pyrolysis of the ASTM3191-com-
Ruß aus Altreifen · Pyrolyse von Altrei- performance of the recovered carbon has pounds containing the 3 carbon blacks
fen · Verstärkung in Elastomeren · Hoch- been made. Commercially some interes- may be considered as the base of the re-
temperaturplasma · Niedertemperatur- ting developments have been reported; covered carbon black problem.
plasma nevertheless a breakthrough and real
closure of the material cycle cannot be
Der Gebrauch von Rußen aus Altreifenpy- expected till the recovered carbon black
rolyse stagniert. Mögliche Gründe hier- can assure a performing use in most car-
für werden auf Basis der letzten Untersu- bon black applications. Work has been
chungen auf diesem Gebiet diskutiert. done in two domains:
Was kann man von dem heutigen Stand ■■ Changing the operating conditions of
der Technik erwarten? Der Mangel an ak- pyrolysis;
tiven Funktionen an der Oberfläche die- ■■ Treating the recovered carbon black
ser Ruße kann einer der Gründe sein. Die in order to reduce the impurity level
Rußliteratur listet eine Reihe von potenti- (Martinez et al.) [2]
ellen Wegen die Oberflächengruppen der
Ruße zu verbessern welche möglicher- Those techniques, although bringing
weise dazu helfen könnten, den Rußzyk- some small improvements, did not
lus in der Gummiindustrie zu schließen. change the situation significantly. Recent
Zwei Verfahren werden diskutiert. Das publications and company presentations
Authors
erste Verfahren ist Niedrigtemperatur- indicate some new attempts to change
plasma, das zweite Verfahren ist Hoch- the surface of recovered carbon black. Nicolaus Probst
temperaturplasma, welches Fullerene Cardona and al. [3] have made a summa- Avenue de Calabre 27A /18
oder fullerenartige Strukturen an der ry and compiled many recovered carbon 1200 Brüssel
Rußoberfläche erzeugt. blacks from different sources. The table Corresponding Author:
Figures and Tables: By a kind a approval of the authors. lists more than 20 carbon blacks, re- Nicolaus Probst
porting their elemental composition and E-Mail: probstwigy@yahoo.fr
www.kgk-rubberpoint.de KGK · 1 2021 351 Green rubber /CB Pyrolysis 1
STSA Weight gain % Figure 1. Specific surface
area (STSA) before and af-
N115 112 20,1 ter pyrolysis [4].
N330 76 15,3
N660 33 10,5
N990 10 7
Table 1 Weight gain during pyrolysis Figure 1.
expected Specific
from surface
rCB without areatreat-
further (STSA) beforerCB inand after compound
a given pyrolysis [4]
containing
relative to the carbon black content of ments. +/- 20% mineral filler is actually only
the green rubber with different carbon Ter Haar investigates also the diffe- for 80% carbon black The specific sur-
blacks [4] rence between rCB with low and high face area of the carbon black, when
Compound pyrolysis generates car- toluene extractables. The observed diffe-
Table 2 reports the rubber compoundedrecalculated data for the from the average
3 furnace blackscarbon
and the
bon residues resulting in a deposit of re- rence, although significant in tensile black type and content in the original
latively amorphous carbonaceous mate- corresponding
strength, recovered
is most probably carbon
related to theblacks.tire, can be situated between 60 and
rial and consequently in a weight gain of increase in modulus. The increase in mo- 70 m²/g.
the recovered carbon over the original dulus when the oily residues on rCB sur- We cannot expect a lot of improve-
compound composition. This weight face are reduced, might indicate that in- ment by playing with the pyrolysis ope-
gain is a function of the aromaticity of Table 2volumes
terstitial Compounded properties
are freed to some ex- in ASTM 3191
rating SBR formulation for N660, N330
conditions.
the polymer. ASTM 3191 compound is tent and consequently the void volume
and N110 for virgin carbon black and rCB [4] The elemental composition (ash) of
based on SBR 1500 and as such quite (structure) is increased. Void volume the recovered carbon black can only be
aromatic. In the case of a waste tyre py- measurements may give more informati- considered to a limited extent as an indi-
rolysis the rCB may also contain the pyro- on as the Oil Adsorption Number (OAN), cation of its performance in rubber; the
lysis residue of other organic ingredients which is strongly affected by the wetting research should be focused primarily on
like textile cords. Ter Haar shows that the properties of the rCB and cannot be con- the potential interaction of the recovered
weight gain is also a function of the spe- sidered as a relevant property. carbon black with the polymer.
cific surface area of the carbon black. The Summarizing the different aspects
amount of surface deposit is proportio- considered above and keeping in mind Supposed that the performance of the
nal to the available surface area in a gi- that only limited aspects of the rein- recovered black is subject to the same
ven volume of compound. This explains forcement are reported in the literature, parameters as for furnace blacks.
the reduction of the specific surface area it may be concluded that: The reinforcement of carbon black in
due to the increase of particle size and elastomers is determined by the interac-
the higher impact of this phenomenon A. In the case of compounds without tion of the carbon black with the elasto-
for high surface area carbon blacks. (Fi- mineral fillers: mer chains. Carbon black is mainly cha-
gure 1) 1. The reinforcing properties of rCB in racterized by two morphological proper-
Table 2 reports the rubber compound- comparison with virgin furnace black ties: Specific surface area (determined by
ed data for the 3 furnace blacks and the are not very much reduced for coarse
It may be concluded that the main drop theinparticle size) and observed
performance structure. on the rCB in
corresponding recovered carbon blacks. particle blacks and slightly affected in
Table 2 Compounded properties in comparison
the case of with the virgin carbon
semi-reinforcing carbon black occurs
Specific witharea:
surface fine particle furnace
ASTM 3191 SBR formulation for N660, blacks? This would explain that a significantly higher performance cannot be
black;
N330 and N110 for virgin carbon black 2. For higher reinforcing carbon black For recovered carbon black the particle
and rCB [4]
expected from rCB without further treatments.
the reduction of the reinforcing per- size is, or should be, if pyrolysis residues
It may be concluded that the main formance is more pronounced. from the polymer and organic additives
drop in performance observed on the rCB and especially mineral residues do not
in comparison with the virgin carbon B. In the case of waste tire pyrolysis: influence the particle size, the weighted
black occurs with fine particle furnace 1. Effects mentioned in A. are added to average of the different carbon blacks
blacks? This would explain that a signifi- the effect of mineral filler deposits; present in the waste tyre used as raw
cantly higher performance cannot be 2. This means that the concentration of material. We can however expect that
1 Physical Rubber properties
N660 N660rCB N330 N330 rCB N115 N115 rCB Reference rCB
UTS (Mpa) 20.7 20.3 23.2 20.4 27.4 20.2 18.9
E@B (%) 497 557 424 455 520 457 537
M100 (Mpa) 2.07 1.90 2.43 2.37 2.15 2.84 1.95
M300 (Mpa) 10.4 7.6 13.6 10.8 10.8 11.7 7.8
Shore A 62.0 61.5 66.0 65.0 65.5 67.5 62.0
Dynamic Properties RPA (60oC Amplitude sweep 1Hz 1-100% Strain)
Delta g‘ (Kpa) 1008 1159 1586 1514 2154 1800 1205
36 KGK · 1 2021 www.kgk-rubberpoint.decomponent is a function of the average graphitic layer distance (Lc). This
relationship is not existing when specific treatments are applied to the carbon
black as for example graphitisation or surface treatment increasing the number
and nature of the energetic sites on the surface.
Schröder [8] has studied (Figure 2) the various surface energy configurations
which can be observed on carbon black surface.
the particle size has increased and conse- 2
quently the specific surface area is redu-
ced due to the pyrolysis residue which is
I II III IV
covering the original particles. This car- Graphitic Crystallite
bonaceous residues resulting from the I Planes III Edges
pyrolysis of organic parts of the tyre Amorphous Slit Shaped
(other than carbon black) are a function II Carbon IV Cavities
of the aromaticity of the polymer and of
the absolute surface of the carbon black
in a given volume. The absolute surface Figure
Figure 2. Attribution
2. Attribution of energy
of energy sitessites I-IV
I IV to to surface
surface [8]. [8]
microstructures
microstructures
area in a given volume of the compound
is the surface area in the given volume in
contact with the polymer. In addition to
the carbonaceous deposit, mineral com- Tunnelling Microscopy might be tech- Wang and Wolff [5] describe the tech-
ponents present in the tyre compounds niques helpful to get a better view of the nique of inverse gas chromatography to
will deposit. The work of Pieter ter Haar surface composition and of the surface determine the surface energy of carbon
[4] studying the residue for several car- arrangements of the carbon deposit. black and discuss its significance for rub-
bon blacks after pyrolysis gives an esti- ber reinforcement. Mainly two parame-
mation of the pyrolysis residue. Ter Haar Structure or void volume: ters are determined by this technique:
confirmed the influence of absolute sur- ■ γSd the dispersive component of the
face area. In the recipe, ASTM 3191, used Structure, actually the volume of the vo- surface energy describing the interac-
by ter Haar, mineral residue is 4.75% and ids within a carbon black and the inter- tion between carbon surface and po-
the carbonaceous residue represents +/- stitial volume, filled to a large extent in lymer;
2% for the N-990; +/-7% for N-660 ; 10% the tyre compound by the elastomer, has ■ Isp the specific component of surface
for N-330 and going up to +/-15% for to be expected to be covered to a large energy.
N-110. Carbon black surface acts as a extent during the pyrolysis process. Wang (6) and Wolff et al. [7] report
catalyst on the deposition of carbon Eventually new voids are created. the evolution of the dispersive compo-
from a hydrocarbon environment. Car- Experimental results by OAN indicate nent, determined by inverse chromato-
bon black is used industrially to increase that structure remains more or less at graphy, as a function of the specific sur-
the yield of hydrocarbon carbonisation the same level as could be expected from
Figure 3 Energy site distribution [9] face area. The dispersive component is
Consequently we can assume that the the carbon black mix. These results have increasing linearly with the specific sur-
deposit of carbonaceous residue from however to be considered carefully, as face area. Similarly they report the bound
the pyrolysis is mainly occuring at the
Figure 3 [9] shows the distribution curve
the OAN test is quite dependent on the
for energetic sites for a Thermal
rubber of an SBR compound of being in
carbon black particle surface. We can Plasma carbon black, which has
wetting process of the oil. More signifi- also a similar shape as furnace
linear relationship with theblack.
dispersive
consider that the average particle diame- cantDifferences
informationbetween
would beplasma
obtainedandbyfurnace black grades
component. High γSare
d
of found in the
the carbon high
black
ter increases and consequently the speci- voidenergy
volumepart with Q 20 kJ/mol of theisdistributions.
measurements. Thebound
imparting higher considered
rubber.plasma
fic surface area is reduced. This is confir- Quite often specific surface area and These observations show that the fact
med in ter Haar’s observations. structure are considered for virgin carbon that surface chemistry is usually not con-
From ter Haar’s investigations we can black as the only determining parameters sidered as a specific property of carbon
conclude that smaller particles have a for the prediction of their performance. black is justified due to its very constant
noticeably more important growth of This interpretation is in the case of nor- relationship to the specific surface area.
the specific surface area than larger par- mal carbon black quite justified. Surface The dispersive component is a function
ticles. This means that we can expect a chemistry of a normal carbon black is well of the crystallite dimension, which is a
trunking of the particle size distribution known as quality parameter; it is however function of the curvature radius of the
and finally the tendency will be during quite constant within a given carbon carbon particle: The smaller the particle,
waste tyre pyrolysis towards a recovered black type with a defined surface area. the smaller the crystallites on the sur-
carbon black having the average particle Ter Haar has studied the effect of oily face and the higher is the concentration
size and specific surface area of a N-660. hydrocarbon residues on the reinforcing of active sites. In the case the normal
This is in fact generally observed. This performance of de recovered carbon furnace carbon black the surface genera-
also indicates that the surface quality of black. In virgin carbon black oily residues ted in the reactor is rearranged to a quite
a recovered carbon black is quite similar are usually more considered as an envi- graphite-like structure. Wang and al.
to the one of virgin furnace black. ronmental and health problem than rela- showed that the dispersive component is
Pyrolysis residue, as well as mineral ted to performance. The difference in a function of the average graphitic layer
residues, are also filling the interstices composition and the amount of oily resi- distance (Lc). This relationship is not
between the particles and the voids dues on recovered carbon black and vir- existing when specific treatments are
within the aggregates. The impact of sili- gin carbon black would have to be inves- applied to the carbon black as for examp-
ca residues is another subject to be in- tigated. In ter Haar’s comparison the ef- le graphitisation or surface treatment
vestigated. fect of the oil seems to be mainly related increasing the number and nature of the
In order to have a better understanding, to a difference in structure, inducing a energetic sites on the surface.
more fundamental investigations should lower modulus for the oily material and Schröder [8] has studied (Figure 2) the
be carried out on the surface of the car- consequently a higher tensile and ulti- various surface energy configurations
bon black. Techniques like TOFF-SIMS and mate elongation which can be observed on carbon black
www.kgk-rubberpoint.de KGK · 1 2021 37Graphitic Crystallite
I Planes III Edges
Amorphous Slit Shaped
II Carbon IV Cavities
Figure 2. Attribution of energy sites I-IV to surface microstructures [8]
waves (150-10000 MHz).
3
Two types of interactions exist:
■ By energy transfer resulting in scissi-
on or excitement of chemical bonds;
■ By transfer of chemical species.
In 1992 Weidong Wang [10] has been
using a cold, high frequency plasma with
a microwave generator. Two actions of
the plasma can exist:
a. Erosion of the carbon black surface
due to the bombardment by ions, acti-
vated species, molecules…;
b. Modification of the surface chemistry
by active species (free radicals, ions…)
or by reaction of the defects created
by the reagents in the atmosphere.
Wang has been using different mole-
cules: H2, Air, NH3 and Ar. He has also
Figure Figure 3 Energy
3 Energy site distribution
site distribution [9]. [9] combined the plasma treatment with a
heat treatment at 900°C. He reported a
Figure 3 [9] shows the distribution curve for energetic sites for a Thermal noticeable increase of the dispersive
may remain on the surface. The surface component of the surface energyγSd. This
surface.
Plasma carbon black, which has also a similar shape as furnace black.
activity of the carbonaceous deposit is increase was mainly visible after the
Differences
Figure 3 [9] shows between plasma and furnace
the distribution certainly black grades
not fully are found
comparable in one
to the the high
plasma treated carbon blacks were ex-
curve forenergy part with
energetic sites Qfora20 kJ/mol ofof
Thermal thethedistributions. The considered plasmaposed to 4 hours heat treatment at
virgin carbon black.
Plasma carbon black, which has also a It is as such very important to regene- 900°C.
similar shape as furnace black. Differen- rate new functional groups able to un- The specific interaction parameter Isp
ces between plasma and furnace black dergo new interactions with the elasto- was also increased but to a lower extent.
grades are found in the high energy part mer molecules or to remove inactive As bound rubber is also strongly af-
with Q ≥ 20 kJ/mol of the distributions. material. No impact from the particle fected by the structure of the carbon
The considered plasma carbon black had size (specific surface area) can be expec- black and considering that Weidong
been obtained at noticeably higher tem- ted as we are in the range of the average Wang observed the same effect on the
peratures than furnace blacks and had size, the mathematical average size of same carbon black in a treated and unt-
consequently a larger graphitic surface. the blend of all carbon black types in the reated form, we can expect that the
For virgin carbon blacks the presence tyre. plasma treatments are an efficient tool
of energetic sites is proportional to the to increase bound rubber due to better
surface defects and graphite plan edges, Generation of active sites on the interaction between filler and polymer.
which due to the curvature radius are surface of the recovered carbon black Recent work done by Millington, Ben-
proportional to the size of the graphitic Several techniques to recreate a more net and Bradley [11] is using low tempe-
plans. Donnet and Custodero [9] (9)have reactive carbon black surface can be con- rature plasma to activate the surface of
shown by Tunnelling Microscopy that the sidered. In the present paper we consider rCB. Ozone, oxygen and peroxide have
carbon black surface has a kind of gra- two: been used as activated molecules, and
phitic scale arrangement. They also sug- 1. Low temperature plasma important changes in the rubber proper-
gested that some fullerenic structures (Cold plasma) ties have been observed.
are present on the surface of the carbon 2. Thermal plasma
black and could be the main explanation Thermal plasma
of the reinforcing properties of carbon 1. Low temperature plasma The most significant improvement in the
black. development of the recovered carbon
We can expect and it is quite obvious Atmospheric plasma or cold plasma has black can be expected from thermal
that the active sites from the original been investigated in the context of mo- plasma.
carbon black have been neutralized du- dification of the carbon black surface. Donnet et al[12] and Johnson et al
ring the mixing of the tyre compound The cold plasma could be generated by [13] have shown that fullerenes are pre-
and have provided the reinforcement to luminous discharges at reduced pressure sent in the toluene extract of furnace
the original tyre. The pyrolysis process (1-10³ Pa), where free electrons, accelera- blacks. According to Cataldo [14, 15] the
may have evacuated some molecules ted in an electric field, transfer their surface activity of carbon is largely de-
which were adhering to the carbon black energy by collision to neutral gas mole- termined by the presence of fullerenic
by physical and even chemical processes, cules. This discharge can be produced at structures on the carbon black surface.
the pyrolysis temperature is not high low frequency (60 Hz) between two elec- Fullerene-like structures would act as
enough to graphitize the carbon black trodes or at high frequency without elec- free radical acceptor sites where the rub-
surface. The original carbon black sur- trodes using different types of genera- ber macro-radicals formed during mi-
face is however not very reactive anymo- tors: by spark initiation (10-50 kHz), ra- xing form chemical bonds between rub-
re, although some functional groups dio frequency (1.5-50 MHz) or micro- ber and filler. These fullerenic structures
38 KGK · 1 2021 www.kgk-rubberpoint.desupply, as mentioned by Fabry F. et al [22] was
maximum power. Each of the three phases was
electrodes of the 3-phase plasma torch located
[23].
would play a major role in bound rubber
4 Plasma gas Plasma gas
formation.
Many publications have reported the 3 PHASE AC
possibility to produce fullerenes using POWER SUPPLY
thermal plasma[16, 17]. The starting ma-
terial is carbon black or other carbon
material.
Mathew and al. [18] have also been CnHm CnHm
able to show how fullerenic structures
Gas
can be used in compounds to significant-
ly enhance the reactivity of a carbon
black. Fullerenes are very reactive species
and improve the interaction between
carbon black and polymer. Probst et al
[19] reported the effect of thermal plas-
ma treatment of a N-330 carbon black.
Mathew used an N-330 and Ensaco 250,
a low reinforcing carbon black for his ex-
periments and plasma-polymerized ace-
tylene on its surface. Carrying gas
The fullerenic soot was prepared by Solid
injecting the virgin carbon black into
thermal plasma in an inert He/Ar atmos-
phere. Carbon from the surface was va-
porized and recondensed as fullerene
Figure 4. Thermal plasma reactor [24]
Figure 4. Thermal plasma reactor [24].
and fullerenic structures.
After 1h plasma treatment with ace-
tylene the virgin N-330 carbon black
gave 1.05 weight percent coating, while Fulchéri at the Centre Persee of Mines – sis chamber into the thermal arc plasma.
the N-330 based fullerenic soot gave Solid recovered carbon black
Paris Tech (PSL Research University), in
The high was
temperature injected
gas/solid aerosol in th
14% deposit. Similarly, the virgin Ensaco Sophia Antipolis a trial in a thermal
was introduced through a quench sys-
250 gave after 1h plasma treatment
with acetylene 2.4% deposit while the
synthesis chamber into the thermal arc plasma
plasma reactor with recovered carbon
tem after having reached sufficiently
black from scrap tires. The trials were
low temperature in a filter system al-
aerosol was introduced
les and through a quench
conditions syste
Ensaco based fulerenic soot gave 17% run successfully as the extract from the
lowing the separation of the solid partic-
deposit. treated sample showed an intense red
the gas. The operating
Schröder et al. [8, 9] show that only color, typical for the presence of a signi-
for the trials as reported by Fabry [24]
the sites II, III and IV are involved in the
interaction with the polymer. Sites I en-
sufficiently low temperature
ficant percentage of fullerenes. The
were:
plasma reactor was a 3-Phase AC reac-
in a filter system a
The recovered carbon black (Table 4)
rgetic functions are graphitic and inert tor, the same reactor used in the pro- was partially vaporized when moving
towards the polymer. For N-330 carbon duction of fullerenic material. The plas- through the high temperature zone (+/-
black, only 10 % of the surface is involved ma power supply, as mentioned by Fabry 4000 K). The vaporization rate is a func-
in the reinforcement. Fullerenic structu- F. et al [22] was 600 Hz, 0-400A, 263 kW tion of the precursor particle size and
res are very reactive; according to Sola et maximum power. Each of the three pha- the residence time in the high tempera-
al. [20] these structures deviate from ses was connected to the graphite elect- ture zone. The vaporization can be de-
planarity and have very high electron af- rodes of the 3-phase plasma torch loca- scribed as an arc discharge, starting
finity. ted in the upper part of the reactor [23]. with the generation of small carbon
In March 2012 Probst and Löffler ha- Solid recovered carbon black was injec- species and finally followed by a quench
ve run, with the help of the team of ted in the continuous gas-phase synthe- and the condensation of the small spe-
3 Operating conditions on the thermal 4 Analytical data of the recovered
Property Unit Value carbon black CT- R 6632 [1]
Average Power kW 36 BET S.A. m²/g 69
CTAB S.A. m²/g 62
Average Current A 180
OAN ml/100g 106
Average Voltage V 150
COAN ml/100g 84
Plasma gas flowrate (N2) Nm³/h 4
Ash Content % 14
Carrier gas flowrate (N2) 4
Carbon Content % 82
Carbon black soot flowrate Kg/h 0.8 Oxygen Content % 9
Recirculation loop gas flowrate (N2) Nm³/h 200 Sulfur Content % 2.5
www.kgk-rubberpoint.de KGK · 1 2021 39cies into fullerenes or/and as fullerenic Jaramillo2 and J D Martínez1; Possibilities of 105-112 | Received 23 Aug 1999, Published on-
structures onto the remaining carbon carbon black recovery from waste tyre pyrolysis line: 23 Apr 2008.
black surface. to be used as additive in rubber goods -a review; [17] L. Fulcheria, Y. Schwoba, F.F abryb G.Fla-
IOP Conf. Series: Materials Science and Enginee- mantb L.F.P. Chibantec D.Laplazed, Fullerene pro-
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