18 Rubber News • February 20, 2023 www.rubbernews.

com www

Technical Te

Devulcanizing scrap OTR tire rubber for

mar
ary
to a
reco

compounding, molding solid tire idlers to p

new

Rub
By Ben Chouchaoui me
Windsor Industrial Development
Laboratory Inc. Executive summary T
econ
There is a growing need to re- Traditionally, one of the biggest issues facing the automotive and transportation ecosystem has
lam
cover raw materials from return- been what to do with scrap tires. When they are no longer suitable for use on vehicles because of wear
pro
ing and discarded products due to or irreparable damage, used tires can become a huge ecological problem. Indeed, about half a billion
from
increasing environmental con- tires are scrapped each year in North America from passenger cars alone (one tire per person per
ed
cerns and the widely adopted year). And then you add to that trucks, buses, off-road vehicles, heavy machinery, etc.
sea
transition to a circular economy. While major strides were made in developing sustainable practices for the disposal and recycling of
Boc
For waste tires, it is necessary to scrap tires, most of these do not add value. Plus, with new developments in technology and engineer-
al.,
continuously develop methods and ing practices continuing to emerge, sustainable tire recycling continues to be a moving target. Unlike
Sab
processes to devulcanize rubber thermoplastics that are theoretically infinitely recyclable (a plastic, heated, melts, then when let to
al.,
vulcanizates with which to then cool, solidifies (into a product), and with heating (a discarded product), the plastic melts again (for Chouchaoui et a
make rubber goods with qualities making another product), rubber is a thermoset and once it cures it cannot go back to its pre-cure
and
and properties approaching those state. In fact, it takes about 600 years for a thermoset rubber to decompose naturally, and burning
made of virgin materials. tires to get rid of them quickly presents huge economical and ecological disadvantages. The author T
The
The idea is thus to try to break the bonds between molecular chains making for a cured thermoset Ben Chouchaoui is from the
gro
TECHNICAL NOTEBOOK rubber (without damaging the chains), then compounding the recyclate to improve its properties and Polytechnic School of Montre-
mic
Edited by John Dick make with the new compound a newly engineered product (and why not a new tire from a scrapped al, and the University of Wa-
ind
tire in a true economy, as tires make for close to 60 percent of all rubber applications). This paper terloo in Canada. His exper-
ach
Currently, the most common, presents emerging research in devulcanizing ground tire rubber and activities at WIDL to devulca- tise is in materials and
from
due to efficiency and perceived nize, compound and manufacture industrial products out of scrap tires. computer-based simulations
pro
eco-friendliness, in recovering (CAE/FEA/CFD computer-aid-
nea
raw rubber from scrapped tires ed engineering, finite element
ers
in particular, is devulcanization mer chains over a wide range of and this is expected to double by Waste tires can be re-used af- analysis, computational fluid
(For
in supercritical carbon dioxide temperatures. This discovery, year 2035 (Becker, 2017). Conse- ter regrooving or retreading, and dynamics).
A
(scCO2) using commercial devul- made by Charles Goodyear in quently, the amount of waste tires those that do not qualify to un- Chouchaoui worked for
et a
canizing agents. Supercritical 1844, was restricted to polymer (on average one per person per dergo these processes are shred- German and American auto-
cove
carbon dioxide is an attractive chains having double bonds (be- year in the Western World) will ded, with steel and fiber materi- motive Tier 1 suppliers for six
cal
alternative compared to tradi- tween natural elements) in the continue to rise and exponentially als removed so that the resulting years (upon completing his
Com
tional liquid-based devulcaniza- polymer chains (backbones). every year with quite a negative rubber nuggets get grinded PhD in 1994), in research and
nize
tion media because of better Vulcanizable materials include impact on the environment. That through various methods into development, on rubber and
low
quality of the resultant devulca- natural rubber (NR) and polyiso- is because of the difficulties of small particles or granules called plastics composites sealing
stre
nized rubber. prene (PI, a synthetic rubber thermosets to break down if set crumb rubber (CR), or ground systems. He then started the
dam
In this study, scCO2 was em- equivalent to NR). However, the aside, under biological degrada- tire rubber (GTR). Table 2 re- Windsor Industrial Develop-
ployed to recover rubber from range has since spread much tion, hydrolysis, or natural de- ports methods used to produce ment Laboratory in 2000, of-
waste truck tires treads and the wider for polymeric elastomers composition, because of their GTR (Abraham et al., 2011; De et fering cost-effective services
recovered rubber was blended above their glass transition tem- structural characteristics (Joseph al., 2005; Forrest, 2014; Rajan et in material and process/prod-
with virgin natural rubber (NR) perature (at or below which rub- et al., 2015; Zhang et al., 2018). al., 2006; Zanetti et al., 2015). uct simulation and testing, to
to various amounts. Curing and ber becomes brittle). Typically, GTR is rigid and aid in product design and
mechanical properties of the As the elastomeric state is un- Rubber recycling cannot be adequately revulca- manufacturing.
blends were matched to proper- stable because chains can slide Finding a viable solution for the nized for repurposing because of In 2006, he started the WIDL
ties of commercial compounds. past one another resulting in re- environmental pollution created surplus crosslinks, whereas un- Seminars to bring people of
The atmospheric toxicity and cost laxation (equivalent to creep) by waste tires is a challenge for the vulcanized virgin rubber is com- various technical backgrounds
of the commonly used devulcani- under static or dynamic loads, tire industry worldwide. The prob- posed of long flexible chains and up-to-speed in materials; prod-
zation agents, oils and solvents chemical crosslinks add stability lem is exacerbated when waste can easily be compounded, pro- uct development through simu-
enabled a shift to greener (organ- to the network for most practical tires are not re-used, recycled, or cessed, and vulcanized. As a re- lation; testing with acceleration
ic) devulcanization alternatives. applications. properly disposed of (Adhikari et sult, rubber reclamation and using time-temperature super-
The paper reports experiments al., 2000; Bell and Cave, 2010); devulcanization processes are position (TTS); and the correla-
taking crumb rubber (CR) from Rubber and the environment Markl and Lackner, 2020). used to convert GTR, as per Ra- tion of numerical results to the
truck tire treads through devul- The global production of natu- “real world.” These are monthly
canization, compounding and ral and synthetic rubber products Table 2: Overview of methods used to produce GTR (Abraham et al., 2011; accelerated training sessions,
molding laboratory samples and continues to grow yearly. Accord- De et al., 2005; Forrest, 2014; Rajan et al., 2006; Zanetti et al., 2015). modular (for increased flexibili-
commercial idlers (solid donuts) ing to Markl and Lackner (2020), ty), for people involved with
for conveyors. 70 percent of natural and syn- polymers, plastics and elasto-
thetic rubbers are consumed in mers (thermosets and TPEs).
Introduction tire manufacturing, with larger Chouchaoui continues to
Most thermoset rubber prod- amounts of NR in truck and off- work on developing novel ma-
ucts are vulcanized, a process the-road (OTR) tires than in chinery to characterize poly-
which involves heating with a passenger car tires (Table 1). mers for computer modeling
prescribed small amount of sul- Since 2017, over 1 billion pas- along with software to post-pro-
fur (or an equivalent crosslinking senger vehicles started hitting cess collected data into materi-
agent) so as to stabilize the poly- the roads daily around the world, al models. He is now looking to
close the loop in the product
Table 1: Average composition of tires for different vehicles (Bell and Cave, development process in terms
2010; De et al., 2005; Fragassa and Ippoliti, 2016; Karger-Kocsis et al., 2013). of recycling polymeric products
and using recycled materials
for new engineered products.
He also is developing compact,
efficient and completed ma-
chinery to test polymers for
FEA and CFD, define design
parameters, and correlate sim-
ulations to product testing.
He belongs to various orga-
nizations in North America.
He often publishes in the Soci-
ety of Automotive Engineers,
the Society of Manufacturing
Engineers and the American
Chemical Society, and partici-
pates in conferences around
the world on materials, prod-
uct development and manu-
facturing, and writes in jour-
nals and magazines.

P018_P022_RPN_20230220.indd 18 2/15/23 6:35 PM

 com www.rubbernews.com Rubber News • February 20, 2023 19
Technical
marad et al. (2015) into a second- lecular weight (Mw), yet higher or no changes to the backbone of Several authors (Asaro et al., canization as far as possible,
ary polymeric material referred glass transition temperature (Tg). rubber during the recovery pro- 2018; Jiang et al., 2013; Kojima et without breaking the bonds of
to as reclaimed, devulcanized or Because of this, the relatively cess. This was achieved with ther- al., 2004, 2005a, 2005b; Lasagni, the rubber’s main chain. During
recovered rubber, to be re-used lower proportions (1-10 wt per- mo-chemical devulcanization in 2013; Liu et al., 2015; Mangili et this process, the monosulphidic,
to produce rubber products and cent) of devulcanized rubber typi- scCO2 using a reactor or an auto- al., 2014a; Rajan et al., 2006) re- disulphidic and polysulphidic
new tires. cally is employed to manufacture clave to speed up devulcanization port minor negative effects on the crosslinks are selectively broken.
new rubber products in the indus- by providing the heat needed to backbone of rubber from elevated The devulcanizing agents are
Rubber recovering try (Abraham et al., 2011; De et activate the devulcanizing agent temperature normally employed used to break only the sulfur-sul-
methods from waste tires al., 2005; Forrest, 2014). used in the process (Jiang et al., during thermo-chemical devulca- fur (S-S) and carbon-sulfur (C-S)
To initiate a rubber circular Normally, properties of devulca- 2013; Kazarian, 2000; Kojima et nization in scCO2. Other re- bonds in a rubber vulcanizate
economy, several methods of rec- nized rubber vulcanizates closely al., 2004, 2005a, 2005b; Liu et al., searchers (Diaz et al., 2018; Gho- (Bockstal et al., 2019; De et al.,
lamation and devulcanization resembles those of virgin rubber 2015; Mangili et al., 2014a, 2014b, rai et al., 2016; Ghosh et al., 2018; 2005; Ramarad et al., 2015). This
processes for recovering rubber vulcanizate if there were minimal 2015; Shi et al., 2013). Jana and Das, 2005a, 2005b; targeted breakage is due to the
from waste tires were investigat- Seghar et al., 2019; Sutanto et al., fact that the sulfur bonds in a
ed over the years. Several re- Table 3: Methods of vulcanized waste rubber reclamation/devulcanization (Asaro 2006; Tao et al., 2013; Thaich- sulfur-vulcanized rubber require
searchers (Asaro et al., 2018; et al., 2018; Bockstal et al., 2019; Mangili et al., 2015; Ramarad et al., 2015; aroen et al., 2010; Zhang et al., relatively lower energies to
Bockstal et al., 2019; Mangili et Sabzekar et al., 2015; Seghar et al., 2019; Yao et al., 2013; Zhang et al., 2018). 2018) reported severe negative break, compared to carbon-car-
al., 2015; Ramarad et al., 2015; effects with the mechano-chemi- bon (C-C) bonds of the rubber’s
Sabzekar et al., 2015; Seghar et cal and thermo-mechanical rub- main chain. Energy values of the
al., 2019; Yao et al., 2013; Zhang ber reclamation. various bonds are reported in
et al., 2018) extensively studied Table 4.
and discussed these methods. Chemical devulcanization A variety of chemical agents
Table 3 shows a summary. of rubber vulcanizates are used at an industrial scale to
They are divided into three Conventional chemical devul- recover rubber from GTR. Gen-
he
groups: physical, chemical, and canization aims at reversing vul- See OTR, page 20
e-
microbiological, and can be used
a-
individually or combined to Table 4: Bond energies in sulfur crosslinks and rubber molecules (Diaz et al.,
er-
achieve efficient rubber recovery 2018; Markl and Lackner, 2020; Ramarad et al., 2015; Sabzekar et al., 2015).
nd
from waste rubber. While some
ns
processes can be operated at or
d-
near ambient temperature, oth-
nt
ers require high temperatures
id
(Forrest, 2014).
Abraham et al. (2011) and Shi
or
et al. (2013) quantified rubber re-
o-
covery with curing and mechani-
ix
cal and dynamic properties.
is
Compared to virgin NR, devulca-
nd
nized rubber vulcanizates had
nd
lower scorch time (ts), tensile
ng
strength, elongation at break,
he
dampening factor (tan δ) and mo-
p-
of-
es
d-
to
nd

DL
of
ds
d-
u-
on
er-
a-
he
hly
ns,
li-
th
o-

to
a-
ly-
ng
o-
ri-
to
ct
ms
ts
als
ts.
ct,
a-
or
gn
m-

a-
a.
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P018_P022_RPN_20230220.indd 19 2/15/23 6:35 PM

 20 Rubber News • February 20, 2023 www.rubbernews.com www

Technical Te

OTR
agents include sol fraction, gel reclaiming oils and solvents also properties sought for a solid tire rubber from whole truck tires tion
fraction, crosslink density, sulfur act as radical acceptors, prevent- idler industrial application (Curve ground at a tire processor in the of t
content, Mw, Tg, Mooney Viscosity, ing the formation of gel content No. 6); and United States, using ther- T
and poly dispersity index (PDI). during rubber recovery (Abra- • Making the same product mo-chemical devulcanization in ing
Continued from page 19 Using these devulcanizing ham et al., 2011; Ramarad et al., using the new formulation and super critical carbon dioxide ligh
erally, these agents are inorgan- agents can achieve high efficien- 2015). For partial replacement of the virgin compound for compar- (scCO2) in an autoclave. and
ic, organic disulphides, or thiols, cy devulcanization by selectively conventional oils and solvents, isons (Curve No. 5) The WIDL program is continu- tom
which have been greatly studied targeting and cleaving crosslinks several researchers suggested Constituents of the devulca- ing with the design and installa- the
for their effectiveness in the (Bockstal et al., 2019; Jiang et economical and eco-friendly sol- nized rubber using thermo-chem- tion of a larger throughput auto- 1
presence and absence of mechan- al., 2013; Kojima et al., 2005b; vents like vegetable oils in the ical devulcanization in scCO2 in clave and the consideration of only
ical shearing and under different Rooj et al., 2011). Another advan- thermo-chemical devulcaniza- an autoclave for improved effi- several industrial case studies. poly
temperatures (Adhikari et al., tage in using these agents, espe- tion process (Song et al., 2018; ciency of the devulcanization Numerous equipment and the in a
2000; De et al., 2006; Ramarad cially with scCO2, is that there Xie et al., 2019). process under the added heat internal rheological laboratory 2
et al., 2015; Rooj et al., 2011). are only minor losses in physical needed to activate the DPDS and the shop floor are upgraded ic c
Chemical devulcanization in- properties of the recovered rub- Compounding devulcanizing agent used, were to handle new and additional ap- pro
volving a reactor or an autoclave ber (Asaro et al., 2018; Bockstal devulcanized rubber as follows. plications, in particular from the com
typically excludes mechanical et al., 2019; Kojima et al., 2004, An experimental program was The devulcanized rubber, run car companies. and
shearing, and is reported to 2005a, 2005b; Liu et al., 2015). started at Windsor Industrial through a two-roll mill and a Rheological curves of the lar
cause minimal to no degradation Devulcanizing agents have Development Laboratory (WIDL) sample cut was run in a rheome- devulcanized rubber from OTR gin
of the C-C bonds of the rubber’s normally been used in the range to evaluate the technical specifi- ter. Torque remained low with tires were established to calcu- 3
main chain, producing recovered of 0.5-10 wt percent, together cations of devulcanized rubber rotations and heat indicating late the required curing virg
rubber of relatively high quality with catalysts and reclaiming from whole truck tires ground to that the devulcanized rubber agent-accelerator using mixture dict
(Kojima et al., 2004; Li et al., oils, to devulcanize sulfur-vulca- mesh-10 at a tire processor in the had no curing element in it (Fig. composition details, then mold mai
2020; Liu et al., 2015; Mangili et nized rubber (Asaro et al., 2018). U.S. The program used ther- 2, Curve No. 1). The devulcanized slabs and buttons of the newly pro
al., 2014a; Mohaved et al., 2015; Abraham et al. (2011) claim that mo-chemical devulcanization in rubber also was run through compounded rubber for mechani- ple:
Shi et al., 2013). the devulcanizing agents accel- scCO2 in an autoclave to speed composition tests, and the results cal properties definitions. Sam- R
erate and introduce new path- up the devulcanization by pro- of the constituent of the devulca- ples were tested under tension scra
Organic devulcanizing ways like the auto-oxidation viding the heat needed to acti- nized rubber are presented in and compression, and for density, suit
agents degradation reactions. The cata- vate the organic DPDS devulca- Table 5. hardness, abrasion, upon mold- tech
The organic devulcanizing lysts used during the process of nizing agent used. Several Properties of the devulcanized ing and after aging for 72 hours rub
agents, in particular for natural recovering rubber are chemical process equipment and the inter- rubber by only adding a vulcani- under 150°C. tain
and synthetic rubbers, are com- compounds, effective even at nal rheological laboratory were zation package (sulfur and an An industrial actual experi- gro
mercially available to recover small quantities (Abraham et al., dedicated to these investigations accelerator) were carried out; mental product, a caster (or solid T
rubber of improved properties. 2011; Ramarad et al., 2015). sponsored by Innovation Guelph Table 6 presents the results. tire), was made for conveyors for furt
The main factors studied to trace And to speed up the oxidation in Ontario. Various new rubber com- Strongco Corp., a wholly owned thre
the efficiency of devulcanizing of the rubber and increase the The program included: pounds were developed and test- subsidiary of Nors S.A., a major grin
rubber vulcanizates by these plasticity of the recovered rubber, • Running rheological curves ed (as in Fig. 3) based on the re- multiline mobile equipment deal- izat
of the devulcanized rubber as is quirements for several industrial er with operations across Cana- pref
Fig. 1: Rheology testing rubber devulcanizates.
(Curve No. 1); products for client real applica- da. The process required metal acti
• Calculating the required tions. Chemical formulae were insert compression-molding in mix
curing agent-accelerator using established based on existing in- contrast to production parts lori
the composition mixture details gredients and virgin base poly- made through faster injection tera
(Curve No. 2); mer but contained various molding (because of differences rub
• Molding slabs and buttons of amounts of replacement devulca- in viscosity between the recycled as r
the newly compounded rubber nized rubber. Subsequent pre- and non-recycled compounds). fille
(containing devulcanized rubber); sentations are to share com- nee
• Measuring tensile modulus pounds physical properties with Conclusions and future con
properties of the various com- various ratios of devulcanized directions in p
pounds (moduli values in Table 6); rubber to base polymer, and some Increasing amounts of waste S
• Making an actual experi- of the industrial products made and discarded tires of various dev
mental product, an anti-vibration and tested for customers in vari- sizes and makes generated to the dus
mount, for a customer, replacing ous industrial sectors. environment each year consti- tive
20 percent of the virgin polymer An experimental program was tute huge and global financial tion
(Curve No. 3); started at Windsor Industrial and ecological problems. This vola
• Preparing a formula using Development Laboratory (WIDL) situation enforced industry and form
the devulcanizate as 100 percent to evaluate the technical specifi- researchers to develop existing can
of the polymer to achieve the cations of devulcanized mesh-10 technologies and continue to
search for new directions to recy- Fig
Table 5: Statistical composition of the basic elements within the devul- cle waste rubber, a starting step pac
canized rubber. supporting circular economy in
the tire industry.
Over the last 10 years, many
attempts in waste tire recycling
focused on direct application of
ground tire rubber (GTR) in var-
ious matrices (e.g. polymers, bi-
tumens, concretes, etc.), which
are downscaling solutions.
Windsor’s laboratories focused
on advances related to sustain-
able development of waste rubber
and tire devulcanization technol-
Fig. 2: Compounding rubber devulcanizates.
ogies. This paper presented a
test program evaluating techni-
cal specifications of devulcanized
mesh-10 rubber from truck tire
treads, using thermo-chemical
devulcanization in scCO2 in an
Table 6: Statistical mechanical and rheology properties of the devulca- autoclave to speed up the devul-
nized rubber with a curing package (sulfur and an accelerator). canization by providing the heat
needed to activate the DPDS
devulcanizing agent used.
Considering advantages and
disadvantages of various meth-
ods applied for reclaimed rubber
characterization, a basic stan-
dard Mooney Viscosity should be
determined along with tensile
strength according to ASTM
D1646 and D312. However, final
values of these parameters are
affected not only by reclaiming/
devulcanization efficiency but
also by curing system composi-

P018_P022_RPN_20230220.indd 20 2/15/23 6:36 PM

 com www.rubbernews.com Rubber News • February 20, 2023 21
Technical
ires tion and vulcanization conditions tionalization of GTR. The impact —Burton G.B. (1990), A Chemical Inves- rubber. Periodicals of Engineering and of the treated material. Padua: Scuola di
the of the revulcanizates. of such compounds (some being tigation of Tulbaghia violacea in Chem- Natural Sciences 6: 154-160. Scienze, Universit a degli Studi di Milano
istry. Grahamstown: Rhodes University, —Haws K., Winterich K. and Naylor - Bicocca, p.114.
her- The summary and key find- carcinogenic) on final product p.111. R. (2014), Seeing the world through —Li X., Deng X-Q and Dong C. (2018),
n in ings of the experimentations in properties and stability (possible —Cao Q., Yan X., Liu S., et al. (2020), green-tinted glasses: Green consumption Effect of temperature on the devulcani-
xide light of past experiences at WIDL migration of degradation prod- Temperature and phase evolution and values and responses to environmentally zation of waste sidewall rubber by super-
and on production floors at cus- ucts to the surface or evaporation density distribution in cross section and friendly products. Journal of Consumer critical ethanol. Journal of the Brazilian
sound evolution during the release of Psychology 24: 336-354. Chemical Society 29: 2,169-2,179.
nu- tomers with natural and syn- during storage), and the environ- dense CO2 from a large-scale pipeline. —Institute of Waste Management of —Li X., Xu X. and Liu Z. (2020), Cryo-
lla- thetic rubbers indicate that: ment or human health should International Journal of Greenhouse Gas Southern Africa (IWMSA) (2017), Waste genic grinding performance of scrap tire
uto- 1. The devulcanized rubber is also be investigated. Control 96: 103011. Management Hierarchy. South Africa rubber by devulcanization treatment with
n of only the replacement for the Third, deals with solutions to —Chen D.T., Perman C.A., Riechert M.E., Climbing up the Waste Management Hier- ScCO2. Powder Technology 374: 609-617.
et al. (1995), Depolymerization of tire and archy. Cape Town: Media Release, pp.1-3. —Liu Z., Li X., Xu X., et al. (2015), Devul-
ies. polymer content of the ingredient convert promising batch methods NR using supercritical fluids. Journal of —Jana G.K. and Das C.K. (2005a), Re- canizaiton of waste tread rubber in su-
the in a product to be made; of GTR modification to continuous Hazardous Materials 44: 53-60. cycling natural rubber vulcanizates percritical carbon dioxide: Operating pa-
ory 2. From understanding organ- processes including profitability —De D., Das A., De D., et al. (2006), Re- through mechanochemical devulcaniza- rameters and product characterization.
ded ic chemistry of the vulcanization estimation of such conversions claiming of ground rubber tire (GRT) by tion. Macromolecular Research 13: 30-38. Polymer Degradation and Stability 119:
a novel reclaiming agent. European Poly- —Jana G.K. and Das C.K. (2005b), Mech- 198-207.
ap- process of natural and synthetic and homogeneity of the feed mer Journal 42: 917-927. anochemical devulcanization of vulca- —Lorenz O. and Parks C.R. (1961), The
the compounds, the devulcanized PI stocks. Optimization and up-scal- —De D., Maiti S. and Adhikari B. (2000), nized gum natural rubber. Progress in crosslinking efficiency of some vulcaniz-
and SBR do not have the molecu- ing laboratory and prototype Reclaiming of rubber by a renewable re- Rubber, Plastics and Recycling Technolo- ing agents in natural rubber. Journal of
the lar behavior expected from vir- lines dedicated for GTR recycling source material (RRM). III. Evaluation of gy 21: 183-199. Polymer Science 50: 299-312.
properties of NR reclaim. Journal of Ap- —Jiang K., Shi J., Ge Y., et al. (2013) —Mangili I,, Collina E,, Anzano M,, et al.
OTR gin polymer structures; and should be performed to verify the plied Polymer Science 75: 1493-1502. Complete devulcanization of sulfur-cured (2014a), Characterization and supercriti-
lcu- 3. The molecular structure of results at larger semi-technical or —De S.K., Isayev A.I. and Khait K. butyl rubber by using supercritical carbon cal CO2 devulcanization of cryo-ground
ing virgin polymer equates to a pre- industrial scale. (2005), Rubber Recycling, 1st ed. Boca Ra- dioxide. Journal of Applied Polymer Sci- tire rubber: Influence of devulcanization
ure dictable glass transition that re- ton: Taylor & Francis Group, p. 493. ence 127: 2397-2406. process on reclaimed material. Polymer
—Diaz R, Colomines G., Peuvrel-Disdier —Joseph A.M., George B, Madhu- Degradation and Stability 102: 15-24.
mold mains critical to developing Acknowledgment E., et al. (2018), Thermo-mechanical recy- soodanan K.N., et al. (2015), Current —Mangili I., Lasagni M., Anzano M., et
wly products requiring safety (exam- This work was supported by a cling of rubber: Relationship between ma- status of sulfur vulcanization and devul- al. (2015), Mechanical and rheological
ani- ple: automotive tires). grant from Innovation Guelph in terial properties and specific mechanical canization chemistry: Process of vulcani- properties of natural rubber compounds
am- Reviews at WIDL indicate that Guelph, Ontario (Canada); https:// energy. Journal of Materials Processing zation. Rubber Science 28: 82-121. containing devulcanized ground tire rub-
Technology 252: 454-468. —Kandyala R., Raghavendra S.P.C. and ber from several methods. Polymer Degra-
sion scrap tire rubber recycling by innovationguelph.ca/. —Forrest M. (2014), Recycling and Re-use Rajasekharan S.T. (2010), Xylene: An dation and Stability 121: 369-377.
sity, suitable grinding and treatment of Waste Rubber. Shawbury, Shrewsbury, overview of its health hazards and pre- —Mangili I., Oliveri M., Anzano M., et
old- technologies of waste OTR tire References Shropshire: Smithers Rapra, p. 346. ventive measures. Journal of Oral and al. (2014b), Full factorial experimental
—Abraham E., Cherian B.M., Elbi P.A., —Fragassa C. and Ippoliti M. (2016), Maxillofacial Pathology 14: 1-5. design to study the devulcanization of
urs rubber and characterizing ob- et al. (2011) Recent advances in the recy- Technology assessment of tire mold clean- —Karger-Kocsis J., Meszaros L. and Bara- ground tire rubber in supercritical carbon
tained products will continue to cling of rubber waste. In: Fainleib A. and ing systems and quality finishing. Inter- ny T. (2013) Ground tire rubber (GTR) in dioxide. The Journal of Supercritical Flu-
eri- grow in the years to come. Grigoryeva O. (eds) Recent Developments national Journal for Quality Research 10: thermoplastics, thermosets and rubbers. ids 92: 249-256.
olid The most promising avenues for in Polymer Recycling. India: Transworld 523-546. Journal of Materials Science 48: 1-38. —Markl E. and Lackner M. (2020), Devul-
Research Network. pp.47-100. —Fuzzi S., Baltensperger U., Carslaw —Kazarian S.G. (2000), Polymer process- canization technologies for recycling of
for further investigations fall into —Adhikari B., De D. and Maiti S. (2000), K., et al. (2015), Particulate matter, air ing with supercritical fluids. Polymer Sci- tire-derived rubber: A review. Materials
ned three principal directions. First, Reclamation and recycling of waste rubber. quality and climate: Lessons learned and ence, Series C 42: 78-101. 13: 1,246.
ajor grinding, modification, functional- Progress in Polymer Science 25: 909-948. future needs. Atmospheric Chemistry and —Khaw K-Y, Parat M-O, Shaw P.N., et al. —Meysami M., Tzoganakis C., Mutyala
eal- ization of GTR (or combinations), —Asaro L., Gratton M., Seghar S., et Physics 15: 8,217-8,299. (2017), Solvent supercritical fluid technol- P., et al. (2017), Devulcanization of scrap
al. (2018), Recycling of rubber wastes by —Gheorghe I.F. and Ion B. (2011), The ogies to extract bioactive compounds from tire rubber with supercritical CO2: A
na- preferably through continuous re- devulcanization. Resources, Conservation effects of air pollutants on vegetation natural sources: A review. Molecules 22: study of the effects of process parameters
etal active extrusion or high-shearing & Recycling 133: 250-262. and the role of vegetation in reducing at- 1,186. on the properties of devulcanized rubber.
in mixing. The approach allows tai- —Becker D. (2017), Global Automotive mospheric pollution. In: Khallaf M. (ed.) —Kojima M., Kohjiya S. and Ikeda Y. International Polymer Processing 32:
arts loring matrix-GTR interfacial in- Executive Survey. Germany: KPMG In- The Impact of Air Pollution on Health, (2005a), Role of supercritical carbon diox- 183-193.
ternational Cooperative, p. 56. Economy, Environment and Agricultural ide for selective impregnation of decross- —Mohaved O.S., Ansarifar A., Nezhad
tion teractions and preparing novel —Belewa X.V. (2009), The effect of Tul- Sources. London: InTech, p. 242. ISBN: linking reagent into isoprene rubber vul- SK, et al. (2015), A novel industrial tech-
nces rubber recycling-based products, baghia violacea plant extract on the 978-953-307-528-0. canizate. Polymer 46: 2016-2019. nique for recycling ethylene-propylene-di-
cled as reinforcing or semi-reinforcing growth of Aspergillus species. Masters —Ghorai S., Bhunia S., Roy M., et al., —Kojima M., Ogawa K., Mizoshima ene waste rubber. Polymer Degradation
. fillers, bitumen modifiers, or engi- Dissertation, Nelson Mandela University, (2016), Mechanochemical devulcanization H., et al. (2003), Devulcanization of sul- and Stability 111: 114-123.
Port Elizabeth, p.103. of NR vulcanizate by dual function disul- fur-cured isoprene rubber in supercritical —Park Y., Hool J.N., Curtis C.W., et al.
neering materials dedicated to —Bell K. and Cave S. (2010) Tire Dis- fide chemicals. Polymer Degradation and carbon dioxide. Rubber Chemistry and (2001), Depolymerization of styrene bu-
construction and building projects posal. Northern Ireland Assembly, U.K., Stability 129: 34-46. Technology 76: 957-968. tadiene copolymer in near-critical and
in particular. p.1-5. —Ghosh J., Ghorai S., Bhunia S., et al. —Kojima M., Tosaka M. and Ikeda Y. supercritical water. Industrial & Engi-
aste Second, further research and —Bockstal L., Berchem T., Schmetz Q., et (2018), The role of devulcanizing agent for (2004), Chemical recycling of sulfur-cured neering Chemistry Research 40: 756-767.
al. (2019), Devulcanisation and reclaim- mechanochemical devulcanization of sty- natural rubber using supercritical carbon —Rajan V., Dierkes W.K., Joseph R., et al.
ous development in academia and in- ing of tires and rubber by physical and rene butadiene rubber vulcanizate. Poly- dioxide. Green Chemistry 6: 84-89. (2006), Science and technology of rubber
the dustry should focus on quantita- chemical processes: A review. Journal of mer Engineering and Science 58: 74-85. —Kojima M., Tosaka M., Ikeda Y., et al. reclamation with special attention to NR-
sti- tive and qualitative characteriza- Cleaner Production 236: 117-574. —Goos E., Riedel U., Zhao .L, et al. (2011), (2005b), Devulcanization of carbon black based waste latex products. Progress in
cial tion of liquid by-products and —Boyce A. (2017) Devulcanization of mod- Phase diagrams of CO2 and CO2-N2 gas filled natural rubber using supercritical Polymer Science 31: 811-834.
el compounds by a variety of diphenyldi- mixtures and their application in com- carbon dioxide. Journal of Applied Poly- —Rajan V.V., Dierkes W.K., Joseph R.,
This volatile organic compounds sulfides. Masters Dissertation, Nelson pression processes. Energy Procedia 4: mer Science 95: 137-143. et al. (2007), Effect of diphenyldisulfides
and formed and emitted during devul- Mandela University, Port Elizabeth, 3,778-3,785. —Lasagni M. (2013) Optimization of su- with different substituents on the rec-
ing canization, modification or func- p.105. —Gursel A., Akca E. and Sen N. (2018), percritical CO2 devulcanization process lamation of NR based latex products.
to A review on devulcanization of waste tire of cryo ground tires and characterization See OTR, page 22
ecy- Fig. 3: Sample tensile testing devulcanized rubber with vulcanization
step package for mechanical properties. Appendix: Abbreviations used in article
y in

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 22 Rubber News • February 20, 2023 www.rubbernews.com

Against the wind

Goodyear nets $20.8B in 2022 sales as
global inflation presents challenges
By Andrew Schunk billion (over the last quarter of 2021), driven
Rubber News Staff mainly by a strong price/mix, according to
AKRON—A weak fourth quarter market Christina Zamarro, executive vice president
driven by soft demand in the Americas and chief financial officer for Goodyear.
and Europe, high energy costs and con- However, net income showed a loss of $104
tinuing inflation dampened Goodyear’s million in the fourth quarter of 2022, a de-
year-end numbers, which saw net sales crease of $657 million against $553 million
increase 16 percent over 2021 results. in net income in the last quarter of 2021.
The world’s third-largest tire manufac-
turer saw net sales of $20.8 billion in 2022 Fourth quarter, by segment energy costs). and mix. Across the portfolio has been
against $17.5 billion in net sales in 2021, Segment operating income was down $155 These costs more than offset the price/ good growth.”
according to Goodyear’s fourth quarter million, or about 40 percent, to $236 million mix in EMEA of $264 million in the fourth Zamarro cited the opening of a non-tire
2022 and year-end financial report, issued in the fourth quarter of 2022 against $391 quarter, Kramer said. rubber goods plant in China that should
to investors Feb. 8. million in segment operating income in 2021. “The escalating raw material environ- assist 2023 financial numbers.
Year-end EBIT, or earnings before tax- “Our fourth-quarter results fell short of ment is true for Goodyear and true for the
es, registered at $399 million for Goodyear our expectations given a significantly weak- industry,” Kramer said. “We need to recov- Cooper integration on schedule
in 2022, against $513 million in 2021. er industry backdrop, particularly in Eu- er that. And there is the potential for a Goodyear said the synergies of the Coo-
And year-end net income decreased to rope,” Kramer said. decrease in raw materials, and we need to per Tire combination during the quarter
$202 million in 2022 against 2021’s $764 “While our businesses have performed capture those benefits when it happens, totaled $40 million, compared with third
million. at a high level through the volatility of the dropping those benefits into earnings. quarter 2022 benefits of $25 million.
“While we anticipated weaker industry past several years, the uncertain near- “The OE business is coming back, we see “We continue to expect synergies to reach
conditions in Europe, the magnitude of the term macroeconomic outlook and continu- that. This is good for the supply-demand an annual run rate of $250 million by mid-
volume softness was greater than expect- ing impacts of inflation make these diffi- equation as well.” 2023,” Kramer said.
ed,” Rich Kramer, Goodyear chairman, cult actions necessary to position our EMEA saw net sales of $1.36 billion for The Goodyear CEO said all retail stores
CEO and president said during a Feb. 9 business for future success.” the fourth quarter of 2022, a 1.5-percent now have Cooper products.
call with the media. The decrease was led by an $80 million drop against the fourth quarter of 2021. “One plus one equals three in this case,”
“Weaker industry vol- loss in operating income in EMEA. Overall volume in EMEA was down 1 Kramer said. “There are distribution ele-
ume in the quarter mag- Net sales in the Americas increased million units for the quarter (12.8 million ments with how they go to market and how
nified already challeng- about 12 percent to $3.4 billion in the last total), or 7.3 percent below 2021 levels they sell to distributors. They do those
ing conditions, given the three months of 2022 over the last quarter (13.8 million total). Replacement volume things really well. We are not going to
Ukraine conflict and ele- of 2021, according to Goodyear. This was was down 1.5 million units in EMEA, touch those.
vated inflation.” driven by a 13-percent increase in revenue while OE fitments were up 500,000 units. “We are keeping where they are strong
“But our business made per tire, Goodyear said. “We expect segment operating income to and integrating at the same time in other
significant progress in a Segment operating income for the Amer- improve during 2023,” Kramer said. “As pric- places.”
very challenging environ- icas came in at $279 million in the last ing continues to catch up to the impact of Kramer said the Cooper and Goodyear
ment in 2022.” Kramer quarter of 2022, a 10-percent drop against higher costs, our goal is for EMEA to break portfolios are becoming more intertwined.
The headwinds of the fourth quarter $308 million in the final quarter of 2021. even for the first quarter and return to ... his- “We are a team,” he said. “We are not re-
mimicked those of the third quarter of last “As I think about the Americas going for- torical run-rates by the middle of the year.” liant on one person. We are keenly focused
year, and similar challenges are expected ward—up 10 percent in the consumer re- Asia-Pacific netted sales of $610 million in getting our structure in line relative to
in the first quarter of this year, according placement channel by volume, that is pretty in the fourth quarter, a 2.9-percent de- competitors, yes, but with the marketplace
to Goodyear officials. healthy—our distributors are building in- crease over the fourth quarter of 2021; and as well. We need to make sure our opera-
“In Europe and the Americas,” Kramer ventory,” Kramer said. “There is no anticipa- segment operating income of $37 million, a tions get more efficient every day.
said, “it was a weaker market in the fourth tion of price reductions, and we are aligned 12-percent decrease against the final “Like with Cooper, we will get creative
quarter, and we expect slowdowns into with where the market is going in 2023. quarter of 2021. with how we can use capacity moving ahead.
quarter one. We reacted in the Americas “It will be a slow start but we see a Zamarro noted that tire volumes in each Our product innovation engine has worked.”
and Europe by taking production down, as strong second half coming.” business segment began stabilizing toward Kramer added he is most excited about
we do not want a high inventory in a slower Overall volume in the Americas was the end of 2022, and high raw material the technology trends in the tire manufac-
market.” similar to the fourth quarter of 2021, at costs—which also saw some abatement to- turing industry moving forward, and the
The third and fourth quarter slowdowns 25.4 million units (OE and replacement ward the end of 2022—were offset by higher company’s role in future mobility.
resulted in the loss of 500 jobs, cuts an- combined) in the last quarter of 2022 revenues per tire (a 28-percent increase in “Among these is our recently unveiled
nounced by Goodyear Jan. 23. The job against 25.5 million units in 2021. revenue per tire in the EMEA, thanks to demonstration tire comprising 90 percent
cuts represent about 5 percent of Good- Europe, Kramer said, presents more price/mix adjustments). sustainable materials,” Kramer said.
year’s work force and are set to take place difficult challenges. “We see benefits in the second half of “This is a significant step toward creating
“globally,” according to Goodyear. About 200 “It is a bit tougher there,” he said. “Ini- this year with higher volume and strong the industry’s first 100-percent sustain-
jobs are expected to be lost in Europe, the tiatives were put in place and we were able growth in the Asia-Pacific region, mainly able-material tire.
company said. to get volume and price mix ahead of raw in China,” Zamarro said. “And we expect “This tire is another example of the in-
The actions will result in a quarterly material (costs) again. So things are work- some tail winds in lower raw material genuity and grit our company has demon-
run-rate benefit of approximately $15 mil- ing in Europe. costs. Historically, this (second half of a strated over its 125-year history. They are
lion beginning in the second quarter. Sav- “Obviously we have seen energy infla- fiscal year) is the time for growth in earn- not revenue-generating today—but chang-
ings in the first quarter of 2023 are ex- tion driven by the war, and the anticipation ings and growth in margins.” es in mobility, going from a ‘dumb’ tire to
pected to be $5 million. of high energy costs can reduce consumer Goodyear’s non-tire rubber product seg- an intelligent tire that has a place on an
These actions are in addition to Good- demand, something we noticed particular- ment “was driven by the chemical busi- intelligent vehicle, there is both an inte-
year’s plans to close the Cooper Tire Melk­ ly in November and December.” ness” in 2022, Zamarro said. grated and service element.
sham, England, tire plant and exit the Kramer noted that the EMEA operating “We were buying butadiene at higher “I am excited for the role that Goodyear
TrenTyre retail operations in South Africa income loss of $80 million was due to high- prices, then prices dropped precipitously,” will play in this.”
to support EMEA’s overall competitiveness. er raw material costs of $252 million and she said. “I think it is more of a timing issue. Goodyear employs about 72,000 people
In the fourth quarter of 2022, Goodyear inflation and other cost increases of $118 “We’ve had good growth driven by avia- and manufactures its products in 57 facili-
saw net sales increase by 6 percent to $5.37 million (including $50 million in higher tion, with a strength in volume, pricing ties in 23 countries.

Technical
OTR
variables on chemical devulcanization of woody-biomass related compounds. In: zate blends with copolyester. European —Warner W.C. (1994), Methods of devul-
of sulfur-cured natural rubber. Polymer Pandey A., Bhaskar T., Stocker M., et al. Polymer Journal 85: 279-297. canization. Rubber Chemistry and Tech-
Degradation and Stability 118: 88-95. (eds), Recent Advances in Thermo-Chem- —Sutanto P., Laksmana F.L., Picchioni nology 67: 559-566.
—Sdrolia E. and Zarotiadis G. (2018) A ical Conversion of Biomass. Amsterdam, F., et al. (2006), Modeling on the kinetics —Xie Y., Hassan A.A., Song P., et al.
comprehensive review for green product Netherlands: Elsevier, pp. 437-453. of an EPDM devulcanization in an inter- (2019), High scission of butadiene rub-
Continued from page 21 term: From definition to evaluation. Jour- —Song P., Wan C., Xie Y., et al. (2018), nal batch mixer using an amine as the ber vulcanizate under thermo-oxidation.
Journal of Applied Polymer Science 104: nal of Economic Surveys 33: 150-178. Vegetable derived-oil facilitating carbon devulcanizing agent. Chemical Engineer- Polymer Degradation and Stability 167:
3,562-3,580. —Seghar S., Asaro L., Rolland-Monnet black migration from waste tire rubbers ing Science 61: 6,442-6,453. 292-301.
—Ramarad S., Khalid M., Ratnam C.T., M., et al. (2019), Thermo-mechanical and its reinforcement effect. Waste Man- —Tao G., He Q., Xia Y., et al. (2013) The —Yao C., Zhao S., Wang Y., et al. (2013),
et al. (2015), Waste tire rubber in polymer devulcanization and recycling of rubber agement 78: 238-248. effect of devulcanization level on mechan- Microbial desulfurization of waste latex
blends: A review on the evolution, proper- industry waste. Resource, Conservation —Sonti T. (2018) Extraction of diallyl ical properties of reclaimed rubber by rubber with Alicyclobacillus sp. Polymer
ties and future. Journal for Progress in & Recycling 144: 180-186. sulfides and other similar compounds thermal-mechanical shearing devulcani- Degradation and Stability 98: 1,724-1,730.
Materials Science 72: 100-140. —Shi J., Jiang K., Ren D., et al. (2013), from Tulbaghia violacea, a South African zation. Journal of Applied Polymer Sci- —Zanetti M.C., Fiore S., Ruffino B., et al.
—Rooj S., Basak G.C., Maji P.K., et al. Structure and performance of reclaimed plant, for potential use as devulcanizing ence 129: 2,598-2,605. (2015), Characterization of crumb rubber
(2011), New route for devulcanization rubber obtained by different methods. agents. Masters Dissertation, Nelson —Thaicharoen P., Thamyongkit P. and from end-of-life tires for paving applica-
of natural rubber and the properties of Journal of Applied Polymer Science 129: Mandela University, Port Elizabeth, p. 99. Poompradub S. (2010), Thiosalicylic tions. Waste Management 45: 161-170.
devulcanized rubber. Journal of Polymers 999-1,007. —Sripornsawat B., Saiwari S., Pichai- acid as a devulcanizing agent for mech- —Zhang X., Sa)ha P., Cao ., et al. (2018),
and the Environment 19: 382-390. —Shirai M., Osada M., Yamaguchi A., et yut S., et al. (2016), Influence of ground ano-chemical devulcanization. Korean Devulcanization of waste rubber powder
—Sabzekar M., Chenar M.P., Mortazavi al. (2015) Utilization of supercritical fluid tire rubber devulcanization conditions on Journal of Chemical Engineering 27: using thiobisphenols as novel reclaiming
S.M., et al. (2015), Influence of process for catalytic thermochemical conversions properties of its thermoplastic vulcani- 1,177-1,183. agent. Waste Management 78: 980-991.

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