Devulcanization: A solution for scrap rubber

by Ben Chouchaoui, Windsor Industrial Development Current waste rubber disposal pathways
Laboratory Landfilling
Disposals at tire mono-filling (i.e., deposits in certified sites
Rubber includes elastomers and thermosets characterized by accepting only waste tires) were among the earliest rubber and
large deformability and the capability to recover their shape upon tire discharge avenues, due to the availability of large land
removal of applied loads. Industrial rubbers divide into natural surfaces and economic feasibility, but with severe drawbacks.
rubber (NR) and synthetic rubbers. The former derives from For example, landfilled tires can release metals and toxic
natural rubber latex mainly constituted by poly(cis-1,4-isoprene), chemicals such as stabilizers, plasticizers, flame retardants and
an unsaturated hydrocarbon produced by over 2,000 plant spe- other low molecular weight additives, which pollute the soil
cies of the Compositae, Moraceae and Apocynaceae families; and decrease its fertility. Moreover, rubber waste acts as a
but the commercially utilized latex is made almost entirely from breeding ground for mosquitoes, rodents and snakes, sources
Hevea brasiliensis. for various deadly diseases. Piles of tires in open dumpsites or
Synthetic rubbers are synthesized monomers from petroleum landfills risk flammability, and tire fires can burn for several
based hydrocarbons, and the most commonly produced are eth- weeks, as they are very difficult to extinguish. Most impor-
ylene propylene diene monomer and styrene butadiene rubber, tantly, landfilling fails in recovering useful materials to be rein-
chloroprene and isobutylene (EPDM, SBR, CR and IS) (refs. 1 troduced in the rubber industry as second generation feedstock,
and 2). and should therefore be used only in the very few cases in
The demand for rubber products has grown steadily over which all other waste management technologies (reducing, re-
recent years. Global NR production in 2018 amounted to al- using, recycling, energy recovery) cannot be put in place. For
most 13.9 million metric tons, the vast majority of which (91%) all such reasons, landfilling end-of-life tires (ELT) became
was produced in the Asia Pacific region; while Europe, the forbidden by the European Commission as early as 1999, and
Middle East and Africa (EMEA) contributed approximately this has boosted the research for alternative options for rubber
6.5%. Natural rubber is largely used to manufacture tires and waste management (ref. 6).
also single use gloves, the production of which has tremen-
dously grown to meet the rising healthcare demands linked to Energy recovery
the recent pandemic. Synthetic rubbers are used primarily in Another rubber waste management is represented by the use of
the transportation industry to produce tires, with overall de- scrap rubber as fuel. Tires are over 90% organic and have a
mand reaching 3.9 billion units last year. This conspicuous and calorific value of 32.6 MJ/kg compared to 18.6 to 27.9 MJ/kg
ever-increasing rubber production demonstrates the versatility for coal, for example. Approximately 45% and 38% of post-
and the widespread application of this class of materials; but it consumer tires and industrial waste in the United States and in
also poses the challenge of how to manage the growing amount the European Union (EU), respectively, are used as supplemen-
of rubber waste. tary non-fossil fuel forms of energy recovery, including incin-
Rubber scrap is a sizeable component of the total solid eration, pyrolysis and gasification (ref. 7).
waste. The majority of such scrap derives from the transporta- Incineration is the oxidation of combustible material to give
tion industry (tires of automobiles, trucks, off-road vehicles and inert waste. It is a highly exothermic process, initiated at con-
motorcycles); but other sources of rubber waste include cloth- trolled high temperatures (in the 1,000°C range) to quickly
ing, footwear, gaskets and furniture. In 2020, the United States become self-sustaining. If the temperature is kept high enough,
generated 9.7 million metric tons (mmt) of rubber waste, out of this process only yields H2O, O2 and CO2; while too low of a
which 5.5 mmt were landfilled (55%), 2.9 mmt were com- processing temperature leads to the emission of several toxic
busted for energy recovery (27%), and only 2.1 mmt were re- gases, such as dioxins or persistent organic pollutants (POPs).
cycled (17%). Recycling rubber waste is challenging, and ef- Incineration is often carried out by the tire industry to dispose
forts in improving related policies and technologies continue to of production waste and rejects, and to produce plants’ own
evolve to increase sustainability and the circularity of the rub- energy. It is also a common process in cement kilns, steel mills,
ber industry (ref. 3). thermal power plants, pulp and paper mills, industrial boilers
As most rubber is used in tires, all of the research on devul- and sewage treatment installations. In the case of cement
canization targets waste tires made of NR and SBR, and with manufacturing, the use of very high temperatures (in the range
the most common being sulfur vulcanized (refs. 4 and 5). The of 2,000°C) ensures the complete combustion of all tire com-
following article provides a concise technical overview of the ponents, converting steel to iron oxide and sulfur to sulfates,
most important devulcanization technologies of sulfur vulca- which are useful ingredients in the final cement product.
nized rubbers such as NR and SBR. Considering the impor- Pyrolysis is the process in which the organic fraction of waste
tance of adopting a circular economy, rubber devulcanizate tires is thermally decomposed at high temperatures (400°C to
applications concentrate on how devulcanized rubber can be 1,200°C) under reducing or inert atmospheres, generating useful
compounded with different polymeric matrices to develop eco- solid, liquid and gaseous products (refs. 8 and 9). The solid resi-
sustainable polymer blends with suitable physical properties. due can be purified from steel, fiberglass and other contaminants,

40 RUBBERWORLD.COM • MAY 2023

and the remaining carbon-rich product is used to produce acti- versa. Notwithstanding these issues, many researchers have
vated carbon, recovered carbon black (CB) and regenerated inor- demonstrated the feasibility of including 10% to 30% of GTR
ganic compounds that can be used as fillers. The liquid fraction into virgin NR and SBR without dramatically impairing the
contains tar, water, aromatic hydrocarbons and organic sub- main mechanical properties of the final products, while bring-
stances with high calorific value, and can be used as a fuel after ing about advantages like a general increase in damping.
sulfur removal. The gaseous products, rich in methane, ethane, The poor GTR-matrix adhesion has been addressed by in-
ethylene, propylene, butylene, carbon dioxide and carbon mon- creasing the GTR surface reactivity with the introduction of
oxide, can also be used as energy sources. Although pyrolysis polar groups. This has been done using several techniques,
primarily saves fuel, it is less industrially widespread than incin- classified as physical methods, such as plasma, ozone, high-
eration, for non-competitive prices, low purity of obtained prod- energy gamma or ultraviolet irradiation; or as chemical meth-
ucts, and high operating and maintenance costs. ods, such as acids, coupling agents and chlorination treatments.
Gasification is a partial oxidation process that employs pres- Another field of research considerably developing over the
sure, heat and a reactive agent such as air, oxygen, hydrogen or last decades is the use of GTR as a cement, concrete and asphalt
steam to convert tire waste into a gas mixture; the synthesis gas, modifier. GTR improves the fracture resistance of concrete,
or syngas, primarily composed of CO, H2, CO2 and light hy- decreases its density, and favors the heat, sound and vibration
drocarbons (CH4). The syngas can energize cells or turbines for absorption properties. Blending GTR with asphalt improves the
a broad range of fuels and chemicals. Advantages of gasification performance and longevity of roads, as it reduces the noise of
include high conversion performance and energy efficiency vehicles, improves crack resistance and enhances driving com-
(approximately 34%). Moreover, syngas contaminants (H2S fort. Finally, in sludge treatment plants, a bed of GTR can ab-
and NH3) can be removed using well established techniques. sorb organic solvents, mercury (II) and other heavy metals due
However, gasification involves higher temperatures (1,200°C to the presence of thiol and other sulfur residues able to im-
to 1,500°C) than pyrolysis. mobilize metal ions.

Grinding Rubber devulcanization

Grinding involves technologies that aim at reducing the size of Devulcanization of post-consumer rubber is most desirable to
waste rubber to produce a rubber powder of variable size rubber waste management (figure 1). Devulcanization converts
(mesh) for several applications. Common grinding technolo- a three-dimensionally interlinked, insoluble, infusible thermo-
gies to mechanically reduce the size of waste rubber compo- set polymer network to an essentially thermoplastic one, while
nents are ambient, wet and cryogenic grinding. ideally keeping the same properties of the virgin rubber to then
Applications of ground rubber include mechanical grinding, process and re-vulcanize into a new product. Hence, rubber
which produces crumb and ground rubbers of different mesh devulcanization is the most promising technology to tackle the
sizes, especially for civil engineering and manufacturing. issue of waste rubber, and at the same time save virgin material
Among all rubber types, a wide variety of applications has been resources.
proposed for ground tire rubber (GTR). This is being used to The first attempts at devulcanizing scrap rubber were docu-
produce ground covers in playgrounds, lower layers of floor mented more than a century ago. Since then, many devulcani-
coverings, walkway tiles, mulch for agricultural purposes, zation technologies developed are broadly classified into two
sports surfaces such as running tracks, crash barriers and shock groups: physical and chemical devulcanization. Physical tech-
absorbers, but also as asphalt modifiers and lightweight fillers. niques consist of mechanical, thermo-mechanical, microwave
In addition, shredded, crumb and ground rubbers can be em- based and ultrasonic processes; while chemical processes in-
ployed to replace gravel, sand and filler material, respectively. clude all methods where chemical compounds or micro-organ-
Blends of GTR with thermoplastics, such as polyethylene isms are used to break the crosslinks (ref. 11).
(PE), polystyrene (PS), polypropylene (PP) and polyvinyl chlo-
ride (PVC), can be shaped into extruded and molded products Rubber reclaiming and devulcanization
whose physical and mechanical properties depend on proper- Any procedure in which vulcanized rubber waste is trans-
ties of the matrix, but also on the GTR fraction, particle size, formed to be mixed with virgin rubber, processed and vulca-
dispersion degree and GTR-matrix interfacial interaction. nized again is called reclaiming or reclamation. Reclaiming has
Moreover, GTR can be compounded with virgin rubber to a high potential to recycle rubber waste products, as it allows
produce conveyor belts, shoe soles and heels, molded and ex- one to break the starting permanent tridimensional network and
truded profiles, car mats, tubes, sealing plates, mattresses, bat- decrease the molecular weight sufficiently to achieve plasticity
tery boxes and other hard rubber goods. However, the direct and reprocessing of the scrap rubber. However, reclaiming
incorporation of GTR in virgin rubbers usually deteriorates mostly leads to degradation, with cleavage of carbon-carbon
their mechanical and viscoelastic properties, especially the (C-C) bonds on the rubber backbone making it impossible to
tensile strength and strain at break. This is because of the lack reobtain the initial macromolecules. So devulcanization is
of reactive sites on the GTR surface, which determines a poor much more desirable to selectively cleave the intermolecular
filler-matrix adhesion (ref. 10). Moreover, GTR may also affect sulfidic, such as carbon-sulfur (C-S) and/or sulfur-sulfur (S-S)
the behavior of rubber during curing, as sulfur or accelerators bonds, breaking down the tridimensional network without in-
may migrate from vulcanized GTR to the virgin matrix, or vice volving main chain scissions and degradation of the polymer.

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 Figure 1 - devulcanization technologies for rubber

Devulcanization

Physical Chemical Biological

Thermal Radial scavengers Aerobic

Mechanical Nucleophilic additives Anaerobic

Thermomechanical Catalytic system Bacterial

Microwave Chemical probes Fungal

Ultrasonic

Thermosonic

Mechanical/thermo-mechanical devulcanization screw speed and barrel temperature for proper devulcanization
Thermo-mechanical devulcanization is the most widely used in is highlighted in many research works correlating processing
industry. Rubber crumb is subjected to mechanical shearing parameters with devulcanization quality and yield, and the re-
and high temperature (approximatively 200°C) brought by in- sponse surface methodology (RSM). It has generally been ob-
ternal friction and from outside sources. Solvents like water, served that the selectivity of crosslink scission decreases as
oils, hexane or supercritical fluids can be added before or dur- temperature increases, with a consequent increase in the C-C
ing grinding to facilitate the process, solubilize the small chains bond cleavage and a reduction in the mechanical performance
and swell the rubber. of the revulcanizate. So the quality of the devulcanization in-
Thermo-mechanical devulcanization has been largely stud- creases at moderate operating conditions.
ied during recent decades because it generally yields high Researchers devulcanized ground rubber from tires in a
devulcanization throughputs. The most common mechanical unique metallic cone-like high shear mixer. In this setup,
and thermomechanical devulcanization technologies can be cooled by a stream of cold water, one cone is static, while the
divided into batch mixers or continuous extruders, but other other rotates and pressurizes the system. The instrument is fed
equipment has also been tried. with large chunks of GTR for size reduction and a decrease in
Devulcanization based on batch mixers is relatively simple, crosslink density. However, such reactions mainly occur at the
low cost and environmentally friendly, generally performed rubber particle surface, classifying this technique as a rubber
without external heating or chemicals. Batch mixers divide into surface activation phenomenon, rather than a proper bulk
(i) open, two-roll mills or Brabender mixers, and (ii) closed, devulcanization.
Lancaster-Banbury or internal batch mixers. Crumb rubber is Another devulcanization technology is high pressure, high
devulcanized through intense mechanical shearing for minutes, temperature sintering (HPHTS), which allows one to recycle
in which the temperature can reach 250°C. To prevent exces- vulcanized rubber powder by applying heat and pressure. The
sive heating and degradation of the polymer chains, a technique applied pressure compresses the particles and increases the in-
has recently been proposed that involves a water cooled two- terparticle contact, while temperatures between 80°C and
roll mixing mill to devulcanize CB filled NR. Still, the resultant 240°C promote cleavage of crosslink bonds. This in turn allows
degree of devulcanization is quite low: between 20% and for the formation of new covalent bonds at the particle inter-
37.8%. face, thereby sintering the particles into a single piece. Re-
The most common mechanical devulcanization is Ficker՚s, searchers found that the mechanical properties of the sintered
or the single/twin-screw extruder method. The technology is rubber compare with those of conventionally manufactured
widely used, as extruders are commonly and readily available rubbers.
in rubber manufacturing and allow for continuous high yield Thermo-mechanical devulcanization can be implemented
devulcanization. The fundamental importance of optimizing with different devulcanizing agents to further promote scission

42 RUBBERWORLD.COM • MAY 2023

of sulfidic bonds. In these cases, the process is called mechano- hydride and methyl iodide, organic solvents like alcohols and
chemical devulcanization. ketones, and ionic liquids (ILs) (ref. 13).
The drawback of chemical devulcanization relates to the
Ultrasonic devulcanization toxicity of the chemicals. This problem could be partially miti-
Ultrasonic devulcanization is one of the most convenient types gated by employing less toxic, more environmentally friendly
of devulcanization, since it allows a high degree of devulcani- non-sulfured agents being investigated and not yet widely dif-
zation and precise control of the properties of the devulcani- fused. The reaction of chemical devulcanization is complex and
zates. This type of devulcanization is fast and does not involve not fully understood for all the solvents involved. A compre-
chemical solvents. However, it requires specialized technologi- hensive explanation of the mechanisms involved in the chemi-
cal equipment, which hinders its large scale application. cal devulcanization of rubber is reported in the literature.
Ultrasonic methods exploit mechanical waves at high fre- The most widely used chemicals in rubber devulcanization
quencies to produce tensile-compressive stresses and cavitation are sulfides and mercaptans, such as disulfides (like DD, thio-
bubbles in the medium, which provides enough energy to break phenols and their zinc salts), thiol-amine reagents, hydroxide or
C-S and S-S bonds. However, under pressure and temperature, chlorinated hydrocarbons, added typically in concentrations of
the ultrasonic waves could also break the carbon backbone 0.5 to 10 wt%.
chains, which is why test conditions must be carefully selected. Amine based devulcanization was patented in 2003 by Van
Duin et al. Their work showed that amines might help high
Microwave devulcanization temperature devulcanization, which is mainly radical. They
Microwave devulcanization uses microwave irradiation to en- also evidenced that the treatment is preferably done with 0.1 to
ergize molecules, thereby raising the temperature and inducing 15 wt% of amine compounds, and works only with amines of
crosslink breakage. And while microwave processes cannot be at least an α-H atom to reduce the crosslink density mainly by
implemented along a production process, they remain among scission. Sulfides and mercaptans, also amine based chemicals,
the most widely investigated devulcanization techniques. are often used in combination with other devulcanization treat-
ments.
Supercritical solvents Dijkhuis et al. employed hexadecylamine (HDA) as an
A supercritical state is a particular aggregation with coexisting agent for EPDM thermal devulcanization, and reported a re-
gas and liquid phases. Because of the absence of liquid/gas duction of crosslink density of 50% in the temperature range
phase boundaries, supercritical fluids (SCF) have no surface from 225°C to 275°C, even though di- and poly-sulfide bonds
tension, show solvent properties similar to those of liquids, and were cleaved. Devulcanizates were then blended with virgin
provide properties similar to those of gases. Therefore, they can EPDM, and the revulcanized materials showed good mechani-
dissolve solutes, are miscible with ordinary gases, and can cal properties compared to virgin vulcanizate. Hexadecyl- and
penetrate pores in solids. Supercritical fluids show liquid-like other amines such as tetraethylenepentamine (TEPA) have also
density; but their viscosity and diffusivity are intermediate be- been combined with ultrasonic or mechanical devulcanization,
tween those of gases and liquids. allowing treatment at lower temperatures.
Supercritical carbon dioxide (scCO2) has recently been re- Other catalysts, inorganic and sulfur-free organic, have been
ported as an innovative and green devulcanization medium due developed in recent decades. They include propane thiol/pi-
to its chemical inactivity, non-toxicity, non-flammability and peridine, Grubbs catalysts, PPh3, trialkyl phosphites, lithium
low cost (ref. 12). Its low temperature, low pressure critical aluminum hydride, methyl iodide, 1,8-diazobicyclo[5.4.0]un-
points (of about 31.1°C and 7.4 MPa) allow the use of simple dec-7-ene (DBU) and benzoyl peroxide (BPO).
equipment; and excess scCO2 can be easily removed by releas- Another organic solvent, 2-butanol, is employed between
ing the pressure. The role of scCO2 is not yet completely under- 200°C and 350°C. To decrease the process temperature and
stood, but it probably relates to swelling vulcanized rubber. As increase the eco-sustainability of the devulcanization, 2-buta-
scCO2 stretches the sulfide links, making them easier to break, nol can be partly substituted with turpentine liquids, and par-
devulcanizing agents penetrate to devulcanize the material. ticularly α-terpineol, derivable from renewable resources.
Deep eutectic solvents (DES), such as mixtures of choline
Chemical devulcanization chloride (ChCl) or ZnCl2 with urea, p-toluene sulfonic acid or
Chemical devulcanization, applied since the 1960s, is currently glycerol, were also proposed as devulcanization agents, espe-
among the most diffused. It employs various organic and inor- cially in combination with ultrasonic processes. These solvents
ganic chemical compounds that selectively break carbon-sulfur are widely tunable, non-flammable, and have low volatility and
and/or sulfur-sulfur bonds. Generally, a supply of thermal and toxicity.
mechanical energy accelerates the treatment. Most chemical Ionic liquids (ILs) such as phosphonium, imidazolium and
devulcanization methods are batch processes in which ground pyrrolidinium salts are also added to physical and chemical
waste rubber is mixed with chemical agents at a controlled devulcanization processes due to their high conductivity, high
temperature and pressure. Many types of chemical compounds thermal stability, low flammability and low volatility. Not only
can be used, such as sulfides, mercaptans, amine based com- are ILs safer and less toxic than other solvents, they can solubi-
pounds, inorganic solvents like propane thiol/piperidine, triphe- lize a large variety of compounds, and their properties are tun-
nylphosphine (PPh3), trialkyl phosphites, lithium aluminum able to the selected cations and anions.

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 Ionic liquids have been used alone or combined with other minimize the loss of original properties while achieving de-
treatments. Further, ILs proved effective as devulcanizing creasing costs or improving processability. Hence, polymer
agents in NR, like trihexyl(tetradecyl)phosphonium chloride or blending is a way to achieve additional properties without the
N,N-dioctylimidaolium bromide combined with a Grubbs cata- need and the cost of creating a new molecule (ref. 14).
lyst, in producing telechelic oligomers such as acetoxy telech- Virgin and devulcanized rubbers can become part of many
elic polyisoprene with high (95% and 99%) yield. different compounds. These elastomer based blends can be di-
vided into two types: (i) blends composed of two or more types
Biological devulcanization of elastomers, and (ii) blends made of thermoplastic and elas-
While vulcanized materials are resistant to microbial attack, it tomeric phases. The latter are called thermoplastic elastomers
is possible to promote biological devulcanization, in which (TPEs) when the main phase is elastomeric, and toughened
microorganisms such as bacteria and fungi selectively break the plastics when the main phase is thermoplastic.
sulfur bonds. However, biotechnological devulcanization pro- Still, revulcanizing a devulcanized rubber is more complex
cesses are still far from being applied industrially, with persis- than vulcanizing virgin rubber, because devulcanization might
tent limitations, such as devulcanization ratios, bacteriological have chemically changed the nature of the rubber in ways not
contamination risks and limitations to the surface of compo- always predictable.
nents.
The scientific literature contains various examples of bacte- Blends based on natural rubber
rial devulcanization on rubber substrates such as GTR, NR and For devulcanized rubber, the greatest attention is devoted to NR
latex. The process in aerobic or anaerobic environments proved based blends and composites. For example, Joseph et al. me-
feasible with several strands of bacteria, such as Sphingomo- chanically devulcanized carbon black filled NR by shearing in
nas, Alicyclobacillus, Gordonia desulfuricans, Nocardia, Rho- a two-roll mill. To simulate recycling end-of-life rubber parts,
dococcus and Bacillus cerus. For anaerobic bacterial devulca- Joseph et al. devulcanized samples aged at 70°C and 100°C for
nization, researchers used sulfur reduction bacteria; while in days. The devulcanized rubber was then incorporated into vir-
aerobic devulcanization, sulfur is oxidized to produce sulfone gin NR at 85/15, 75/25 and 60/40 proportions, and various
groups on the rubber surface. Reports indicate a reaction time amounts of fillers were added during blending. Blend proper-
of one to 30 days, at 30°C, a decrease in sulfur content in the ties were adjusted by adding fillers, improving mechanical
sample of 8% to 30%, resulting in a partly devulcanized prod- devulcanization and compound optimization in recycling NR.
uct that can be revulcanized into a material with similar or im- Other researchers prepared blends incorporating up to 50 phr of
proved mechanical properties compared to those of virgin rub- mechanically devulcanized and non-devulcanized GTR virgin
ber. NR, and evidenced the importance of devulcanization on the
Another type of biological devulcanization uses fungi. Fun- mechanical properties of end materials.
gal devulcanization was studied by Bredberg et al. on three Further work compared different devulcanization strategies
white rot fungi (i.e., Pleurotus sajor-caju, Trametes versicolor on the properties of final blends, since each devulcanization
and Recinicum bicolor) to degrade Poly-R478. The study process uniquely affects the structure of rubber, and therefore,
showed R. bicolor with the highest efficiency and growth rate the properties of the final blends. Mangili et al. compared
proportional to the sulfur oxidation rate in the rubber matrix. In scCO2, ultrasonic and biological devulcanization of GTR,
another study, a white rot basidiomycete, Ceriporiopsis subver- blending the devulcanizates into neat NR at a 10 phr concentra-
mispora, degraded vulcanized NR sheets on a wood medium. tion. Ultrasonic and scCO2 methods yielded higher devulcani-
The fungus promoted cleavage of sulfide bonds and decreased zation; while biological treatment, although more selective,
sulfur content in rubber by 29% in 200 days; thus showing the was limited to the particle surface. The mechanical properties
potential of ligninolytic basidiomycetes for rubber biological of the blends containing biologically devulcanized GTR were
devulcanization. comparable with those containing non-devulcanized GTR;
Despite an increased number of research papers on rubber while the GTR from ultrasonic treatment showed the greatest
biological devulcanization, the commercial exploitation of this improvement in mechanical properties, up to a certain ultra-
technology is currently only performed by few companies on a sonic amplitude.
small to medium scale. For example, the Recircle group in
England (https://www.recircle.com/) applies bacterial devulca- Blends based on synthetic rubbers
nization on various types of natural and synthetic ground rub- Devulcanized rubber has also been blended with different syn-
ber, yielding an intermediate to revulcanize. thetic rubbers. Valentini et al. (refs. 15 and 16) compounded
various amounts of devulcanized and non-devulcanized recy-
Applications of devulcanized rubber cled rubber from truck tires with a virgin EPDM rubber, and the
The most established pathway to devulcanized or revulcanized resulting compounds were expanded with azodicarbonamide.
elastomers is the production of polymeric blends: namely, Devulcanized particles were better encapsulated within the
physically mixing the devulcanizated rubber with one or more EPDM matrix, and showed a better interfacial adhesion, prob-
polymers. Producing polymer blends aims at improving prop- ably due to revulcanization, in which the free crosslinking sites
erties compared to neat polymers; i.e., obtain materials with that typically characterize devulcanized rubber could form link-
additional or improved physical and mechanical properties, or ages with EPDM. Tensile and impact behaviors of expanded

44 RUBBERWORLD.COM • MAY 2023

EPDM/recycled rubber blends highlighted a strong improve- canized and non-devulcanized rubber from waste truck tires
ment of the normalized total absorbed energy, the normalized with PS. Devulcanized rubber domains were smaller and better
impact strength and the elongation at break compared to the dispersed in the surrounding matrix, and exhibited improved
neat expanded EPDM for all investigated compositions, espe- interfacial interaction compared to non-devulcanized rubber.
cially with a devulcanized rubber content of 20 wt%. The However, surface hardness, tensile modulus and stress at break
preparation of expanded EPDM containing considerable were negatively affected, with the limited compatibility be-
amounts of devulcanized rubber was, therefore, demonstrated tween PS and rubber particles and the relatively large size of
to be a practical route to reduce the costs and improve the prop- rubber domains. High rubber fractions showed an increase in
erties and environmental sustainability of rubber goods. ductility, with an enhancement of tensile strain at break and
Other researchers reported devulcanization of GTR and impact resistance.
SBR crumbs using microwave processes prior to the introduc- Hittini et al. (ref. 17) used devulcanized rubber powder from
tion in virgin SBR. Devulcanization significantly increased the waste tires as a filler for PS thermal insulators. Devulcanized
properties of the blends compared to blends with non-devulca- rubber was added to PS in 0% to 50 wt% proportions using a
nized rubber powder. Karabork et al. measured a strain at break melt extruder, and the resulting materials were hot pressed.
of 445% on composites with devulcanized GTR, and only Composites with less than 40 wt% devulcanized rubber exhib-
217% on composites with untreated GTR. This was due to an ited superior properties, with thermal conductivity ranging
improved interfacial interaction between treated GTR and the from 0.050 to 0.071 W/mK, density from 463 to 482 kg/m3,
surrounding matrix, as evidenced by scanning electron micros- compressive strength from 11.7 to 7.5 MPa, and flexural
copy (SEM). strength from 40.4 to 19.3 MPa. These mechanical properties
Additional researchers compared low temperature mecha- further increased after alkaline treatment of the devulcanized
no-chemical devulcanization (LTMD) and the traditional high rubber, which increased the interfacial adhesion between
temperature atmospheric devulcanization (HTAD) to reclaim devulcanized rubber and PS.
waste rubber powders mixed with additives; then revulcanized
the reclaimed rubber after blending with all-terrain vehicle Conclusions and future perspectives
(ATV) tread rubbers. They noticed that not only did the LTMD Considering the ever increasing production, consumption and
yield a higher devulcanization fraction, but the devulcanized disposal rates of scrap rubber based products, proper valoriza-
blends also achieved higher mechanical properties, even with- tion of rubber waste is becoming one of the most critical chal-
out additional additives. lenges to globally address. However, the sustainable disposal of
waste rubber is not an easy solution. Most rubber based prod-
Blends with thermoplastics ucts are vulcanized, and if the resulting three-dimensional mo-
Devulcanized rubber is used for full elastomeric blends and lecular network endows rubbers with useful thermo-mechani-
rubber/thermoplastic compounds. It has been blended with cal properties, such as high elasticity and damping, it also poses
several thermoplastics, including polypropylene (PP), high- severe challenges for their reprocessing and recycling. This
density polyethylene (HDPE), copolyester (COPE) and poly- analysis leads to the following observations:
styrene (PS). • As landfilling and open burning are unsustainable and
Mechanical-chemical devulcanization of waste rubber tire polluting, downsizing waste rubber to rubber based pellets
powder mixed with PP in different proportions indicated a de- and powder is being adopted. Resulting materials are
crease in hardness of the devulcanized rubber fraction, and an added to various cementitious and rubber based blends to
increase with radiation up to 50 kGy, especially at higher devul- produce rubberized asphalt and concrete, playground
canized rubber fractions. A similar trend was observed for the mats, running floors, etc. However, this approach is
tensile strength, which increased with radiation, but was insufficient to valorize all rubber waste generated yearly,
strongly impaired by the incorporation of devulcanized rubber. and the scarce adhesions between rubber particles and
The strain at break increased, with devulcanized rubber load- surrounding polymer matrices strongly limit the amount
ings of up to 75 wt%; but decreased with radiation doses. Thus, of rubber waste that can be incorporated into virgin
the devulcanized rubber was proven good as a filler to tune the polymers.
mechanical properties of PP. • The most suitable approach to sustainable recycling of
Jang et al. prepared GTR/HDPE blends by combining rubber products is devulcanization, a process that
chemical surface devulcanization of GTR with tetraethylene selectively breaks the crosslink (S-S and C-S) bonds in a
pentamine (TEPA) and in situ grafting of HDPE by styrene and material, leaving the main chains intact in order to
glycidyl methacrylate. This combination strongly improved the recover a material similar to virgin rubber, which can be
compatibility and mechanical properties of the blends, and the reprocessed and turned into high value added parts.
properties could still be tailored by adjusting the initiator/graft- • Devulcanization can be performed through mechanical,
ing monomer ratio. Moreover, the d-GTR/HDPE blends thermal, thermomechanical, chemical, microwave,
proved to have stable processing and reprocessing ability. ultrasonic technics or biological agents, applied alone or
Other researchers incorporated devulcanized rubber in a combined. These methods present advantages and
brittle matrix such as PS. Recent work by Valentini et al. (refs. limitations, so proper combinations are required to
15 and 16) melt compounded and compression molded devul- enhance the degree of devulcanization, limit main chain

FOLLOW US ON TWITTER @rubberworld 45

 degradation and further optimize the properties of the tires through the circular economy model,” Waste Manag.,
devulcanizates. Properly selecting the devulcanizing 126. pp. 309-322 (2021).
agents and operational conditions, like temperature, 8. A.J. Bowles, G.D. Fowler, C. O'Sullivan and K. Parker,
pressure, time and shear rate, is important. “Sustainable rubber recycling from waste tires by waterjet: A
• Devulcanized rubbers can be used to partially replace novel mechanistic and practical analysis,” Sustain. Mater.
virgin materials, thereby saving primary feedstock and Technol., 25, e00173 (2020).
reducing cost. Devulcanized rubber can also be mixed 9. M.M. Phiri, M.J. Phiri, K. Formela and S.P. Hlangothi,
with different elastomeric and thermoplastic matrices into “Chemical surface etching methods for ground tire rubber as
blends with desirable physical properties. However, when sustainable approach for environmentally friendly composites
using devulcanized products, particular attention should development: A review,” Compos. B Eng., 204, 108429 (2021).
be paid to revulcanization and the role of additives and 10. X. Colom, J. Canavate, K. Formela, A. Shadman and M.R.
fillers in the process. Saeb, “Assessment of the devulcanization process of EPDM
Many challenges remain open for a correct implementation waste from roofing systems by combined thermomechanical/
of sustainable and effective devulcanization, and the develop- microwave procedures,” Polym. Degrad. Stabil., 183, 109450
ment of a consolidated market for devulcanized and revulca- (2021).
nized rubbers. This can be achieved with a more in-depth un- 11. L. Asaro, M. Gratton, N. Poirot, S. Seghar and N. Ait Ho-
derstanding of the precise correlation among the physical and cine, “Devulcanization of natural rubber industry waste in
chemical properties of the initial vulcanizate, the devulcaniza- supercritical carbon dioxide combined with diphenyl disul-
tion technique and parameters, and properties of the resulting fide,” Waste Manag., 118, pp. 647-654 (2020).
devulcanizates (ref. 18). 12. M. Vahdatbin and M. Jamshidi, “Using chemical agent in
microwave assisted devulcanization of NR/SBR blends: An ef-
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Adhesion and Adhesives Technology 4th Edition $215.00

This book describes, in clear understandable language, the three main disciplines of adhesion technology:
mechanics of the adhesive bond, chemistry of adhesives, and surface science. Some knowledge of physical and
organic chemistry is assumed, but no familiarity with the science of adhesion is required. The emphasis is on
understanding adhesion, how surfaces can be prepared and modified, and how adhesives can be formulated to
perform a given task. Throughout the book, the author provides a broad view of the field, with a consistent style
that leads the reader from one step to the next in gaining an understanding of the science.

46 RUBBERWORLD.COM • MAY 2023