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Current Progress in Waste Tire Rubber Devulcanization

Ricky Saputra, Rashmi Walvekar, Mohammad Khalid, Nabisab Mujawar Mubarak,

Mika Sillanpää

PII: S0045-6535(20)33230-6
DOI: https://doi.org/10.1016/j.chemosphere.2020.129033
Reference: CHEM 129033

To appear in: ECSN

Received Date: 23 September 2020

Revised Date: 16 November 2020
Accepted Date: 17 November 2020

Please cite this article as: Saputra, R., Walvekar, R., Khalid, M., Mubarak, N.M., Sillanpää, M.,
Current Progress in Waste Tire Rubber Devulcanization, Chemosphere, https://doi.org/10.1016/
j.chemosphere.2020.129033.

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 1 Current Progress in Waste Tire Rubber Devulcanization
2
3 Ricky Saputra1, Rashmi Walvekar2*, Mohammad Khalid3*, Nabisab Mujawar
4 Mubarak4, Mika Sillanpää5,6,7
5
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6 School of Computer Science and Engineering, Taylor’s University Lakeside Campus,
7 No. 1 Jalan Taylor’s, 47500 Subang Jaya, Selangor, Malaysia
2
8 Department of Chemical Engineering, School of Energy and Chemical Engineering,
9 Xiamen University Malaysia, Jalan Sunsuria, Bandar Sunsuria, Sepang, 43900,
10 Selangor, Malaysia
3
11 Graphene & Advanced 2D Materials Research Group (GAMRG), School of Science
12 and Technology, Sunway University, No. 5, Jalan Universiti, Bandar Sunway, 47500
13 Subang Jaya, Selangor, Malaysia
4
14 Department of Chemical Engineering, Faculty of Engineering and Science, Curtin
15 University, 98009 Sarawak, Malaysia

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16 Institute of Research and Development, Duy Tan University, Da Nang 550000,
17 Vietnam.

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18 Faculty of Environment and Chemical Engineering, Duy Tan University, Da Nang
19 550000, Vietnam.
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21
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School of Civil Engineering and Surveying, Faculty of Health, Engineering and
Sciences, University of Southern Queensland, West Street, Toowoomba, 4350 QLD,
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22 Australia.
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24 *Corresponding authors: rashmi.walvekar@xmu.edu.my

25 khalids@sunway.edu.my
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26 Abstract
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27 Vulcanized rubber, due to its superior mechanical properties has long been used in
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28 various industries, especially automotive. The rubber industry has evolved and

29 expanded over the years to meet the increasing global demands for tires. Today tires

30 consist of about 19% natural rubber and 24% synthetic rubber, while plastic polymer

31 and metal, filler and additives make up the rest. Over 1.6 billion new tires are

32 produced annually and around 1 billion waste tires are generated. Tires are

33 extensively designed with several complex processes to make them virtually

34 indestructible. Since tire rubber does not decompose easily, their disposal at the end

35 of service life creates a monumental environmental impact. However, waste tire

36 rubber (WTR) consist of valuable rubber hydrocarbon, making its recovery or

37 regeneration highly desirable. The conventional recovery method of WTR tends to

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38 produce undesirable products due to the destruction of the polymeric chain and

39 exponentially degenerates the vulcanizates’ physical properties. Since then, multiple

40 devulcanization processes were introduced to effectively and selectively cleave

41 vulcanizate’s crosslinks while retaining the polymeric networks. Different

42 devulcanization methods such as chemical, mechanical, irradiation, biological and

43 their combinations that have been explored until now are reviewed here. Besides, an

44 overview of the latest development of devulcanization by ionic liquids and deep

45 eutectic solvents are also described. While such devulcanization technique provides

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46 new sustainability pathway(s) for WTR, the generated devulcanizate also possesses

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47 comparable physical properties to that of virgin products. This further opens the

48
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possibility of novel circular economic opportunities worldwide.
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49 Keywords: devulcanization; waste rubber tire; sustainability; crosslinks;

50 reclamation; circular economy.

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51 1.0 Introduction
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52 Solid waste generation from industries as well as daily societal necessities has caused

53 enormous environmental concerns due to the limited amount of treatment available to

54 safely and efficiently recycle them [1, 2]. These waste materials could range from

55 particulate matter, food wastes and elastomers. The latter, especially vulcanizates, are

56 the most persistent entity due to their innate ability to be non-biodegradable [3]. With

57 the ever-increasing societal and industrial needs, automotive has become an integral

58 part of human life. This can be seen in the 2017 statistical annual report released by

59 the International Organization of Motor Vehicle Manufacturer or Organisation

60 Internationale des Constructeurs d’Automobiles (OICA) in 2019, which shows a

61 global increase of 7.9% in the total number of sales of new vehicles from the year of

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62 2015, amounting to 96,804,390 units [4]. This number shows a tremendous impact of

63 rubber tire usage solely in the transportation sector of various fields, as shown in Fig.

64 1.

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66 Figure 1. Tire circular economy [5]

67 Lee Schipper et al. [6] reported in their modelled study that there are about

68 ±1.3 billion vehicles globally in 2019. The authors also expect that this number will

69 be doubled in the coming 30 years. Their finding is also supported by the World

70 Business Council for Sustainable Development, where amongst all the global

71 contributing countries in the statistics, China ranks number one [7]. Vehicle annual
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72 growth is forecasted to increase in the coming years as personal vehicle ownership,

73 especially car, is preferred over the recommended shared usage. Tao et al. [8] and

74 Peterson et al. [9], in their vehicle’s consumer survey studies, concluded that

75 convenience and flexibility of usage are the top two affecting factors. However, such

76 substantial use of transportation makes it a major contributor to the environmental

77 pollution compared to wastes generated from household appliances (e.g., cooking,

78 heating and cooling system) or religious practice (e.g., oriental incineration of incense

79 and joss paper) [10]. Furthermore, a study conducted by Namdeo et al. [11] regarding

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80 the impacts of land transport vehicles also concluded that transportation and its wastes

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81 enormously affect the air, land, and water quality by ninety percent of the urban

82 population solely in Cambridge.

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83 Out of all vehicle parts, the main contributors to environmental pollutions are
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84 the stockpiling and disposal of end-of-life WTR [12]. These large volumes of sulphur-
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85 vulcanized polymeric materials are persistent to degradation. They can also generate

86 sulphur oxide gases from the oxidation of sulphur crosslink presents in the
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87 vulcanizates’ matrix during an open burning process, as a quick effort to minimize

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88 landfill. Additionally, an annual increase of dumping activity of used vulcanizates in

89 landfill sites creates nesting ground for infectious rodents, pollutes groundwater with

90 heavy metals that leach underground and produce flammable sites.

91 Nonetheless, various methods have been researched by academics as well as

92 industries to reclaim WTR. Generally, WTR would be processed and sheared to

93 ground tire rubber (GTR) that has a granular and irregular texture with specific

94 gravity, density and particle size of 0.565 ± 0.035, 0.4 kg/dm3 and 0.241 ± 2.338 mm,

95 respectively [12]. These GTRs are then used for controlled-low strength materials

96 such as thermal backfilling, pavement, anti-corrosion-fill, etc., due to their low

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 97 mechanical and tensile properties caused by their interfacial-adhesion incompatibility

98 between the virgin and reclaimed rubbers’ polymeric matrices. Such incompatibility

99 is because of the existence of sulphur cross-linkages within the GTR network.

100 Reclamation is not preferred in this case as it destroys the carbon backbone in

101 polymeric structure and significantly reduce the treated rubber’s physical properties.

102 On the other hand, selective sulphur cross-link scission - known as devulcanization, is

103 more favourable. Thus, this paper comprehensively reviews the currently available

104 research on various devulcanization methods to effectively minimize the

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105 environmental impacts caused by WTR.

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106 2.0 -p
Vulcanization, Cross-linkages and Their Chemistry
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107 Before understanding how the devulcanization process happens, the vulcanization
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108 process needs to be fully understood. Vulcanization is described as a process of

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109 crosslink formation between rubber or polymer molecules through the help of

110 crosslinking agent with unsaturated polymeric bonds such as double or triple bonds.
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111 This results in the formation of a 3D-polymeric network that is interconnected [13].
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112 Such phenomena significantly reduce the degree of hysteresis (ratio between

113 polymerics’ degree of plasticity towards its degree of elasticity) or deformation in

114 vulcanizates, owing to the formation of cross-linkages [14]. Cross-linkages are

115 typically measured by means of crosslink density, which is defined as the inter-chain

116 or segment’s density that links two infinitely long polymeric networks or the amount

117 of linearly-extended polymeric support chain that connects polymeric network

118 junctions per unit volume. The typical change in the molecular structure of polymer

119 along with its properties before and after vulcanization is depicted in Fig. 2.

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120

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121 Figure 2. Vulcanization change in (a) molecular structure and (b) properties [14]
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122 This process, which Charles Goodyear invented in 1839, has since

revolutionized automotive industries, especially in rubber tire productions.

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123

124 Vulcanization allows the generation of highly elastic but low plasticity vulcanizates
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125 that have excellent physical properties, as shown in Fig. 2(b) [14]. Since the formation
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126 of cross-linkages is of significance to alter vulcanizates’ properties, 90% of

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127 vulcanization process uses sulphur as the crosslinking agent as it is readily available

128 and economical compared to tellurium, metal oxides, organic peroxides and selenium,

129 etc. [14]. However, sulphur-based vulcanization alone proves to be inefficient as it

130 proceeds at a prolonged rate. For instance, vulcanization of simple double-bonded

131 hydrocarbon that requires 40 to 55 sulphur atoms, occurs for 6 hours at 140 oC [13].

132 This production is not just impractical, but it also produces vulcanizates that are

133 susceptible to oxidative degradation and deteriorate their physical properties. Hence,

134 to tackle such issues, accelerators are introduced.

135 Accelerator in vulcanization process is defined as a substance that is used to aid

136 the process of vulcanization to proceed at a higher rate, lower temperature and sulphur

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137 content without compromising vulcanizates’ properties even after ageing takes place.

138 Since its introduction, accelerators have appeared in many types. Different

139 accelerators accelerate the vulcanization process differently. However, a general

140 guideline to select the suitable type of accelerator needs to be considered, such as; (1)

141 requirement for cure rate, (2) higher degradation temperature than the maximum

142 vulcanization temperature, (3) no health hazard or adverse effect, (4) adequate scorch

143 time, (5) obtain the desired vulcanizate’s properties, etc. According to ASTM D-4818

144 [15] and also compiled by Joseph et al. [16], the general types of accelerator used in

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145 many rubber vulcanization processes are illustrated in Fig. 3. In tire manufacturing

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146 industries, sulfenamide is the class of accelerator that is commonly used due to its fast

147
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curing property and producing vulcanizate with excellent stress-strain property.
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148

149 Figure 3. General classes and types of accelerators [15, 16]

150 Since accelerators' introduction, sulphur-accelerated vulcanization has

151 developed further through the introduction of different curing processes. It was found

152 that by changing the accelerator to sulphur (A/S) ratio, the produced vulcanizate also

153 possesses different properties [13]. These vulcanization processes are conventional

154 vulcanization (CV), semi-effective vulcanization (SEV) and effective devulcanization

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155 (EV). The general recipe in parts per hundred rubber (phr) for each of these types is

156 listed in Table 1, where the CV system offers the lowest A/S ratio. The resulting

157 vulcanizate is expected to have high fatigue, tensile and tear strength, but low

158 reversion (resistance to flexing), which is favourable for tire production. This owes to

159 its chemistry, where vulcanizate’s cross-linkages are dominated by polysulfidic bonds

160 (-Sx-) from excess sulphur. On the other hand, EV provides vulcanizate with the

161 opposite properties to CV due to more monosulfidic (C-S-C) and disulfidic (C-S-S-C)

162 bonds produced, whereas SEV compromises between CV and EV systems.

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163 Table 1. Common recipe (in phr) for different curing system [17]

Curing System CV
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Sulphur (S) 2.0 – 3.5 1.0 – 1.7 0.4 – 0.8
Accelerator (A) 0.4 – 1.2 1.2 – 2.4 2.0 – 5.0
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A/S ratio 0.1 – 0.6 0.7 – 2.5 2.5 - 12

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164 The addition of accelerator also increases the vulcanization’s rate of reaction

and lower the required curing temperature, which in turn affects the cross-linkages. It
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165

166 is commonly known that optimum properties of vulcanizate can be achieved at a

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167 lower temperature. However, such an approach increases production time and not

168 economical. As such, high temperature is most commonly used in industries as it cuts

169 production time.

170 Although CV, SEV and EV processes give different percentages of mono-, di-

171 and poly-sulfidic bonds depending on the desired final properties, types of crosslink

172 extend in a more complex way and are not limited to the aforementioned three types.

173 The following Fig. 4 illustrates some other common crosslinking types that exist in

174 vulcanizates, typically observed using infrared (IR), Raman, 13C-NMR and ultraviolet

175 [17]. Understanding these crosslinking structures provides various advantages to alter

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176 the vulcanizate’s properties, translating to understanding their chemical reaction

177 mechanism. Although such processes have existed for decades, its intricate

178 mechanism(s) is still vaguely understood. Until now, two different mechanisms have

179 been proposed by various scholars and compiled by Coran [14], which consists of free

180 radical and ionic mechanisms. To understand these two mechanisms and as an

181 exemplary pathway, Scheme 1 has been illustrated in this manuscript. Overall, the

182 main difference between the two is in the initial reaction. For the free radical pathway,

183 homolytic scission occurs, while for the ionic pathway, heterolytic scission occurs.

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184

185 Figure 4. Additional crosslinking types in rubber vulcanization

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187 Scheme 1. Free radical (left path) versus ionic vulcanization (right path) mechanism
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188 The primary importance of the vulcanization process is to establish cross-

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189 linkages within the rubber network in a certain way, to produce vulcanizate with the
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190 desired or enhanced properties. Despite that, another major impact of curing must not
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191 be overlooked in the current technological and industrial eras, which is its end-of-life

192 solution. Sulphur crosslinked vulcanizates are large in volume and non-biodegradable.

193 This has continuously been observed to cause environmental pollutions that shaken

194 global sustainability. Many countries have enforced various measures to tackle such

195 challenges by limiting the number of tire production and controlling the toxic fumes

196 generated from rubber tires combustion. An alternative and a better solution would be

197 implementing a “free market system” to manage, treat and reprocess these WTRs as

198 valuable sources of raw materials for profit in recycling or recovery industries [18].

199 3.0 Rubber Tire Wastes Management and Utilization

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200 Recycling, reclamation or recovery of WTRs has created several challenges for

201 industries, scientists and researchers globally. Even though most countries opt for

202 incineration, this method is not environmentally friendly due to a large amount of

203 toxic gases being released into the environment. The ashes produced from such

204 activity are also incredibly rich in heavy-metal content (e.g., lead and cadmium),

205 polluting the land and groundwater [19]. The general composition of WTR for

206 passenger car and truck is shown in Fig 5, with the general ratios of natural rubber

207 (NR) to synthetic rubber is at 4:3 and 2:1, respectively [20]. Thereby, a more

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208 acceptable solution to manage these WTR is highly sought after, preferably, to

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209 convert these waste products to more useful products.
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210

211 Figure 5. Composition by percentage for passenger car and truck tires [21]

212 As illustrated in Fig 5., WTR is rich in materials due to their constituent,

213 making it a valuable raw material source. However, some additional processes are

214 required to salvage these materials from WTR. The process of using waste as raw

215 material and transforming them into useful product(s) is called valorization. Fig. 6

216 illustrates the different valorization stages on how WTR can be (re)utilized before

217 considering them to landfills.

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Figure 6. Stages of valorizations for WTR utilisation
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220 The report published by the European Union (EU) in 2019 on the valorization
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221 approach used in 2017 to manage and provide solutions to used tires is detailed in Fig.
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222 7 [22]. Based on the figure, it is clear that about 92% of WTRs generated in the

223 European country were successfully recovered as raw materials (57%) and additional
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224 energy (35%). In terms of raw material recovery, most of the recovered WTRs were
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225 granulated into small particles and embedded in various rubberized materials such as

226 concrete, asphalt, conveyor belt and playground mat. Only small fraction of WTRs,

227 however, were reused and pyrolized due to the pollution that they may emit. On the

228 other hand, energy recovery from WTRs was mostly utilized to fuel power plants and

229 heating of urban households during cold season.

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231 Figure 7. EU used tire management [22]

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232 Primary valorization for WTR, following the earlier Fig. 6, is defined as a
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233 method to mechanically reprocess WTR that has been partially worn-out but can still
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234 provide good value(s) with equivalent usage similar to its original state. Two groups

235 fall under this, which are reusing and retreading. The earlier is when a waste tire still

236 has its tread and can be used again on the road. On the other hand, retreading referred

237 to a waste tire that has completely lost all of its treads but still usable if the new treads

238 are redrawn onto it (provided that other parts of the waste tire are still in acceptable

239 conditions) [18]. In this way, valorization focuses on practicality and economic values.

240 However, the safety factors, price competitiveness towards new tire and the number

241 of times WTR can be reprocessed have sparked concerns. Wang et al. [23] suggested

242 that treatment through primary valorization should only be done twice per WTR

243 before considering it for the next valorization stage.

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244 Secondary valorization is also known as the downsizing process. This stage

245 requires WTR to be mechanically granulated to certain particle size(s) after all other

246 components (mainly metals and textiles) have been removed. It is generally carried

247 out in complicated machinery that requires several stages, including shredding,

248 granulating, and pulverizing. Notably, it can be grouped into a few types such as

249 ambient, wet ambient, waterjet, cryogenic [18] and temperature-modified method [24].

250 Their differences are thoroughly reviewed and shown in the work of Ramarad et al.

251 [18]. Since the primary purpose of implementing secondary valorization is to embed

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252 granules for re-polymerization, re-vulcanization or fillers, excessive polymeric

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253 scissions resulting from this treatment may deteriorate the physical properties of the

254
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regenerated products. Hence, only 1% of downsized WTR are commonly used [25].
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255 Tertiary valorization is considered as the most beneficial valorization approach
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256 taken to handle WTR, which can be grouped into two large families; (1) pyrolysis and
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257 (2) devulcanization. Pyrolysis refers to thermally degrade WTR in the absence of O2

258 at a temperature range of 400-800 oC [26]. Valuable products generated are pyrolysis
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259 gas, oil and char (consists of carbon black, ashes and inorganic particulates) in
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260 percentages of 10-20, 40-50 and 30-40, respectively. These three types of products

261 can be further processed as a source of fuel, energy or chemicals. In their recent study

262 on WTR’s tread and sidewall's pyrolytic behaviour by Wang et al. [27], the authors

263 found that sidewall contains a higher percentage of fixed carbon than tread but it has a

264 lower surface area. This indicates that tread could be more beneficial as adsorbent.

265 Additionally, compared with the commercial products, pyrolyzed sidewall at 500 oC

266 gives a higher carbon and ash quality. On the other hand, devulcanization (also known

267 as decrosslinking) is a new method that is currently being explored extensively. This

268 particular term is described as a method to selectively cleave sulfidic bonds within a

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269 vulcanizate or WTR while retaining the polymeric backbone responsible for good

270 mechanical and tensile properties [28]. However, it is not to be mistaken with

271 reclamation, which referred to random bond cleavages [18]. Devulcanization is a

272 favourable method to reset or assuming the renewal of WTR to its original raw

273 materials. Currently, devulcanization is being approached by a few different methods

274 such as thermal [29], mechanical [30], chemical [31], biological [32], microwave [33],

275 ultrasonic [34] and any combination of these methods (e.g., thermochemical [35],

276 thermomechanical [36], mechanochemical [37], thermosonic [28]).

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277 The least favourable valorization technique is the quaternary stage, whereby it

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278 includes incineration. The WTR energy content is around 32.6 MJ/kg, which

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approximately has a 10% less value than heavy oil [26]. Energy recovery from the
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280 incineration process provides an exceptionally valuable and economical service.
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281 However, this particular approach's major drawback is the exceptional amount of
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282 toxic emissions produced (e.g., NOx, SOx, COx, HCN, etc.) that is sustainably

283 unacceptable [38]. Looking at these four stages of valorization, industries and
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284 researchers widely favour the tertiary stages (primarily devulcanization) due to its
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285 high return values. The next section describes the currently explored devulcanization

286 technology.

287 4.0 Rubber Devulcanization Technologies

288 Due to the ever-changing waste management legislation in various countries, post-

289 consumer tires are required to be subjected to recycling as there are tremendous

290 environmental and economic reasons. As mentioned earlier, one of the oldest

291 recycling methods, retreading, is still being applied in a few industries. Retreading not

292 only extends the lifespan of the tire, but it also saves energy, raw material and cheaper

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293 compared to a new tire. However retreading is labour intensive, compromises the

294 quality of tire [39], the process posses health hazard to the worker as it emits volatile

295 organic compounds (VOCs) [40] and most importantly it is not sustainable in the long

296 run.

297 Reclamation of waste rubber tire comes next for the valorization method.

298 This process requires the incorporation of reclaimed rubber into a new polymeric

299 blend. For this process, the waste tire is first stripped out of its steel and fabric

300 components to ensure that they do not hinder the reclamation process. After their

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301 removal, the waste tire is downsized through a grinding process. The product is

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302 typically GTR in the form of fine rubber powder [41]. This process is extremely

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complicated and requires heavy machinery due to the tire’s strong physical properties.
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304 Reclamation of GTR to reclaimed rubber (RR) can be done by various methods such
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305 as thermal, chemical and physical. However, as reclamation randomly cleaves

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306 polymeric and polysulfidic bonds, a limitation of 1% is set for many companies for

307 the incorporation of RR into the production of a new tire. This is mainly due to the
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308 drop in both quality and physical properties of the final product at high RR content
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309 due to incompatibility between raw and RR polymeric matrices. Nevertheless, an

310 amount of about 5-15% of RR is sometimes incorporated as filler [42].

311 Due to all these disadvantages, most tire industries are not interested in such

312 technology and have not reached the commercialization stage. To address this

313 particular issue, developments and researches to selectively break sulfidic bond

314 without or with little polymeric scission are widely being investigated. Many existing

315 and novel devulcanization methods have been explored by researchers that can be

316 grouped into 3 major categories: physical, chemical and biological devulcanization as

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317 illustrated in Fig. 8. Furthermore, understanding the vulcanization and its chemistry,

318 degree of devulcanization, soluble content and crosslinking density is crucial.

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320 Figure 8. Devulcanization category break down [43]

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321 Due to the formation of crosslinks during vulcanization, vulcanizates become

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322 robust, hard, infusible and insoluble in any solvent [44]. Thereby, successful
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323 devulcanization could be measured through how many fractions of the vulcanizate has

324 become soluble after treatment. This parameter is called soluble content.

325 Accompanying soluble content, crosslink density, defined as the density of sulphuric

326 chains that connect two infinite parts of vulcanizates’ polymeric matrix, also plays an

327 important role. Hence, by measuring the difference between the rubber’s crosslink

328 density before and after treatment, the precise degree of devulcanization or how much

329 a vulcanizate loses its crosslinking chain can be measured. Generally, the acceptable

330 range of the degree of devulcanization is about 50-70% [45].

331 4.1 Physical Devulcanization

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332 4.1.1 Thermal devulcanization

333 The thermal devulcanization refers to a method to devulcanize rubber by subjecting it

334 to heat as an energy source. Thus, understanding the bond energy and type present in

335 vulcanized rubber is of importance. For instance, the amount of energy required to

336 break C=C, C-C, C-S and S-S bonds are 614, 347, 273 and 227 kJ/mol respectively

337 [36]. For effective devulcanization, only C-S and/or S-S bonds are to be cleaved. As

338 the energy required to break C-S and S-S bonds is very similar to the energy needed

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339 to break the C-C bond, there is a significant level of difficulties to devulcanize WTR

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340 without breaking C-C bonds.

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As reported by Sutanto [46] and De et al. [47], thermal devulcanization or
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342 heated pan process is the oldest devulcanization method, invented nearly 14 decades
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343 ago. Initially, fibres and steels present in WTR are removed using cyclones mixer to

344 increase the treatment surface area. The rubber compound is then downsized to GTR
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345 and autoclaved using steam at 15 bars pressure or higher and a temperature of 180-
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346 260 ºC for half a day. Later the treated feedstock is passed through a dehydrating
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347 system to separate rubber and water, as shown in Fig. 9. Although this treatment

348 process will cause substantial bond scission, it has no control over crosslink breakage

349 selectivity. Hence, successful devulcanization is expected to be very low as WTR (in

350 suspension) experiences a substantial breakdown [48].

351

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353 Figure 9. Thermal devulcanization process [45]

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354 A similar conclusion was also drawn from the study by De et al. [47], where

355 they showed that, unlike natural rubber (NR), styrene-butadiene rubber (SBR), which
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356 is one of the main types of rubber incorporated in tires, remains indestructible by this
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357 treatment. This could be due to the higher thermal stability of SBR than NR.
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358 Additionally, the material's hardness also increases, hindering the overall treatment
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359 and ultimately results in a low degree of devulcanization. Such drawbacks do not limit
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360 thermal devulcanization method. Instead, it is further developed by incorporating it

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361 into other technologies as heating is the key factor for bond scission.

362 4.1.2 Mechanical and thermo-mechanical devulcanization

363 This particular devulcanization technique is considered as a physical process,

364 commonly combined with a thermal process. Similarly, for its first stage, WTR

365 requires to be separated from its fabrics and metals, followed by a down-cycle process

366 for the formation of GTR. Later, as reported by Liang [39], Sutanto [46], Adhikari et

367 al. [49] and Abraham et al. [48], GTR is introduced into a 2-roll mill (or Brabender

368 mixer) in an open environment where mechanical and shearing force is applied on

369 vulcanizates, which happens rapidly for about 3 to 15 mins. Due to such excessive

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370 shearing, the process temperature can reach up to ±250 oC. This process is known as

371 Lancaster-Banbury or the internal batch mixer method. Furthermore, this process

372 provides an economic benefit in terms of cost and prevents chemical waste disposal.

373 Nevertheless, the exceptionally high shear and stress experienced by GTR most often

374 causes its macromolecular structure to be severely damaged [39]. This particular

375 method was recently re-studied by Joseph et al. [50] by devulcanizing carbon black

376 filled NR by a water-cooled two-roll mixing mill (15 x 30 cm) at a friction ratio of

377 1:1.25. The resultant degree of devulcanization was between 20-37.8%. This

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378 particular study proved that heating was needed for effective decrosslinking. Zhang et

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379 al. [51] implemented mechanical pan-milling reactor at 30 rpm (for several cycles –

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25 to 40 seconds per cycle) and at ambient temperature that operated free from any
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381 chemical. The study was made based on comparing virgin NR and NR with
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382 devulcanized GTR (dGTR) blend vulcanizates. Result shows that there is an increase
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383 in tensile strength by 69.3% and elongation at break by 47% of the new vulcanizates

384 made from the blend. However, this was achievable only for 10% dGTR and 90% NR
ur

385 blend. As the dGTR content increased, the mechanical properties decreased, which
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386 did not really provide an answer for the prevailing issue and further improvement is

387 necessary. Such a result was anticipated because the maximum reduction in crosslink

388 density was about 0.4 from 0.7 mol/dm3. This indicates that the degree of

389 devulcanization is averagely about 42.85% that is expected due to certain degree of

390 polymeric scissions.

391 The findings by Zhang et al. [51] were in agreement with Adhikari et al. [49],

392 who performed a similar study where vulcanizates were made and analysed for

393 various blend proportions of NR and GTR. The author found that the produced

394 vulcanizates failed the Mooney viscosity test because its value was too high and

21
395 caused plasticity of the material to be highly compromised. In addition, findings have

396 also shown that as the percentage incorporation of GTR into the vulcanizate blend

397 increases, resistance to reversion, modulus elasticity tear strength and resilience

398 decreases. These are commonly shown to be the indicators for the increase in

399 crosslink density or in other words, low degree devulcanization of which value was

400 not reported. Lancaster-Bradbury is the oldest mechanical devulcanization method

401 and least preferred, but advancing method from it is called Ficker’s or single/twin-

402 screw extruder method. In such technique, screw extruder is considered as a series of

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403 continuous stirred tank or plug-flow reactors and has since caught the attention of

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404 researchers. This is primarily due to the fact that extruder (majorly twin-screw) is

405
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commonly and readily available in rubber manufacturing industries, are continuous,
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406 have ability for mass production as well as practical. Fig. 10 illustrates the schematics
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407 of a generally used twin-screw extruder.

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408

409 Figure 10. Twin screw extruder (a) external and (b) internal screw configuration [36]

410 As reported by Sutanto [46], the first continuous single screw extruder process

411 generally operates for about 1 to 3 mins at a temperature range between 323– 400 oC

22
412 where the mechanical shearing force acts between the wall of the extruder – barrel

413 and the screw at a rotational speed of 100-400 rpm. These two are the most important

414 parameters that affect the devulcanization outcome. However, if the operating

415 temperature reaches below 50 oC, the devulcanization process occurs at an extremely

416 slow rate, while beyond 400 oC results in polymeric scission. A similar study was

417 conducted by Bilgili et al. [52] where GTR was introduced into solid-state shear

418 extrusion. At the same time, Klingensmith et al. [53] applied the concept of blending

419 virgin rubber (VR) with GTR at 50:50 ratio with the rotational speed of 60 rpm and

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420 200 oC. This results in a significant reduction in elongation at break, tensile and tear

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421 strength by 20-30%, 30% and 10%, respectively, with a degree of devulcanization in

422
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the range of 13-16%. On the other hand, twin-screw devulcanization study with the
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423 screw L/D ratio of 40 was reported by Yazdani et al. [54]. The experiment's operating
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424 temperature and screw rotational speed were varied as they are the main determining
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425 factors. The study concluded that moderate operating conditions is more preferred

426 (220 oC at 120 rpm) in a RR/GTR blend of 15:85 wt%. This seems to be agreeable
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427 with the result obtained by Edwards et al. [55], where selectivity of crosslink scission
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428 decreased as temperature increased. Scaffaro et al. [56] also reported a similar

429 reduction in the tensile strength of devulcanizate by 26.67% when the operational

430 condition was set too high.

431 A comparison between single and twin-screw extrusion of WTR was reported

432 by Ujianto et al. [57]. The authors found that twin-screw extruder reduces gel content

433 by 50% from 85% at 300 oC and 100 rpm, while single screw and/or internal mixer by

434 40% from 85%. Such finding proves that extruder-based technique has higher efficacy

435 compared to the thermal devulcanization method.

23
436 Recently, Seghar et al. [36] reported their study on devulcanization of NR using

437 an industrial twin-screw extruded illustrated in Fig. 10. The authors only altered the

438 barrel temperature between 80 to 220 oC while keeping the rotational speed fixed at

439 240 rpm. The outcome resulted in a 90% reclamation instead of pure devulcanization

440 proven by Horikx curve fitting. Nonetheless, sulfidic cleavage seemed to favour lower

441 barrel temperature due to rubber’s self-heating property. Furthermore, blending

442 devulcanized NR with virgin NR also resulted in similar physical properties. Similar

443 studies were also reported by Maridass and Gupta [58] and Jalilvand et al. [59] by

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444 using GTR and ethylene-propylene-diene-monomer (EPDM) rubber, respectively.

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445 Maridass and Gupta [58] proceeded the study at 30 rpm and a barrel temperature of

446
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170 oC, while the other was at 140 rpm and a barrel temperature of 220-340 oC. Both
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447 studies agreed with Seghar et al. [36], where no significant difference in the
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448 percentage devulcanization with respect to barrel temperature was observed. Hence, a
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449 lower temperature was preferred. As suggested by Mouri et al. [60], this approach's

450 mechanism is shown in Scheme 2. When the heat is applied to vulcanized thermoset
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451 elastomer within the extruder, the first bond to break is the -Sx- bond as it has the
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452 lowest bond energy. Such phenomena resulted in the significant increase in C-S bond

453 percentage within the vulcanizates network, which is then exposed to high shearing

454 stress to cleave it. At the end of the thermo-mechanical process, it was expected that

455 some percentages of SO2, H2S, CS2 gaseous compounds and polymeric bond scission

456 would be produced.

24
457

458 Scheme 2. Thermo-mechanical expected mechanism [60]

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459 Li and team [30] have recently published a method to thermo-mechanically

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460 devulcanize GTR with the help of a fixed concentration of waste engine oil (WEO) in

461
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a 150 rpm and 3 kg/hr twin-screw extruder. The temperature of the barrel was varied
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462 between 150 to 280 oC. Treated GTR resulted in a decrement of gel fraction as WEO
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463 content increased, which could be related to the increasing degree of devulcanization
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464 and decrease in crosslink density. Although these two parameters were not reported

465 using Horikx fitting, the authors concluded that low-bound barrel temperatures
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466 between 180-210 oC were preferred as it gives better rheological properties (e.g.,
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467 dynamic viscosity, tensile, storage modulus). This corresponds to the studies

468 performed by Seghar et al. [36], Maridass and Gupta [58] and Jalilvand et al. [59]

469 discussed earlier. Nunes et al. [61] had also published twin-screw-based

470 devulcanization of WTR (with NR as the major component) at different processing

471 parameters and particle sizes. Their study concluded that higher screw rotating speed

472 (550 rpm) and smaller particle size (6 mesh) produced a high percentage of soluble

473 content. Despite the absence of percentage devulcanization and Horikx fitting being

474 reported, the authors claim that high soluble content is proportional to the high degree

475 of devulcanization. On the other hand, Song et al. [62] and Sousa et al. [63] indicate

25
476 that there should not be a too high degree of soluble fraction during devulcanization

477 as it will significantly shift the data point within the Horikx curve upwards. This

478 means greater polymeric scission, and as such, the degree of devulcanization is

479 reduced considerably. Ghorai et al. [64] and Song et al. [65] further validated such

480 findings and concluded that high sol fraction could most often contribute to the high

481 degree of polymeric scission. For instance, cleavage of C-C bond between two

482 different polymeric chains, which consists of C-S and -Sx- would still increase

483 soluble fraction and decrease in crosslink density. Hence, a higher decrement in

of
484 crosslink density and medium to low increment of the soluble fraction is preferable. In

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485 other words, higher selectivity towards sulfidic cleavage compared to polymeric

486
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scission. Such is the definition of Horikx theory [66].
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487 It was seen that barrel temperature and screw speed are the two most important
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488 parameters in screw-extruder type devulcanization. Hence, Edward et al. [55]

na

489 reported their study on response surface methodology (RSM) optimization upon these

490 two significant factors by central composite design (CCD), whereby barrel
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491 temperature was varied between 175-275 oC and rotational speed is between 30-90
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492 rpm. The authors reported that soluble content increases and crosslink density

493 decreases significantly with an increment of temperature but mildly with an increment

494 of screw speed. However, the high soluble content was suspected due to

495 devolatilization and thermo-oxidative degradation around 247.5 oC, as reported from

496 the derivative thermogravimetric analyser (dTGA) analysis. This is because acetone

497 extraction was not conducted to remove small VOC before toluene extraction was

498 performed. The optimise point was at 275 oC and 90 rpm, despite heterogeneous

499 results shown by Horikx fitting. Statistical CCD-RSM was repeated when diphenyl-

500 disulphide (DPDS) was added as devulcanizing agent following the same initial

26
501 procedure. Interestingly, the authors found that the degree of polymeric scission was

502 reduced and devulcanization occurred at milder condition (220 oC and 32 rpm). The

503 findings, in concurrence with mechanochemical devulcanization study by Ghorai et al.

504 [67], concluded that the addition of a suitable devulcanizing agent greatly assisted the

505 devulcanizing process of GTR as the degree of sulfidic selectivity increased.

506 In a different approach other than the two-roll mill, Brabender internal mixer

507 and single-/twin-screw extruder, Diaz et al. [68] performed thermomechanical

508 devulcanization of GTR between two unique metallic-cone-like high shear mixer as

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509 illustrated in Fig. 11. In this setup, one cone was static, while the other rotated and

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510 pressurized the system. The system was cooled by flowing in a stream of cold water.

511
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In the study, the authors varied both rubber temperature and mechanical energy
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512 consumed in operation. The author fed the instrument with large chunks of GTR,
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513 while the machinery performed its job by reducing the particle size through rotor
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514 rotation. This reduces the GTR’s particle size, while at the same time increasing the

515 rubber’s soluble content and lowering its crosslink density. The same observation was
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516 also concluded by Dobrota et al. [69]. However, the authors emphasized that such
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517 reduction mainly occurred at the rubber surface while the internal network

518 experiences negligible change. Myhre et al. [70] defined this process as a surface

519 activation phenomenon where only the surface of GTR was delinked, as seen in their

520 study.

27
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521

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522 Figure 11. High shear mixer; metal cone (left) and setup (right) [68]
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523 A novel physical decrosslinking technique was taken by Cheng et al. [71] in
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524 their study of GTR liquefaction to re-phase GTR from thermoset to thermoplastic and

525 viscous for the objective of easiness in (re-)processing. Generally, GTR liquefaction
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526 occurred at a high temperature of 220-300 oC as conducted by Wu et al. [71].

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527 However, in GTR liquefaction study, the operating temperature was significantly
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528 lowered (140-180 oC) but aided with aromatic oil for 2-24 hours. As expected, with

529 time, gel content decreased (down to 31.66%) and swelling ratio increased.

530 Additionally, nano-sized carbon black was also recovered and treated as an indication

531 of damages experienced by the crosslinked structure in the GTR network. Crosslink

532 reduction and soluble content were then fitted onto Horikx curve. It was found that

533 devulcanizates experienced heterogeneous scission.

534 4.1.3 Devulcanization by microwave electromagnetic irradiation

535 Devulcanization treatment by wave irradiation (i.e., microwave) considers as a batch

536 process and one of the most explored methods. The GTR is subjected to microwave’s

28
537 electromagnetic field radiation and the material’s ionic conductivity or dipole rotation

538 (i.e., material’s polarity) plays a vital role in absorbing the radiation and convert it to

539 heat or thermal energy in a uniform manner to cleave the targeted bond. Typical

540 microwave devulcanization treatment is illustrated in Fig 12. The radiation’s

541 wavelength and frequency range from 1 to 1,000 mm and 300 MHz to 300 GHz,

542 respectively [29, 63]. The very first microwave devulcanization technique was applied

543 and patented by Goodyear Tire & Rubber Co. [72]. The GTR at 6-10 mm of size was

544 introduced into a microwave system at a range of either 0.915 or 2.45 GHz. It was

of
545 found that the GTR’s temperature rapidly increased to 260-350 oC. The author

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546 reported that this is not because of the GTR’s polarity, but instead, the polarity of the

547 carbon black filler.

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548 Despite the high recovery of rubber’s properties, as much as 90-95% [73], the
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549 process is disadvantageous in terms of economic benefit due to high equipment cost
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550 [45]. Moreover, the process is also not industrial viable in terms of the operational

551 condition because of high thermal runaway possibility.

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552

553 Figure 12. Devulcanization by microwave irradiation technique [29]

554 A review performed by Adhikari et al. [49] suggested that the devulcanization

555 process will minimize and control environmental pollution. The product generated

556 can act as a compounding stock to be mixed with VR and the result shows that

557 mechanical and tensile properties obtained were similar to those reported by Fix [73].

29
558 On the other hand, Landini et al. [74] and Scagliusi et al. [75] studied the impact of

559 devulcanization with respect to irradiation time (9-25 minutes) and power supply (1-3

560 kW) on bromo-butyl rubber (BIIR) and chloroprene rubber (CR) respectively. The

561 result showed that the degree of devulcanization increased proportionally along with

562 these parameters. In both the studies, the devulcanizates produced were revulcanized.

563 The produced revulcanizates were then tested in terms of their hardness and ash

564 content. The results showed that the revulcanizates lost their hardness with no

565 significant loss in organic materials’ composition. This possibly indicates the

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566 retention of the polymeric networks. Similar study was also reported by Seghar et al.

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567 [76]. The author studied SBR devulcanization between the energy level of 110-440

568
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Wh/kg for 0-100 seconds and found that the highest devulcanization efficiency
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569 achieved is 60%, at 440 Wh/kg and 100 seconds. Zanchet et al. [77] studied a similar
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570 effect at magnetron power of 0.9 kW and exposure time of 2-4 mins. They reported
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571 their study’s degree of devulcanization to be valued at 67.6%, but with a decrease of

572 75% in elongation at break and tensile strength as exposure time increase.
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573 Another interesting study was reported by Hirayama and Saron [78] regarding
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574 SBR’s chemical change(s) after microwave treatment. The authors first compounded

575 a fresh SBR of themselves at variable carbon black (0-49.1 %) to be vulcanized and

576 shredded to 20-mesh of GTR for devulcanization at 0.7 kW for 120 seconds. The

577 result showed that polysulfidic bonds were broken along with other sulphur-

578 containing groups, while mono-sulfidic bonds were retained. However, from the

579 scope of the study, these results are only valid for SBR at high carbon black content

580 because SBR is non-polar while carbon black is polar. Hence the more carbon black

581 present, the higher the degree of polarity, which results in better microwave treatment.

582 This could be seen through the low gel content of SBR (7.8%) when it consists of

30
583 high (49.1%) carbon black percentage, while in the absence of carbon black, SBR

584 shows a much higher gel content of 71.68%. Garcia et al. [79] reported similar

585 findings where structural bonds were analyzed using Fourier transform infrared

586 (FTIR). The authors reported a decomposition of thiol and sulphur-oxygen (i.e.,

587 sulfones, sulfonamides and sulfoxides) groups. On the other hand, peak intensities in

588 the 800-600 cm-1 region were seen to be reduced from vulcanizates to devulcanizates.

589 This indicates fraction disappearance of mono-, di- and poly-sulfidic bonds.

590 Additionally, the FTIR analysis on the produced devulcanizate also shows intensity

of
591 reduction with respect to the C=C bond. Since the existence of this particular bond is

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592 important during revulcanization, the loss of its intensity in devulcanizate could

593
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potentially signify the proportional loss of the revulcanizates’ physical properties. The
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594 thermostability reported by Garcia et al. [79] shows that increasing microwave
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595 treatment did not just increase the soluble content but may also shift the degradation
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596 temperature to a lower value due to entanglement and reduction in molecular mass.

597 Hirayama and Saron [78] suggested that for a higher degree of devulcanization,
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598 wave treatment should be incorporated with a chemical treatment to break sulphur
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599 cure network easily. Their conclusion was supported by a study performed by Seghar

600 et al. [76], where a comparison of devulcanizates was made with and without

601 chemical treatment. The novel devulcanizing agent chosen was a pyrrolidinium-based

602 IL, pyrrolidinium hydrogen sulphide (PHS). It has a property to readily absorb wave

603 energy and convert it to thermal energy and high heat capacity. Under fixed

604 microwave magnetron power of 440 Wh/kg, PHS pre-treated SBR showed a degree of

605 devulcanization of 50%, while the non-treated SBR is at 20% lower. However, the

606 batch-operated microwave process has high operational and capital costs coupled with

31
607 ILs being costly, toxic, non-biodegradable, viscous, and typically non-recyclable are

608 some of the main factors for its rejection by various tire industries [16, 21].

609 An earlier study by Movahed et al. [80] also coupled microwave irradiation with

610 aromatic oil that has been mixed with six different devulcanizing agents. They soaked

611 the EPDM rubber in these oils for 24 hours to allow sufficient imbibition before

612 subjecting to microwave irradiation at a temperature range of 200-260 oC. The authors

613 concluded that the highest degree of devulcanization was achieved by N-cyclohexyl-

614 2-benzothiozyl sulfenamide (CBS), hexadecylamine (HDA) and

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615 mercaptobenzothiazole (MBT) as the devulcanizing agents. On the other hand,

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616 treatment by 2-mercaptobenzothiazole disulphide (MBTS) gave the best mechanical

617
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and tensile properties upon revulcanization. In the same manner, Molanorouzi et al.
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618 [81] performed a similar study by mixing CBS, HDA, diphenyl disulphide (DPDS)
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619 and MBTS with aromatic and paraffinic oil at variable ratios as well as irradiation
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620 temperature. The result verified that DPDS served as a better devulcanizing agent

621 than the other three, with 48% degree of devulcanization. Specifically, the treatment
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622 condition was with DPDS/aromatic oil ratio of 6:30 (in phr) and a treatment
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623 temperature of 260 oC. The authors also reported that most -Sx- bonds were cleaved,

624 but reformations were possible due to radical formation. The predicted free radical

625 mechanism is shown in Scheme 3.

32
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626

627 Scheme 3. Devulcanizing agent-assisted microwave devulcanization [81]

na

628 In a recent study by de Sousa et al. [82], GTR from the truck tire of an unknown
ur

629 recipe was devulcanized at 0.820 kW in a conventional (kitchen) microwave oven for
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630 3 to 5.5 mins. Devulcanizates were then revulcanized for 5 mins at 180 oC and 44.13

631 bar. The authors reported similar findings to their previous study [63], where longer

632 exposure to microwave irradiation proportionally increased the final treated GTR

633 temperature. This is expected to be caused by the GTR’s carbon black content as

634 reported by Hirayama and Saron [78]. The authors further emphasized that

635 devulcanization was confirmed through the decrease in gel content and crosslink

636 density of devulcanizates by the Flory-Rehner approach and the reduction of rubber’s

637 soft phase seen through its morphological study performed by atomic force

638 microscope (AFM). FTIR analysis further indicates that NR and SBR fractions in the

639 GTR were not significantly degraded. However, gel analysis of devulcanizates
33
640 indicates the possibilities of decrosslinking, sulphoxide group formation and

641 recrosslinking to be in resonance with each other. The latter could be due to excess

642 sulphur during vulcanization process. Mechanism for this reaction is proposed to be a

643 free radical reaction as shown in Scheme 4. The formation of polysulfidic tends to

644 outperform their cleavage at longer microwave exposure, whereas monosulfidic

645 cleavage on the other hand, outperformed their formation. However, FTIR spectra of

646 revulcanization of devulcanizates also exhibited the formation of sulphoxides which

647 suggests that free radical rearrangement could occur and implication upon application

of
648 is subjected to suitable applications.

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649

650 Scheme 4. Microwave devulcanization reaction scheme; X is S or O atom [63]

651 In a different study, Canavate et al. [33] devulcanized 60 g GTR through their

652 in-house build microwave oven at 700 W, 80 rpm and the variable exposure time was

653 limited between 3 to 10 mins to ensure minimal degradation. They reported that their

654 design favours homogeneous irradiation throughout the sample. The devulcanizates

34
655 produced were compounded with NR and nitrile butadiene rubber (NBR). Mechanical

656 testing of their results showed that adding devulcanizate into NR/NBR blend

657 increased rubber blend’s Young modulus and tensile strength when microwave

658 treatment was between 3 to 5 mins. On the other hand, when microwave treatment

659 was set to 10 mins, decrement of Young modulus and tensile strength were

660 experienced. Such decrement was analysed through their FTIR-ATR spectra

661 regarding zinc stearate (ZnSt) migration, whereby a higher degree of migration

662 indicated higher crosslink density. Apparently, devulcanizates produced by 0 and 3

of
663 mins irradiation possessed significant ZnSt peak, unlike treatment at 5 and 10 mins. A

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664 similar study with the addition of rubber ageing properties was also performed by

665
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Zanchet and de Sousa [83] using powdered SBR-composite in a microwave for not
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666 more than 3 mins. The result was agreeable, whereby increasing microwave treatment
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667 above three minutes did not influence the properties further. The physical properties
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668 of the obtained SBR-composite devulcanizate were then compared to the author’s

669 reference sample, ground butyl rubber scraps. With respect to the reference, a 175%,
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670 107% and 90% increase in tensile strength, tear strength and compression set was
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671 seen.

672 Simon et al. [84] also performed microwave devulcanization study using two

673 types of GTR, namely mechanically produced GTR and waterjet-milled GTR. The

674 treatment was performed for 30 and 60 seconds, by subjecting 50 gr of GTR to

675 microwave that operates at 650 W at 100 rpm. In addition, two types (conventional

676 and temperature-controlled) of microwave ovens were also used. The authors found

677 that the repeatability and quality of devulcanizates produce through temperature-

678 controlled oven is better and more uniform. The authors also concluded that both

679 devulcanizates (produced from the microwave treatment of mechanical and waterjet

35
680 GTRs) have a better elongation at break, tensile strength and tear strength when

681 compounded with SBR-based rubber instead of untreated GTR. This phenomenon

682 was explained in an earlier microwave devulcanization study by Column et al. [85],

683 whereby devulcanizing GTR increased the interfacial adhesion between itself with

684 NR. Furthermore, such a result is more evident for GTR that is mainly produced from

685 the truck tire as higher NR content could be found, as shown in Fig. 5.

686 Despite various advantages microwave devulcanization has, some pressing

687 limitations recently reported by Formela et al. [86] need to be addressed. As indicated

of
688 by Zedler et al. [85], these limitations include exceptionally high operational cost, hot

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689 spot issues, inefficient mixing, and high VOC emissions. However, the VOC

690
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emissions could be reduced through operation in vacuum or inert environments, but
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691 this will increase the overall treatment cost.
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692 4.1.4 Devulcanization by ultrasonic and thermosonic irradiation

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693 Irradiation stands as the most advanced and promising method of devulcanization as
ur

694 the process is simple, fast and efficient. It uses mechanical vibrational wave which
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695 consists of large fraction of energy that dissipating through electron excitation and

696 ionization process [87]. Additionally, extension-compression stresses produce

697 mechanically-induced cavitation bubbles at high frequency [43, 88]. This

698 phenomenon overstressed the chemical bonds within the vulcanizate’s network which

699 resulted in the possibility of bond cleavage (forming free radicals) and bond

700 weakening. In the rubber structure for devulcanization, the selective 3D-crosslink

701 network of mono- and poly-sulfidic bonds are the targets due to their low bond energy.

702 Upon treatment, devulcanizates will be soft and have a high degree of flowability.

703 Moreover, the process can be both batch and continuous; hence, it is preferred by

36
704 industries [39]. Fig. 13 is the typical ultrasonic treatment setup, ultrasonic extruder

705 (end-extruder). The extruder can also be located in the middle, mid-extruder.

706 Nevertheless, different setups are also available (e.g., ultrasonic probe and water bath)

707 and are reviewed here.

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708
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709 Figure 13. Typical ultrasonic extruder devulcanization setup [29]

na

710 The first attempt on ultrasonic devulcanization was reported by Pelofsky, who

711 patented the process and reviewed by Adhikari et al. [49]. The author reported two
ur

712 different ultrasonic devulcanization process. In the first study, GTR was subjected to a
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713 frequency of 20 kHz and magnetron power of 100 W, whereas in the second study,

714 NR was treated for 50 kHz for 20 mins. The result showed that the process managed

715 to cleave –C-S- and –S-S- bonds without polymeric cleavage, resulting in

716 devulcanizates having properties equivalent to fresh vulcanizates [45]. However,

717 Mangaraj [49] indicates that the rubber degradation phenomenon might occur in the

718 process. It was also further identified by Tukachinsky et al. [88] that to maintain good

719 physical properties of devulcanizates with minimum degradation, exposure of

720 ultrasonic irradiation onto the sample must be sufficient enough. Overdosing the

721 exposure of ultrasonic irradiation onto the sample will most often result in

37
722 reclamation, while under treatment would result in insufficient cleavage of the cross-

723 linkages. Throughout the developments, ultrasonic treatment has shown its

724 practicality to be used for devulcanization of various types of rubber tires such as

725 SBR [89], silica-filled poly-dimethyl-siloxane [90], NR and EPDM [91].

726 In the study reported by Isayev et al. through simulation [92] and modelling

727 [93], ultrasonic devulcanization requires concentration of local energy which has a

728 proportional effect on the degree of devulcanization, crosslink density and sol-gel

729 fraction. Additionally, Abraham et al. [48] also reported that the degree of

of
730 devulcanization is highly proportional to temperature and frequency. In another type

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731 of ultrasonic devulcanization study [93], the experiment was carried out in a 1.5-inch

732
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co-axial ultrasonic reactor with a frequency of 20 kHz, 3000 Watt of magnetron
re
733 power and utilisation of accelerators (i.e., stearic acid, ZnO and N-cyclohexyl
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734 benzothiazole-2-sulphenamide) [94]. Within the system, three zones were

na

735 temperature-controlled and the screw is electrically heated and can be cooled by

736 circulation of pumped water. The conclusion was similar to Abraham et al. [48], but
ur

737 with the degree of devulcanization higher than most of any previous methods and
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738 physical properties of revulcanized rubber exceeding the virgin vulcanizates [93].

739 Moreover, it was found that during the treatment process, ultrasound amplitude of

740 ultrasonic irradiation, temperature due to die extrusion pressure, as well as magnetron

741 powers, play an important role. This was reported by Isayev et al. [95] in their study

742 on the effect of particle size on ultrasonic devulcanization. The results showed that

743 between 10 and 30 meshes, the 30-mesh sample provides a higher surface area for

744 energy absorption at 250 oC rather than at 180 oC. Hence, 30-mesh sample produced a

745 higher degree of devulcanization than the 10-mesh. On the other hand, Lewis et al.

746 [95] indicated that an increase in amplitude did not proportionally increase

38
747 devulcanization degree. The study also observed that there was a competition between

748 crosslink reformation and devulcanization at excessively high amplitude. This causes

749 the soluble content of the rubber to be greatly lowered which is in agreement with

750 observation done by Hong et al. [96].

751 The effect of amplitude, temperature, screw speed and flowrate was further

752 studied by Mangili et al. [97] through ultrasonic co-rotating twin-screw extruder

753 devulcanization of GTR. The authors analysed the responses in terms of crosslink

754 density and gel fraction for devulcanizates; while complex viscosity, tensile strength

of
755 and modulus for revulcanizates. In addition, regression and optimization studies by

ro
756 RSM were also conducted. As expected, all of the input parameters were significant,

757
-p
and interactions were also evident. However, the most influencing factor turned out to
re
758 be the ultrasonic amplitude for this particular setup, especially regarding
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759 devulcanizates and revulcanizates’ reusability. Furthermore, the reasonably low

na

760 ultrasonic amplitude was emphasized to enhance selective sulfidic cleavage and

761 minimal polymeric degradation. In a different study performed by Liang et al. [98],
ur

762 star SBR was treated with ultrasonic exposure at amplitude in the range of 3.5 to 10
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763 μm and their molecular structure was predicted. At the low range of amplitude, 3.5

764 and 5 μm, the latter produced a smaller amount of gel fraction. In contrast, the other

765 produced a negligible amount of gel with a molecule that has higher molecular weight

766 and long-chain branch. On the contrary, the ultrasonic amplitude at the higher range

767 creates higher gel content that hinders filler addition for mechanical and tensile testing.

768 Moreover, the long-chain branching of molecules produced from treatment at 3.5 μm

769 was claimed to have higher mechanical and tensile properties (e.g., elongation at

770 break and tensile strength) due to the higher surface area resulting from the branching

771 and produced a better filler-rubber interaction. This was expected due to the reduction

39
772 of flocculation behaviour. In contrast to star SBR, linear SBR is absent in terms of

773 branching. Hence, it has a lower surface area and therefore, they have insufficient

774 filler-rubber interaction with low bound rubber content.

775 Moon et al. [34] also recently reported their study on devulcanization of

776 polyurethane foam from seat cushion with ultrasonic horn oscillation approach to

777 increase its comfort properties. In their study, the devulcanizate produced a 25%

778 reduction in its gel content and proportionally lowered the crosslink density and the

779 glass transition temperature. As glass transition temperature decreases compared to

of
780 virgin polyurethane foam, it is expected that the revulcanizate will be softer.

ro
781 In a different approach than ultrasonic extruder, ultrasonic water bath and deep

782
-p
eutectic solvent (DES)-assisted devulcanization was first carried out by Saputra et al.
re
783 [28]. Similar to the IL-assisted microwave devulcanization study reported by Seghar
lP

784 et al.[76], DES (an analogous solvent towards IL) was used as a devulcanizing agent.
na

785 In their study, GTR was soaked overnight in three different DESs of 1:20 mass ratio.

786 These DESs were choline chloride (ChCl):urea, ChCl:zinc chloride (ZnCl2) and
ur

787 ZnCl2:Urea at molar ratio of 1:2, 1:2 and 2:7. The mixtures were first sonicated using
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788 a water bath sonicator (connected to water bath circulator) for 60 mins at 37 kHz and

789 25oC. Afterwards, the sonicated samples were heated on a hotplate stirrer at 180 oC

790 and 30 rpm for 5, 15 and 30 mins. The results of this DES-assisted thermosonic

791 treatment shows that 15 mins was the best condition as the crosslink density was at

792 the lowest with an enhanced degree of devulcanization. FTIR spectra also indicated a

793 reduction in C-S and S-S bandwidth’s intensity and/or shifting, characterizing

794 cleavages. The authors further fitted their data to the Horikx curve and the result

795 indicated selective cleavage. In another study, the impact of different water dilution

796 ratio of DES on devulcanization was performed. As expected, higher dilution resulted

40
797 in lower efficiency [99]. However, a sudden spike in the degree of devulcanization

798 was also observed in the trend. This could be related to sonoluminescence or

799 sonolysis phenomenon produced from metallic substance present and low ultrasonic

800 frequency, which generates hydroxide radicals that act as scavengers. These

801 hydroxide radicals cause cavitation that further creates implosions of microbubbles

802 that have high pressure and temperature, enough for bond cleaving purposes. A

803 similar phenomenon was also reported by Shim and Isayev [100], where the authors

804 ultrasonically devulcanized GTR in the presence of water. Although a high percentage

of
805 of devulcanization could be achieved, it still needs further understanding of its

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806 application at industrial-scale application.
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807 4.2 Chemical Devulcanization
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808 Chemical devulcanization is another devulcanization method to obtain devulcanized

na

809 rubber, where the treatment is done through the utilisation of chemical or

810 devulcanizing agent to cleave rubber tire’s sulfidic cure network and, frequently, this
ur

811 particular method is coupled with thermal [101] and mechanical [37] devulcanization
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812 process to enhance the efficiency. The devulcanizing agents commonly reported in the

813 literature are organic, inorganic solvents and oils. Commercially, these chemicals

814 come from the classes of aliphatic, alkyl phenol sulphides, amine, aromatic

815 mercaptans, zinc salts, di/sulphides and unsaturated compounds [102]. Since these

816 compounds have the properties and tendency to be involved in the reaction with

817 radicals formed from crosslink scission, they are often used to prevent molecules'

818 recombination phenomenon. Table 2 lists some chemicals which have been studied as

819 a devulcanizing agent according to their group of classifications, whereas Fig. 14

820 illustrates the typical chemical-based devulcanization approach.

41
821 Table 2. Some devulcanizing agents classification [49]

Amine and ammonium Organic sulphide Sulphur free organic and

compounds and mercaptans inorganic compounds
Thiol-amine Xylene thiols Molten sodium
Tetra-butyl-ammonium
Diphenyl disulphide Lithium aluminium hydride
zincate (II)
N, N-dialkyl aryl amines Phenol sulphides Supercritical CO2

822

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823
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824 Figure 14. Chemical-based devulcanization system [29]

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825 4.2.1 Amine and ammonium

826 Amine-based devulcanization study for sulphur-cured rubber was first patented

827 in 2003 by van Duin et al. [103]. The article explains that devulcanization could occur

828 without a devulcanizing agent, resulting in an incomplete process. Furthermore,

829 devulcanization by thiophenols and disulphides at a temperature range of 200-250 oC

830 poses a disadvantage that these compounds only fractionally cleave -Sx- bond, while

831 majorly cleaving polymeric chain. The invention claimed that the devulcanization

832 process is preferably done with 0.1-15wt% of amine compounds (e.g., primary,

833 secondary and tertiary), specifically amine with α-C that has at least one H atom,

42
834 where one or more aliphatic and/or aromatic group was attached to the nitrogen. The

835 existence of other substituents into the aromatic or aliphatic group is acceptable, and it

836 was further suggested that the reaction be carried in an inert or oxygen-free

837 environment. This is to prevent unwanted secondary reactions that may degrade

838 devulcanizates. Chan et al. [104] explained that the hydrogen atom(s) attached to α-C,

839 also called α-H, possessed an abstraction effect. Such an effect promotes the

840 fragmentation of α-C-H bond to occur more readily. The generated fragment(s),

841 however, is more susceptible to nucleophilic attack. Hence, in the devulcanization

of
842 process, the generated fragments is attacked by the nucleophilic sulphur cross-

ro
843 linkages. Such a process is typically referred to as captodative interaction.

844
-p
Sutanto et al. [105] reported the modelling of amine-assisted ultrasonic
re
845 devulcanization and included crosslink density, HDA concentration, time, shear rate
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846 and temperature within the developed model. Additionally, the developed model was
na

847 claimed to accurately predict the degree of decrosslinking within the specified

boundary and reactor design. However, the authors indicated that beyond the
ur

848

849 temperature boundary, significant polymeric degradation was experienced. Dijkhuis et

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850 al. [106] also performed their study using HDA as the devulcanizing agent in EPDM

851 thermal devulcanization. Over the temperature range of 225 to 275 oC, it was reported

852 that the percentage reduction in crosslink density was about 50%, indicating a 50%

853 degree of devulcanization was achieved. However, this reduction in crosslink density

854 by HDA was mainly upon di- and poly-sulphide bonds. Devulcanizates were then

855 blended with virgin EPDM and revulcanized. Good mechanical properties (e.g.,

856 modulus, tensile, compression set and hardness) was observed compared to the pure

857 virgin vulcanizate. Premachandra et al. [107] also reported their study on the

858 utilisation of amino-based compound as the devulcanizing agent for GTR

43
859 mechanochemical devulcanization in a two-roll mill. Interestingly, devulcanization

860 occurred at a much lower temperature (30-70 oC) compared to other thermal-assisted

861 devulcanization with scorch resistance and hysteresis that is lower than the individual

862 constituents. Unfortunately, authors did not disclose the amino-based compound used.

863 Jiang et al. [108] proposed a tetraethylenepentamine (TEPA)-assisted

864 mechanochemical devulcanization of GTR by taking advantage of partial

865 devulcanization outcome to tailor rubber blend properties through in-situ grafting

866 concept as shown in Fig. 15. The grafting phenomenon of TEPA was confirmed by

of
867 FTIR-ATR analysis. The produced rubber blend consisted of GTR and high-density

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868 polyethylene was mixed with styrene, glycidyl methacrylate and dicumyl peroxide at

869
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the optimised ratio of 4, 4 and 0.6 phr to maximize the blend’s mechanical properties.
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870 Additionally, their rheological study (e.g., apparent viscosity and shear-strain rate) on
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871 the blend indicates stable processing and reprocessing.

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872

873 Figure 15. Blend of GTR/HDPE through grafting technology [108]

874 Other than primary, secondary and tertiary amine, quaternary amine (or

875 ammonium salt) was also previously studied as a devulcanizing agent. For instance,

876 the use of ammonium-based DESs as a devulcanizing agent was earlier reviewed in

877 ultrasonic devulcanization [28]. Previously, Nicholas [109] implemented N-methyl-

878 N,N,N-tri-n-alkylammonium chlorides as a phase-transfer catalyst (PTC) in an effort

879 to delink WTR with the help of benzene and water. The author found that a fraction of

44
880 catalyst decomposition through selective demethylation and its dependency on

881 crosslink density reduction was evident. Additionally, demethylation phenomenon

882 was also predicted to perform capping or grafting phenomena unto the thiolate ion

883 produced from delinking. 1H-NMR study was then performed onto the exhausted N-

884 methyl-N,N,N-tri-n-alkylammonium chlorides. The result indicates the loss of α-H

885 during such treatment. In another study, Walter [110] reported that the PTC worked

886 through the transportation of hydroxide ion to the organic phase (fine GTR) to

887 achieve polysulfidic cleavage and derivatized monosulfidic bond with minimal

of
888 polymeric chain. Such a phenomenon was made possible by quaternary ammonium

ro
889 chloride catalyst. Milani et al. [111] also performed an in-depth reaction study of PTC

890
-p
performance in devulcanization. The authors explained that PTC assisted in
re
891 transporting nucleophile (OH-) to the rubber network to cleave the sulfidic bonds,
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892 forming sulfoxide first and then oxidizing rapidly to sulfone. Further oxidation, or
na

893 second-degree elimination reaction on sulfone was possible with the help of excess

894 sodium hypochlorite and tetrabutylammonium chloride (TBAC), thus, producing

ur

895 unsaturated hydrocarbon chain and sulfonic acids. Overall, the rate of reaction
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896 favoured second-order reaction, first order with respect to both substrate and TBAC.

897 The proposed reaction mechanism is illustrated in Scheme 5.

45
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898
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899 Scheme 5. Disulphide cleavage in rubber network by ammonium-based PTC
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900 4.2.2 Organic sulphides and mercaptans

na

901 Compared to the other devulcanization techniques, chemical devulcanization

ur

902 appears to be the most common technique as it provides a large selection of possible
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903 promising agents. De et al. [42] reported the usage of tetra-methyl-thiuram disulphide

904 (TMTD) as devulcanizing agent for GTR, treated in an open two-roll miller, which

905 was then blended with virgin NR to study the blend’s physical properties. The

906 investigation showed when GTR to NR ratios were 20:80 and 60:40, tensile strength

907 was depleted by 7 and 46%, respectively. The authors explained such interesting

908 observation to be caused by the high gel content of devulcanizates (69.7%), which

909 marks a poor degree of devulcanization. The authors further studied GTR reclamation

910 by TMTD, but blended the produced GTR devulcanizates with virgin SBR [112]. The

911 blend vulcanizates' cure characteristics indicate that minimum torque and Mooney

46
912 viscosity increases with GTR devulcanizates content, unlike scorch time that

913 remained the same but decreased in optimum cure time. Surprisingly, the authors

914 found that the modulus, tensile strength, and elongation at break were increased due

915 to the blend’s higher resistance to swelling. In another study by Rodsuk et al. [113],

916 different diphenyl disulphide concentration (1-10 phr) was added to act as

917 devulcanizing agent. As expected, crosslink density decreased with the increase in its

918 concentration.

919 Kojima et al. [114] studied devulcanization through swelling of the rubber

of
920 matrix by supercritical CO2 as an environmentally friendly approach. They showed

ro
921 that tensile strength recovery reached up to 90% with the presence of diphenyl

922
-p
disulphide. Still, the outcome of the soluble content of devulcanizates was only
re
923 between 26-29%, indicating the rubber was poorly devulcanized. The results
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924 disagreed with Jiang et al. [115] but came in corroboration with the study conducted
na

925 by Tzoganakis et al. [116]. The earlier authors, Jiang et al. [115], experiment showed

926 that the soluble fraction of such treatment could reach up to 98.5%. The observed
ur

927 discrepancy between Kojima et al. [114] and Jiang et al. [115] study was mainly due
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928 to three reasons: (1) the pressure used by Jiang et al. [115] was double to that of

929 Kojima et al. [114], (2) Kojima et al. [114] only purged the samples with CO2, in

930 contrast to the direct contact between supercritical CO2 with the sample in the study

931 performed by Jiang et al. [115], (3) Jiang et al. [115] used dry-ice in an autoclave,

932 where once the critical point is reached, CO2 directly swells the polymeric matrices

933 opening a path for the chemicals to impregnate the cross-linked network easily. This

934 resulted in chemical’s radicals joining with polymer’s radicals. In prolonged reaction

935 time, the rubber's gel component decreased and the chemical’s radical concentration

936 increased in the rubber matrix. Hence, the increase of soluble fraction is apparent, but

47
937 at the expense of tremendously high-power output as the operating condition must be

938 maintained above carbon dioxide critical pressure and temperature above 160 oC. It

939 was observed that supercritical CO2 greatly enhanced the degree of swelling of rubber

940 which theoretically allowed solvent penetration to be effective. Through such

941 understanding, Jiang et al. [115] proposed the mechanism for devulcanization as

942 shown in Scheme. 6. The polymeric scheme starts at (A and/or B), while

943 devulcanizing agent’s scheme starts at (C). Under the influence of heat (180 oC),

944 pressure (15 MPa) and supercritical CO2, crosslink cleaved in a different reversible

of
945 manner as shown in (A) and (B), while diphenyl disulphide was irreversibly cleaved

ro
946 to form sulphur phenyl radicals. These radicals would then combine with sulphur

947
-p
radicals at (1) and (2) that were created from crosslink cleavage as indicated by
re
948 reaction (D) and (E). This phenomenon is known as capping. Since sulphur crosslink
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949 lost its crosslinking capability, this part of the rubber network turned to sol fraction
na

950 from its original gel fraction. Simultaneously, this causes the reduction of product in a

951 reversible reaction (A) and (B). In accordance with the reversibility (Le Châtelier)
ur

952 principle: modification in factor(s) in reversible reaction would change the

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953 equilibrium principle to countermeasure that modification. Hence, the equilibrium of

954 reaction (A) and (B) favours forward reaction and creates more polymeric sulphur-

955 radical that proportionally increases the rate in reaction (D) and (E). Nevertheless, a

956 certain degree of reformation and/or chain extension reaction is also expected to occur

957 following reaction (F).

48
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na
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958

959 Scheme 6. Supercritical CO2 devulcanization assisted by diphenyl disulphide

960 Another similar study was performed by Mangili et al. [117], complemented

961 with a full factorial statistical analysis. The two significant factors that majorly

962 influence the degree of devulcanization were temperature, the fraction of diphenyl

963 disulphide and their interaction. Such a result agrees with Liu et al. [118] in their two-

964 level full factorial study. However, the addition of processing oil was seen to increase

965 the selectivity of -Sx- bond cleavages in the diphenyl disulphide-assisted supercritical

966 CO2 devulcanization study published by Edward et al. [55]. To further enhance

49
967 sulphidic bond cleavage selectivity, Meysami et al. [119] employed supercritical CO2-

968 assisted devulcanization in a twin-screw extruder, followed by fractional factorial

969 experimental design. The decreasing order of significant parameters was found to be

970 temperature, screw speed and flow rate. Additionally, Horikx fitting indicated that the

971 selectivity was achieved with a much lower fraction of polymeric scission.

972 A different devulcanizing agent than TMTD and diphenyl disulphide, bis(3-

973 triethoxysilyl propyl) tetrasulphide (TESPT), was introduced by Ghorai et al. [67] and

974 Gosh et al. [120]. This particular disulphide possesses dual functions and can act as a

of
975 devulcanizing agent as well as coupling agent during silica filler dispersion in

ro
976 devulcanizates. In the study conducted by Ghorai et al. [67] using NR vulcanizates,

977
-p
the author varied the concentration of TESPT and devulcanization time in a two-roll
re
978 mill. On the other hand, Gosh et al. [120] conducted the same experiment but using
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979 SBR vulcanizates instead. Through monitoring of sol fraction and degree of
na

980 devulcanization, both authors, surprisingly, concluded that 6 mL of TESPT was the

981 optimum concentration for the treatment. On the other hand, optimum devulcanization
ur

982 time was found to be 40 mins. This was determined by comparing the tensile
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983 strengths of revulcanizates with and without silica filler. Additionally, capping

984 phenomenon also happened in both studies for different types of vulcanizates. The

985 mechanism for this reaction is similar to Scheme 6. However, instead of being

986 assisted by heat and pressure, TESPT and rubber network cleavage were both

987 performed by mechanical milling in an irreversible reaction. The products from these

988 two cleaving processes would then combine through capping phenomenon and

989 simultaneously disperses silica in the devulcanizates by means of silane bridges. Such

990 phenomenon causes the bound rubber to increase. This was also seen in the work

991 reported by van Hoek et al. [121], with a simplified mechanism shown in Scheme 7.

50
 992

Scheme 7. Silica reinforced devulcanizates [120]

of
993

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994 Another novel sulphide compound, which has a similar structure to diphenyl

995
-p
disulphide, namely 4,4’-dithiobis(2,6-di-t-butylphenol) (TBBT), was synthesized by
re
996 Zhang et al. in 2018 [122]. Its concentration and temperature were investigated in
lP

997 thermochemical devulcanization of GTR at 0-3phr and 180-200 oC, respectively.

998 Their work suggested that the increase in soluble content and the decrease in crosslink
na

999 density and Mooney viscosity of devulcanizates were experienced when the
ur

1000 temperature and TBBT’s concentration were increased. However, limitation to the
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1001 soluble percentage needed to be controlled (stickiness of the rubber) to produce

1002 revulcanizates with good mechanical properties. Hence, 200 oC and 0.5 phr of TBBM

1003 were selected as the optimum operating conditions. Liu et al. [37] also proposed a

1004 different sulphide compound to act as GTR’s devulcanizing agent, namely, 2,2'-di-

1005 benzo-thiazole-disulfide. High-shear mechanochemical devulcanization in the twin-

1006 screw extruder was employed. These dual activities, high-shear and chemical, caused

1007 the produced devulcanizates to have a lower rate of weight loss while at the same time

1008 increasing their oxygen content. This was suggested due to the improvement of

1009 surface activity of devulcanized GTR compared to the untreated GTR. Upon blending

1010 the surface-modified GTR devulcanizate with NR to produce devulcanizate/NR blend,

51
1011 the rubber processing analyser showed a significant loss in hysteresis. Hence, an

1012 increase in tensile strength by 31% (to 18.87 MPa) compared to untreated GTR/NR

1013 blend (12.87 MPa).

1014 4.2.3 Sulphur free organic and inorganic

1015 Pedro et al. [123] performed and reported that for environmental protection,

1016 the only class of devulcanizing agent considered and used was amine-based solvent.

1017 In their previous study, an organometal-based solvent called zinc (II) tetra-butyl-

of
1018 ammonium-bis-(4-methyl-phenyl-sulfonyl-di-thio-carbimate) (ZNIBU) was utilized

ro
1019 for vulcanization accelerators and the result showed that carcinogenic compound (i.e.

1020
-p
nitrosamines) was not produced. The devulcanization study concluded that ZNIBU
re
1021 can act as both vulcanizing and devulcanizing agents during the treatment. However,
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1022 at a lower concentration of ZNIBU but high operating temperature, the polymeric
na

1023 structure of rubber is rich in radicals that are ready to be attacked by the nitrogen

1024 group (i.e., radical scavenger). Hence, the reformation of crosslink is most likely to be
ur

1025 not possible. As such, soluble content proportionally increased. The study did not
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1026 report the soluble and devulcanization percentage, but physical properties were

1027 assessed. The paper concluded that tensile strength, torque and modulus of elasticity

1028 are higher in comparison with an initial sample, which makes it relevant to assume a

1029 high degree of devulcanization. This study was in agreement with Sutanto and co-

1030 workers’ work [124]. Additionally, Fukumori et al. [125] also reported and assumed

1031 that as sulfidic bond has a lower elastic constant, the chances of it being stretch by

1032 stress are higher and resulted in selective cleavage.

1033 SBR devulcanization was carried out by Rios et al. [126] in a controlled

1034 oxidation process with the help of 63% concentrated nitric acid at 110 oC. In the

52
1035 process, the strong oxidising agent (nitric acid) was reported to have dual functions:

1036 first, it acts as a devulcanizing reagent to oxidise sulphidic bonds to form hydrogen

1037 sulphide and second, it can functionalize the carbon in the polymeric network through

1038 the oxidation process as well, forming -COOH and -NO2 groups. However, these two

1039 roles compete against each other, and the risk of producing toxic NO2 gas is inevitable.

1040 Thaicharoen et al. [127] evaluated the influence of thio-salicylic acids, at 1 phr, in

1041 devulcanizing NR vulcanizates at 140 oC for 30 mins as a substitute towards diphenyl

1042 disulphide. Devulcanizates were then blended with virgin NR at variable ratios.

of
1043 Although at devulcanizate content of 5-15%, tensile strength decreased by 5-10%,

ro
1044 elongation at break was increased by about 5-15%. Franco et al. [128] proposed a

1045
-p
thermomechanical devulcanization study through the utilisation of alkali metal salts
re
1046 (e.g., LiCl-KCl), HNO3 with and without KOH. The variation in reagents combination
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1047 and temperature of treatment was investigated.The authors found that 400 oC was the
na

1048 optimum operating condition, with evident chemical composition changes within

1049 GTR devulcanizates through X-ray diffraction analysis. Formation of metal sulphides
ur

1050 and/or varying sulphur compounds were observed. This process was also called
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1051 demineralisation, whereby combinations of the aforementioned reactants (effectively

1052 when GTR treated with LiCl-KCl-KOH first, then by HNO3), resulting in the cleaved

1053 crosslink to be anionic and it attracted high-affinity cations such as zinc and iron.

1054 Furthermore, the presence of KOH, at the same time, would oxidise some of the

1055 anionic sulphur. Rooj et al. [129] studied the impact of benzoyl peroxide (BPO), as

1056 the devulcanizing agent for NR vulcanizates in two different treatments, chemically

1057 and mechanochemically. The effect of treatment time and concentration were also

1058 investigated. In chemical devulcanization, BPO-treated NR was found to have a lower

1059 volume fraction (Vr) than untreated NR, indicating that -Sx- and/or C-S bond was

53
1060 cleaved. This was also proved by the reduction of crosslink density and increase of

1061 percentage devulcanization, with the latter valued at not more than 50%. Such trends

1062 were also seen as heating time increased and analytically proven by FTIR-ATR,

1063 where primarily -Sx- peak intensity was reduced from the initial sample. At treatment

1064 temperature of 80 oC, it was reported that BPO would experience homolytic scission

1065 due to its symmetrical molecular structure, producing benzoate radical and eventually

1066 reduced to phenyl radical as shown in step 1 of Scheme 8. Phenyl radicals were highly

1067 unstable and transversely reacted with -Sx- bonds that caused sulphidic scission, as

of
1068 shown in step 2 of Scheme 8. Additionally, toxic SO2 could also be produced from

ro
1069 sulphur free radical oxidation in step 3 of Scheme 8. On the other hand,

1070
-p
mechanochemical treatment of NR vulcanizates in that study gave superior properties
re
1071 compared to initial NR vulcanizates as it was observed to act as filler upon
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1072 revulcanization. Additionally, concentration of BPO was found to be higher in

na

1073 chemical devulcanization compared to mechanochemical. This is as expected as the

1074 latter implements high-shear process. In a similar BPO-based chemical

ur

1075 devulcanization study by Temram et al. [130], degree of devulcanization was seen to
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1076 reach a constant value after 5 phr, indicating that increase in concentration has no

1077 further impact on devulcanization. Moreover, treatment between 80-150 oC did not

1078 result in any significant differences in the degree of devulcanization as well as

1079 crosslink density.

1080 Simple inorganic salts (e.g., CuSO4, ZnCl2, CdCl2 and Bi(NO3)3) and HNO3-

1081 assisted microwave devulcanization study of GTR was performed by Paolo et al.

1082 [131]. These salts were dissolved in 60 mL of water, incorporated in 25 g of GTR,

1083 dried at 100 oC for 4 hours and subjected to microwave (700W, 40 rpm for 2 mins).

1084 When these salts alone act as the devulcanizing agent, only Cd2+ favours reformation,

54
1085 while the other metal cations favour devulcanization to a small extend. However, the

1086 addition of HNO3 resulted in a significant increase towards the degree of

1087 devulcanization. The increase was expected due to the oxidation of -Sx- bond by

1088 HNO3 and promoted the penetration of the cationic salt into the crosslinked network.

1089 Zhang et al. [132] employed the utilization of subcritical fluids (e.g. water, ethanol, n-

1090 propanol) as devulcanizing agents in EPDM devulcanization using a twin-screw

1091 extruder. Two best devulcanizing agents were subcritical ethanol and n-propanol due

1092 to their ability to significantly reduce the gel content and increase the Mooney

of
1093 viscosity of the EPDM devulcanizates. Gas permeation chromatography was also

ro
1094 conducted and results show that these subcritical fluids enhanced chemical

1095
-p
distribution on EPDM in a uniform manner. Hence, homogeneity was easier to be
re
1096 achieved. This is expected due to the high entropy of these substances, which in turn
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1097 increases the surface contact area. In addition, 1H-NMR was conducted on the soluble
na

1098 part of the devulcanizates. Surprisingly, α-H content in subcritical ethanol was high,

1099 pointing to the excellent swelling and penetrating properties. Further parametric
ur

1100 analysis, in subcritical ethanol condition, shows that optimum operating condition was
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1101 at 180 oC, 2 MPa and 500 rpm. Similar results were also obtained by Li et al. [133] in

1102 devulcanizing butadiene rubber. However, authors further fitted their data into Horikx

1103 relation, showing lower temperature (210-250 oC) favoured reclamation, while higher

1104 temperature (260-270 oC) favoured polymeric scission.

55
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1105

1106 Scheme 8. Benzoyl peroxide mechanism in devulcanization of NR vulcanizates

1107 Contrary to the earlier reports, Song et al. [62] utilized vegetable (soybean) oil

1108 as a devulcanizing agent as well as a green plasticiser, to thermally devulcanized GTR

1109 at 150 oC, as it easily enables swelling phenomena of GTR, which could increase the

1110 sulphidic scissions. Preparation was simple, as GTR and soybean oil (SBO) only

1111 needed to be mixed at different ratios and subjected to 150 oC heating for 4 hours.

1112 Evolution with respect to the increase of soluble content as SBO concentration

56
1113 increase was evident due to its swelling activity and contribution toward

1114 heterogeneous oxidative cleavage. Horikx theory proved that all of the samples

1115 experienced polymeric cleavage, and a significant reduction in molecular weight also

1116 proved this phenomenon. Thereby, due to such a high degradative effect, carbon black

1117 and bound rubber present in its soluble fraction could provide an excellent reinforcing

1118 effect in SBR solution. The bound rubber is a product of grafting phenomenon of

1119 SBO and degraded rubber. Its simple illustration is provided in Fig. 16 [134]. In a

1120 similar study through the utilisation of SBO, Xie et al. [135] reported that 70.7%

of
1121 achievement of the soluble fraction was possible and during the process, oxidative

ro
1122 cleavage, crosslink scission and reformation happen simultaneously. Pegollo et al. [35]

1123
-p
further researched the potential of SBO, specifically oxidized SBO, in
re
1124 mechanochemical devulcanization of sulphur-cured NR by 22 full factorials.
lP

1125 Devulcanization time and concentration of oxidized SBO were the input parameters.
na

1126 Surprisingly, decrement of crosslink density by 71.1% and increment of soluble

1127 content by 228.2% could be achieved at lower treatment time (20 mins) and oxidized
ur

1128 SBO concentration (6 phr). Hence, the feasibility of using oxidized SBO for
Jo

1129 devulcanization was proven to be possible. However, further study on bond cleavage

1130 and mechanical properties could add further value to this initial study.

1131

1132

1133 Figure 16. Bound rubber; grafting of soybean oil with degraded GTR [134]

57
1134 In the earlier microwave treatment, IL has been proven to be able to assist the

1135 devulcanization study. In addition to that, Stowe [136] patented the utilisation of IL to

1136 treat GTR at 330 oC. The article described how IL enabled GTR to be soluble. In the

1137 same year, Ferraz et al. [137] used Grubbs catalyst along with

1138 trihexyl(tetradecyl)phos- phonium chloride and N,N-dioctylimidaolium bromide IL

1139 for NR depolymerisation process. The authors conducted the experiment at a low

1140 temperature (30-50oC) and with a generous amount of catalyst. The objective of using

1141 IL in their study was to prevent ruthenium contamination while promoting yield

of
1142 percentage. They reported a yield of 95 to 99% could be achieved. Besides, the used

ro
1143 IL can be recycled up to five times. A similar study was published by Mouawia et al.

1144
-p
in 2016 [138], whereby IL was described as a ring opener in metathetic
re
1145 polymerisation. As such, thermal and chemical stability allowed better and
lP

1146 homogeneous catalyst distribution. However, IL is known to be toxic, expensive, non-

na

1147 practical, etc. as described earlier [139], substitution with DES approach was made by

1148 Walvekar et al. [140] and further continued by Saputra [141], as described earlier in
ur

1149 ultrasonic devulcanization section. Joseph et al. [50], utilised 4-hydroxy tempo (4HT)
Jo

1150 to assist stable free radical mechanical devulcanization of NR/BR vulcanized blend. It

1151 was found that 4HT is a satisfactory devulcanizing agent showing a high degree of

1152 devulcanization (≤61.6%) with the quickest time and satisfactory revulcanizates’

1153 properties. 4HT was then utilized to devulcanized GTR and the resultant mechanical

1154 properties of its revulcanizates were proven to be better for NR/BR blend

1155 revulcanizates, but lower compared to fresh pre-cured tire tread (it was expected due

1156 to ageing of GTR).

1157 With respect to chemical devulcanization review, it is seen that for various types

1158 of chemicals, the percentage of devulcanization can be positively leveraged instead of

58
1159 treatment that solely was performed by physical processes. Additionally, different

1160 chemicals can favour different types of crosslink cleavages, as shown in Table 3. But

1161 the issue identified is that some of the processes or chemicals used were proven to be

1162 not economical for the industrial process, as a huge volume of the vessel is required

1163 and not to mention the level of toxicity and hazard these reagents possess [123]. The

1164 effect of some chemical used is reported in Table 4. As such, greener and more

1165 sustainable chemicals/methods are highly favoured, such as using IL and DES, that

1166 are currently being explored.

of
ro
1167 Table 3. Some devulcanizing agent with the type of crosslink cleavage [49]

Bond
broken
-p
Mono- Di- Poly-
re
sulphide sulphide sulphide
Agents
lP

Dithiothreitol

Hexane-1-thiol
na

Lithium aluminium hydride

ur

Methyl Iodide
Jo

Phenyl lithium in benzene

Sodium di-n-butyl phosphite

Tri-phenyl phosphine

1168

1169 Table 4. Chemical devulcanizing agent and their effects

Devulcanizing Agent Category Effect Reference

Alkyl phenol sulphide Organic Toxic & carcinogenic [142]

DBTS Organic Toxic & carcinogenic [49]

Organic/ Biodegradable, tuneable and
DES [141]
inorganic green

59
 HDA Organic Expensive, biodegradable [106]
Organic/ Tuneable, non-biodegradable,
IL [76]
inorganic toxic
Supercritical CO2 + Oxides + High power output, toxic &
[114]
diphenyl disulphide organic carcinogenic
Can be economical & safe,
Supercritical fluids Organic [132]
but VOC threat
TBAC Organic Biodegradable [110]

TMTD Organic Toxic & carcinogenic [42]

ZNIBU Inorganic Green and safe [123]

of
1170 4.3 Devulcanization by Bioremediation

ro
1171 -p
These type of devulcanization methods in the industry are considered in the
re
1172 emergence stage (or lesser preferred) because, in 1 month and 10 days, the amount of
lP

1173 sulphur that can be removed is maximum 4.7% [49]. The removal process is done

1174 through the help of chemo-lithotrophic microorganisms – sulphur oxidizing bacteria

na

1175 (i.e. Narcadia and Thiobacillus) or fungi in aqueous suspension that oxidizes the
ur

1176 sulphur in the cured network, which has the percentage of sulphur of 1.6%, into
Jo

1177 sulphate, sulphuric acid or others [46]. The typical flowchart for devulcanization by

1178 bioremediation is shown in Fig. 17.

1179

1180

60
1181 Figure 17. Typical microbial-based devulcanization setup

1182 Fungal detoxification method of devulcanization was studied by Bredburg et al.

1183 [143] whereby the authors used three aromatic degrading white-rot fungi (i.e.,

1184 Pleurotus.sajor-caju, Trametes Versicolor and Recinicum bicolour) as they have

1185 similar aromatic structure, to degrade a specific polymer called Poly-R478. The study

1186 showed that these white-rot funguses managed to bio-degrade such polymer where R.

1187 bicolour being the one that has the highest efficiency as its growth rate on the rubber

of
1188 increased proportionally with the oxidation rate of sulphur in the rubber matrix. The

ro
1189 results are in agreement with biotransformation study conducted by Vorlop et al.

1190 -p
[144]. Another type of detoxification is through bacteria reported by Haroune et al.
re
1191 [145]. They used Rhodococcus bacteria to degrade mercapto-benzo-thiazole (MBT)
lP

1192 that exists in rubber structure or road dust and is a hazardous chemical that causes

1193 bladder cancer and dermatoses as reported by Ruze et al. [146] and Whittaker et al.
na

1194 [147]. The MBT in rubber structure was metabolized by this bacterium, making tire
ur

1195 disposal to be safer for the environment but does not solve the sustainability issue (i.e.
Jo

1196 landfill).

1197 Anaerobic devulcanization by bacteria as an effort to devulcanize rubber tire is

1198 another alternative method studied through the usage of sulphur-reducing bacteria

1199 (archaeon) called Pyrococcus furiosus [148]. Such archaeon is a thermophilic

1200 heterotroph – absorbs and lives in high-temperature environment and growth rate is

1201 controlled by self-produced hydrogen which can be stopped by sulphur to produce

1202 hydrogen sulphide. P. furiosus is a type of bacteria that cannot live in the presence of

1203 zinc salt and benzothiazole, which exist in a rubber tire. Hence, prior leaching of

1204 rubber with solvent (i.e., ethanol) and culturing the bacterium into the process is

1205 necessary. However study by Bredburg et al. [149] showed that after treatment, there

61
1206 are various changes in rubber’s properties, including structural changes and flexibility

1207 reduction, although revulcanization occurred effectively. Watcharakul et al. [150], in

1208 their biodegradation of polyisoprene through the utilisation of Rhodococcus strain

1209 RPK1, concluded that oxidative cleavage reaction was experienced by polyisoprene

1210 backbone due to extracellular rubber oxygenase activity promoted by this gram-

1211 negative bacteria strain. Gram-negative bacteria is defined as a bacteria that has a

1212 thick lipid layer with thin to no peptidoglycan layer. The study was performed in a

1213 mineral salt medium for 2 weeks at 30 oC. The study was in agreement with Sharma et

of
1214 al. [151] and Jendrossek et al. [152] in their bio-devulcanization study using other

ro
1215 different gram-negative bacteria strains (e.g. Steroidobacter cummioxidans sp. and

1216
-p
Xanthomonas sp. respectively). The authors also emphasize that oxygenation
re
1217 occurrence which cleaved polymeric backbone was identified to form a low molecular
lP

1218 weight oligoisoprenoids that consist of terminal -CHO and -COCH3.

na

1219 Ghavipanjeh et al. [153] performed a bacterial-based devulcanization study

1220 using eleven different strains of bacteria. The list of bacteria used in this study is
ur

1221 listed in Table 5. The authors treated GTR in a mineral medium and devulcanization
Jo

1222 was quantitatively determined by increasing the sulphate of the bacterial medium and

1223 decrement on GTR’s sulphur. The Taiguchi statistical optimization approach analysed

1224 factors that were incubation time (10 and 20 days) and percentage of GTR (0.5 and 5

1225 w/v%) in the bacterial medium. As expected, the process is slow, and no result or

1226 changes could be observed in 10 days. However, after 20 days, sulphur content was

1227 found to decrease in a range between 6-21% with respect to the sample with 0.5%

1228 GTR. On the other hand, samples with 5% GTR experience a reduction in sulphur

1229 content by 15 and 27% for PTCC 164 and DSMZ 583, respectively. Hence, DSMZ

1230 583 was the best bacteria selected for further 11-factor optimization study. Their

62
1231 statistical results show that the amount and particle size of GTR were the two most

1232 important parameters.

1233 Table 5. Eleven strains of bacteria in bioremediation by Ghavipanjeh et al. [153]

Name of bacteria Classification German bank collection code

Acidothiobacillus ferrooxidans Thiobacillus DSMZ 14882
Thiobacillus ferrooxidans Thiobacillus DSMZ 583
Gordonia westfalica Gordonia DSMZ 44215
Gordonia polyisopreniyorans Gordonia DSMZ 44302
Gordonia polyisoprenivorans Gordonia DSMZ 44266

of
Gordonia alkanivorans Gordonia DSMZ 44369

ro
Nocardia sp. Nocardia DSMZ 43572
Nocardia sp. Nocardia DSMZ 46002
Amycolaptopsis sulphurea -p
Amycolaptopsis DSMZ 46092
Pseudomonas putida Pseudomonas DSMZ 291
re
Acidithiobacillus ferrooxidans Thiobacillus PTCC 1647
lP

1234 Kaewpetch et al. [154] utilized gram-positive bacteria, Bacillus cerus TISTR
na

1235 2651 as a bio-devulcanizing agent to treat CV, SEV and EV vulcanized NR.
ur

1236 Devulcanization was carried out in 2 steps. First, 10 g of vulcanized NR was soaked

in 100 ml of 75 v/v% ethanol for 24 hours to disinfect possible bacteria existing on

Jo

1237

1238 the rubber. Upon completion of the disinfecting process, the rubber was dried. In the

1239 second step, 2.5 g of vulcanized NR was added into 100 ml of the cultured medium

1240 that consisted of 24-hour cultured Bacillus cerus TISTR 2651. The incubation period

1241 lasted for 20 days and at 30 oC as earlier described by Ghavipanjeh et al. [153]. It was

1242 found that this particular treatment works best to devulcanize CV-cured NR with

1243 maximum sulphur removal percentage of 26.44%. The repetition of this experiment

1244 was conducted with GTR, and surprisingly after 20 days, 27.98% of sulphur content

1245 removal was achieved. FTIR-ATR spectra illustrated the formation of S=O bond,

1246 which indicates the oxygenase process happened due to crosslink cleavage. The

63
1247 observation is in agreement with their X-ray photoelectron spectroscopy analysis. In

1248 further reaction, some sulphurs that are present in the cross-linkages would be

1249 released as SO4-2 anions. Such is the 4S pathway reaction, illustrated in Fig. 18.

1250 Additionally, the decrease in molecular weight was also evident and served as an

1251 indication of heterogeneous cleavage, which was also seen in Horikx curve fitting.

of
ro
-p
re
lP
na

1252
ur

1253 Figure 18. Oxygenase and desulfinase mechanism in microbial devulcanization

Jo

1254 In a different study, Gordonia desulfuricans DSM 44462 and Rhodococcus sp.

1255 AF21875 were used by V. Tatangelo et al. [32] in microbial devulcanization study of

1256 GTR. Two bioreactors at 1.5 L were used to treat 150 g of GTR with a mineral salt

1257 medium at 30 oC for 1 day. The analysis was performed through the utilisation of

1258 automated ribosomal intergenic spacer analysis (ARISA). The GTR treated with

1259 DSM44462 was found to be more effective in comparison with AF21875. This is

1260 because treatment with AF21875 gave a matching ARISA fragment structure

1261 compared to original GTR. Biodevulcanized GTR was compounded with NR at 10

1262 phr and revulcanized. Interestingly, the vulcanizates exhibited better mechanical as

64
1263 well as rheological properties than initial GTR. Furthermore, the revulcanizate’s

1264 properties were also comparable with the reference rubber compound, NR.

1265 Review in regards to the biological method of devulcanization indeed is very

1266 limited and laborious, not to mention that the devulcanizates’ performances are highly

1267 compromised due to the alteration of samples’ composition and structural (and

1268 functional) rearrangement. Although anaerobic treatment by archaeon is preferable

1269 compared to fungal detoxification, as the rubber with the bacteria are left to be

1270 cultured in a closed chamber, further improvement and investigation are required.

of
ro
1271 5.0 Discussion

1272
-p
The various devulcanization techniques reviewed in this paper have been
re
1273 selectively compiled and presented in Table 6. The table is generated to provide easy
lP

1274 and direct comparisons between such vast devulcanization techniques reported in the
na

1275 literature, along with their respective devulcanizing agent, rubber type, treatment

1276 parameters, (re)vulcanizates and devulcanizates properties.

ur

1277 The very first devulcanization technique introduced was thermal

Jo

1278 devulcanization process. Despite that the method is simple, selective cleavage over

1279 sulphidic bonds is highly limited due to the uncontrollable reaction as reviewed in the

1280 past by Abraham et al. [48]. In the next stage, the combination of thermal with

1281 mechanical treatment, thermomechanical, in devulcanization process seemed to

1282 enhance the degree of devulcanization. Treatment is typically conducted in a two-roll

1283 mill, Brabender internal mixer or screw extruder, the latter being the most studied

1284 recently [33]. Generally, mechanical-based treatment is favoured as all of the

1285 instrumental needs have been provided within the industrial vicinities, especially in

1286 rubber processing industries. Furthermore, parameters that affect thermomechanical

65
1287 devulcanization are typically the screw speed, temperature, and processing time as

1288 could be seen in Table 6 [43]. However, the downside of such treatment is the high

1289 possibility of H2S, SO2 and CS2 toxic gaseous emission being released as reported by

1290 Mouri et al. [60]. These gasses are respectively produced from the hydrogenation of

1291 free sulphur, oxidation and desulfinase of carbon. Thermomechanical treatment

1292 generally resulted in a drop in mechanical properties [50] with the degree of

1293 devulcanization not more than 50% [51].

of
ro
-p
re
lP
na
ur
Jo

66
 Table 6. Comparison between selected devulcanization processes

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
P= 15 bar
Thermal GTR Steam T= 180 oC N/A N/A N/A [48]
t= 4-12 h
Ts= 25.4±0.57 MPa Ts= 11±0.52 MPa

f
oo
T= 40 oC Eb= 547±28.8% Eb= 310±20.4%
Thermomechanical NR None FR= 1:1.25 ML= 1.5 dNm %D= 20 -38% ML= 4.5 dNm [50]

pr
70 rpm MH= 18.9 dNm MH= 14.8 dNm
CD= 0.97x10-4 mol/cm3 CD= 0.77x10-4 mol/cm3

e-
Ts= 2.3 MPa

Pr
T= Ambient Eb= 70.1 % Ts= 10.9 MPa
%D= 42.6%
Thermomechanical GTR None t= 25-40 s H= 75 Eb= 289.4 % [51]
S= 12-25%

al
30 rpm CD= 0.7x10-3 mol/cm3 H= 61

rn
S= 9.5%
Ts= 14.8 MPa Ts= 14 MPa
u T= 220-280
Eb= 325% %D= 60-88% Eb= 450%
Jo
o
Thermomechanical GTR None C [54]
H= 63 S= 27-44.7% H= 70
30-120rpm
CD= 1.6x10-4 mol/cm3 CD= 6.98x10-4 mol/cm3
T= 100-300 Ts= 6.7 MPa
o Ts= 9.2 MPa
Thermomechanical NR None C Eb= 319% S= 22-56% [57]
Eb= 469%
100-400 rpm S= 15%
Ts= 16.1 MPa Ts= 15.5 MPa
T= 220-340
o Eb= 354% %D= 48-86% Eb= 334%
Thermomechanical EPDM None C [59]
H= 67 S= 5-43% H= 65
60-140 rpm
CD= 4x10-4 mol/cm3 CD= 5x10-4 mol/cm3

67
 Table 6. Comparison between selected devulcanization processes (continued)

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
T= 220-270 oC
Thermomechanical GTR None S= 11.08% S= 6-20% N/A [61]
150-550 rpm
T= 25-78 oC
%D= 42-55%
Thermomechanical EPDM None t= 30-60 s CD= 6.2x10-5 mol/cm3 N/A [68]

f
S= 48-50%

oo
20 rpm
T= 140-180 oC CD= 0.25x10-3 mol/cm3 %D= ~52%

pr
Thermomechanical GTR None N/A [71]
t= 2-24 h S= 6% S= 37-64%

e-
Pw= 820W
CD= 12.4x10-5 mol/cm3 %D= 0.1-14%
Microwave GTR None t= 1-5.5 min N/A [63]

Pr
S= 12.2% S= 12-26.2%
100 rpm
Pw= 656 W Mv= 30 MU

al
%D= 10-50%
Microwave SBR IL t= 30-120 s CD= 3x10-4 mol/cm3 Mv= 56-76 MU [76]
S= 18.2-28%

rn
40 rpm S= 18%
Pw= 820 W
Microwave GTR None u t= 3-17 min S= 14% S= 16-31% N/A [79]
Jo
100 rpm
CBS, HDA, Ts= 3.7 MPa
Pw= 900 W -4 3
MBT(S) & CD= 1.9x10 mol/cm %D= 72-94% Eb= 210.6%
Microwave EPDM T= 200-260 oC [80]
TMTD in S= 0.5% S= 2.8 – 13.6% H= 79.1
t= 3 min
aromatic oil CD= 1x10-3 mol/cm3
CBS, HDA, Ts= 19 MPa
DPDS & Pw= 900 W Eb= 540% Ts= 10 MPa
%D= 3-73%
Microwave GTR MBTS in T= 180-240 oC H= 68 Eb= 226% [81]
S= 10-23%
aromatic & t= 3 min CD= 1.9x10-4 mol/cm3 H= 62
paraffinic oil S= 7.5%

68
 Table 6. Comparison between selected devulcanization processes (continued)

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
Ts= 2.2 MPa
Pw= 900 W Ts= 4.3 MPa
Eb= 50%
T= 45-80 oC Eb= 350%
Microwave SBR None ML= 4.9 dNm S= 10-68% [83]
t= 1-3 min ML= 7.4 dNm
MH= 24.5 dNm

f
40 rpm MH= 26.4 dNm

oo
S= 7%
Ts= 22 MPa

pr
Pw= 650 W Ts= 18 MPa
Eb= 355%
Microwave GTR None T= 150-250 oC S= 22-24.5% Eb= 425% [84]

e-
H= 70.3
t= 9-30 min H= 69.9
S= 7-10%

Pr
Ts= 26.1 MPa Ts= 16.4 MPa
Pw= 700 W Eb= 854% Eb= 728%

al
Microwave NR None t= 3-10 min H= 49 N/A H= 48 [85]
CD= 1.3x10-4 mol/cm3 CD= 1.16x10-4 mol/cm3

rn
80 rpm
S= 3.1% S= 5.9%
u A= 10-15 μm
Jo
CD= 1.25x10-4
F= 20 kHz %D= 12-65%
Ultrasonic SBR None mol/cm3 N/A [89]
T= 120 oC S= 14-40%
S= 4%
t= 5-40 s
A= 5-13 μm
F= 40 kHz CD= 1.9x10-4 mol.cm3 %D= ± 89% CD= 1.5x10-4 mol.cm3
Ultrasonic GTR None [95]
T= 150-250 oC S= 18.25% S= 42.5-67.5% S= 20-22.5%
t= 5-40 s
A= 1-12 μm Ts= 6.39 MPa
Ultrasonic GTR None F=40 kHz N/A N/A Eb= 183% [97]
T= 130-210 oC CD= 2.3x10-4 mol/cm3

69
 Table 6. Comparison between selected devulcanization processes (continued)

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
Ts= 1.5 MPa Ts= 2.23 MPa
A= 3.5-10 μm
Eb= 310% Eb= 318%
Ultrasonic Star SBR None F= 20 kHz N/A [98]
CD= 1.3x10-4 mol/cm3 CD= 1.3x10-4 mol/cm3
T= 120 oC

f
S= 1.3% S= 1.5-5.5%

oo
F= 37 kHz

pr
T= 180 oC
Ammonium CD = 1.5x10-2 mol/cm3 %D= 93-97%
Ultrasonic GTR tH= 5-30 min N/A [28]

e-
DES S= 2% S= 3.2-8.1%
ts= 60 min

Pr
300 rpm
F= 37-80 kHz

al
T= 30-200 oC
Ammonium CD = 3.2x10-4 mol/cm3 %D= 42-72%

rn
Ultrasonic GTR tH= 5-60 min N/A [141]
TDES S= 1.8 % S= 2.6 %
ts= 10-60 min
u 300 rpm
Jo
T= 150-220 oC
%D= 35-93%
Mechanochemical GTR DPDS t= 10 min N/A N/A [55]
S= 3-41%
30 rpm
Ts= 4.74 MPa Ts= 9.19 MPa
o Eb= 465.29% Eb= 248.41%
T= 70 C
H= 58 H= 76.5
Mechanochemical NR TESPT FR= 1:1.25 N/A [64]
ML= 0.05 dNm ML= 0.116 dNm
t= 20-60 min
MH=0.51 dNm MH= 1.62 dNm
CD= 0.7x10-3mol/cm3 CD= 0.84x10-3mol/cm3

70
 Table 6. Comparison between selected devulcanization processes (continued)

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
Ts= 12 MPa Ts= 11.8 MPa
o
T= 225-275 C Eb= 950% Eb= 850%
%D= 46-59%
Mechanochemical EPDM HDA t= 7.5 min H= 58 H= 57 [106]
S= 27.5-40%
75 rpm CD= 2.4x10-4 mol/cm3 CD= 2.25x10-4 mol/cm3

f
oo
S= 25% S= 25.5%
DPDS and P= 4-15 MPa Ts= 1.7 MPa Ts= 6.8 MPa

pr
Mechanochemical BR Supercritical T= 140-190 oC Eb= 400% S= 12-98.5% Eb= 1010% [115]

e-
CO2 t= 0-240 min H= 34 H= 29
Supercritical T= 100-180 oC CD= 10.6x10-4mol/cm3 %D= 87-89% Ts= 11.4 MPa

Pr
Mechanochemical GTR [119]
CO2 300-600 rpm S= 5.8% S= 10.6-22.3 Eb= 225%
24 hr soaking
Ts= 9.55 MPa

al
T= 65-70 oC CD= 1.11x10-3mol/cm3 %D= 3.6-16%
Mechanochemical SBR TESPT Eb= 120.55% [120]

rn
FR= 1:1.25 S= 4.003% S= 9-30%
H= 91
t= 20-60 min
Thio-bis- u
T= 180-200 oC
Jo
Ts= 6.7 MPa
Mechanochemical GTR phenol in t= 10 min N/A S= 15-19% [122]
Eb= 350%
aromatic oil 45 rpm
FR= 1:1.33 Ts= 1.4 MPa Ts= 4.6 MPa
Mechanochemical SBR ZNIBU T= 50-60 oC Eb= 116.9% N/A Eb= 79.6% [123]
24-32 rpm H= 48 H= 70
Subcritical T= 160-200 oC Ts= 15.91 MPa Ts= 14.6 MPa
Mechanochemical IIR S= 60- 75% [132]
fluids 200-600 rpm Eb= 483.62% Eb= 515%
T= 200-260 oC
Supercritical %D= 42-72%
Mechanochemical GTR P= 8-12 MPa N/A N/A [133]
ethanol S= 3.5-36.6%
t= 30-120 min

71
 Table 6. Comparison between selected devulcanization processes (continued)

Devulcanizing Parametric Vulcanizates Devulcanizates Best revulcanizate’s

Technique Vulcanizate Ref.
agent conditions properties properties properties
Ts= 8.4 MPa Ts= 17.8 MPa
o
T= 150 C Eb= 592% Eb= 592%
Thermochemical GTR SBO S= 77.8% [134]
t= 4 hr ML= 2.7 dNm ML= 5.5 dNm
MH= 13.4 dNm MH= 31 dNm

f
oo
T= 130-160 oC CD= 8x10-3mol/cm3 %D= 88-95%
Thermochemical BR SBO N/A [135]
t= 0.5-7 h S= 8% S= 20-70.7%

pr
T= 30 oC GTR/NR blend

e-
Gordonia sp. and t= 24 h Ts= 27 MPa
Bioremediation GTR S= 2.3% S= 2.9-3.3% [32]
Rhodococcus sp. pH= 7 Eb= 465%

Pr
500 rpm CD= 1.28x10-4 mol/cm3
T= 30 oC

al
11 strains of t= 10-30 days
Bioremediation GTR ST= 1.65-1.77% ST= 1.2-1.67% N/A [153]

rn
bacteria pH= 1.4
140-200 rpm
u CD= 1.17x10-
Jo
T= 30±2 oC 4 %D= 69.2%
mol/cm3
Bioremediation NR Bacillus cereus t= 20 days S= 18.32% N/A [154]
S= 2.09%
150 rpm ST= 0.1-0.27%
ST= 1.08-2.76%

Legend:

%D = Degree of devulcanization FR = Friction ratio Pw = Power t = Time

A = Amplitude MH = Maximum torque S = Soluble content tH = Heating time
CD = Crosslink density ML = Minimum torque ST = Total sulphur ts = Sonication time
Eb = Elongation at break Mv = Mooney viscosity T = Temperature
F = Frequency P = Pressure Ts = Tensile strength

72
1295 In some studies, the thermomechanical procedure was found to slightly increase

1296 [54] and decrease [59] the mechanical and tensile properties of revulcanizates. The

1297 decrease was expected due to the incompatibility between virgin and reclaimed

1298 rubbers’ polymeric networks. At the same time, the increase was found due to the

1299 large content of virgin rubber compared to devulcanizates [57]. While

1300 thermomechanical was a significant step up, microwave and ultrasonic irradiation

1301 treatment were also explored. The earlier is considered a batch process where

1302 vulcanizates are rapidly introduced to the electromagnetic field of radiation, and it

of
1303 significantly lowered the treatment time. Colom et al. [85] employed this method to

ro
1304 conclude whereby tensile strength and elongation at break of the revulcanizates were

1305
-p
reduced by 37% and 15%, respectively. On the other hand, Zanchet reported an
re
1306 increase and decrease in tensile and elongation at break [83]. This was expected due
lP

1307 to the unequal distribution of heat during the microwave treatment, causing hot spots
na

1308 formation[81]. To equalize and homogenize the heat distribution, Seghar et al. [76]

1309 pre-treated their SBR vulcanizate through imbibition with IL. However, Garcia et al.
ur

1310 [77] reported the drawback of IL for being toxic, non-biodegradable and impractical
Jo

1311 for industrial usage. Hence, in another study by Saputra et al. [28], DESs, an IL

1312 analogous substitute, for the first time was used in ultrasonic devulcanization to

1313 provide a greener and more sustainable alternative. Specifically, amino-based DESs

1314 were used due to their high sulphur attractivity and the role of α-H [103]. In general,

1315 ultrasonic treatment utilizes the knowledge of sonochemistry whereby sonocavitation

1316 bubbles could be produced to cleave and/or loosen bonds present in rubber network.

1317 In addition, it can be done in both batch and continuous processes [141], as well as

1318 lower temperatures, compared to that in the mechanical process [43]. Liang et al. [98]

1319 performed their devulcanization study on star SBR and concluded an increase in

73
1320 mechanical properties, while Mangili et al. [97] reported the increase in tensile

1321 properties with no significant change in elongation at break. On the other hand, Isayev

1322 et al. [95] reported the degree of devulcanization for ultrasonic could potentially reach

1323 up to 90%.

1324 The chemical devulcanizing agents also have further improved the

1325 devulcanization process as well as revulcanizates properties. Their implementation

1326 can be done easily with the help of any of the physical processes. For instance, Seghar

1327 et al. [76] reported the increase in the degree of devulcanization when GTR was pre-

of
1328 treated with ionic liquid before subjecting it to microwave treatment, compared to

ro
1329 pure microwave treatment. Similarly, Ghorai et al. [64] reported the increase in

1330
-p
tensile strength of revulcanizates from NR vulcanizates by 93.88% through TESPT
re
1331 imbibition. This is suspected to be a good indication of the selective and controlled
lP

1332 devulcanization process, with limited polymeric chain degradation that depletes the
na

1333 mechanical and tensile properties. EPDM devulcanization study through the

1334 utilisation of HDA by Dukhuis et al. [106], has also proven to act similarly as tensile
ur

1335 strength and elongation at break reduction is only by 1.67 and 10.5% respectively.
Jo

1336 The study provides a possible alternative devulcanizing agent to the commonly used

1337 disulphide-based agents that are toxic, health hazard and giving off sulphur specific

1338 odour [43], despite many devulcanizing agents revolves around such type type [55,

1339 122]. Supercritical fluid (e.g., CO2, ethanol, water) injection has also been utilized as

1340 an alternative to these disulphides. The advantages of switching to supercritical fluids

1341 are promoting a safer working and natural environment [121] and their high solvating

1342 and swelling capabilities that allow deep solvent penetration onto the sulphidic bonds

1343 [132]. In terms of properties, both Jiang et al. [115] and Paulo [132] reported an

1344 increase in tensile and elongation at the break by 5.1 MPa and 600% and 1.31 MPa

74
1345 and 31.38%, respectively. In a similar sustainable manner, SBO was also employed

1346 by Hassan et al. [134] and Xie et al. [135] as a devulcanizing agent. Its potential was

1347 revealed by the enhancement of revulcanizates’ tensile properties and a high degree of

1348 devulcanization. Although such devulcanization processes provide good degrees of

1349 devulcanization, tensile and mechanical properties as well as being environmentally

1350 benign, the utilisation of microbes to assists devulcanization has not been overlooked.

1351 Bacteria that are mostly used are those from the Rhodococcus, Gordonia [32],

1352 Norcania and Thiobacillus [153] species due to their sulphur affinity. However, the

of
1353 limitation of complex sample preparation, the need for a clean and hygienic

ro
1354 environment as well as an extremely slow process (up to months) are the major

1355
-p
drawbacks of this technique, especially in the industrial setting, despite their
re
1356 environmentally friendly characteristics.
lP

1357 6.0 Conclusion and recommendation

na

1358 With regard to the ever-increasing feedstock of tires along with WTR generated,
ur

1359 a proper valorization technique remains to be one of the most critical challenges that
Jo

1360 need to be globally addressed. The approach of downsizing WTR to GTR, up until

1361 this point, is still vastly used due to the easiness of the process. Such GTR can be

1362 applied to various products to produce rubberized asphalt, concrete, playground mat,

1363 tiles, shock resistance reinforcement in buildings, footwear, conveyor belt and many

1364 more. However, considering that millions of tonnes of WTRs are generated and

1365 wasted annually, it would seem that such an approach is incredibly insufficient.

1366 Furthermore, landfilling and open burning have been strictly banned in many

1367 countries due to the toxic pollutions they generate.

75
1368 Recently, researchers and industries have taken a much more sustainable

1369 approach to treat these complex waste vulcanizates material, especially WTR and/or

1370 GTR, and turn them into reprocessed materials that possess the capability to be turned

1371 into high value-added products. This process is called devulcanization and can be

1372 carried out through thermal, mechanical, chemical, microwave, ultrasonic, and

1373 combinations. Among these methods, the combinations of these techniques have been

1374 proven to enhance the degree of devulcanization further. For instance,

1375 mechanochemical is far more superior to chemical or mechanical treatment alone.

of
1376 Mechanical-based devulcanization was seen to be the most favourable in industrial

ro
1377 processes as it utilizes the readily available equipment. Furthermore, addition to

1378
-p
environmentally friendly supercritical CO2 in the process promotes equivalent
re
1379 swelling as well as the degree of devulcanization. In terms of chemical-based
lP

1380 devulcanization, disulphide-based chemicals have been proven to be more effective

na

1381 than mechanical processes in carrying out the objected task. However, their toxicity

1382 and non-sustainable characteristics are some of the major drawbacks. To tackle that,
ur

1383 more environmentally friendly devulcanizing agents have emerged (e.g., IL, DES,
Jo

1384 amine, ammonium, etc.) and provide similar devulcanizates’ properties to that treated

1385 with diphenyl disulphide. Some even coupled various devulcanizing agents with

1386 microwave, ultrasonic or twin-extruders to further enhance the extent of

1387 devulcanization. Through such an approach, it is believed that a fraction of virgin

1388 natural as well as synthetical rubber can be used at a much lesser amount in the

1389 production line, as devulcanized waste materials replace it in the blend. Observation

1390 found that through the blending of this mixture and vulcanization, this particular

1391 blend vulcanizate exhibits acceptable mechanical and tensile properties, even at

1392 higher devulcanizate content in some study. Although the addition of a small fraction

76
1393 of graphene and its derivatives have been published in many papers to satisfactorily

1394 enhance virgin vulcanizates’ properties [155–157], its application with respect to

1395 blending with devulcanizates has not been comprehensively reported and strongly

1396 recommended to be studied. With such background, it is expected that the addition of

1397 a small percentage of graphene and/or its derivative in the revulcanization of

1398 devulcanizates would potentially increase the revulcanizate’s (or blend’s) mechanical

1399 and tensile properties.

of
1400 Acknowledgement

ro
1401 This work was supported by Taylor’s University through its TAYLOR’S PhD

1402 SCHOLARSHIP Programme.

-p
re
lP

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Highlights:

1. Waste vulcanizates disposal is a global sustainability and industrial challenge

2. Chemical, mechanical, microwave, ultrasonic are typical reclamation methods

3. Greener technologies promote value-added product generation from waste

4. Ultrasonic treatment with green devulcanizing agent enhances devulcanization efficiency

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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