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Journal of Thermal Analysis and Calorimetry

, Volume 133, Issue 1, pp 279–287 | Cite as

Behaviour of tyres in fire

Determination of burning characteristics of tyres
  • Zsuzsanna Kerekes
  • Éva Lublóy
  • Katalin Kopecskó
Article

Abstract

The increasing numbers of used tyres constitute a serious threat to the natural environment. The progress made in recent years in the management of polymer wastes has meant that used tyres are starting to be perceived as a potential source of valuable raw materials. The objective of this research was to study the burning characteristics of various used tyres. Waste tyres of seven producers have been tested. In order to understand thermal properties, three different assessment methods were used to study the behaviour of the material: (1) determination of ash content, (2) flame propagation test and (3) thermal analysis. The ash content test can be used to analyse how many percentage of the tyre leaves in the form of smoke or gas. The flame propagation test gives information on the duration of the combustion and the degree of smoke generation. Results of thermal analysis (TG/DTG/DTA) show the degree and speed of the mass changes of the different tyre types, the enthalpy change and the temperature of the reactions during heating. By combustion tests, it was modelled how the tyres behave when they are burning in incineration plant. In terms of recycling, those tyres are better, which have low decomposition temperature and smaller residual mass. This also means that maximum combustion heat can be recovered. After burning, the samples showed the greatest difference in loss of mass; however, all are different in flammability, afterglow time and their thermal stability.

Keywords

Thermal properties Thermal analysis Smoke generation Flame propagation of tyres Waste tyre 

Introduction

Environmental pollution is meant to include all changes that have an unfavourable impact on the health, survival and activities of humans and other living organisms. These changes are changes in the physical, chemical and biological properties of the soil, water and air. Not only physical damage should be considered in this context. Changes involving psychological or aesthetic damage are also defined as pollution [1].

As regards waste production, the tyre industry plays a decisive role. Developers have found a number of ways to recycle waste tyres; despite this, the annual quantity of discarded tyres is very high, and storage and recycling thereof is a problem. The tyres accumulated during the past years and formed ‘hills’; in addition to aesthetical pollution, deposits of tyres may cause huge environmental damage if they catch fire. During recent decades, such fires have indeed occurred in great numbers both in Hungary and in abroad. Therefore, the issue is unquestionably timely.

The objective of this research was to study the burning characteristics of various used tyres. In order to understand thermal properties, three different assessment methods were used to study the behaviour of the material: determination of ash content, flame propagation test and thermal analysis. By combustion tests, it was modelled how the tyres behave when they are burning in incineration plants. In terms of recycling, good tyres are with low decomposition temperatures and with smaller residual mass. This also means that maximum combustion heat can be recovered. Rubber fires are difficult to control and inhibit their industrial recycling because have a very long glow time, i.e. have a long solid-phase combustion. The slow process raises the cost of extinguishment or industrial firing. The ash content test can be used to analyse how many percentage of the tyres leaves in the form of smoke. The flame spread test gives information on the duration of the combustion and the degree of smoke generation. The complex thermal analysis shows the degree and speed of the mass changes of the different tyre types, the change in enthalpy and the temperature of the materials during heating.

The burning behaviour of tyres

The burning of tyres is an incomplete process. Harmful liquid, solid and gaseous combustion products are emitted into the atmosphere and soil during the process. During tyre fires, the following substances are emitted into the atmosphere: particulate matter, carbon monoxide, sulphur oxides, nitrogen oxides, volatile organic compounds, cyclic aromatic hydrocarbons, dioxins, furans, hydrogen chloride, benzene, polychlorinated biphenyls, arsenic, cadmium, nickel, zinc, mercury, chromium and vanadium. In case of fire, both short-term and long-term consequences should be considered due to the emitted materials [2]. Fire hazard could be experimentally determined by test results obtained from calorimetric measurements or flammability tests [3, 4]. However, in order to efficiently use the waste tyres for recycling purposes, their actual rubber composition needed to be determined [5].

The emissions during burning represent acute and chronic health hazards for firefighters and local inhabitants alike. The effects of the emitted substances on humans include skin irritation, mucosal and eye irritation, central nervous system injury and frequent development of various respiratory effects and cancerous diseases. The smoke contains large amounts of soot, which endangers the environment in the form of particulate matter. Wind can transport such hazardous substances over long distances, and this may lead to a situation in which neighbouring cities, states or countries may also be at risk besides the given city or country [6].

The resulting residues may form a dense, oily, lava-like material. Burning of one tyre produces approximately 2 L of oil residues. This is particularly dangerous in the vicinity of natural water bodies because oil residues spread on the surface when released into the water, and thereby shut off the oxygen supply of the aquatic flora and fauna. If infiltrated into the groundwater, they present direct and indirect risks to human health. The analysis of the oil revealed that it contains naphthalene, toluene, benzene, xylene, anthracene, aromatic hydrocarbons, sulphur compounds, caprolactam, benzothiazole, arsenic, cyanide, cadmium, chromium, nickel, zinc and other metals [7].

Tyre fires

The analysis of the causes and consequences of tyre fires worldwide may provide important experiences and may contribute to their future avoidability. In 1983, a company named Rhinehart (Virginia, US) used to recycle tyres and resell those that were still useable. Non-usable tyres were stored at the company site. By 1983, 7 million tyres were stockpiled up to a height of 80 feet over an area of 5 hectares at the site. The fire erupted in October 1983 and was burning for 9 months. The toxic smoke rose to a height of 4500 feet. The pollution affected four states. The residual dense oily substance was released into the creek running beside the site. The most frequent compounds among the pollutants included caprolactam, benzothiazole and other aromatic compounds. To protect the soil, firefighters built a remediation pool and the oil was later removed from this pool and carried away by trucks. By September 2000, the soil and the groundwater were declared clean but harmful substances were still detected in the neighbouring lakes and the creek itself. Remediation of the area took more than 20 years. The cause of fire was never clarified. Experts could only conclude that the pile might have been ignited by the prolonged impact of some open flame [7].

In 1984, stockpiled waste tyres were ignited next to the city of Everett. The fire was probably caused by some youngsters. The fire at the storage comprising more than 4 million tyres was extinguished after 9–10 months under controlled circumstances. Black soot deposited everywhere in the city. Debris removal and clean-up operations were still ongoing in 1993 [8, 9].

1989 Wales: The fire at the tyre storage was probably caused deliberately. About 10 million tyres were burning. This fire was burning for the longest time, that is, for more than 15 years. This type of burning is a flameless solid-phase burning, in other words, glowing. The precise date when the fire finally ceased is unknown. Continuous monitoring was carried out, and intensive heat emission was detected. In addition to heat emission, occasionally black smoke rose from the glowing pile of tyres [10].

1999 California: The tyre fire was caused by lightning. There were 7 million tyres at the 40-hectare storage site, and 5 million of them were burnt off. The resulting smoke rose to a height of approximately 3000 feet. Those intervening decided to let the fire burn down under surveillance. The tyres were burning for about 34 days. Authorities ordered inhabitants to shelter indoors. The generated pyrolytic oil was removed by tank trucks. The smoke also put the neighbouring agricultural areas at risk [11].

1999 Ohio: In 1999, four teenagers set an arson fire at a site of Kariby Tyre Recycling 5 million tyres caught fire and were burning for about a month. The dense black smoke could also be detected at a distance of 60 miles. The fire resulted in 56,000 L of oil. This oil flowed into a nearby river and resulted in the death of 20,000 fish. Remediation operations were still ongoing in 2006 [12].

2012 Kuwait: The largest tyre graveyard in the world is located in Kuwait. The fire was probably caused by people collecting waste metals. About 5 million tyres were burning for 3 days. The smoke was blown by the wind towards the sea. Despite this, authorities requested local inhabitants to stay away from the fire and to wear masks. The environmental effects of the fire are still being investigated [13].

In 2013, a tyre storage site caught fire near Boba, Hungary. About 10,000 tyres were stockpiled up to a height of 2–3 m over an area of 2 hectares. Emergency management services managed to extinguish the fire within 22 h. Official and voluntary firefighters were both involved in the operation. Follow-up works took a week to complete [14].

In January 2016, tyres caught fire at an industrial site in Melbourne. About 150,000 tyres were piled up at the site. The cause of fire is yet unknown. The flames were subdued after more than 36 h [15].

Upon studying the above fire events, the following conclusions were made. There may be three causes of fire: lightning, negligence and arson. One criterion of a deliberate criminal act is the perpetrator being aware of, desiring or reconciling to the consequences of his/her actions. The motivations behind causing a tyre fire may include revenge, anger, seeking political benefits or some psychological motives such as pyromania or a desire to be noticed. Inadvertent criminal acts include those when the perpetrator is unaware of the potential consequences or when he/she pursues his/her activities without due attention and care. For example, tyre ignition may be caused by the inappropriate use of open flames. Such activities include welding—be it arc welding or flame welding— or the use of illuminating tools operated with open flames. For example, storing a faulty accumulator or materials with a propensity to self-ignite, which would in turn ignite the waste tyres if burning, is also defined as inadvertent fire-setting. The harmful effect of lightning on tyres is a thermal effect given that tyres are flammable materials. Thus, ignition may also occur as a consequence of lightning.

Experimental

Thermal analysis

Thermal analysis is a useful method to characterise polymeric materials [16, 17]. In our experiments, thermoanalytical changes were followed by TG/DTG/DTA curves using simultaneous measuring instrument MOM Derivatograph-Q 1500 D. The first derivative of thermogravimetric curve (TG) was obtained by analogue mode (DTG). During the measurements, the reference material was alumina (Al2O3), and the mass of the samples was approx. 250–500 mg. The samples were heated at a rate of 10 °C/min up to ~ 1000 °C under air atmosphere. Before the investigations, the specimens were chopped and put into alumina crucibles. The thermoanalytical test results were evaluated by the Winder (Version 4.4.) software.

Flame propagation test

A frequently applied standard method to study horizontal flame propagation is burning in a horizontal combustion chamber [18]. During the test, ADL Atlas HMV equipment was used, where the sample is placed horizontally between the two U-shaped holders, and then exposed to a flame for 15 s. This test determines the time after which the flame is extinct if the sample becomes ignited, and the duration of the studied period is also measured. The dripping material is captured in a plate. The flame is generated with a Bunsen burner fed by a gas with a calorific value of about 38 MJ/m−3. The specimen is placed in the chamber with the side to be tested facing downwards. For testing horizontal flame propagation, samples with a size of 300 × 100 mm were prepared.

During vertical flame propagation testing, the sample is exposed to the flame in a vertical orientation. Specimens are fixed onto sample holder consoles. The gas supplied to the burner used during the testing may include propane or butane. The burner is placed in front of, and below, the specimen in a way that the burner is within the plane of the central axis of the specimen. The test is conducted at a temperature interval of 10–30 °C (during our tests the following conditions were measured: temperature: 9 °C; relative humidity: 70%; and air speed: 0.5 m s−1). The specimen is exposed to the igniting flame for 5 s. Ignition is considered successful if the self-sustaining burning continues for at least 5 s after the ignition. For testing vertical flame propagation, samples with a size of 30 × 10 cm were prepared.

Determination of ash content and combustion residues testing

Ash content determination is useful for measuring the percentage of the mass of tyres released as smoke, while flame propagation test indicates the duration of the burning process, and the thermal test helps to determine the rate and speed of mass changes of various types of tyres, the changes in enthalpy and the temperature of the materials during the thermal effect. The objective of the test is to determine the amount of residues remaining after burning the sample. The calculations involve the percentage of the mass of the samples released as smoke and volatile compounds, which is a good indicator of the level of air pollution. For ash content determination, samples with a mass of 4–5 g were used.

Test materials

During the tests, samples of tyres from seven different producers were tested. The tyres were produced between 1993 and 2009. The samples included winter tyres, summer tyres, and tyres for both personal cars and trucks. When selecting the samples, our objective was to cover an as wide use range as possible in terms of manufacturers, the year of manufacturing and type. The key properties of the tyres applied are listed in Table 1.
Table 1

Properties of the tyres examined

Name of tyre

BFGoodrich

Debica

Firestone

Hankook

Michelin

Roadstone

Semperit

Year of manufacturing

2009

2000

2006

2004

2006

2007

1993

Type

Summer

Summer

Summer

Summer

Summer

Winter

Summer

Experimental results

Results of the thermoanalytical tests

The materials comprised by tyres can be divided into two main groups, that is, synthetic polymeric rubber and additives. The ratio of polymers is around 50%, that is, their quantity is largely the same as that of the non-polymeric additives. Additives may then be subdivided into subgroups based on molecular size: small molecule additives and large molecule additives. Such detailed classification of the constituents of tyres is indispensable for analysing thermal characteristics on the basis of the thermoanalytical curves.

Thermal behaviour of the tyre samples may typically be divided into three larger stages by their DTG curves. These stages are shown in Fig. 1. The method of evaluating the thermoanalytical curves is described in case of the sample of Michelin tyre (Fig. 1). The transformations occurring during the first low-temperature stage were termed as ‘initial steps’. The first stage starts at about 27 °C and finishes at approximately 300 °C. For the Michelin sample, the initial steps start at 29.2 °C and finish at 241.6 °C.
Fig. 1

Thermoanalytical test results of the sample tyre Michelin

Additional features of the first phase are exothermic processes, and the parallel mass loss is insignificant in this stage. The Michelin sample only lost 3% of its mass during the first stage. The low-temperature range and the low mass loss indicate that volatile, that is, small molecule additives are released during the initial step.

The second stage is the ‘main step’. This range supplies the most important data regarding the energy generation applications of tyres. This stage is producing the greatest mass loss comparing with the mass losses during the first and the final stage. On average, 60% of the mass of the samples is lost. The main step starts at about 300 °C and finishes at about 500 °C. We concluded that in this stage the flame burning occurs, and this finding is also supported by the literature indicating that the ignition temperature of tyres is 300–350 °C [19, 20]. The DTA curve clearly shows that both exothermic and endothermic processes occur during the second stage (Fig. 1). As regards energy generation applications, tyres are better when the second stage starts earlier and is associated with greater mass loss. The values of the temperature ranges are summarised for each tyre separately in Table 2. The temperature intervals clearly demonstrate that the second stage is the shortest. Polymeric constituents are likely to be ‘released’ in this stage, which may also explain the great mass loss. Based on thermal properties, the Michelin tyre is considered good in terms of energy generation applications because the main stage starts already at 242 °C, and 60.44% of the mass of the sample was lost by the end of that stage.
Table 2

Mass losses of the different tyre samples associated with thermal steps

Samples

Mass losses of tyre samples associated with thermal steps/m% and the related thermal intervals

Initial thermal reactions

Main thermal reactions

High-temperature reactions

Debica

m1D = 5.04%

31.8–330.4 °C

m2D = 56.67%

332.3–503.7 °C

m3D = 38.06%

503.7–984.8 °C

Firestone

m1F = 2.69%

26.5–181.9 °C

m2F = 58.81%

330.7–491.8 °C

m3F = 32.22%

491.8–895.7 °C

Hankook

m1H = 4.58%

27.7–310 °C

m2H = 57.54%

316.4–493.2 °C

m3H = 24.87%

493.2–906.8 °C

Michelin

m1M = 3.04%

29.2–241.6 °C

m2M = 60.44%

290.4–487.5 °C

m3M = 35.65%

487.5–931.9 °C

Roadstone

m1R = 2.21%

30.4–250.6 °C

m2R = 54.60%

292.1–505.1 °C

m3R = 28.02%

505.1–987.3 °C

Semperit

m1S = 5.75%

32.1–327 °C

m2S = 51.93%

341.0–511.2 °C

m3S = 28.79%

511.2–989.8 °C

BFGoodrich

m1B = 5.44%

27.1–316.6 °C

m2B = 71.54%

316.6–495.4 °C

m3B = 30.92%

495.4–988.6 °C

The third stage was termed ‘high-temperature steps’. In this range, flameless solid-phase burning is likely to occur mostly. The third stage has the longest duration. Mass loss is continuous and even, and there are no characteristic temperature peaks. By the end of the 100-min test, four of the seven samples lost 100% of their mass. The mass losses associated with the different tyres and thermal steps are given in Table 2.

In the third stage, DTA curves may take two different courses (Fig. 2). In Sample Group A (Firestone, Michelin, Hankook and Debica), a last exothermic reaction is still clearly detectable in the third stage. In case of Sample Group B (Semperit, BFGoodrich and Roadstone), the third stage shows continuous exothermic reactions upon the temperature interval of the test (Fig. 2a, b).
Fig. 2

a DTA curves of the tyre samples (Sample Group A—Firestone, Michelin, Hankook and Debica). b DTA curves of the tyre samples (Sample Group B—Semperit, BFGoodrich and Roadstone)

Results of the flame propagation test

Specimens were cut from the lateral walls of the tyres. Given that steel threads are also present in the lateral walls of tyres, sparkling was detected with all samples. The results are indicated in Fig. 3. The sample taken from the Michelin tyre was burning for the longest period of time, but the glowing period was not significant. Burning started the latest with the Roadstone sample, but glowing was the longest in this case. Clearly visible black smoke rose from the residues during glowing too. During dripping while burning, it was observed that the burning drops did not only fall under the sample. When several drops fell simultaneously, they scattered within a circle of approximately 0.5 m in diameter. The Semperit, Michelin and Hankook specimens needed longer ignition times to develop a self-sustaining combustion. The samples of the Semperit and BFGoodrich products failed to burn completely. In our opinion, they did not need a long time to ignite, and the tyre samples easily caught fire.
Fig. 3

Burning and glowing time of the specimens

During the test, large amounts of black smoke rose even from the small specimens. The particulate matter provokes coughing and causes headache, nausea and vertigo. In addition, clearly visible burning particles were also present in the smoke and the air and these could cause burns.

Results of the ash content determination tests

The primary objective of this test was to identify the mass losses. Furthermore, observations are made regarding ignition time, the duration of burning with flames, flame height and post-flame phenomena.

In the burning residues test, specimens with a mass of 4–5 g were burned. Each specimen was separately fastened with a wire and was then exposed to a flame qualifying as match flame for 3 s. In general, burning became self-sustaining after 3 s. The results are summarised in Fig. 4.
Fig. 4

Mass of tyre specimens before and after burning, mass losses expressed in %

Self-sustaining burning of the samples developed very quickly. Among the tested samples, the Semperit and Firestone samples required more time to develop self-sustaining burning. The Firestone sample was burning with flames for the longest period; despite this, it was the Debica sample that lost the highest percentage of its initial mass, namely 66.78%. Unlike the others, the Semperit tyre sample only lost 18.07% of its mass in spite of the fact that the period when it was burning with flames did not differ from the duration of burning with flames of the other samples. During burning with flames, the flame rose to as high as 15–20 cm. The temperature of the flame is about 700 °C. During the burning, dripping while burning was also observed. At first, the falling pieces were burning with flames, and then a prolonged, flameless solid-phase burning was observed. On average, 60% of the mass of the tyre samples disappeared in the form of smoke.

The tests revealed that even after the end of burning with flames, tyres glow at an extreme level. The flameless solid-phase burning is also associated with a continuous mass loss.

During glowing, tyres continue to emit harmful substances into the environment. One consequence of the prolonged glowing and the shape of tyres is that the extinction of fire tyres is a slow process and, therefore, contaminates the environment and endangers human health for a prolonged period.

This test revealed that the duration of the burning process and the onset of self-sustaining burning are not influenced by the type of tyre, that is, whether it is winter tyre or summer tyre, or personal car tyre or truck tyre.

Conclusions

The behaviour of various tyres upon exposure to heat and flame was studied. In order to understand thermal properties, three different experimental methods were used to study the behaviour of the material: determination of ash content, flame propagation test and thermal analysis. Waste tyres of seven producers have been tested. Based on the thermoanalytical test results, the thermal behaviour of tyres can be typically subdivided into three main ranges. Based on the DTA curves, the third thermal stage is characterised by two types of behaviour: whereas in Sample Group A (Firestone, Michelin, Hankook and Debica), a last exothermic reaction is still clearly detectable in the third stage, in Sample Group B (Semperit, BFGoodrich and Roadstone), a prolonged thermal conversion is typical in the third stage.

During the flame propagation testing, given that steel threads are also present in the lateral walls of tyres, sparkling of all samples was detected. The sample taken from the Michelin tyre was burning for the longest period of time, but the glowing period was not significant. Burning started the latest with the Roadstone sample, but glowing was the longest in this case. Clearly visible black smoke rose from the residues during glowing too. During dripping while burning, it was observed that the burning drops did not only fall under the sample. When several drops fell simultaneously, they scattered within a circle of approximately 0.5 m in diameter. This could explain the rapid propagation of the fire in the fire cases. The Semperit, Michelin and Hankook specimens needed longer ignition times to develop a self-sustaining combustion. Samples of Semperit and BFGoodrich products did not burn completely.

During the ash determination test, it was observed that self-sustaining combustion of the samples developed very quickly. Among the tested samples, samples of Semperit and Firestone required more time to develop self-sustaining burning. Sample of Firestone was burning with flames for the longest period; despite this, sample of Debica lost the highest percentage of its initial mass, namely 66.78%. Unlike the others, sample of Semperit tyre lost only 18.07% of its mass in spite of the fact that the period when it was burning with flames did not differ from the duration of burning with flames of the other samples. During burning with flames, the flame rose to as high as 15–20 cm. The temperature of the flame was about 700 °C. During the burning, dripping while burning was also observed. At first, the falling pieces were burning with flames, and then a prolonged, flameless solid-phase burning was observed. On average, 60% of the mass of the tyre samples disappeared in the form of smoke. This test revealed that the duration and temperature range of the burning process and the onset of self-sustaining burning are not influenced by the type of tyre, that is, whether it is winter tyre or summer tyre, or personal car tyre or truck tyre.

For utilisation of commodities produced before 2010, burning them in pyrolysis plants or in specific furnaces seems to be the most suitable procedure. When we are recycling energy, while creating the specific furnaces for this, we need to take in consideration the thermodynamic features of the tyres. Thermal tests made provide us with useful information to set the right temperature. It is sufficient to heat the furnaces up to about 900 °C because at this temperature the mass loss is almost 100% so in fact there is no ash residue.

After burning, the samples showed the greatest difference in loss of mass; however, all were different in flammability, afterglow time and their thermal stability.

Notes

Acknowledgements

Second author acknowledges the support by the János Bolyai Research Scholarship of the Hungarian Academy of Sciences.

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Fire Protection Testing Laboratory, Ybl Miklós Faculty, Institute of Fire Protection and Safety EngineeringSzent István UniversityBudapestHungary
  2. 2.Department of Construction Materials and Technologies, Faculty of Civil EngineeringBudapest University of Technology and EconomicsBudapestHungary
  3. 3.XRD and Thermoanalytic Laboratory, Department of Engineering Geology and Geotechnics, Faculty of Civil EngineeringBudapest University of Technology and EconomicsBudapestHungary

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