Energy and Resources Research Institute Fire and Explosion Research Group

Electrical Cable Fires using the Cone Calorimeter for Toxic Gas Investigations
Al- Sayegh, W.A., Aljumaiah, O., Andrews, G.E. and Phylaktou, H.N. Energy and Resources Research Institute, School of Process, Environment and Materials Engineering The University of Leeds

INTRODUCTION - 1

The majority of deaths in fires (66%) are due to the effects of toxic gases rather than flames [1]. PVC is the second largest contribution after wood to fires in non-domestic premises [2] and its use in electrical cable insulation is one of the main sources of PVC in fires. It has been estimated that there are 250m of electrical cable per house (50m per room) and 140 fires/million km cable/year [3]. Electrical cable fires may occur as part of a fire load that has started elsewhere and spread to ignite the cables externally. This is simulated in the present work using the cone calorimeter to represent radiant heating from a fire that engulfs the cables.

INTRODUCTION - 2

Sundstrom [4] has reviewed methods of testing of cables for their fire resistance and concluded that current tests concentrate on fire propagation rates and not on toxicity. However, he concludes that the future must address the toxicity issue and the measurement requirements, as reliable test methods are lacking. ISO TC 92 is working on this issue [4].
[4] Sundstrom, B., Flammability Tests for Cables Flammability Testing of

Materials used in Construction, Transport and Mining. Ed. Apte, V.B., Woodhead Publishing Ltd., 2006, p. 187-199.

INTRODUCTION - 3

Hirschler [5, 6] has compared the large scale cable tray fire tests of ASTM D9.21 and IEC 332-3 with the cone calorimeter and concluded that the HRR and smoke production measured in the cone calorimeter can be used to predict the results of the larger scale tests. This was the reason for the use of the cone calorimeter in the present work, which used heated FTIR analysis for full acidic and irritant toxic gas production measurements for PVC and polypropylene cable sheaths.
[5] Hirschler, M.M., Comparison of large and small-scale heat release tests with electrical cables. Fires and Materials,18: 2, 61-76, 1994. [6] Hirschler, M.M., Can the Cone Calorimeter be Used to Predict Full Scale Heat and Smoke Release Cable Tray Results from a Full Scale Test Protocol, Proc. Interflam, Interscience Communications, London, 2001.

Author Theoretical Babrauskas Babrauskas Babrauskas Babrauskas Persson and Simonson Bowes Blomqvist Hull et al. Hull et al. Purser This work

Ref. 7 7 7 7 2 8 9 10 11 12

Method PVC C2H3Cl NBS Cup Furnace SwRI/NIST Cone Calorimeter 35, 50, 75 kW/m2 Real Scale Fires PVC board Large scale fire Pyrolysis of 1kg of rigid PVC in 1m3 furnace Vertical cable fire test with FTIR ISO Furnace Test Purser Furnace with FTIR Purser Furnace Test Purser Furnace Test Cone Calorimeter + heated FTIR, electrical cables

COg/g 0.09 0.11 0.086 0.090 0.066 0.076 0.19 - 0.47 0.116

HClg/g 0.58 0.2 0.3 0.21 0.26 0.3 0.32 0.09-0.22 0.32 0.09

HCl% 0.21 0.37 0.31 0.57

0.04-0.14

3.38

0.04-0.13 0.025 -0.12 0.23-0.46 0.01-0.17 0.09-0.12

0.0450.13 0.11-0.15 0.15 0.16-0.56 0.2 0.5 0.025

TOXIC GAS ASSESSEMENTS

Toxic Gas 15 Min Limit COSHH[17] CO NO2 HCN C 6 H6 CH2O C 3 H5 O CH2O2 SO2 HCl 200 5 10 3 2 0.3 5 5 5 500 3,700 250 300 LC50 30 min [18,19] 3,000 500 135 COSHH To CO Ratio 1 40 20 67 100 667 40 40 40 6 0.8 12 10 LC50 Ratio to CO limit 1 6 22

Carbon Monoxide Nitrogen Dioxide Hydrogen Cyanide Benzene Formaldehyde Acrolein Formic Acid SO2 HCl

EXPERIMENTAL METHODS

Samples of polypropylene (PP) and PVC sheathed electric cables were burned on the cone calorimeter at three different heat fluxes (20, 30 and 40 Kw/m2). Prior to burning the samples the heat release measure by the apparatus was calibrated using natural gas. Strips of electrical cable 9cm long were place side by side until the whole of the cone calorimeter square test section was full with one layer deep of electrical cable. The copper core was retained in the wires as they may contribute to the temperature rise, as a thermal heat sink.

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A Temet FTIR (Gasmet) was used for the toxic gas analysis. The FTIR had a multi-pass cell with gold-coated mirrors with a 2m path length and volume of 0.22l. This had an 8 cm-1 wavelength resolution and a 900 4250 cm-1 scanning range. This low resolution was used as this has a much better signal to noise ratio for complex multi-component gas analysis. A liquid nitrogen cooled MCT detector was used that scans 10 spectra per second and several scans are used to produce a timeaveraged spectrum. The response time of the instrument is 2s to reliably resolve all 51 species that it can measure. The Temet FTIR gives a typical 2ppm resolution with an accuracy of 2% and a precision that is 0.1% of the measurement range. The FTIR has been calibrated for all the significant species that are present in the gas sample from fires. The only calibration necessary prior to the test was to zero the instrument on nitrogen. The calibration was checked for some gases, CO, CO2, benzene and methane using certified span gases and the agreement was satisfactory.

HEATED SAMPLING SYSTEMS AND HEATED ANALYSERS

Samples were taken from the cone calorimeter exhaust duct and transferred to the FTIR using a 190oC heated sample line, heated pump and filter and a second 190oC heated sample line between the pump and the FTIR. The FTIR measurement zone was also heated at 190oC so that no loss of HCl and other condensable gases occurred. There are two reasons to use completely heated sampling and analysis systems when sampling directly from fire product gases: loss of condensable species, mainly hydrocarbons and aldehydes and loss of species by solution in the water that condenses in unheated systems.

THE PROBLEM OF SAMPLE LOSSES IN UNHEATED GAS SAMPLING AND ANALYSIS SYSTEMS Species CO Benzene Naphthalene Acrolein NO2 HCN HCl SO2 Boiling Point -192oC 80oC 218oC 53oC 21oC 25.6oC -85oC -10oC Solubility in Water at 20oC 0.006 g/litre 0.8 g/litre 0.03 g/litre Extremely Soluble Very Soluble Hydrolyses to HNO3 Completely Miscible Extremely soluble 720g/litre Extremely soluble 80 vol/vol Heated Sampling System? No Yes >80oC Yes > 220 oC Yes > 100oC Yes > 100oC Yes > 100oC Yes > 100oC Yes > 100oC Yes > 100oC

Formaldehyde 96oC

THERMAL GRAVIMETRIC ANALYSIS

The PVC and PP samples and their residues from the cone test were analysed using thermal gravimetric analysis (TGA). A sample weight of about 5 mg was used and the weight resolution was 1 g. The sample was heated in nitrogen to evaporate any volatile components followed by a phase of combustion in air to burn the remaining fuel. The sample was heated at 20oC per minute until a temperature of 100oC was achieved. The temperature was kept at 100oC for five minutes which allowed the sample to dry out and any water content to be determined. The sample was then heated to 550oC at a rate of 20 oC per minute for 10 minutes this allows the volatile components to evaporate but not to combust as no oxygen is present. This determines the HCl released as this is the only volatile product for PVC. Finally, the air combustion was introduced and the duration of this phase is 20 minutes where the sample is heated to 560 oC at a rate of 10 C per minute. This determines the carbon proportion of the sample, as any hydrocarbons or hydrogen would have been devolatilised by 550oC.

Energy and Resources Research Institute Fire and Explosion Research Group

Two types of electrical cable covering were used. PVC electrical cable covering: - This had a thickness of 2.9mm. It was intended for use with voltages between 300 and 500 volts. The calorific value for PVC is 19.9 MJ/Kg. PP electrical cable covering: - This had a thickness of 2.6mm and was used for electric control circuit cables. The calorific value for PP is 46.4 MJ/Kg.

ELEMENTAL ANALYSIS
Fuel Nitrogen Chlorine Carbon Hydrogen H/C Total

PVC

N/A

55.26

39.67

5.07

1.53

100

PVC [7]

0.004

43.08

38.05

4.93

1.55

86.1

PVC, C2H3Cl Polypropylene

56.8

38.4

4.8

1.5

100

0.69

N/A

65.97

8.76

1.59

75.42

Polypropylene n(C3H6)

85.7

14.3

2.0

100

TGA ANALYSIS
Normalised values for TGA of PVC electrical Cable
1 0.8 0.6 0.4 0.2 0 500 1000
o

Normalised Value for TGA of PVC Residue

weight / original weight (mg/mg)

1 0.9 0.8 0.7 0.6 0.5 0.4 0 500 1000 1500 Temperature (o C) Pyrolysis Combustion

mass/(original mass) (mg/mg)

Combustion Pyrolysis

1500

Temperature ( C)

The weight loss when heating the sample in nitrogen was due to the release of HCl, this occurs between 250 and 300oC and is identical for heating in nitrogen and air. The elemental analysis gave 55% of the PVC mass as chlorine; this would produce a yield of HCl of 58% as shown in Table 1. Fig. 1a shows there was a 42% weight loss due to HCl loss in air and nitrogen. However, there is evidence of another volatile loss at 400-500oC and assuming that this is also HCl the total weight loss due to release of HCl is 52% close to the expected total yield of HCl. Bowes [8] commented that 70% of the expected HCl yield (41%) occurs rapidly at 272oC and this was found, as shown in Fig. 1a.

MASS LOSS ON THE CONE CALORIMETER

After 500oC there was little combustion of hydrocarbons, as the pyrolysis weight loss was small. At around 700-750oC both pyrolysis and combustion show a weight loss and this could be due to release of hydrogen. After 800oC there was no further weight loss for heating in nitrogen or in air and this indicates that there is about 30% of residual char that does not burn. This will be shown later to be a feature of the cone calorimeter results.

MASS LOSS AND HEAT RELEASE RATE ON THE CONE CALORIMETER

PVC weight Loss at different Heat Fluxes
1

Polypropylein Weight Loss at Different Heat Fluxes

Weight/initial weight (g/g)

Weight / initial weight(g/g)

0.95 0.9 0.85 0.8 0.75 0.7 0 500 Time (S) 1000 1500 20 Kw/m2 30Kw/m2 40Kw/m2

1 0.95 0.9 0.85 0.8 0 500 Time (s) 1000 1500 20 KW/m2 30 Kw/m2 40 Kw/m2

Weight loss and HRR as a function of time in the cone calorimeter tests for three incident radiant fluxes for PVC and PP .
Heat Release Rate at Varying Heat Fluxes for a PVC Sample
200
HRR(Kw/m2)

Heat Release Rate at Varying Heat Fluxes for a Polypropylein Sample

300 250 200 150 100 50 0 -50 0

100 50 0 -50 0 200 400 600 Time(s) 800 1000 1200

20Kw/m2 30Kw/m2 40 KW/m2

HRR(Kw/m2)

150

20Kw/m2 30Kw/m2 40Kw/m2 200 400 600 Time (s) 800 1000 1200

MASS LOSS AND HEAT RELEASE RATE ON THE CONE CALORIMETER

Comparison between PVC and PP will be made at 40 kw/m2 as PVC burns freely at this condition. On all the graphs PVC is on the left and PP on the right.

TOTAL HYDROCARBON EMISSIONS BY FTIR

Total HC 1200 1000 800 600 400 200 0 0 200 400 600 Time s 800 1000 1200 Total HC

Concentration of THC Vs Time (s)

700 600 500 400 300 200 100 0 0 100 200 Time(s) 300 400 500
Concentration (ppm)

Total FTIR HC ppm

Total FTIR hydrocarbons for PVC and PP for 40 kw/m2 For the PVC fire the total HC results show a continuous release of hydrocarbons throughout the later stages of the fire and these do not get oxidised. For the PP cable fire the hydrocarbons are mainly release quickly along side the benzene release that is shown later and then burn out and are very low in the later stages of the cable fire.

TOXIC YIELDS OF HCL g/g

Yields of HCl at Varying Heat Fluxes
0.02 Yield HCl

0.6 0.5
Yield (g/g)

0.018 0.016 0.014

HCl Yield g/g

0.4 0.3 0.2 0.1 0 -0.1 0 500 1000 Time (s) 1500 2000

20 Kw/m2 30 Kw/m2 40 Kw/m2

0.012 0.01 0.008 0.006 0.004 0.002 0 0 50 100 150 200 250 Tim e s 300 350 400 450 500 Yield HCl

These yields are comparable with those reported by others for both large and small scale equipment. They are higher than most previous work has found, especially in small scale tests such as the Purser furnace test [10,11]. However, the agreement was very good with the previous cone calorimeter work of Babrauskas for PVC sheet samples.
Babrauskas, V., Harris, R.H., Braun, E., Levin, B., Paabo, M. and Gann, R.G., The Role of Bench Scale Test Data in Assessing Real-Scale Fire Toxicity, NIST Technical Note 1284, 1991.

TOXIC YIELDS OF HCL - 2

The HCl yields were significantly lower than the 100% conversion of chlorine to HCl yield of 0.58. This may be due to incomplete conversion of the chlorine in the fire. The cone calorimeter debris was tested by TGA, as discussed above. There was a low temperature volatile gas loss, but at a lower temperature than was found for the fresh PVC. However, it was possible that the second stage HCl loss that occurred at higher temperatures in the TGA was the source of the Chlorine that was not released in the cone calorimeter tests. This was about 30% of the total Chlorine and if this was the case then the measured yield of HCl would be close to achieving a chlorine balance. There was a low yield of HCl from polypropylene electric cables, which was at least a factor of 10 below the yield for PVC electric cables. The chlorine may have come from a chlorine based fire retardant added to the cable sheath composition.

Yields of Acrolein for PVC and Benzene for PP

Yield for Acrolein in 40 Kw/m2 fire 0.06 0.05 0.04
Yield

Yield Vs. Time (s)

0.3 0.25 0.2
Yield

ACROLEIN PVC

BENZENE PP

0.03 0.02 0.01 0 -0.01 0 200 400 600 Time(s) 800 1000 1200

0.15 0.1 0.05 0 0 100 200 Time (s) 300 400 500

There was no significant acrolein for PP and no significant benzene for PVC. The yield of benzene from PP was very high and the yield of acrolein was very significant for PVC. This was not expected as acrolein is generally formed from HCO elemental fire loads such as wood and cotton. For example I reported yesterday acrolein yields of a peak of 0.016 for smoldering cotton towels and here it is 0.05 for PVC.

YIELDS OF FORMALDEHYDE
Yield for formaldehyde in 40 Kw/m2 fire 0.04 0.03
Yield

Yield Vs Time
0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 -0.005 0

Yield

0.02 0.01 0 0 -0.01 Time (s) 200 400 600 800 1000 1200

Yield

100

200

300

400

500

Time (s)

Yields of formaldehyde for 40 kw/m2 for PVC (left) and PP (rt) Peak yields were similar but lasted longer with PVC. As for acrolein, the generation of formaldehyde from PVC or PP was unexpected as they normally occur with HCO Type fire loads. However, they are a low temperature combustion pollutant and it may be the entrained air that is responsible for their generation.

YIELD FOR 1.3 BUTADIENE FOR PVC (left) AND METHYL BENZENE FOR PP (Right)
Yield for 1,3 Butadiene Vs Time
0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 -0.005 0 Series1 0.005 0.004 0.003
Yield

Yield Vs. Time (s)

Yield

0.002 0.001 0

500

1000 Time (s)

1500

2000

-0.001 0

100

200 Time (s)

300

400

500

Virtually all the toxicity for polypropylene fires was due to the hydrocarbons benzene and small quantities of tri-methyl benzene. For the PVC fires 1,3 butadiene was the most significant hydrocarbon in the later stages of the cable burning.

RELATIVE TOXICITY
Comparing Total COSHH N for Varying Heat Flux
200
80
COSHH (N)

Comparing Total COSHH N for Varying Heat Fluxes

150
COSHH N

20 Kw/m2 100 50 0 0 500 1000 Time (s) 1500 2000 30 Kw/m2 40 Kw/m2

60 40 20 0 0 200 400 600 Time (s) 800 1000 1200

20Kw/m2 30 KW/m2 40 KW/m2

The total COSHH 15 min. total relative toxicity N values are shown for PVC and PP. For the LC50 toxicity the N values are much lower but occur at the same time and the trends with time are the same. The total toxicity was sensitive to the heat flux as this essentially changes the pyrolysis temperature in the fire zone. The air dilution of the fire products in the freely ventilated test conditions of the cone calorimeter encourages oxidation of products in the mixing area. If the air entrainment is rapid then species are quenched and realistic yields can be measured, but for CO oxidation and the lower equilibrium Values that occur for leaner mixtures make the test unrealistic for CO toxicity.

RELATIVE TOXICITY ON A COSHH 15 MIN. BASIS FOR HCL

Ratio of HCL concentration to COSSH Value
3 COSHH HCL

60 50 40
T im e (s )
RELATIVE COSHH HCL

2.5 2 1.5 1 0.5 0 -0.5 -1 0 50 100 150 200 250 300 350 400 450 500 COSHH HCL

30 20 10 0 -10 0 200 400 600 Ratio 800 1000 1200

Time s

HCl for PP was significant, which was not expected and indicates that the polypropylene may have had some PVC in its blend or had some chlorine based fire retardant added. The HCl levels are much lower than for PVC but have a similar toxicity contribution to that of CO. The highest toxicity occurs in the time period of the highest HRR.

RELATIVE TOXICITY FOR CO ON A COSHH 15 MIN. BASIS

COSHH ratio for CO Vs Time(s)
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -0.1 0

COSHH ration for CO

3.5 3 2.5 2 1.5 1 0.5 0 -0.5 0

COSHH ratio

200

400

600 Time (s)

800

1000

1200

Cosh Ratio

100

200 Time (s)

300

400

500

For PVC the overall toxicity was dominated by acrolein and HCl, CO were not a major contributor. This conclusion would not change if toxicity was assessed based on LC50, as the toxicity concentration ratio for HCl and acrolein is 12 on an LC50 basis and 16 on a COSHH 15 min. basis. For PP the toxicity was dominated by the production of benzene and again CO was a low contributor.

RELATIVE TOXICITY FOR ACROLEIN FOR PVC AND BENZENE FOR PP

COSSH ratio for acrolein

ACROLEIN
120 80
Ratio

BENZENE
35 30 25 20 15 10 5 0 0 100
COSHH Ratio

COSHH ratio Vs Time (s)

100 60 40 20 0 -20 0 200 400 600 Time (s) 800 1000 1200

200 Time (s)

300

400

500

Peak relative toxicity for acrolein was 110 and for CO it was 0.7 and for HCL it was 50. Thus acrolein dominates the toxicity. On an LC50 basis the conclusion in relation to CO would not change as the change in relative toxicity of CO to acrolein for LC50 relative to COSHH 15 min. was 67 and the acrolein to CO COSHH toxicity ratio is 157.

CONCLUSIONS
1. The cone calorimeter with freely ventilated fires is a good method for

the evaluation of toxicity from materials in fires, but is unrepresentative of CO yields due to the high post flame oxidation of CO. 2. A heated sample system and FTIR is essential for work on toxic gases as the losses if water condenses in the sample system will remove many of the important toxic species. 3. A comparison of toxic emissions for cable sheath materials of PVC and PP was carried out and this showed completely different toxic gas emissions but only slightly lower overall toxicity for PP, which was not expected. 4. For PVC the dominant toxic gas was acrolein and this was absent in the PP tests. HCl was a significant toxic species but not as important as acrolein and this has not previously been reported. 5. For PP the dominant toxic gas was benzene and this was not present in the PVC cable fires. Further work is required on these surprising results in relation to understanding the pyrolysis kinetics and to ensure that similar conclusions are valid for air starved fires.

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Thank You Any questions?

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