233

A NEW ABLATIVE ELASTOMERIC INSULATION

J R Paterson
University of Manchester Institute of Science & Technology (UMIST), United Kingdom

INTRODUCTION
A new ablative elastomeric insulation has been invented primarily for insulating cables so that they can function in a nuclear environment, Paterson (1). Such cables would be subjected through their lifetimes to nuclear irradiation as well as thermal ageing and superimposed on this background may be higher levels of nuclear irradiation which would occur in an accident situation. In a loss of coolant accident, such as would occur in a pressure water reactor, fire will follow and in addition the insulation will be subjected to cycles of high pressure steam at high temperatures. It is essential that the cables continue to supply power and serve communication circuits during the emergency and for some time atlerwards. This means that, as distinct from low fire hazard cables, the new insulation must continue to function under actual fire conditions. It has been designed to function at lo00 to 1100C when subjected to an extemal heat flux density of 50 to 200 kWlm. It has virtually no toxic or corrosive gases.
as far as possible all elements that could be converted into radionuclides. It contains additional fillers of silicon carbide and red iron oxide. Silicon carbide was used because it has a very low neutron absorption crosssection and the red iron oxide because it will react with the hydrocarbons given off during buming to form a silicate layer, possibly after the reaction:-

2F,0+C,H,,Si,01

with 0 - 2F,Si0,+4COl+6H10

The red iron oxide absorbs a large amount of heat. Other fillers can be used, such as aluminosilicate microspheres or pyrophyllite rock, particularly for purely tire protection. The elastomer can be used alone or made up as a composite with amorphous silica glass cloth or it can be coated onto glass cloth and used for fire curtains.

Fire is the common hazard. It can occur in a number of places, such as operating rooms, engine and control rooms or on oil production facilities. As the research proceeded, it was realised that because of its resistance to fire, the new elastomers would also be used very effectively in protecting structural members, walls and bulkheads from collapse and thus preventing personnel from being trapped in addition to protecting them from injury due to inhaling toxic or corrosive fumes. It can also withstand shock, vibration and resistance to impact so that it also offers protection from falling objects. The paper will concentrate on the effects of fire and will briefly describe some of the items of equipment that have been constructed. The development of the ablative elastomer makes possible the design and manufacture of bushings and cables which will allow electrical supplies to pass through a compartment which is on tire to an adjacent compartment. DESCRIPTION OF ELASTOMER

FIRE HAZARDS
As a result of a fire, failure of a structural element extemal to a building may occur, such as a supporting leg for an offshore petroleum platform or a fire might occur in a compartment. Drysdale (2) has pointed out that there are three stages in the growth of a fire in a compartment:1. The growth or pre-flashover stage. In this stage,

the average temperature is low and the fire is localised in the vicinity of its origin.
2. The fully developed or post-flashover fire, during which all combustible items in the compartment are involved and flames appear to fill the whole compartment. It is during this stage that structural damage can occur and flame may spread to other compartments, even to other adjacent buildings. There is a threat to occupants remaining in other parts of the building.
3. The decay period classified as the stage where the average temperature has fallen to 80% of its peak value.

An addition reaction polydimethylsiloxanewas used as

the base elastomer with a platinumcatalyst and ethylenic cross-links. This system was selected because it was found to have the best thermal and hydrolytic stability and reversion resistance. The elastomer has been checked by means of gamma spectrometry to eliminate

Electrical Safety in Hazardous Environments, 1S21 April 1994, Conference Publication No. 390, @ IEE, I 1994

234

If a person has not been evacuated from a compartment before flashover occurs, he is unlikely to survive. Time must be allowed for evacuation from ignition to when the fire renders impossible the occupation of the compartment. Marchant (3) has classified this time as being made up of the time for a series of events to occur as follows:t
+

(3)

re + t "

'*,

(2)

where { is a "viewing factor" calculated from viewing factor algebra; Qc is the rate of heat release in kW; P is the flame height in metres; and D is the diameter of the fuel bed (base of the flame rectangle).
The flame height measured in the cone calorimeter and 2 5 " and 32mm, the thermal imaging device were 1 respectively, Paterson (1). The cone calorimeters and the thermal imaging device have been described by Paterson, Paul and Warren (4). Even at the higher limit of the flame height, the flame is unlikely to reach and travel along the ceiling of a compartment so that there will be no extemal radiation from the heated ceiling or upper walls to raise the temperature of surrounding areas to the fire point. With an incident extemal radiant heat flux density of 75 kW/mz and a peak heat release rate of 137.7 KW/m2 and calculated "viewing factors" of 0.185 and 0.007, the radiant flux density from the flame at 150mm and 300mm along the surface are 7.95kW/m2 and 0 0 3 KW/m2, respectively. The minimum flux density for ignition is 24kW/m2, so that ignition at the surface will not occur at these points.

where is the elapsed time from ignition to detection of the fire; f is the delay between detection of the fire and the beginning of the escape activity; ,t is the time to move to a position of relative safety; 4. is the time from ignition to the fire producing untenable conditions. The first step was to study changes that take place in the material during intense. fire conditions and then to apply the knowledge to help protect buildings and personnel. Thermogravimetric analysis, differential thermal analysis, dielectric measurements, infra-red gas analysis and surface analysis using static fast atom bombardment secondary ion mass spectrometry have all been used to study the material. At 200C the ablative elastomer will give off some vapours and behueen 300 and 500C further breakdown will occur with the production of low molecular weight siloxanesgiven off as vapours. Above 500C complete degradation of the molecule will occur with burning and oxidation. Water vapours, carbon dioxide and some carbon monoxide will be produced; and silicon dioxide will be formed, some of which will remain behind to form a protective ash. The action of the red iron oxide in helping to develop silicate layers has already been pointed out. Changes in the thermal conductivity will take place as well as changes in the specific heat and density. The thermal conductivity will change from 0.0632 to 0.4847 W/m"K; the specific heat changes from I.Ok.J/kg"K at 60K to 4.63kJkg"K; and the density changes from 1600 kg/m3 to 830kg/m3. Changes will occur in the thermal diffusivity and also in the emissivity so that some of the incident energy is reradiated.

The rate of surface flame spread will determine how

rapidly a fire will develop. The first step is to control the growth of flame spread. Flame will spread from the point of ignition and the leading edge of the flame will provide an advancing source of heat which will raise the temperature at a local point to the ignition temperature. This is illustrated by considering the flame on the surface as a rectangle. The situation is then analogous to two rectangles at right-angles to each other and the radiant flux density at a distant point can be calculated from:

While the surface is being heated, heat will penetrate into the material to a depth given by Jut where o is the thermal diffusivity (k/pc where k is the thermal conductivity in W/m"K; p is the density in kgln?; and c is the specific heat in kJ/kg"K); and t is the time. It can be shown that the velocity of flame spread is inversely proportional to the thermal inertia (kpc). For a solid, k is roughly proportional to the density of the solid and as the density of the ablative elastomers is high, it will not spread flame rapidly. It has also been pointed out that changes in the thermal diffusivity will occur so that the passage of heat through the insulation will be slowed down and the red iron oxide will absorb energy and will combine with hydrocarbons which have been established to be given off by infra-red as analysis, to form a silicate-like structure. This structure will prevent the escape of volatiles so that again the flame travel will be limited since the fuel supply to the surface will be restricted. From the above it will be seen that the ablative elastomer is stable up to 200C and that it will increase the time to flashover. Hirschler and Shakir (5) consider that the ratio of time to ignitiodpeak rate of heat release is proportional to the time to flashover and m y therefore be the best individual indicator of overall fire hazard. The higher the ratio, the less the fire hazard. Table 1 compares the ablative elastomer with other materials

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Table 1 New ablative elastomer compared with other materials. Time to Ignition (Swonds) New ablative elastomer (17mm thick) 5OkWlm 75kWlm 1OOkW/m 5OkW/m 75kWlm IOOkWIm 155 52 24 195 74 39

Peak Rate of Heat Release (kWlm)

90.8 137.7 125.3 137.3 132.7 149.4

TTIIPRHR (mlkw
1.71 0.38 0.19 1.42 0.56 0.26

New ablative elastomer with one layer of amorphous silica glass cloth (17mm thick)

/I

Beechwood (25mm thick)

5OkWIm

29.8

136.0

0.22

Cross-linked polyolefinlEPR

75kWlm 100kWlm

3 6 17

240 280

0.16
0.061

of the compositeblock containing amorphous silica glass cloth. The average temperature rise at the end of 2 hours was 128C. thick blocks were used to measure the The 80 thickness of material converted into a silicate-like structure. Table 2 shows the thicknesses in the centres of the sample. Table 2 Thickness of material converted into a silicate type structure.

% n e in Furnace (Minutes)

Cenlre of Sample (ntd

8 11 15 12* 28

15
30 45 60 120

(* this apparent anomalous result is as yet unexplained)

Figure 3 is a photograph of a block removed from the furnace after 60 minutes testing. The surface crust and silicate layer can be seen, together with some 38mm of undamaged elastomer, at the bottom. Tests were also camecl out using the Standard Test Regime in accordance with I S 0 834 Fire Resistance Tests - Elements of Building Construction, the fumace temperature following the relationship:-

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T-T,=345 log h e 10(8t+l)

(5)

where t is time in minutes, T is furnace temperature "C and To is the initial furnace. temperature "C. The fumace temperature was 960C and a 60" thick block used; after 60 minutes, the 'cold' face temperature was 70C. In both cases, the 'cold' face temperatures were well below the acceptance criteria. Cables. Fig.4 is a photograph of lengths of the new cable after fire testing in the cone calorimeter. These cables were placed in a simulated duct and were fitted into the simulated duct with their surfaces slightly proud. Hirschler and Shakir (5) found that the cone calorimeters gave comparable results to a full-size cable tray test such as laid down in I S 0 338. Fig.4 shows the cables removed from the artificial duct. The new ablative elastomer was used as core and sheath insulation. The cables have been subjected to a flux density of 100 kW/m2. The minimum amount of damage should be noted. Buming is restricted to the upper surface because of the close proximity of the cables to each other in the duct. There is no damage to the cores. Smoke. Smoke tests were carried out in the cone calorimeter because. this gives a quantitative value. It measures the specific extinction area (m'/kg) with time. Fig.5 show curves of the variation of specific extinction area with time. The relationship between the specific extinction area and time was found to be:-

Toxicity. Repeated testing with Draeger tubes, infrared analysis and the cone calorimeter have indicated only carbon dioxide, carbon monoxide and water vapour. With an external radiant heat flux density of 100kw/m2, the peaks of carbon dioxide and carbon monoxide are 3.14 and 0.455 kg of gas/kg sample bumt. At the end of six minutes, the level had fallen to 1.92 kg/kg and 0.0061 kgkg, respectively. Overall toxicity index by specification NES 713 is 0.75 which o the carbon is very low and which may well be due t dioxide. It must be accepted that certain gases such as CO, will be present. Corrosivity. Specially formulated so that no corrosive gases would be present and subsequent test confirmed this.

BUSHINGS
Figure 6 is a bushing which has been constructed for use in switchgear up to 12kV. The bushing has withstood 35kV for 1 minute at power frequency and an impulse withstand voltage of 75kV in accordance with IEC 1980, List 2. The bushing is insulated with the new ablative elastomer. A modified bushing can be constructed to go through a wall. The new cable can be connected to the bushing, the connection being sleeved with the new insulation. and supplies can be maintained even though there may be a serious fire in the compartment. In a separate test, the cable has withstood 1000 volts between cores while the surface was at 1000C. MECHANICAL TESTS The elastomer will withstand shock in excess of 200g. under impact the depth of penetration is 0.8mm when a 0.28kg mass with point t a p e d at 45" is dropped through 0.76mm on to a 4mm thick sheet of ablative elastomer. Truncated projectiles with an impact velocity of 540mlsecond and a kinetic energy of 416kJ will penetrate up to 75mm of the elastomer. The cable has been vibrated for an amplitude of 4mm at 16Hz for 1% hours.

where x, is peak value in seconds; x is the time from peak in seconds; y is the specific extinction area in m2kg and k and c, are constants. It will be seen from the figure that different quantities of filler modifying the peaks but then falls to 450m'/kg in 1400 seconds and finally dies away in 2600 seconds. Table 3 Comparison of new cable with other insulation. External Irradiance 75 k W h 2 17.5mm wall

Time to Ignition

Peak Heat R e l e a s e Rate

kW/m2

11 11

CSP low fire hazard cable 12.5mm wall

XLP/silicone (not ablative)

I 5 kW/m2
I 5 kW/m'
24 310

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A s d temperature rise was detected but there was no evidence of flexural cracking. The insulation is resistant to cut through.

3. Marchant. E.W. 1976. 5th International Fire Protection Seminar, Karlsruhe.

4. Paterson, J.R., Warren, L. and P d ,

K.T. 1992,

NUCLEAR IRRADIATION
The insulation has been irradiated to greater than 4.17 x io7 rads g a " n concomitant with 5.01 x neutrons/cm2. Negligible effects on the mechanical or electrical performance of the elastomer up to 2 . 1 x io7 rads gamma concomitant with 2 . 5 5 x loi6 neutrons/cm2 was observed.

Dielectric Measurement and Materids md ADDhtiOnS, Conference.

5. Hirscbler, M.M. and Shakir, S. 1992. Conference

on Flame Retardants.

CONCLUSION
It will be seen that a versatile new insulation has been developed. It will function under tire conditions and it has the advantage of absorbing impact, for example, from falling crane blocks and gives off uirtually no toxic and no corrosive gases, and will not pass fire or hot gases if used as duct seals. It will give protection to steelwork and electrical terminals against corrosion and more importantly it will protect personnel from horrendous injuries. It can be repaired on site. The material lends itself to design for increasing the fire resistance of structures economically and effectively.

F i g u r e 1. Sample of e l a s t o m e r b e f b r e f i r e test.
140 WAmblent

ACKNOWLEDGEMENTS
The author is grateful to the Principal, Professor HanLins and to the Dean, Professor C B Cooper for permission to carry out this work at UMIST. Also to Dr Paul of RAPRA for assistance with the cone o Mr M Shipp of the Fire Research calorimeter and t
Station.

REFERENCES
1. Paterson. J.R. 1992. PhD Thesis. 2. Drysdale, D. 1985. An Introduction to Fire pmamiq, John Wiley & Sons L t d .

J
F i g u r e 2. T e m p e r a t u r e r i s e of ' c o l d ' f a c e w i t h time.

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-.7.

tigurc

L.

I e n g t h s of new c a b l e

F i g u r e 3. E l a s t o m e r removed f r o m furnace after 60 minutes.

a f t e r fire test & L .. __ radiant flux density o f 10 0k W / m?

'

3 "

700

'

1 1 "

'

Secon&

1400
F i g u r e 6. Bushing i n s u l a t e d w i t h t h e new elastomer

F i g u r e 5 . V a r i a t i o n of s p e c i f i c e x t i n c t i o n area with

time.