WO1999024120A1

WO1999024120A1 - Fire or explosion suppressants and methods

Info

Publication number: WO1999024120A1
Application number: PCT/GB1998/003360
Authority: WO
Inventors: Adam Chattaway; Stephen Richard Preece
Original assignee: Kidde Graviner Ltd
Current assignee: Kidde Graviner Ltd
Priority date: 1997-11-12
Filing date: 1998-11-10
Publication date: 1999-05-20
Anticipated expiration: 2000-05-12
Also published as: EP1035897B1; DE69804663T2; DE69804663D1; GB2331457B; ES2175809T3; GB2331457A; ATE215391T1; GB9723916D0; EP1035897A1

Abstract

A fire or explosion suppressant is described comprising water or an aqueous alkali metal salt solution together with a surfactant. The surfactant is selected so as to be fast-acting - that is, so that upon dispersion of the water or water-based solution towards the fire or explosion (e.g. in a jet or under atomisation), the surfactant acts to produce a surface tension value which becomes low (preferably at least as low as about 25 mN/m) within the time taken for the dispersed water to reach the fire or explosion (less than 50 ms and preferably less than 20 ms). Examples of suitable surfactants are disclosed.

Description

FIRE OR EXPLOSION SUPPRESSANTS AND METHODS The invention relates to fire or explosion suppressants or methods. More particularly, the invention relates to such suppressants and methods comprising or using water. Fire or explosion suppressants according to the invention, and to be

described in more detail below by way of example only, comprise water with an additive comprising a surfactant.

According to the invention, there is provided a fire or explosion suppressant, comprising a water-based solution containing a surfactant characterised in that the surfactant is capable upon dispersion of the solution of producing a predetermined value for the surface tension which becomes at least as low as about 25

mN/m m less than 50 milliseconds.

According to the invention, there is provided a method of suppressing a fire or explosion, comprising the steps of adding

to a water-based solution a surfactant and dispersing the

solution to the fire or explosion, characterised in that the surfactant is capable upon dispersion of the solution of producing a predetermined value for the surface tension which becomes at least as low as about 25 mN/m in less than 50 milliseconds .

Fire or explosion suppressants embodying the invention, and methods of suppressing fires or explosions according to the invention, will now be described, by way of example only, with reference to the accompanying diagrammatic drawings m which:

Figure 1 shows a volume of water-based suppressant for explaining the operation of suppressants according to the invention;

Figure 2 is an enlarged view of part of Figure 1 ;

Figure 3 shows an oscillating et arrangement for testing the

effectiveness of various surfactants;

Figure 4 is a section on the line IV-IV of Figure 3; and

Figure 5 is a graph for comparing the effectiveness of various

surfactants .

The fire or explosion suppressants to be described m more detail use water. Water is of course a well-known fire or explosion

suppressant. It acts only as a physically-acting agent, producing a heat absorption or extraction effect without any chemical suppression mechanism. However, it has a high surface tension and high mterfacial tensions on most materials and is therefore a poor wetting agent. On most solid surfaces, water remains as discrete droplets (with a contact angle greater than 90°) and therefore does not effectively wet the surface. Therefore, heat transfer from the burning substance to the water would be impeded - because this depends on the surface area of contact - and thus the suppressant action would be poor.

It is advantageous to apply water as a suppressant in the form of very small water droplets (having a diameter of less than 100 and preferably less than 50 micrometres for example) , because such droplets have a high specific surface area. However, because of its high surface tension it is quite difficult to

atomise water to produce droplets of this size. If the droplets

are to be produced by atomising water using pneumatic dispersion through a nozzle, it may be necessary to use very high pressures (greater than 50 bar) or low flow rates, both of which raise

difficulties m practice.

It is therefore known to add surfactants to water m order to reduce its surface tension with a view to overcoming the above disadvantages. By reducing surface tension, surfactants improve the wetting action of water. More speci ically, reduction of surface tension can have a beneficial effect on median droplet

size. Thus, it has been empirically shown that

vm.soluaon _ _t ' solution >Q 5/ ~ 3 [ 1 ]

D vm , water 73 1.0

[see Perry, R.H. and Green, D.W., Eds. Perry ' s Chemical Engineer ' s Handbook . Fifth ed. 1984, McGraw-Hill: New York]

where

D_vm = volume median droplet diameter

Y = surface tension, mN/m μ = solution liquid viscosity, cP p_L = solution liquid density, g/cm³

Equation 1 shows that the parameter with the greatest effect on droplet size is surface tension (γ) .

Figure 1 shows a volume of water 5 with the water/air interface being shown as 6. Surfactant molecules are shown (purely diagrammatically , of course) as 8. Each surfactant molecule comprises a hydrophilic "head" 8A and a hydrophobic "tail" 8B. The surfactant molecules 8 thus congregate along the interface or surface 6 with their "tails" 8B extending through the surface of the water, and thus reducing the surface tension forces acting there. In addition, however, assuming a sufficient concentration of the surfactant material, other surfactant molecules will form micelles indicated diagrammatically in Figure 1 at 10. Figure 2 shows one of the micelles 10 m enlarged (and, again, purely diagrammatic) form. Because of the hydrophilic "heads" 8A and

hydrophobic "tails" 8B, the surfactant molecules congregate in groups or micelles 10 which are typically spheroidal in shape, with their "tails" 8B extending towards each other and to the centre of the micelles forming central areas m each micelle from

where the water is repelled by the hydrophobic action of the "tails" of the surfactant molecules. In the general case, there

are many micelles in a volume of water.

Because the surfactant molecules m the micelles 10 are not effective at the surface 6 of the water, they are not acting to reduce the surface tension of the water. The surface tension-

reducing action is only performed by the surfactant molecules at the surface as shown in Figure 1. In Figure 1 , it is assumed that the surface 6 of the water is substantially fully occupied by the surfactant molecules. However, when the water is dispersed (for example, directed as a j et towards a fire) and, in particular, when it is atomised into droplets, new water/air interfaces are created. In order that the surfactant molecules can be effective m such changed circumstances for reducing the

surface tension of the water, the molecules have to diffuse to the new interfaces - m particular, they have to diffuse to the interfaces from the micelles. In order for the surfactants to be effective in reducing the surface tension of the water in conditions of fire or explosion - m other words, in order for

the surfactant molecules to be m position to reduce the surface tension of the water when it is applied to the fire or explosion - the time taken for the surfactant molecules to diffuse from the micelles to the new surfaces must be shorter than the time taken for the water to travel from the point of discharge (e.g. the

atomising nozzle) to the fire. In many practical applications,

this time period is less than 50ms. Therefore, in accordance with the invention, surfactants capable of lowering the surface tension of the water within the same order of time scale are added to water-based fire or explosion suppressant solutions. By "fast-acting" is meant surfactants which act within a time

period of less than 50ms and preferably of the order of 10 to 20ms, and which reduce the surface tension at least to the order of 30mN/m and preferably 25mN/m.

The water may be pure water or it may be water containing an alkali metal salt such as potassium bicarbonate, potassium lactate, potassium acetate or potassium citrate.

Specific examples of suitable surfactants will be discussed

below. Generally, though, the surfactant has the structural

formula RXM.

Within this structural formula, M is a cation of an alkali metal (lithium, sodium, potassium, rubidium, caesium) or of a

protonated amme.

X in the structural formula RXM is an amonic group. Suitable

groups are a sulphate (-OS0₃), a sulphonate (-S0₃) or a carboxylate (-C0₂); the sulphate is preferred.

R in the formula RXM is an alkyl (preferably, a branched chain alkyl group) or is an alkylaryl group, in each case containing four to twenty carbon atoms and preferably at least one atom of silicon. A preferred example for R contains the trimethylsilyl group ( ( CHJ Si-) . The molecular weight of the RX fragment should be below 400

Daltons and preferably below 300 Daltons .

A preferred example of a suitable surfactant is a

trimethylsilylbutane sulphate salt of the form

(CH₃) ₃SιCH₂CH₂CH₂CH₂-0S0₃ ^~M⁺, where M is an alkali metal cation of

sodium or potassium or of a protonated amine .

The water-based solution may be pure water or water containing

an alkali metal salt such as potassium bicarbonate, potassium

lactate, potassium acetate or potassium citrate. More specific

examples are : -

(a) water containing potassium bicarbonate m the

concentration range 1 - 24 weight %, preferably 15 - 24

weight % ;

(b) water containing potassium acetate in the

concentration range 5 - 60 weight %, preferably 40 - 60

weight % ;

(c) water containing potassium lactate in the

concentration range 5 - 60 weight %, preferably 40 - 60 weight % ;

(d) water containing potassium citrate, m the concentration range 5 - 60 weight %, preferably 40 - 60

weight %.

Because the surfactants operate to reduce the surface tension within such a short time scale, the droplet sizes of the water are much smaller, producing better heat transfer from the fire or explosion and thus a better suppressant effect. The rapid reduction in the surface tension facilitates further atomisation

of the droplets as they move through the air from the discharging nozzle to the fire or explosion (enhanced droplet stripping) . The droplets have improved wetting ability for hot surfaces (e.g. the hot surfaces of clutter within a room or container such as an engine compartment of a vehicle or a crew compartment of a military vehicle), thus producing enhanced heat transfer.

The rapid reduction of surface tension also is particularly advantageous for explosion suppression applications.

Tests have been carried out to examine the effectiveness of various surfactants and their ability to reduce the surface tension in the short timescales required. Because of these short timescales, measurement of equilibrium surface tension values may not be of significance, because for some surfactants the

equilibrium surface tension value may not be reached until a relatively long time has elapsed - possibly tens of seconds. What is important m the present instance s the surface tension value which is reached after time periods of the order of 10 to 25ms; it is therefore necessary to measure the surface tension dynamically. A suitable method is to use an oscillating et as shown in Figures 3 and 4. Here, the liquid under test (that is, the water-based solution containing a particular surfactant) is discharged through a nozzle 12 having a non-circular orifice 14, which is elliptical m cross-section in this example. The

resultant et 16 will be mechanically unstable: its initial cross-section will be non-circular (corresponding with the shape of the orifice) and will collapse to a circular cross-section which has the lower surface energy. However, the momentum of the jet will carry the cross-section beyond the desired circular one to a non-circular form. This process continues, producing

oscillations in the jet which continue until insufficient momentum remains to maintain a coherent jet, when collapse into droplets occur. Figure 3 shows the form of jet produced when the orifice is el ptical. In the oscillating jet, λ is taken as the distance between two

successive maxima (or minima) in the jet. The surface tension

Y relative to water at a particular value for γ is found from the

relationship : -

Ys = Y„ [λ_w/λ_s] ² [ 2 ]

where λ = wavelength (distance between successive nodes)

Y is surface tension (mN/m) and the subscript S denotes surfactant solution and the subscript

W denotes pure water.

The time taken to reach a particular surface tension value may

be calculated by measuring the flow rate at the nozzle 12 and the

distance of a node from the nozzle.

Figure 5 shows a graph illustrating the results produced when

testing three different solutions - that is, solutions which

contain respectively different surfactants in water, all at 0.5%

by volume.

The surfactant which produces curve A causes the solution to

reach a low value of surface tension very quickly - a value of about 26.5mN/m after 20ms and slightly less after 40ms.

The surfactant which produces curve B also reduces surface

tension quickly but the value of the surface tension reached

after about 20ms is higher, at 35.0mN/m and about 32.6mN/m after

40ms .

Finally, the surfactant which produces curve C does not reduce

the surface tension very quickly and the value of the surface

tension reached after about 20ms is higher still at about 40mN/m

and about 36.2mN/m after 40ms, although m this particular case

the equilibrium surface tension reached after a very much longer

period of time is 22.6mN/m.

In these tests, therefore, it is the surfactant which produces

curve A which is suitable for reducing the surface tension

sufficiently quickly and to a sufficiently low value. The

surfactants producing curves B and C are not satisfactory because

the value of surface tension is too high (curve B) or the

reduction m surface tension is too slow (curve C) . In Figure

5, the surfactant producing curve A is a trialkylamonium salt of

trimethylsilylbutane sulphate (referred to below as SURFACTANT

A) , the surfactant producing curve B the sodium salt of is dodecylbenzenesulphonic acid (referred to below as

SURFACTANT B) , and the surfactant producing curve C is a cationic fluorine-containing surfactant

(C₆F₁₃CH₂CH₂SCH₂CH₂CH(OH)CH₂N⁺(CH₃)₃Cl (referred to below as

SURFACTANT C) .

In a further set of tests, various extmguishants have been tested for extinguishing fires in obstructed or cluttered spaces such as military vehicle crew compartments. These tests were carried out on water-based extmguishant solutions intended to replace Halon. The Table below shows tests carried out on a

number of different extmguishant solutions. The tests were carried out under standard conditions (standard volumes containing standard fires) representing the characteristics of and in crew compartments. In some cases, clutter was present in the volumes and m others there was no such clutter. In each case, the minimum quantity of the suppressant (in kg/m³) to

achieve suppression was measured.

TABLE ONE

The tests show that the addition of SURFACTANT A (a

trialkylamonium salt of trimethylsilylbutane sulphate) improves

the operation of the extmguishant solution ( particular, its

atomisation) to the extent where its fire suppression performance

is equal to that of Halon 1301.

Tests have also shown that fast-acting surfactants as defined

herein, such as SURFACTANT A mentioned above, are effective in

significantly improving the effectiveness of water and water-

based extmguishants m suppressing Class A fires (cellulose-type

material such as wood and paper) . Without the addition of such

surfactants the ability of such extmguishants to suppress such

fires is hampered by their high surface tension and thus their

inability to wet the surfaces of the burning material properly.

The addition of the fast-acting surfactant ensures that this

problem is overcome by lowering the surface tension sufficiently

and within the timescale of the suppression process. In a

particular series of tests a standardised hydrocarbon fire was established m a wooden "crib" m a test chamber. Tests were carried out using a succession of extmguishants under standardised conditions to check whether actual cooling of the crib was achieved by the extmguishant. The extmguishants were

sprayed from a predetermined distance to the crib, the time of travel from the nozzle to the crib being about 19ms. In each case, the extmguishant was pure water but with the addition of 0.5% of a particular surfactant. The following results were

achieved :

Claims

1. A fire or explosion suppressant, comprising a water-based

solution containing a surfactant characterised in that the surfactant is capable upon dispersion of the solution of producing a predetermined value for the surface tension which

becomes at least as low as about 25 mN/m m less than 50

milliseconds .

2. A method of suppressing a fire or explosion, comprising the steps of adding to a water-based solution a surfactant and dispersing the solution to the fire or explosion, characterised m that the surfactant is capable upon dispersion of the solution of producing a predetermined value for the surface tension which

becomes at least as low as about 25 mN/m in less than 50

milliseconds .

3. A suppressant or method according to claim 1 or 2, m which

the predetermined surface tension value is reached within less

than 20 milliseconds.

4. A suppressant or method according to any preceding claim, m which the water-based solution is pure water.

5. A suppressant or method according to any one of claims 1 to 4, m which the water contains an alkali metal salt.

6. A suppressant or method according to any preceding claim, m which the alkali metal salt is present in a concentration

greater than 5 weight %.

7. A suppressant or method according to any preceding claim, in which the alkali metal salt is a potassium salt.

8. A suppressant or method according to claim 5, in which the alkali metal salt is potassium bicarbonate.

9. A suppressant or method according to claim 8, n which the potassium bicarbonate is present in the concentration range 1 -

24 weight %.

10. A suppressant or method according to claim 8, in which the potassium bicarbonate is present in the concentration range 15 - 24 weight %.

11. A suppressant or method according to claim 5, m which the alkali metal salt is potassium acetate.

12. A suppressant or method according to claim 11, m which the

potassium acetate is present m the concentration range 5 - 60

weight % .

13. A suppressant or method according to claim 8, m which the

potassium acetate is present in the concentration range 40 - 60

weight % .

14. A suppressant or method according to claim 5, in which the

alkali metal salt is potassium lactate.

15. A suppressant or method according to claim 14, in which the

potassium lactate is present in the concentration range 5 - 60

weight %.

16. A suppressant or method according to claim 15, which the

potassium lactate is present m the concentration range 40 - 60

weight %.

17. A suppressant or method according to claim 5, m which the

alkali metal salt is potassium citrate.

18. A suppressant or method according to claim 17, m which the potassium citrate is present in the concentration range 5 - 60

weight % .

19. A suppressant or method according to claim 18, m which the

potassium citrate is present in the concentration range 40 - 60

weight %.

20. A suppressant or method according to any preceding claim,

which the surfactant has the structural formula RXM, where:

M is a cation of an alkali metal (lithium, sodium, potassium,

rubidium, caesium) or of a protonated amme; X is an anionic

group; and R is an alkyl or alkylaryl group containing 4 to 20

carbon atoms.

21. A suppressant or method according to claim 20, in which the

anionic group is taken from the group comprising a sulphate, a

sulphonate and a carboxylate.

22. A suppressant or method according to claim 20 or 21, m

which the alkyl group is a branched chain alkyl group.

23. A suppressant or method according to any one of claims 20

to 22, m which R contains at least one atom of silicon.

24. A suppressant or method according to claim 19 or 20, in which R contains the trimethylsilyl group ((CH₃)Sι-).

25. A suppressant or method according to any one of claims 20 to 24, m which the molecular weight of the RX fragment is less

than 400 Daltons.

26. A suppressant or method according to claim 25, in which the molecular weight of the RX fragment is less than 300 Daltons.

27. A suppressant or method according to any one of claims 20

to 26, in which the surfactant is present in the concentration m the range 0.1 to 2 weight % .

28. A suppressant or method according to claim 27, in which the

surfactant is present in the concentration range 0.1 to 0.5

weight % .

29. A suppressant or method according to any preceding claim,

in which the surfactant is a trimethylsilylbutane sulphate salt, (CH₃) ₃SιCH₂CH₂CH₂CH₂-OS0₃ ^"MJ where M is an alkali metal cation selected from the group comprising sodium, potassium and a protonated amme.

30. A method according to any one of claims 2 to 29, m which the solution is dispersed to the fire or explosion in droplet sizes of less than 50μm.

31. A method according to any one of claims 2 to 29, m which the solution is dispersed to the fire or explosion m droplet sizes of less than 100μm.

32. A fire or explosion suppressant, substantially as described herein.

33. A method of suppressing a fire or explosion, substantially

as described herein.