Fire Hazards in Chemical Plant From Friction Sparks Involving The Thermite Reaction
Fire Hazards in Chemical Plant From Friction Sparks Involving The Thermite Reaction
Fire Hazards in Chemical Plant From Friction Sparks Involving The Thermite Reaction
SYNOPSIS
Impacts involving aluminium and rusty mild steel can initiate a thermite reaction. It is shown that the glancing
impact of stainless steel, mild steel, brass, copper-beryllium, bronze, aluminium, copper, and zinc on to
aluminium smears on rusty mild steel can initiate a thermite reaction of sufficient thermal energy to ignite
flammable gas-air and solvent-air atmospheres and dust clouds typical of those found in the chemical industry.
The conditions of impact under which the different metals are most likely to produce an incendive thermite
reaction are described.
The data indicate that although the No. 1 Wheeler Test and Godbert-Greenwald Furnace Ignition Tempera-
tures of a dust cloud may not indicate its sensitivity to ignition by this form of friction " spark ", Class I dusts
are much more likely to be ignited than Class II dusts.
and a visual assessment made as to whether or not the impact (a) The presence of loose aluminium on the smear: this
produced a thermite reaction. appeared to aid the initiation of a thermite reaction.
The visual evidence could be placed into one of three
categories: (b) The number of impacts to which the striking area on
(a) N o visible evidence of a spark of any kind—symbol- the hammer head had been subject: the zinc and aluminium
ised by N. hammer heads rarely, if ever, gave a thermite reaction on
the first impact. However, if the same area of the hammer
(6) A red spark similar in appearance to the spark pro- was used for a number of blows without being cleaned
duced when two metals impact in the absence of aluminium. between each blow a thermite reaction could be produced.
When this occurred it was considered doubtful whether a During repeated impact the softer metals become impreg-
thermite reaction had been initiated by the impact and even nated with aluminium and rust and this appears to aid the
if it had, it had not propagated through the aluminium dust initiation of the thermite reaction. The effect of these two
cloud—symbolised by S. factors can be seen from the results given in Table I, for
(c) A white flash indicating a propagating thermite reac- five successive impacts with each experimental situation.
tion—symbolised by R.
The harder metals (stainless steel, mild steel, and brass) not
All the metals produced thermite reactions but with the only initiated reactions under all conditions of impact but
softer metals with lower melting points (i.e. aluminium, also on the first impact. Because of their hardness there was
bronze, copper, and zinc) a thermite reaction did not occur at little, if any, impregnation of the impact area by aluminium
every impact. Photographs of two thermite reactions pro- and rust and this was not necessary for a thermite reaction to
duced by each metal striker are shown in Figs 5 and 6. In be produced. Two reactions were obtained from five impacts
one photograph of each pair background lighting has been with the copper striker having a clean surface and no loose
used to show the position of the hammer. The size of the aluminium. Five successive reactions were obtained with an
thermite reaction shown in the photographs should not be impregnated surface. The same increase in reaction frequency
taken as characterising the relative magnitudes of the thermite was obtained from a clean surface when loose aluminium was
reactions that are possible using the different metals because present in the target area. The aluminium and bronze
the size of the thermite reaction for each metal varied some- strikers did not give reactions under either condition with
what from impact to impact. clean surfaces, but both readily initiated reactions when
Two factors were found to be important in determining aluminium and rust had become embedded in the impacting
whether or not a reaction was produced. faces. Five successive reactions could be obtained with the
zinc hammer only when it had an impregnated striking surface and the percentage of reactions causing ignition was calcu-
and loose aluminium was present in the target impact area. lated. If an impact did not initiate a thermite reaction then
It cannot be concluded from these results that a thermite it was not included in the results.
reaction could never be initiated under those conditions for
which five successive non reactions were obtained. Neverthe- Coal gas-air atmospheres
less the results do show the relative frequency with which The glancing impact apparatus was enclosed in a metal
impacts involving the different metals can be expected to explosion cubicle filled with coal gas-air mixtures of known
initiate a reaction under the different impact conditions. The concentration in the range 4-20% (v/v).
results also indicate that, with soft metals, the chance of Thermite reactions produced by all the metals caused igni-
obtaining a reaction increases with the number of impacts tion of certain concentrations of the coal gas-air atmosphere
between the hammer surface and the aluminium smear. and a similar relationship between percentage ignitions and
The other conclusion of importance is that the use of coal gas concentration was obtained with each metal. The
copper-beryllium in so-called " non-sparking " tools does not relationship shown in Fig. 7 obtained with the copper-
significantly decrease the possibility of a thermite reaction beryllium striker is typical. Ignition was quickly obtained in
when the impact is on to aluminium-coated rusty mild steel. every case once the gas concentration exceeded a certain
minimum value. The minimum ignitable concentrations for
the different metals were:
The Incendivity of the Thermite Reactions
hardened mild steel, 5-0%
The incendivity of the thermite reactions produced by stainless steel, 5-0%
impacts involving the various metals has been examined using brass, 5-0%
flammable coal gas-air, methane-air, acetone-air, toluene- copper, 5-0%
air, and methanol-air atmospheres, and dust clouds. aluminium, 6-0%
Impacts were produced in each flammable atmosphere, a copper-beryllium, 6-0%
note made of the number of reactions that produced ignition, bronze, 6-0%
zinc, 6-0%.
All the minimum concentrations on the threshold of igni-
tion are at or just greater than the lower limit of flammability
of coal gas-air atmospheres (5%). The thermite reactions
produced in impacts involving the four metals with the lowest
D.P.H. hardness ratings—namely, aluminium, copper-
beryllium, bronze, and zinc—required slightly greater concen-
trations of coal gas before ignition was obtained and could
therefore be considered less incendive than those from the
harder metals. The change in coal gas concentration from
5 % to 6 % to give ignition is however too small to be of any
practical significance. It must be concluded that when the
concentration of coal gas is above the lower limit of flamma-
bility the thermite reaction produced by the impact of any
of the metals tested could ignite the flammable atmosphere.
Methane-air atmospheres
The equipment and test method for methane-air atmos-
pheres were identical with those used in the coal gas experi-
ments. Methane-air mixtures in the concentration range
4 % - 1 5 % (v/v) were examined.
Rae has shown 37 that strikers made from steel, brass, and
aluminium can ignite methane-air atmospheres. Tests were
only carried out therefore on the metals not used by Rae
(i.e. bronze and copper-beryllium) and on zinc, the metal
with which he could not obtain ignitions. The copper striker
was not available during the experiments with methane.
The experimental results were similar in form to those
Fig. 3.—Frictional impact apparatus obtained with coal gas. The three metals again produced
Start of impact
TEnd of impact
10 20 30 40
TIME (ms)
thermite reactions that could ignite the flammable atmosphere that can burn with explosive violence when exposed to a
provided the methane concentration was above a certain source of ignition (e.g. a hot surface, an electric spark) in a
minimum value (zinc, 6-2%; copper-beryllium, 5-3%; confined space.
bronze, 6-1 %). The lower flammability limit of methane-air The sensitivity of a dust cloud to ignition by a heat source
is 5-3%: thus, as with coal gas, it can be concluded that for can be measured by the No. 1 Wheeler Test and the Godbert-
all practical purposes the thermite reaction can ignite Greenwald Furnace Test. A dust cloud that ignites in both
methane-air mixtures in the flammable concentration range. the No. 1 Wheeler and the Godbert-Greenwald Furnace Test
Thermite reactions and ignitions were only obtained with the is classified as Class I, a dust cloud that does not ignite in
zinc striker after it had become impregnated with aluminium the No. 1 Wheeler Test but ignites in the Furnace Test is
and rust by contact with the aluminium smear. classified as Class II. A dust cloud that does not ignite in
either test is classified as Class III and will not ignite in normal
Solvent vapour-air atmospheres manufacturing processes.
Flammable acetone-air, toluene-air, and methanol-air In order to determine whether the thermite reaction pro-
atmospheres were used to test the possibility of ignition with duced during impact is a potential source of ignition, thermite
solvents. The concentrations of acetone and toluene were reactions have been produced in dust clouds from 95 products,
4-7 % and 2-3 % respectively. The concentration of methanol selected to be representative samples of Class I and II dusts.
vapour tended to vary due to condensation in the explosion In all the tests the stainless steel striker was used to produce the
chamber. A reaction giving non-ignition was not included in thermite reaction.
the data if an electric spark released in the impact area imme- A dust cloud of the powder under test was produced by
diately after impact did not cause ignition. placing a small cone-shaped heap of powder on the mild steel
The incendivity was determined with and without loose target at the edge of the impact area (Fig. 8). As the hammer
aluminium on the mild steel target. The experimental results moves in an arc it strikes the aluminium smear a glancing
from five successive thermite reactions are summarised in blow, initiates the thermite reaction, and projects burning
Table II. aluminium particles forward. These pass through the dust
These results indicate that if the impact involving any of cloud produced as the hammer continues its forward move-
these metals except zinc produces a thermite reaction then ment and strikes the heap of powder.
ignition of a surrounding flammable vapour-air atmosphere Up to five attempts were made to ignite each powder; if
will almost certainly follow. With a zinc striker it is more ignition occurred before the fifth reaction the tests were
difficult to produce a thermite reaction but when this occurs stopped and the number of the reaction that caused ignition
there is a reasonable probability that ignition will follow was noted. If ignition did not occur after five reactions " no
although it is possible to produce a small thermite reaction ignition " was recorded. The visual evidence after impact
that does not propagate throughout all the combustible depends not only on whether or not ignition occurs, but also
aluminium and which does not generate sufficient heat to on the form in which the burning is propagated through the
ignite these solvent vapour-air atmospheres. dust cloud. It was possible to divide the results into three
categories:
Clouds of chemical dust (1). Those in which, after impact, flame propagated clear
A wide number of powder products manufactured in the of the region of the thermite reaction, in some cases up to
chemical industry, whilst not explosives, can form dust clouds distances of two to three feet. This evidence indicated that
1 1 1 1
- I - O 0 o
o
<
r-:
UJ I , -
L
j O o -
- O 0 -
I,' 4 -
=
°° Class I dusts
c
xx Class 13 dusts
_
1
I. -
Fig. 10.—Comparison of sensitivity
to ignition by thermite reaction and
<si N .
-_ ..„.:i.|i:.;.g.g >i\ . X _ Godbert-Greenwald furnace
tion temperature
igni-
i • . i
| oo Class I dusts
13 33
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46/1928. Ser. 7, 30, 437.
14 34
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54/1929.
15
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36
16
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70/1931. 37
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17
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81/1933.
39
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40
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1
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2
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43
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357. werksch-Kasse, 1951, l , N o . 2.
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Appendix I
Description of Striker Metals
Hardness
Approximate
Major Melting D.P.H. Data
Metal Constituents Point Remarks
(%) (°C) Load (kg) Hardness
Stainless steel Fe 72 1450 30 224 The hardness of the grades of austenitic chromium nickel steel that are
Cr 17-5 widely used in the chemical industry is 200 D.P.H. maximum in the
Ni 8 fully softened condition in which they are usually supplied.
Mild steel Fe 99-9 1530 10 177 Ordinary low-carbon mild steel which is in the normalised condition
would have a hardness of about 100-120 D.P.H. This material is
probably in a cold worked condition.
Brass Cu 57 900 10 144 In the annealed condition brass would have a hardness in the range
Zn 40 65-75 D.P.H. This sample is in a work hardened condition.
Cu-Be Cu 9S 975 10 140 This sample was machined from the head of a " non-sparking " hammer.
Be 2 The fully heat treated alloy that would be used for chisels, etc., could
have a hardness of 350 D.P.H.
Bronze Cu 87 1032 10 110 This is the order of hardness expected in r. chill cast 10% tin-bronze
Sn 10
commonly used for bearings, etc.
Aluminium Al > 9 9 660 10 106 Typical value for heat treatable alloy in fully heat-treated (WP) condition.
Mg < 0 - l
Copper Cu > 9 9 1083 2-5 54 Typical of commercially pure copper in the annealed (soft) condition.
Zinc Zn > 9 9 420 2-5 40 This is a " mean " value; the hardness varied according to the direction
it was determined relative to the internal structure of the metal.
DISCUSSION work had been done on this by the Safety in Mines Research
Establishment. His department tended to follow them. As
Mr. F. J. OWEN asked if there was a thermite reaction if there far as aluminium paint on objects was concerned, it depended
was rust on aluminium instead of the other way round, and if on the base of the paint; some were safer than others. At
so had this been investigated? present, in his department, they tended not to use them if they
could avoid it but there was a tradition in the chemical in-
Dr. GIBSON said that it had never been done. Aluminium dustry to use aluminium paint. He was in a research depart-
was such a soft metal that it was very difficult to get rust to ment and there was a credibility gap between them and the
stay on it for any length of time. engineers. He did not think that was peculiar to ICI but it
was fairly common. He did not wish anyone to get the wrong
Dr. H. S. EISNER welcomed the paper because it was clear impression; they were not saying " Don't use the aluminium ",
that the aluminium hazard described by Gibson was still not they were saying: " This could be a danger and it should be
as well known throughout industry as it deserved to be. One used sensibly."
still came across the belief that, on the contrary, aluminium
was a " non-sparking " metal. Indeed, kits of so-called non- Mr. Z. W. ROGOWSKI said that he worked on fire dangers in
sparking tools containing some that were made of aluminium respect of use of aluminium paint many years ago. Sixteen
were still on sale. In the petroleum and gas industries the use commercial paints of various compositions were tested and the
of aluminium containing several per cent of magnesium results indicated that whether the incendive sparks would be
(which increased the hazard) was rapidly gaining ground. produced depended very much on the vehicle incorporated
The safe use of those materials depended on the constant into the paint. No commercial paint produced incendive
awareness of the hazard by all concerned in the design, sparks unless heated. As a result of this work certain re-
construction and use of equipment made of them. commendations were issued by Factory Inspectorate and some
Answering Mr. Owen's question, he thought that if the restrictions were placed on paints based on cellulose nitrate.
conditions of impact were right it would be possible to obtain It should be noted that since then aluminium paints of other
a thermite reaction when powdered rust placed on aluminium compositions had appeared on the market.
was struck by an external striker.
Dr. GIBSON said that the work he was thinking of was the
Mr. P. L. KLAASSEN asked what was Gibson's attitude work of Grice at SMRE (Ref. 23 of the paper). He suggested
towards the use of aluminium paint. Moisture caused rust in his report that the surface did not need to be heated and
behind the paint and could thus create possibly the right that there was sufficient heat from the impact to cause
mixture for ignition. ignition. That was an important point. Very often one could
paint a cold surface—not a radiator or steam pipe—and
Dr. GIBSON replied that aluminium paint had not been Grice had pointed out that the impact itself would give
examined by himself and Messrs Lloyd and Perry. Much sufficient heat and no prior heating was needed.