Chemical

Eng,negr,ng
ana
Processing
ELSEVIER Chemical Engineeringand Processing, 34 (I995) 141-149

Explosion behaviour oJ" the 'non-flammable' CFC substitute

1,1,1,2-tetrafluoroethane (R 134a)
S. Dietlen, H. Hieronymus, B. Plewinsky, V. Schr6der, H. Steen*
Bundesanstattfiir Materialforschung und-priifung (BAM), Abt. 'Chemische Sicherheitstechnik', Unter den Eichen 87, 12205Berlin, Germany

Dedicated to Prof. Dr. Dietmar Werner on the occasion of his 60th birthday

Abstract

The explosion ranges of R134a/nitrogen/oxygen mixtures have been investigated at atmospheric pressure. The results of these
full flammability tests at 20 °C and at 280 °C are presented in a triangular diagram. In addition, the influence of pressure on the
flammability of R134a/air mixtures has also been studied.
Under normal conditions, R134a is a non-flammable gas but exhibits an explosion range at higher oxygen percentages than
those in air. At increased temperatures or pressures, R134a also has an explosion range in air, i.e. without any higher oxygen
percentage.
Using a detonation tube, the detonability of R134a/air mixture has been investigated for pressures between 8-20 bar and
temperatures from room temperature to 200 °C. Stable detonations with detonation velocities of 1506-1535 m s-1 were initiated
by incoming detonation waves. For an oxygen-enriched R134a/nitrogen/oxygen mixture at 10 bar, using a glowing wire as the
ignition source a pressure-piling effect was observed. In this experiment a pressure of more than 1200 bar was attained.

Keywords: ExpIosion behaviour; 1,1,1,2-Tetrafluoroethane; Flammability; Pressure-piling effect

1. Introduction unit for R134a in Germany has initiated investigations

New refrigerants are being developed that utilize
hydrogen in the molecule to reduce atmospheric stabil-
ity (HCFC) and also to replace chlorine which con-
tributes to ozone layer depletion by fluorine (HFC).
One benefit of the old chlorofluorocarbon refrigerants
(CFC) is their non-flammable nature. Substitution of
hydrogen atoms for halogen atoms imparts shorter
atmospheric lifetimes but may also change the
flammability characteristics of the molecule. The refrig-
erant R134a was developed as a non-flammable re-
placement for the ozone-depleting CFC dichlorodi-
fluoromethane (R12). It is used as a pure substance or
in refrigerant blends in mixtures with other HCFCs and
HFCs, e.g. R22, R32, R125 and R152. Since Sand and
Andrjeski [1] found that R22 (another non-flammable
HCFC) could become combustible under certain condi-
tions, the study of the corresponding behav:iour of
other refrigerants, and especially of R134a, has been
stimulated. In addition, an accident in a production
* Corresponding author.
of the explosion and detonation behaviour of R134a/air
mixtures at higher initial pressures.
2. Experimental details
2.1. Arrangements for explosion measurements
Tests at atmospheric pressure
The explosion ranges of R134a/nitrogen/oxygen mix-
tures at atmospheric pressure have been determined
using a test apparatus and test procedure in accordance
with German Standard DIN 51 649, Part 1. This ap-
paratus complied with the test apparatus of Method
A.11, EC Directive 92/69/EWG used for the classifica-
tion of gases and gas mixtures in the scope of EC
Directive 67/548/EWG.
The explosion vessel was a vertical glass tube with a
diameter of 60 mm and a height of 300 ram. The igni-
tion electrodes were placed 60 mm above the bottom of
the glass tube with a spark gap of 5 ram. The induction
142 S. Dietlen et al. / Chemical Enghwering and Processhlg 34 (1995) 141-149

spark was supplied by means of a high voltage trans-
former. The apparatus allowed flammability testing up
to 300 °C.
Metering gas pumps were used to feed a test mixture
of accurate composition into the glass cylinder. A gas
volume 10-times the volume of the test vessel was used
to purge the vessel before the next test. Ignition was
always attempted in the flow-free test mixture. Whether
or not a flame became clearly detached from the igni-
tion source was observed visually. It was not necessary,
however, for the flame to be propagated over the full
height of the explosion vessel.
The percentage of substance investigated was varied
step-by-step until the explosion limit was reached. If the
fraction of test substance was less than 10% by volume
then these steps were 0.1% by volume. With test sub-
stance fractions above 10% by volume, tests were car-
ried out with 0.2% steps. If with a particular mixture
flame detachment just failed to take place, five check
tests were carried out. The explosion limits given in this
paper are the limiting percentages of a combustible
substance in a mixture with an oxidizing gas at which a
flame just failed to detach from the ignition source. The
explosion range is the percentage range of substance
under test between the lower explosion limit (LEL) and
the upper explosion limit (UEL).
Calibration testing of the apparatus with the well-
known manner with methane showed an LEL of 4.3%
by volume and a UEL of 16.8% by volume. These
experimental values corresponded to the recommended
values (LEL = 4.4% by volume; UEL = 16.6% by vol-
ume) [2].
nents being determined by measurements of partial
pressures during filling.
The percentages of R134a in the test mixtures were
varied in 1% steps by volume. As a spot check, samples
of the test mixtures were analyzed by means of a
paramagnetic oxygen analyzer (the results corre-
sponded to the partial filling pressures in all cases).
The criterion as to whether there was reaction or not
after ignition was a 10% rise of the initial absolute
pressure (pcx/pi>~l.1). Pressure/time histories were
measured by means of a piezoresistive pressure gauge
and were recorded with the help of a storage oscillo-
scope.
2.2. Experhnental arrangements for detonation
measurements
Investigation of the detonation behaviour of R134a/
air mixtures has been carried out using a heatable tube
6460 mm in length and 40 mm in diameter. The experi-
mental set-up is shown schematically in Fig. 2. The
detonation tube consisted of four segments connected
in a way that precisely continued the cylindrical inner
surface. The tube was mounted on a supporting base
that could be swivelled by means of a pneumatic sys-
tem. Before filling with sample gas, the tube was evacu-
ated to a pressure less than 10 mbar. In addition to the
positions of gas inlets and outlets, the positions of the
ignition source and the detection devices are also shown
in Fig. 2.

Tests at higher initial pressures

Investigations at higher initial pressures were carried
waste gas
out in steel autoclaves. The testing equipment is sche-
7
matically shown in Fig. 1. Different from the standard
apparatus an exploding wire ignition was used. An
electronic control unit with a 3 kVA/230 V insulating
transformer provided the ignition energy. Two fnsu-
%
lated electrodes at a 6 mm distance supported a Nicke-
line wire of 0.2 mm diameter. The ignition sources were
placed in the middle of the test vessels. After the wire
had been melted, an electric arc burned between the
electrodes for a time extending to a half period of the
supply voltage (0.01 s).
One of the autoclaves was a vertical cylindrical steel
vessel with a hemispherical bottom (height 185 ram,
diameter 132 mm) of 2.2 dm 3 total volume. Sufficient
homogeneity of the gas mixtures was ensured by using
a special filling tube with small nozzles.
The other autoclave was a sphere of 14 dm 3 volume
constructed of stainless steel. It was, therefore, possible 1, 2 - gas s u p p l y 3 - ignition device 4 - steel autoclave
to homogenize the test mixtures with the use of a
5 - filling tube 6 - vacuum pump 7 - pressure registration
magnetic stirrer. The test mixtures were prepared di-
rectly in the test vessels, the percentages of the compo- Fig. 1. Apparatus for explosion tests at higher initial pressures.
 S. Dietlen et al./ Chemical Engineerhzg and Processing 34 (1995) 141-149 I43

laS inter fo vacuum pump gas ouHef

D D 9 D D D D
_..i~l ~iI .__ I I _ _ I ~ I I[~f

ignifion/~ II II If H II II II II
source

" - ic device

fube swivelling ,_
61+60mm
D=pressurefransducel"
L=fibre optics
Fig. 2. Experimental set-up for detonation experiments.

Sample gas mixture Detection of detonation

The sample gas mixture consisting of R134a and air
or R134a and a given mixture of 02 and N 2 w a s
prepared in a separate vessel of 35 dm 3 volume. In
addition, by means of the partial pressure method, the
mixture was prepared in several steps in order to
avoid condensation of R134a during compression to a
storage pressure of 30 bar.
A stable detonation is characterized by the steep
front of a shock wave propagating at constant velocity
which is undamped in its pressure amplitude. The time
dependence of pressure after the ignition of the sample
gas mixture was measured by piezoelectric pressure
gauges placed at several positions along the tube. The
positions of these gauges are also shown in Fig. 2.

Ignition 3. R e s u l t s and d i s c u s s i o n
For detonation measurements of the sample gas, the
following three ignition sources were used alterna- 3.I. Explosion limits of Ri34a
tively: a glowing wire, an exploding wire and an in-
coming detonation wave. The glowing wire was heated Explosion ranges at atmospheric pressure
by a direct current voltage of 30 V. The wire used was Figure 3 depicts the explosion ranges for R134a/ni-
of Nickeline, 0.2 mm in diameter and 40 mm in length trogen/oxygen mixtures at room temperature and at
partly wound as a coil with four windings 2.5 mm in 280 °C. The line representing mixtures of R134a with
diameter. The distance of the coil from the mounting air i the so-called air line - - is also shown in this
flange was 10mm. The exploding wire method de- diagram.
scribed above was also used for detonation experi-
n
ments. explosion lim/ts at: ~100
Ignition of the sample gas by an incoming detona- • 2ooc ,//.\
tion wave was undertaken as follows. After filling the .2 oo 20
tube with the sample gas, an ignition mixture consist-
ing of 11% by volume of acetylene, 61% by volume of
nitrogen and 28% by volume of oxygen was filled into 40 X
the tube via a valve located at the flange carrying the r%~,trv°#leu~ne. 4 ~ b//~-<60 o R134a
glowing wire. Since turbulence was avoided during the [ Y .^J ? - / /:Jx/~', ........ )~ [~byvolume]
filling procedure and since diffusion is a slow process,
the ignition mixture did not mix with the sample gas.
The sample gas was compressed by the ignition mix-
ture in a similar manner to a piston up to required / air line d- /~ ~
\20
\
initial pressure. The length of the ignition gas column
in the tube was 1.0-1.6m according to the choice of 0i
)i i
, 20_/
/I > ,._)
/ 4"0/ / 60/
, ;
i 80/
, , ,
/100i
x, 0

pressures after each step of the filling procedure. The oxygen [%by volume]
detonation wave travelled from the ignition mixture Fig. 3. Explosionranges of R134a/nitrogen/oxygenmixtures at room
into the sample gas mixture in direct contact with the temperature and at 280 °C, measured at atmosphericpressure accord-
ignition gas. ing to German Standard DIN 51 649.
144 S. Dietlen et al. / Chemical Engineerhlg and Proeessblg 34 (I995) 141-149

160
30
l 0tI [m(dp/dt)max
x = I26.9 bar/s at3.07 s /
322 1 ,.~ 2.5
120i L.....~ .______=~ J ...........
~""20

.... ............. , (dp/dt)ma ~15

e-,

,01 . . . . . . . .
'N10
.9
5
.................. ~ .... pressure limit (7,3 bar)

20 . . . . . :........ i............ . . . . . . . .
0
0 500 1000 1500 2000
time [ms]
Fig. 4. Pressure/time history of an R134a/air explosion (13% by
volume of R134a in a mixture with air) at 100 °C and 15 bar initial
pressure in a 14 dm 3 spherical autoclave.
At room temperature, the nose of the explosion
range does not cross the air line. This means that
R134a has no explosion range in air under such condi-
tions. This is why it is classified in Germany as a
non-flammable gas; R134a only becomes flammable in
oxygen-enriched environments.
On drawing the tangent from the point '100% R134a'
at the top of the triangle to the explosion range, the
maximum oxygen/nitrogen ratio for non-flammability
is obtained at the point of intersection with the oxygen
axis. The value obtained indicates that R134a is non-
flammable in oxygen/nitrogen mixtures with an oxygen
percentage less than 34°,/0 and is flammable in mixtures
with an oxygen percentage above 34% at room temper-
ature and atmospheric pressure.
The squares in Fig. 3 represent the explosion range at
a temperature of 280 °C. Here the air line just touches
the explosion range. The maximum oxygen/nitrogen
ratio is that of air (21:79). This means that R134a is
flammable in air at temperatures above 280 °C at atmo-
spheric pressure.
Our results correspond to those reported elsewhere
[3,4]. Dekleva et al. carried out some flammability tests
with R134a/nitrogen/oxygen mixtures at 100°C and
170 °C and found flammability at oxygen/nitrogen ra-
.
'l; 1'5 . . . . 2'o . . . . 2; 30
R134a in mixture with air [% by volume]
2500 3000 3500 4000
Fig. 5. Pressure dependence of explosion limits of an R134a/air
mixture at a temperature of 25 °C as measured in a 2,2 dm 3 auto-
clave.
pressure. The maximum pressure was observed after a
time period of more than 3 s, Normally, flammable
gases such as methane result to time periods of a few
hundred ms. Nevertheless, the explosion pressure am-
plitudes are similar to those of usual flammable gases
and need to be taken into consideration from the safety
point of view.
The results of measurements in the 2.2 dm 3 autoclave
are shown in Fig. 5. In this case, the limiting points are
non-ignition points. The curve depicted could not be
fitted mathematically to these points. However, it en-
closes all the limiting points and was plotted in accor-
dance with safety considerations. In these experiments
the R134a percentage was varied in I% by volume
steps. No ignition was found with R134a in the 2.2 dm 3
autoclave up to 7bar, with the first ignition being
observed at 8 bar.
The results of tests in the 14 dm 3 spherical autoclave
are shown in Fig. 6. The same ignition source was used
as in the 2.2 dm 3 vessel. The first reactions were ob-
served at 12 bar initial pressure in the 14 dm 3 vessel.
Obviously the volume of the test vessel has a significant
influence on the ignition pressure limit.
30

tios above 30:70 (30vo1.% oxygen in nitrogen) at 25

100 °C and above 28:72 at 170 °C. However, in contrast ,-ff
to our test equipment, Dekleva et al. used an 8 dm 3 "~'2o
autoclave with a hot wire ignition source. E

___i ......
"Nt0 pressure limit 11,2 b a r )
Explosion limits at higher initial pressures
In another series of studies, we investigated the ex- .9
5
plosion limits of R134a/air mixtures at higher initial
pressures. In general, we observed very smooth pres- ' '1; .... 15 . . . . 2'0 . . . . 25 30
sure/time histories during the explosion tests. Figure 4 R134a in mixture with air [% by volume]
shows a typical pressure curve for an R134a/air explo- Fig. 6. Pressure dependence of explosion limits of an R134a/air
sion employing a nearly stoichiometric mixture in a mixture at a temperature o f 25 °C as measured in a 14 dm 3 spherical
14 dm 3 spherical autoclave at 100 °C and 15 bar initial autoclave.
 S, Dietlen et al./ Chemical Engineering and Processing 34 (I995) 141-I49
30
I ................. ........................................ i ...................... !
~ 2 0 ......... ~* ....... . . . . . . . . . . . . . . . . . . . . . . .
15 ] . . . . . . ,:'" ...................... .............................
.~ 1o: ........... 1K ..................~.......... : / / ................. ......................
.......... ~ .... :
....................................: ...............pressure limit ,(5,5 bar) ....
10 15 20
R134a in mixture with air [% by volume]
Fig. 7. Pressure dependence of explosion limits of an R134a/air
mixture at a temperature of 100 °C as measuredin a 14 dm:~spherical
autoclave.
Results which deviate from our observations have
been obtained by Reed and Rizzo [5]. They reported
that R134a becomes flammable at conditions as mild as
1.4 bar and 22 °C with an explosion range of 7.8%-
17.9% by volume of R134 in a mixture with air. They
observed single ignitions at atmospheric pressure and
room temperature. A possible reason for such different
results is that Reed and Rizzo used a 1.7 dm 3 vessel
with an exploding wire ignition source. In the neigh-
bourhood of such a hot ignition source a forced reac-
tion will take place in any case, but for mixtures outside
the explosion range the reaction does not propagate
throughout the mixture. The ignition source used by
Reed and Rizzo was supplied by a 5 kVA/110 V insu-
lating transformer. This type of ignition equipment
leads to a high current in the electric arc and hence a
high ignition energy in a relatively small volume'.. In our
experience the use of such small vessels in the presence
of strong ignition sources can lead to problems in
interpreting the pressure rise data. It is possible to
misinterpret the pressure rise resulting from such a
forced reaction as the criterion necessary for self-sus-
tained explosion.
In our tests we used an exploding wire ignition
source with a 3 kVA/230 V insulating transformer and
either a 2.2 dm 3 autoclave or a 14 dm 3 autoclave. Un-
der these conditions we also found that the volume of
the vessel influenced the minimum ignition pressure.
Normally, small vessels have a greater tendency to
remove heat from the chemical reactions involved in
burning. This should make the explosion limits nar-
rower and the minimum ignition pressure higher. How-
ever, tests have shown the contrary result. With
marginally flammable substances, e.g. halocarbons, at
mild pressures in particular, we observed influences
such as the vessel volume and ignition source on the
observed limits. Tests with common flammable gases
such as hydrocarbons showed that a volume of 2.2 dm 3
is sufficiently large to exclude artefacts caused by the
ignition source.
145
• Figure 7 shows a curve measured at 100 °C in the
14 d m 3 vessel. The minimum ignition pressure obtained
. . . . . . . . . . . . . . . . . . .
was nearly 5 bar. Obviously the temperature also has a
...... ,/e ,; . . . . . . . .
strong influence on the observed minimum ignition
pressure.
' ....................
3,2. Detonation behaviour of R134a/air mixtures
The detonability of R134a mixtures was investigated
under various conditions involving the composition of
25 30 the mixture, the pressure, the temperature and the
ignition source. In the following we present the results
obtained according to experiments with R134a/air mix-
tures with wires as ignition sources, experiments with
R134a/air mixtures and an incoming detonation as the
ignition source and finally experiments with oxygen-en-
riched R134a sample mixtures.
Experiments with wires as the ignition source
This section relates to experiments conducted to in-
vestigate the explosion behaviour of R134a/air mix-
tures. The two described wire ignition sources were
used. The initial conditions and results of these experi-
ments are summarized in Table 1. With only three
exceptions, the amount of R134a in the sample mixture
was 13% by volume. This mixture was assumed to
possess the highest ignition probability. The initial pres-
sure was varied from 10-20 bar while the temperatures
in the system were 20, 100 and 200 °C, respectively.
Both wire ignition methods were used but did not
reveal any significant difference. For temperatures o f
20 °C and 100 °C, no reaction, i.e. no pressure rise,
could be observed in the sample gas mixture. These
results appear to contrast with measurements per-
formed in autoclaves, but can be explained by heat
losses in the long narrow horizontal tube. At an initial
temperature of 200 °C and initial pressures greater than
or equal to 15 bar, a slight pressure rise was found after
ignition. The values for the resulting maximum pres-
sures listed in Table 1 were attained slowly with the
maximum pressure rise being 3-4 bar s -I. Although
these results indicate that the gas mixture reacts weakly
(especially at lower initial temperatures), this was no
evidence for non-detonability as shown by the experi-
ments presented in the following section.
Experiments with an incoming detonation as the ignition
source
The R134a/air mixture with 13% by volume of
R134a was investigated under circumstances where a
shock wave was created by detonation of the ignition
mixture as described above. The experimental condi-
tions and results of these investigations are summarized
in Table 2. For initial temperatures corresponding to
the room temperature and for initial pressures between
8.5-12 bar, 10 experiments were carried out and in two
146 S. Dietlen et al./ Chemical Engineering and Processhzg 34 (I995) I41-149

Table I
Detonation experiments with R134a/air mixtures ignited by wires

RI34a Pressure Temperature Ignition source Explosion Detonation

concentration (bar) (°C) pressure obse~'ed
(% by volume) (bar)

12.3 10.0 20 glowing wire none

12.3 12.5 20 glowing wire none
13.0 15.0 20 glowing wire none
13.0 15.0 20 glowing wire none
13.0 15.0 20 exploding wire none
13.0 17.5 20 exploding wire none
13.0 17.5 20 glowing wire nolle
13.0 12.5 100 glowing wire none
13.0 15.0 100 glowing wire nolle
13.0 17.5 100 glowing wire nolle
13.0 12.5 200 glowing wire nolle
13.0 15.0 200 glowing wire 18.0 none
13.0 17.5 200 glowing wire 22.0 110110
I3.0 17.5 200 exploding wire 22.0 none
I3.0 17.5 200 exploding wire 23.5 llone
13.0 20.0 200 exploding wire 25.0 llone
I3.0 20.0 200 glowing wire 27.0 none
I5.0 20.0 200 glowing wire 25.0 none

cases a detonation was observed. At an elevated initial
temperature of 100 °C and with an initial pressure of
10 bar, a detonation occurred in one of the two mea-
surements conducted.
Figures 8 and 9 show the pressure curves for a
non-detonative and for a detonative reaction initiated
by an incoming detonation wave. The initial pressure
for both measurements was 9 bar and the sample gas
was initially at room temperature. The pressure/time
histories shown as (a) to (d) in both figures were
recorded at distances of 176 cm, 304 cm, 465 cm and
594 cm from the wire employed to detonate the ignition
mixture. Figures 8(a)-(d) depict the decrease in the
pressure amplitude and velocity of the shock wave
created by the initial detonation during its propagation
through the sample mixture. However, in contrast to
Fig. 8, the pressure/time histories shown in Fig. 9 reveal
a detonation propagating through the sample gas. The
velocity of the corresponding shock wave exhibited
only small fluctuations around 1535 m s-i. The detona-
tion pressure in the C - J surface was also virtually
constant at ca. 175 bar and was evaluated from the
pressure curves according to the procedure suggested
in, for example, Ref. [6]. The pressures for the first
peaks shown in Fig. 9(b)-(d) are .substantially higher
than this value and originate from the time dependence
of the relaxation processes in the shock front. Further
peaks occurred at a repeat frequency of 12 kHz and
relate to the cellular structure of the detonation front
indicating a characteristic dimension of the cells in the
order of the tube diameter. A theoretical estimation of
the detonation velocity and pressure was carried out
using the STANJAN computer code [7]. The value for the
standard enthalpy of formation needed as an input
value for the detonation calculation was estimated ac-
cording to the method of Benson [8]. The detonation
velocity and pressure were, as a consequence, calculated
to be 1639ms -~ and 182bar, respectively, in good
agreement with the experimental values.
The detonation limits could not be inferred fi'om the
data presented here. This would require a large number
of further experiments. Nevertheless, it should be noted
that mixtures of R134a/air were capable of detonation
at elevated pressures.
Experhnents with oxygen-enriched RI34a sample
mixtures
Four experiments were carried out with mixtures
consisting of 20% by volume of R134a, 50% by volume
of nitrogen and of oxygen. Compared to the sample
mixture discussed in the previous sections, the relation
between the amount of R134a and oxygen was nearly
the same but the relative amount of nitrogen was lower.
As can be seen from Table 3, the sample gas mixtures
were initially at 10 bar and room temperature.
An incoming detonation wave was twice impacted on
the sample gas mixture which in both cases reacted with
a stable detonation. The corresponding detonation ve-
locities and pressures given in Table 3 are comparable
but as expected slightly higher than those observed for
the R134a/air mixture. Although insufficient experi-
ments were undertaken to provide reasonable statistics,
a plausible suggestion is that detonation is more likely
in this system than in the sample gas mixture with air.
Experiments with an incoming detonation as the
ignition source resulting in a stable detonation provide
 S. Dietlen et al. / Chemical Engineering and Processing 34 (I995) 141-149 147

Table 2
Detonation experiments with R134a/air mixtures ignited by a detonation wave

Pressure Temperature Detonation Detonation pressure Detonation velocity

(bar) (°C) observed (bar) ( m s - i)

8.0 23 none - -
8.5 24 none - -
9.0 20 yes 175 1535
9.0 24 yes > 150 1506
9.0 24 none - -
10.0 24 none - -
10.0 24 none - -
10.0 24 none - -
12.0 24 none - -
12.0 24 none - -
10.0 100 yes 148 1506
10.0 100 none - -

one important aspect of the risks involved in handling
R134a/oxidizer mixtures. However, as will be shown by
the experiments described in the following section, there
is one effect which points to an even greater danger in
handling R134a mixtures. This is the occurrence of
pressure piling resulting in final pressures exceeding
those expected for stable detonations by an order of
magnitude. As can be seen from Table 3, two experi-
ments were carried out with this sample mixture using a
glowing wire as the ignition source. Although the initial
conditions were the same in both experiments, the
behaviour of the reaction differed substantially. In one
case the sample gas mixture exploded with a maximum
final pressure five-times the initial pressure and with a
maximum slope of 3000 bar s -I. In the other experi-
ment the final local pressure greatly exceeded 1200 bar,
i.e. 120-times the initial pressure. This was inferred
from the complete mechanical destruction of one of the
pressure gauges which had been constructed to with-
stand pressures up to 1200 bar. The destroyed pressure
gauge was mounted a distance of 6.26 m from the
ignition wire and 0.185 m from the rear flange. From its
destruction and from the pressure curves measured at
different positions along the tube, a deflagration-to-det-
onation transition (DDT) occurred at a time and posi-
tion where the unburned gas involved was in a state of
elevated pressure caused by a pressure wave initially
preceding the flame front which was overtaken by the
accelerated flame front at a later stage. Similar effects
of pressure piling have been discussed by Craven and
Greig [9] for different gas mixtures, and extremely high
pressures due to this effect have been reported by
Kogarko [10]. As an illustration, the signals measured
by the pressure gauges located at 4.65 m, 5.30 m and
6.26 m from the ignition wire are shown in Fig. 10(a)-
(c). The pressure wave generated by deflagration in the
early stage of the reaction increased in amplitude and
slope during the propagation directed towards the rear
flange of the tube. As can be seen in Fig. 10(a) and (b),
the maximum pressure of this pressure wave increased
from 90 bar to 210 bar during its propagation from the
gauge at 4.65 m to that at 5.30 m relative to the ignition
source. The average velocity of this pressure maximum
between these two positions was 770 m s -1. Figure
10(c) shows the pressure history at the position of the
destroyed gauge is shown up to the point of the de-
struction of the latter at 36 ms on the corresponding
time scale. The signals shown in Fig. 10(b) and (c)
indicate that a deflagration-to-detonation transition oc-
curred between the positions of the corresponding
gauges and that the pressure at the position of the DDT
was a multiple of the initial filling pressure. This ex-
plains the extremely high detonation pressure which led
to the destructive forces mentioned above. The two
steep pressure fronts shown in Fig. 10(a) and (b) prop-
agating from the rear flange towards the ignition source
are the detonation shock wave generated by the DDT
and the shock wave of the detonation after reflection at
the rear flange.
In all the experiments described in this contribution,
only for an oxygen-enriched R134a sample gas mixture
was the effect of pressure piling observed. However,
since pressure piling effects are known to have a poor
reproducibility, they cannot be totally excluded for
mixtures with air.
4. Conclusion
R134a is a non-flammable gas under normal condi-
tions (room temperature, atmospheric pressure) which
exhibits an explosion range in oxygen-enriched atmo-
spheres. It also becomes flammable at increased temper-
atures or pressures. The use of R134a under such
Conditions could result in accidental fires and explo-
sions. The explosion ranges of R134a in mixtures with
148 S. Dietlen et al. / Chemical Engineering and Processhtg 34 (1995) 141-I49

00.
air are strongly influenced not only by temperature and
bar
a)
pressure but also by energy, the type of ignition system ~400.
employed and by the volume of the test vessel. The
minimum ignition pressure was influenced accordingly. 200.
Compared with our results and those reported by
t~, O.
~- .~llri ,, ,
Dekleva et al. [3] the results of Reed and Rizzo [5] give
3 5ms 7
exceptionally low figures for the temperatures and pres-
sures at which certain mixtures of Ri34a and air are time --~
capable of ignition.

6OO
bar b)
,~ 2OO a) 4OO
¢~ bar r.~
200
~= loo
r.~ 0
3 5ms 7
O- I I l
3 5ms 7 time
time --~
600
bar c)
200 4O0
b)
© bar r.~ 2O0
~= 100
0
3 5ms 7
O"
3 5ms 7 time --~
time - ~
00,
"~ bar
200 ~400
c)
bar
2OO
100,
¢,) 0 I I
3 5ms 7
0 t 1 1
3 5ms 7 time - - ~
Fig. 9. Detonation wave propagating in an R134a/air mixture (13%
time --~ by volume of R134a). Pressure cu~'es were measured at (a) 1760 mm,
(b) 3040mm, (c) 4650mm and (d) 5940mm from the flangeat which
the ignition source was situated.
200
d)
bar
100

The de tonability of an R 134a/air mixture was investi-

0 t I 1
b gated for pressures between 8 bar and 20 bar and tem-
3 5ms 7 peratures from room temperature to 200 °C using a
detonation tube 6460 mm in length and 40 mm in di-
time --~ ameter. At 9 bar and 10 bar, stable detonations with a
Fig. 8. Damping of a shock wave during propagation in an R134a/ detonation pressure of 148-175bar and detonation
air mixture (13% by volume of R134a). Pressure curves were mea- velocities of 1506-1535 m s -~ were initiated by incom-
sured at (a) 1760mm, (b) 3040mm, (c) 4650 nun and (d) 5940mm
from the flangeat which the ignition source was situated. The shock ing detonation waves. When an oxygen-enriched
wave was generated by the detonation of an acetylene/nitrogen/oxy- R134a/nitrogen/oxygen mixture was studied at 10 bar
gen mixture. rather than an R134a/air mixture, use of a glowing wire
 S. Dietlen et al./ Chemical Engineering and Processhrg 34 (I995) 141-149 I49

Table 3
Detonation experiments with oxygen-enriched R134a sample mixtures

Pressure Temperature Ignition Detonation Explosion Detonation Detonation

(bar) (°C) source observed pressure pressure velocity
(bar) (bar) (m S-1)

10 23.0 detonation wave yes - 205 1690

10 24.0 detonation wave yes - 222 1637
10 24.0 glowing wire none 5I - -
10 24.5 glowing wire yes - > 1200 -

300. as an ignition source led to the generation of a pres-

bar sure-piling effect. Pressures much greater than 1200 bar
200. were generated in such an experiment. Measurements
showed that the risk of detonation must be considered
loo when R134a/air mixtures are generated at elevated
pressures. Furthermore, the possibility of pressure-pil-
0 t 1 I ing effects causing destructive forces exceeding those of
30 34 38 ms 42 a stable detonation cannot be excluded.
time

300.
t bar
References
b)
200.
[I] J. Sand and D. Andrjeski, Combustibility of chlorodifluoro-
methane, ASHRAE d., (May 1982) 38-40.
100-
[2] K. Nabert and G. Sch6n, Sicherheitstechnische Kennzahlen
brennbarer Gase und Diimpfe mit 6. Nachtrag, Deutscher Eichver-
0 E l I lag, Braunschweig, 1990.
30 34 38 ms 42 [3] T.W. Dekleva, A.A. LindIey and P. Powell, Flammability and
reactivity of select HFCs and mixtures, ASHRAE J., (December
time
1993) 40-47.
[4] ICI product information on the refrigerant 'KLEA 134a'.
300 [5] P.R. Reed and J.J. Rizzo, Combustibility and stability studies of
bar CFC substitutes with simulated motor failures in hermetic refrig-
c) eration equipment, Proc. I7th Int. Congr. Refrigeration, August
20O
I0-17, 1991, Montreal, Quebec, Canada.
[6] M.A. Nettleton, Gaseous Detonations; Their Nature, Effects and
100 Control, Chapman and Hall, London/New York, 1987, p. 58.
[7] W. Glinka, Warsaw University, personal communication, 1994.
0 I 1
[8] R.C. Reid, J.M. Prausnitz and B.E. Poling, The Properties of
30 34 38 ms 42 Gases and Liquids, 4th edn., McGraw-Hill, New York, 1989, pp.
173-190.
time [9] A.D. Craven and T.R. Greig, The development of detonation
Fig. 10. Pressure piling effect after ignition of an oxygen-enriched over-pressures in pipelines, In'st. Chem. Eng. Syrup. Ser. No. 25,
R134a/nitrogen/oxygen mixture (20% by volume of Ri34a; 50% by (1968) 41-50.
volume of nitrogen; 30% by volume of oxygen). The initial pressure [10] S.M. Kogarko, Investigation of the pressure at the end of a tube
was 10bar. Pressure curves were measured at (a) 4650mm, (b) in connection with rapid non stationary combustion, Soy.
5300 mm and (c) 6260 mm from the ignition source. Phys.-Tech. Phys., 28 (1958) 1875-1879.