Fire Safety Journal 91 (2017) 1059–1067

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Fire Safety Journal

journal homepage: www.elsevier.com/locate/firesaf

IAFSS 12th Symposium 2017

Early fire detection: Are hydrogen sensors able to detect pyrolysis of house MARK
hold materials?
⁎
Simone Krügera, , Marie-Claire Despinassea, Tina Raspea, Kai Nörthemannb, Werner Moritzb
a
Division 7.5 Technical properties of polymeric materials, Bundesanstalt für Materialforschung und –prüfung, Unter den Eichen 87, 12205 Berlin, Germany
b
Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany

A R T I C L E I N F O A BS T RAC T

Keywords: We analysed the hydrogen generation during the smouldering of polymeric materials, which are typically used
Fire chemistry in the household, in the Smoke Density Chamber coupled to a new developed hydrogen sensor to detect early
Detection stages of fires. The results of hydrogen generation were compared with the emission of carbon monoxide and
Compartment fires smoke during the fire scenarios. Additionally, the results were compared with parameters used in traditional
Smoke
commercial detection systems. In this scenario, the hydrogen sensor showed encouraging results for the
detection of fires in earlier phase compared to traditional detectors. Furthermore, we tested the new developed
hydrogen sensor in a real room with different fire scenarios. We have also investigated interferences, e.g. steam
and cigarette smoke. The hydrogen sensor could detect hydrogen generation in the earliest stage of fire, even
before CO and smoke were developed in detectable amounts. Therefore, the hydrogen sensor can be applied for
early fire detection in case of pyrolysis. The sensors are quite good for detecting pyrolysis gases. But when it
comes to a fast ignition other techniques are more suitable for it. The sensors are best for combination with
other techniques, such as smoke detectors.

1. Introduction tion of a fire in an early stage. Hydrogen is already generated at the

Smouldering fires are often difficult to detect, and can lead in closed
rooms to personal damage through intoxication, which are detected too
late because of unspecified symptoms. The fires could also develop to
open fire with flames, leading to materials damages. Fire detection is an
effective way to save lives and reduce loss of material properties caused
by fire. A fire needs to be detected as earlier as possible, to allow people
to escape the burning building, and to extinguish the fire source to
avoid propagation and further development of the fire.
Up to now, the commonly used fire detectors are based on the
detection of smoke, heat or flame. These show the disadvantages, that
they lose an alarm, only when enough heat is produced (heat detector),
or when enough light from the flickering of the flame is received (flame
detector), or when enough smoke with relevant particles are produced
(optical smoke detector or ionisation detector). All of these factors (light,
heat, smoke) have to appear in sufficient quantities. Fire detectors for
optical or energetic parameters need well developed fires, to avoid false
alarms. Gas sensors, especially, those for carbon monoxide (CO), are also
commercially available, but also need a relatively high amount of CO
being release which relates to relative long time of decomposition
(pyrolysis) before the alarm is activated.
Hydrogen sensing technology has the advantage, to allow a detec-
beginning of the chemical decomposition of a material (pyrolysis) that
means at an early stage during the development of a fire. Thanks to the
development of a new hydrogen sensor, it is not only possible to detect
a fire in a really early stage, but also to detect the hydrogen in a really
sensitive way. Thanks to the early recognition and extinguishment of
the fire at an early stage (in the best case, the extinction of pyrolysis
before open flames appear), reduction in damage of properties and
people can be achieved. Moreover, our own work showed previously
that FTIR (Fourier transformed infrared) spectroscopy is suitable for
the detection of smoke gases like carbon monoxide CO or carbon
dioxide CO2 [1–4] during different fire scenarios.
Hydrogen is present in the air at a 0.3–0.5 ppm (parts-per million)
level. It is known that under pyrolysis conditions organic matter
releases hydrogen [5–8]. Therefore, the possibility of the application
of hydrogen sensors for the detection of decomposition of materials by
pyrolysis was investigated [9]. The detection of hydrogen for the
detection of fire has been already investigated for some decades [10–
14]. A comprehensive analysis of the hydrogen sensors on the market
has been published by Boon Board et al. [15,16] and Hubert et al. [17].
However, the technologies developed were not selective enough or the
level of energy needed for their functioning was too high for a long term
usage in household, and thus not commercialised. Moreover, the

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.firesaf.2017.04.035
Received 18 February 2017; Received in revised form 12 April 2017; Accepted 18 April 2017
Available online 28 April 2017
0379-7112/ © 2017 Elsevier Ltd. All rights reserved.
S. Krüger et al.
amount of hydrogen produced in different fires has been given contrary
values in the literature, and no clear trend in different fire scenarios
like in the Test Fire scenarios of the EN 54: Fire detection and fire
alarm systems have been emitted.
There are various fire phases according to ISO 19706. Any organic
material, when irradiated to a sufficient heat flux, will decompose,
emits gases, and give off smoke. Smouldering is a process, which is
slow, has low-temperature and is a flameless form of combustion,
caused by heat when oxygen directly attacks the surface of a con-
densed-phase fuel [18]. In contrast little or no oxidation is usually
involved in this gasification process during pyrolysis during pyrolysis,
and thus is mainly an endothermic process. Hydrogen generation is
most likely to occur in pyrolysis processes. For example, an overview of
a pyrolysis mechanism of guaiacol as lignin model compound can be
found in [19].
In this study we investigate a new developed technology for the
detection of hydrogen by capacitance sensors. Therefore, we simulated
the pyrolysis to detect hydrogen generation in the earliest stage of fire,
and compared it with the emission of CO and smoke. The concentra-
tions of the combustion gases components were quantified by FTIR
(Fourier transformed infrared) spectroscopy, and compared with the
hydrogen sensor signal. Interferences of fire gases on the sensor were
evaluated, and conclusions were drawn on the different fire detection
systems.
2. Materials and methods
We simulated different scenarios in the Smoke Density Chamber
(SDC similar to ISO 5659-2) with polymeric materials, which are
typical present in living rooms, e.g. polyethylene (PE), polyurethane
(PUR) and wood. The hydrogen evolution was monitored during the
test by the new developed hydrogen sensor, which was coupled to the
SDC. we further simulated the scenarios with the same materials and
household items in a two room house. In this case the hydrogen
detectors had been mounted on the ceiling of the room. The effectivity
of the hydrogen sensors has been compared with commercially
available smoke and carbon monoxide detectors. Furthermore, we
investigated interferences with other emitted gases, humidity and
smoke.
2.1. The hydrogen MEIS sensor
The hydrogen sensors used in this study are based on a metal/solid
electrolyte/insulator/semiconductor (MEIS) structure [7]. On the
silicon wafer isolators silicon oxide and silicon nitride are grown,
followed by the solid electrolyte lanthanum trifluoride. This ionic
conductor amplifies the signal of the MEIS sensor. As gate material a
palladium layer is deposited on the top. A capacitance element results
from this structure. A capacitance element results from this structure.
When hydrogen is present, the chemical potential of the palladium gate
is changed which results in a change the capacitance of the MEIS
structure. By a feedback mode the capacitance was held constant
during the measurement. So the applied voltage shift is the change of
the chemical potential. The sensors were heated once prior to the test
for reactivation. This heating was performed via a set up based on a
platinum thin film around the palladium gate. The increase in hydro-
gen concentrations is correlated with an increase in the related voltage
shift. A logarithmic dependency between these two parameters exists.
Details of the measurement principle and concentration to voltage
conversion are published elsewhere [7,20,21].
In order to assess the hydrogen concentration during the fire tests,
the determined hydrogen signals in mV must be converted in the
corresponding concentration in ppm. For this purpose, a suitable
calibration is essential. This calibration is very complex and following
parameters must be considered, for example, humidity, other gases like
CO as well as the temperature during the calibration, the concentration
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Fire Safety Journal 91 (2017) 1059–1067
ranges, and number of calibration points, the flow rates and ultimately
a mathematical calibration curve model. The calibration of the MEIS
sensor in different conditions has been evaluated previously [7]. This
calibration was carried out with various hydrogen reference gas
concentrations taking into account this specified parameters (40%
relative humidity, concentration range 1–60 ppm (1; 2; 5; 10; 20; 40
and 60 ppm)) with the relation Um=U0+log(k c), the hydrogen con-
centration c is correlated to the measured voltage Um by the acalibra-
tion parameters U0 and k. More details are published earlier [7,20,21].
The limit of detection of the hydrogen sensor was determined to be
0.5 ppm. The response time and accuracy of the sensor is depending on
gas concentration. At concentrations smaller than 10 ppm the response
time t50 (time to 50% of signal change) is smaller than 1 min and the
accuracy about 5%. A temperature correction was realized to correct
the influence of the temperature on the hydrogen signal. Each sensor
was calibrated before use. To remove any influence of the calibration
used an amount of hydrogen calculated, the measured signal has been
given for most of the test, and the approximated hydrogen value
calculated for the discussion part.
2.2. Bench-scale tests: coupling of the hydrogen sensor with the
Smoke Density Chamber
We simulated different pyrolysis scenarios in the Smoke Density
Chamber (Fire Testing Technology, East Grinstead, UK) with polymeric
materials, which are typical present in living rooms, e.g. polyethylene
(PE), polyurethane (PUR) and wood. The experimental set-up is shown
in Fig. 1.
The SDC was used for determination of the optical smoke density
Ds according to ISO 5659-2. Additional determinations of qualitative
and quantitative composition of smoke gases in order to identify
interferences were measured by directly connecting a FTIR spectro-
meter (Nicolet type 380, Thermo Fisher Scientific GmbH) to the SDC.
The optical density and the smoke gas composition were measured
simultaneously. The sampled gas was conveyed to the FTIR spectro-
meter (0.5 l gas cell heated at 180 °C) through a 1-micron particulate
filter (all heated to 180 °C) via a 2 m long heated transfer line. The
FTIR spectra were measured at a gas temperature of 180 °C, with a
resolution of 0.5 cm−1(16 scans pro spectrum) with a DTGS detector, in
the domain 900–4250 cm−1. The hydrogen evolution was monitored
during the test by the hydrogen sensor, which was coupled to the SDC.
When hydrogen was present, the interaction with the palladium gate
changed the potential. The increase in hydrogen concentrations
correlated with an increase in the related voltage shift.
Fig. 1. Experimental set-up in the Smoke Density Chamber coupled with a FTIR
spectrometer and a hydrogen sensor.
S. Krüger et al.
Fig. 2. Schematic representation of the two rooms used for the tests (dimensions in meter). a) plan (view from top), b) front elevation (view from side).
2.3. Real-scale tests: coupling of the hydrogen sensor and other
detection systems in a 2-room apartment
We performed different fire tests in a 2-room apartment under
smouldering and flaming conditions with the same virgin materials
which were investigated in the bench-scale test, a combination of
materials as a mixed crib and furnishings. The structure of the room
and the location of measurement technology are similar to EN 54, but
with reduced dimensions. The specimens stood in the middle of the
room on a hot plate (pyrolysis) or on the ground in a fire pan (flaming).
In the middle of the room was a heating plate, which proved in
preliminary tests an appropriate pyrolysis source. Different tempera-
tures between 350 and 600 °C could be set. A Bunsen burner was used
for fire scenarios with flaming conditions.
The measurement technology was positioned on a ring-on the
ceiling of the room with a radius of 1.8 m from the room center. The
used experimental set-up is shown in Fig. 2.
The new developed hydrogen sensor MEIS [7] was used to measure
the emitted hydrogen concentration at four different positions. The CO
emission was determined in Room 1 using a mobile FTIR spectrometer
(Gasmet Dx4000N, Ansyco GmbH). The emitted gases were collected
through a removable probe sensor corresponding to the H2 sensors.
The sampling gas was conveyed to the FTIR spectrometer through a 1-
micron particulate filter, directly behind the probe tube. The gases were
continuously collected and analysed during the fire tests. The FTIR
spectra were measured online by a MCT detector with a resolution of
8 cm−1 and 16 scans pro spectrum, keeping a gas temperature of 50 °C
in the gas cell (0.5 l) of the spectrometer in the domain 900–
4250 cm−1. The path length was 5 m, and the sampling flow 3 l/min.
The spectrometer was calibrated for the relevant chemical substances
contained in smoke, allowing the quantitative evaluation of smoke
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gases concentrations. Commercially available CO detectors (gas cell)
were located on the ceiling. The CO concentration values measured in
FTIR were compared to the indication of CO detectors (alarm or not).
In addition, a paramagnetic oxygen analyzer was used to measure
the oxygen availability, and in order to identify problems with cross-
sensitivities. The temperature was measured by thermocouples (TE) at
various positions to identify the influence of temperature on the
hydrogen sensors. Furthermore, different commercially available
smoke detectors were located on the ceiling, so a direct comparison
with the hydrogen sensor in terms of the limits of use and functionality
in these particular fire scenarios was possible.
To avoid false alarms, it must be excluded that the sensors react to
noises, such as water vapor. Therefore 300 ml of water were evaporated
in a pan during the test. We investigated the influence of cigarette
smoke on the hydrogen signal. For this purpose, four cigarettes and two
cigarillos were smoked directly underneath the ceiling sensors (CO,
smoke, H2).
3. Results and discussion
3.1. Hydrogen generation during pyrolysis of different materials in
the Smoke density chamber (SDC)
The hydrogen sensor could detect hydrogen generation in the
earliest stage of fire, so quantitatively measurable hydrogen concentra-
tions were detectable with a heating source set in the temperature
range of 300–400 °C. These temperatures correspond approximately to
an external heat flux of 4.6–9.3 kW/m2. In addition to the specific
optical density, the concentration of smoke gas components was
evaluated and compared with the hydrogen generation. A comparison
of the resulting H2 detection signal, the mass loss, the CO concentra-
S. Krüger et al. Fire Safety Journal 91 (2017) 1059–1067

for wood, PE, PUR. The transmission value is above 80%, which means
no alert by smoke detector. The CO emission is very low, which means
no alert by CO detector. Carbon monoxide is produced in detectable
concentrations (above 3 ppm) at later time (9 kW/m2) compared with
the hydrogen signal (already at 5 kW/m2). Conclusion of this bench-
scale fire tests is, that the hydrogen sensor is suitable to detect the
decomposition of the material in an early phase of fire, that means
smouldering conditions, before ignition of the materials due to the
early release of hydrogen by thermal decomposition. The measured H2
signal voltage rises corresponded to a hydrogen concentration value
higher than 40 ppm, reached at source temperature of 350 °C for wood,
400 °C for PUR and 500 °C for PE.

3.2. Hydrogen generation during fire tests in a 2-room apartment

In order to validate the efficiency of hydrogen sensors under real

Fig. 3. H2 detection signal, mass loss, CO concentration and light transmission under
different external irradiances in the Smoke Density Chamber coupled with FTIR
spectrometer and the hydrogen sensor during pyrolysis of wood.
tion and the light transmission depending on different external
irradiances are shown in Fig. 3 for the example of wood.
The evolution of hydrogen during the pyrolysis of a sample was
evaluated by increasing the irradiances depending on time (Table 1).
The decomposition of the material was monitored by the mass loss. The
original mass of the wood specimens was e.g. about 33 g and the
relative mass loss in summary was 7.4 g. For low irradiances, the H2
sensor detected the pyrolysis of the material, with the release of
hydrogen. The H2 signal from the detector was intense enough to give
a recognizable output (Fig. 3, example wood). At the same time, values
for CO concentration are under the threshold of most CO detectors
(mainly around 20–30 ppm). The release of smoke was characterized
by the decrease in the light transmission in the SDC by a photometric
system. The change in the light transmission is dependent on the
material. The decrease was strong at the beginning of the pyrolysis.
Depending on the material, the recorded H2 signals prove the decom-
position of the material at the same time, or even earlier, than a smoke
detector based on light transmission could do.
The resulting hydrogen signal corresponds to the decomposition of
the material. Table 1 shows the comparison of CO emission, light
transmission and H2 signals during pyrolysis depending on the
material: PE, wood and PUR foam. The H2 emission starts with low
irradiances (5 kW/m2) with concentrations in hydrogen under 10 ppm
conditions, different fire scenarios have been successfully implemented
in a 2-room apartment container. First, the positive results for
hydrogen detection should be confirmed from the bench-scale tests
and transferred to the real scale tests. For this reason, the same
materials as in the SDC experiments were tested in a 2-room apartment
container. Later a combination of materials and different household
items were tested. Furthermore, the influence of water vapor and
cigarette smoke were investigated to identify interferences and in order
to avoid false alarm.
3.2.1. Pyrolysis of pure materials
The emitted hydrogen concentration of pure materials was determined
during pyrolysis or flaming conditions. Additionally, the CO emission was
determined by FTIR spectroscopy. These values were compared to the
indication of CO detectors, which were positioned on the ceiling to identify
interferences with the hydrogen sensors. In addition, other gases were
detected online and quantified in order to identify problems with cross-
sensitivities. A comparison with existing technologies such as CO
detectors and smoke detectors is drawn.
The different materials were tested during pyrolysis at a heating
source temperature between 350 and 600 °C, see Table 2. Results of the
different detection technologies, H2 signal, CO concentration and
smoke detector responses are summarized in Fig. 4. The behavior
during pyrolysis is as expected dependent on the material. CO detectors
did not give any alarm during all the fire scenarios, and are then not
represented in Fig. 4.
The new hydrogen sensors showed a fast response to the decom-
position of wood, PVC and polyurethane (PUR) foam by strong
increase of the H2 signal during the first ten to twenty minutes. In
case of pyrolysis of wood, the smoke detectors alarmed after 4 min and
9 min. But also the hydrogen signal increases very quickly, therefore
both technologies would be suitable for early fire detection.
In case of PUR foam and PVC only a very small concentration of CO
could be detected during pyrolysis. Therefore, both CO detectors didn’t
alarm over the entire test period. Also no smoke detector alarmed

Table 1
Results from pyrolysis at increasing heat fluxes in the SDC, no pilot flame.

Material Irradiance Duration H2-signal H2 CO Transmission Mass loss

[kW/m2] [min] [mV] [ppm] [ppm] [%] [g]

Wood 4.6 16 0–8 < 10–15 0 1. 100–92 0.4

6.7 49 8–30 15- < 40 0–1 2. 92–91 2.2
9.3 29 30–52 > 40 1–9 3. 91–80 1.4

PUR foam 4.6 10 0–2 < 10 0 4. 99–98 0

6.7 20 2–10 10–20 0 5. 98–54 0.43

PE 4.6 13 0–2 < 10 0 6. 100–98 0.06

6.7 23 2–6 < 10–15 0–5 7. 98–78 0.17
9.3 20 6–12 15–20 5–13 8. 78–53 0.27

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Table 2
Emitted gases from pure materials during the fire tests in the 2 room apartment.

Material Conditions Gas detected Max. CO [ppm] CO2 release H2O release Other gases

Wood Pyrolysis 600 °C CO, CO2, H2O 27 80 0.15 –

Pyrolysis 600 °C CO, CO2, H2O 27 39 0.15 –
PUR Pyrolysis 350 °C CO2, ethane 12 0 0 Ethane (5 ppm)
PVC Pyrolysis 350 °C CO2 – 59 0 –

PE Flaming 600 °C CO, CO2, H2O, ethane, ethylene 25 1190 0.15 Ethane (16 ppm)
Ethylene (4 ppm)
Pyrolysis 450 °C H2 O – 0 0.17 –

during the duration of the test, but the hydrogen detection technology
was appropriate in this case for early fire detection, with increasing
signal over time.
The concentration measured by FTIR at the roof was under 25 ppm
for most of the tests, over the whole test duration. The CO concentra-
tion reached the 25 ppm limit only for wood after 40 min of the test
(Fig. 4). The 25 ppm limit is the limit for an alarm defined by the BS
EN 54–26:2015 Fire detection and fire alarm systems for carbon
monoxide detectors. That means that only in the case of wood, an
alarm by a CO detector would occur. In our case, the two CO detectors
mounted on the ceiling did not given any alarm during the test times.
Furthermore, the two H2 sensors showed reproducible results, even
though they were placed diametrically opposite of each other (Position
1 and 2).
Bench-scale and large scale tests of the pure materials, apart from
PE, show similar good results in terms of hydrogen detection, also
compared to CO and smoke detectors. If we compare all the measure-
ment of the pure materials at low heating plate temperatures, including
PE, we see the limit of the H2 sensor. The detection of hydrogen is not
always possible, as demonstrated by the example of PE. Emitted gases
reduce the hydrogen signal during the fire tests. The proposed thresh-
old for the hydrogen sensor in the range of 20–25 mV is not reached. In
this case both smoke detectors triggered an alarm, so that should be the
preferred technique.
3.2.2. Reproducibility of the H2 sensors
The H2 sensors showed good reproducibility results in similar
pyrolysis conditions with the same materials (Fig. 5). In case of wood
and polyurethane (PUR), the signal response to the pyrolysis is
respectively, similar, with a strong slope between the start and 15 min,
and then levelled off after 25 min, or 30 min, respectively. The plateau
occurred at different values between the two tests of the same material,
and a difference in the amount of hydrogen produced is expected.
3.2.3. Pyrolysis of mixed cribs
According to the fire tests of the pure materials, a combination of
different materials in form of a mixed crib was pyrolysed to validate
hydrogen sensors. The selected materials reflected a typical average
living room and the mixed crib contained 50% wood, 20% PE, 20%
PUR and 10% PVC.

Fig. 4. Results of the different technologies used in a 2 room apartment: The H2 sensors (H2 signal), CO concentration measured by FTIR (for the CO detectors) and smoke detectors
(0=no alarm, 1=one detector alarm, 2=two detectors alarm) during pyrolysis of wood, PUR foam, PVC and a mixed crib.

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S. Krüger et al.
Fig. 5. Reproducibility of the investigated H2 sensors in two tests at two positions on the
ceiling (position P1 and P2) for Wood and PUR foam.
The hydrogen sensors responded very early and the hydrogen
signals increased until the end of the test to value about 30 mV, which
is shown in Fig. 4. This signal corresponded approximately to a
hydrogen concentration of 4 ppm.
The smoke detectors gave no alarm until 88 min, after this long
time only a single smoke detector responded and none of the CO
detectors triggered an alarm.
No emission of carbon monoxide was detected using FTIR spectro-
scopy. In contrast both hydrogen sensors on the ceiling showed
significant hydrogen signals. In case of the mixed crib the hydrogen
technology was the only detection technique that could detect the
pyrolysis, while smoke and CO detectors triggered no clear alarm.
3.2.4. Pyrolysis of household items
Various fire scenarios with household items were performed in
order to test the hydrogen sensors over a wide range in terms of
different material used, and fire scenario which are typical for everyday
life. Following typical household materials and scenarios were inves-
tigated: glowing ashes on an arm chair, kitchen paper roll left on a
stove, kitchen sponges left on a stove and in the pan burnt food.
In Fig. 6 are summarized the results of the hydrogen sensor signals
(with temperature correction), the CO concentrations on the ceiling as
well as the triggering of an alarm of the smoke detector. In Table 3 are
shown the emitted gases measured by FTIR spectroscopy in order to
identify interferences.
All of the investigated household items smouldered in the per-
formed fire scenarios with the exception of the forgotten kitchen paper
roll that additionally ignited. The left kitchen paper roll on stove ignited
after 97 min. The smoke detectors triggered an alarm after 93.9 min
and 92.8 min. The hydrogen generation is about 25 mV at this time and
increases up to 70 mV. The hydrogen sensors were able to reach a
significant signal for an alarm in case of flaming combustion. CO
detectors triggered no alarm. In case of the left kitchen sponges on
stove the CO detectors gave no alarm, the smoke detectors triggered an
alarm after 2.9 and 1.1 min. At this time the hydrogen signal was about
25 mV. In case of the burnt food in a pan the CO detectors gave no
alarm, the smoke detector showed several false alarms, the alarm
triggered only for a few seconds and stopped again. The hydrogen
signals were about 30 mV, when the smoke detectors released a signal.
The hydrogen technology in this case is able to reach a significant signal
for an alarm, without false alarm.
In conclusion it could be shown that the hydrogen sensors were able
to detect smouldering in closed rooms in a very early stage of the fire
phase in the performed scenarios and it gave a good reproducibility
between the two independent sensors on the ceiling. The measured
hydrogen signals were about 25 mV. The CO concentration was in two
from the four scenarios of household items pyrolysis higher than
25 ppm, but none of the CO detectors triggered an alarm during test
duration. The smoke and CO detector in the next room triggered no
alarm in none of the performed fire scenarios.
When comparing the hydrogen sensors with the smoke detectors,
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Fire Safety Journal 91 (2017) 1059–1067
the smoke alarm was triggered in all four cases. In case of the
smouldering arm chair, the second smoke detector between the trigger
an alarm 20 min after the first one, even if they were positioned
equidistant from the fire position. The reproducibility of the smoke
detectors is not satisfactory in this case, whereas both hydrogen
sensors showed reproducible results in this test.
3.2.5. Limits of the technology
Various fire scenarios were performed to simulate a developed fire
in order to validate the H2 sensor under flaming conditions. Firstly, a
scenario implicated the ignition of PE after pyrolysis at about 600 °C
heat source temperature, and secondly, the ignition of a carpet has
been forced by the use of a Bunsen burner.
In case of the first fire scenario, PE ignited after 9.5 min of pyrolysis
on the hot plate (600 °C). The hydrogen signal showed a negative value
just before ignition. This behavior has been also observed due to the
interaction of non-quantifiable pyrolysis products with the sensor
surface during the bench-scale fire tests and could be confirmed for
the real scale fire test too. The smoke detectors were able to detect the
decomposition already after 5 min and the related smoke. Both smoke
detectors triggered an alarm. The CO concentration measured in FTIR
was low and the CO detectors could not trigger an alarm. In contrast
when PE was only pyrolysed at lower temperatures (300–500 °C)
without ignition, even before the CO detectors could trigger, the
hydrogen sensors have already reached the threshold of 25 mV
proposed by us as a threshold for an alarm.
In case of the second forced flame conditions, a carpet sample was
ignited first on two corners (Tepp_01) and secondly ignited on all four
corners (Tepp_02) with use of a Bunsen burner. The hydrogen sensors
showed a not reproducible signal, due to cross-sensitivities. The oxygen
concentration for both tests was ca. 21%, and a reduction in oxygen is
excluded as a cause for a cross-sensitivity. None of the fire detection
techniques could detect the fire at an early stage for Tepp_01, neither
smoke or CO detectors triggered an alarm. In case of Tepp_02 the
smoke detector triggered an alarm due to the more developed fire. In
contrast the hydrogen sensors and CO detectors were not suitable for
the detection of these scenarios.
The hydrogen sensors are not suitable for each fire scenario. They
show limits of use during decomposition of certain materials, due to
the emission of degradation products (such as in the decomposition of
PE) and/or oxygen consumption. In case of the presence of a flame, the
sensors show a strong decrease of the hydrogen signal. The reasons for
this decrease are probably in the cross sensitivity to water. These
products are formed particularly in the presence of a flame, and/or by
oxygen consumption. The cross-sensibility of the sensors needs to be
further improved for the fast developing fires. In this case, combina-
tions with smoke detectors are required.
3.2.6. Hydrogen production over all the tests and noises
The maximal hydrogen concentrations calculated from the hydro-
gen signals during each fire test in the 2-room apartment are
summarized in Fig. 7. The calculated hydrogen concentrations are in
the range between 1 and 19 ppm and a domain for a possible alarm
would be between 2 and 3 ppm. This alarm threshold is reached for the
majority of the fire scenarios tested in this study.
Additionally new scenarios have been carried out to evaluate noises
on the hydrogen measurements, such as cigarette smoke and water
steam (H2O). They are reported in Fig. 7 too. In the case of water
boiling generating water steam, none of the commercial fire detectors
triggered a signal.
After 30 min of test the hydrogen signal reached the threshold value
of 25 mV. That means that the water vapors influenced the hydrogen
signal, even after a long time. In order to eliminate this influence, the
calibration of the hydrogen sensor must be further improved.
The influence of cigarette smoke on the hydrogen signal was
investigated. No smoke detector triggered an alarm during smoking.
S. Krüger et al. Fire Safety Journal 91 (2017) 1059–1067

Fig. 6. Results of the different technologies used in a 2 room apartment: the H2 sensors (H2 signal), CO concentration measured by FTIR (for the CO detectors) and smoke detectors
(0=no alarm, 1=one detector alarm, 2=two detectors alarm) during pyrolysis of house hold items.

Only after 11 min, when the cigarette was held directly under the
smoke detector, the smoke detector gave an alarm. CO2 concentration
rose twice; CO could not be detected during this time. The CO detectors
did not emit any warning signals. The hydrogen signals increased
during smoking and reached values of 17–37 mV. The hydrogen
sensors are able to detect the smouldering of the cigarettes, with
signals above the proposed threshold at the end of the test. This
unwanted effect is a limitation of the sensors, and cross-sensibility
need to be improved.

3.2.7. Comparison of the hydrogen sensors with CO and smoke

detectors
An overview for the performed fire tests is given in Fig. 8, in which
the CO concentration versus H2 concentration are plotted and the 17
fire scenarios depending on the detection technologies (Smoke, CO and
H2 detector) and their success are included.
The experiments represented with a black symbol are fire tests with
a flame; there is no detectable hydrogen emission (cross sensitivity).
The grey-color symbolized tests are attempts of the influence of
Fig. 7. Determined H2 concentration (max. H2 concentration of hydrogen sensors H004
and 007 on the ceiling) in [ppm] depending on the fire scenario and possible alarm
limits.
interferences, such as cigarette smoke and steam. It has been found
that the CO detectors are not suitable for very early fire detection in the
performed fire tests, except three scenarios containing cellulose (wood,

Table 3
Emitted gases from the household items during the fire tests in the 2 room apartment.

Material Conditions Temp. Sample [°C] Gas detected Max. CO [ppm] CO2 release H2O release Other gases

Carpet Forced ignition n/A CO, CO2, H2O 6 959 0.17 Ethane (9 ppm)
Forced ignition n/A CO, CO2, H2O, 12 1199 0.14 –

Mixed crib Pyrolysis 250–270 °C CO2, H2O – 77 0.09 –

Pyrolysis 250–270 °C CO2, H2O – 44 0.14 –
Kitchen roll Flaming 290 °C CO, CO2, H2O, methane 47 972 0.19 Ethane (5 ppm)
Kitchen Sponge Pyrolysis 300 °C H2O – 38 0.05 –
Food (burnt cheese) Smouldering (Frying) 240 °C CO2, – 95 0.03 Ethane (3 ppm)
Armchair Pyrolysis n/A CO, CO2 30 125 0.03 Ethane (13 ppm)

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S. Krüger et al.
Fig. 8. Representation of the three fire detection technologies used (smoke, CO and the new developed H2 detectors) and the corresponding extremum obtained over the tests time.
armchair and paper roll). The two most effective technologies are
smoke and hydrogen sensors. The developed hydrogen sensors are
competing with the commercially available smoke detectors in most of
the case. In seven fire scenarios the hydrogen sensor triggered an alarm
earlier than the smoke detector, and in three fire scenarios, they trigger
an alarm at the same time than the smoke detectors, considering a
threshold of 25 mV for an alarm of H2 detector. The hydrogen sensors
are recommended for pyrolysis detection in an early stage. Reasons for
the good results of the hydrogen sensor can be: (1) H2 is released
earlier and at lower temperature during the pyrolysis process and (2)
H2 can be easier and more accurate detect. The early detection of
hydrogen is due to the volatility of H2 and the high sensitivity of the
sensor. The limit of quantification of the hydrogen sensor is 0.5 ppm.
This concentration is in the same range of environmental amount of
Hydrogen in the atmosphere [20]. Due to the logarithmic dependency
between Hydrogen concentration and measured signal the sensor is
able to detect even small concentration changes.
Regarding the pyrolysis, we could show in our experiments, that H2 is
released earlier than CO. The detection is depending on the sensitivity of
the sensors. The limit of quantification of CO is 11 ppm (FTIR measure-
ments). In contrast the threshold of most commercial CO detectors is
mainly around 20–30 ppm. We orientated our interpretation on this
threshold. Under these circumstances the hydrogen sensor showed the
better results in comparison with the FTIR and the CO detectors, in
particular regarding practical applications.
A theoretical work in [19] showed that CO is released earlier than H2
in the case of the pyrolysis of cellulose, hemi-cellulose and lignin. The
release of H2 and CO is dependent on the composition and structure of
the material. These natural components contain oxygen groups in their
chains, and the pyrolysis of the chains releases CO as decomposition
product. The release of CO as pyrolysis product is not possible in
material that do not contain oxygen, without additional oxidation. We
used in our study a new generation of hydrogen sensor that are more
sensible that the existing sensors used in this study, and a direct
comparison is not possible. Further investigations that use CO detecting
methods with higher sensitivity and lower limit of quantification
combined with our hydrogen sensors will allow a better evaluation of
the time of release of H2 compared to CO. If settings are lower e.g. 2–
3 ppm for CO sensors, maybe CO sensor can give also an early alarm.
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Fire Safety Journal 91 (2017) 1059–1067
But due to the limitations of the hydrogen sensors, especially due to
the need of further developments, the hydrogen sensors are not
recommended for every fire scenario. When fast developing fire
scenarios are possible, the most successful system would be a combi-
nation of smoke detector and hydrogen sensor for the highest safety.
4. Conclusion
The hydrogen sensor could detect hydrogen generation in the
earliest stage of fire, even before CO and smoke were developed in
detectable amounts. Therefore, the hydrogen sensor is adapted for
early fire detection in case of pyrolysis.
In bench-scale tests we could identify advantages of the sensor for
the early detection of smouldering fires when the external irradiance is
lower as 15 kW/m2 and the source temperature under 500 °C. Under
these conditions we could find an evidence of low concentrations of
hydrogen, before smoke and/or CO detectors could alert. The investi-
gated hydrogen sensors have a significant advantage in comparison to
the CO detectors in this case.
We could determine a maximum hydrogen concentration of 3–
40 ppm, in bench-scale tests and in a 2-room container apartment the
fire tests with household items typical for a habitation. The concentra-
tions depend on the fire conditions and the materials. The hydrogen
sensor is a possible alternative or supplement to traditional smoke and
CO detectors for improved safety.
In some cases of forced flaming conditions, the hydrogen sensors
signals showed strong cross-sensitivities, and the signal did not reach a
reliable value. This is a limitation of the sensors. No systematic
correlations could be made between the change of the hydrogen signal
by cross-sensitivity and the oxygen concentration, the gas concentra-
tion of the by-products (measured by means of FTIR spectroscopy) and
the presence or absence of a flame. For the end use applications of the
detectors, the main influencing factors and cross-sensitivities need to
be further evaluated and meliorated. Moreover, a combination with
smoke detectors is advised for an alarm in almost all scenarios tested.
The MEIS hydrogen sensors have the advantage, that their fabrica-
tion is based on the semiconductor technology. Low production costs
can be achieved, which gives a basis for the competitive improvement
of fire detectors. Moreover, a combination with smoke detectors still
S. Krüger et al.
provides a positive economical aspect. The results presented in this
study give an outlook for the further development of the hydrogen
sensing technology, for an improved fire safety.
Acknowledgements
The authors thank the Federal Ministry for Economics and
Technology, Germany, for its financial support (KF 2201068DF3).
The authors thank Vinicius Da Silva Duarte and Benjamin Klaffke for
the technical support during the room fire tests.
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