This article was downloaded by: [University of Auckland Library]

On: 13 October 2014, At: 14:48

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Combustion Science and Technology

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gcst20

Ignition Temperatures of Metals in Oxygen Atmospheres

a a
N. M. LAURENDEAU & I. GLASSMAN
a
Guggenheim Laboratories, Princeton University , Princeton, New Jersey
Published online: 10 May 2007.

To cite this article: N. M. LAURENDEAU & I. GLASSMAN (1971) Ignition Temperatures of Metals in Oxygen Atmospheres,
Combustion Science and Technology, 3:2, 77-82, DOI: 10.1080/00102207108952274

To link to this article: http://dx.doi.org/10.1080/00102207108952274

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the
publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations
or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any
opinions and views expressed in this publication are the opinions and views of the authors, and are not the
views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be
independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses,
actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever
caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Combustion Science and Technology, 1971, Vol. 3, pp. 77-82 © GoRDON AND BREACH, SCIENCE PUBLISHERS LTD.
Printed in Belfast, N. Ireland

Ignition Temperatures of Metals in Oxygen Atmospheres

N. M. LAURENDEAU AND I. GLASSMAN
Guggenheim Laboratories, Princeton University, Princeton, Nell' Jersey

. Abstract-The ignition temperature of ten common non-toxic metals has been determined experimentally in an
oxygen environment. In this investigation a induction furnace facility that emphasized the pre-ignition surface
oxidation effects upon the ignition temperature was used. The bulk ignition temperatures of barium, bismuth,
calcium, iron, lead. magnesium, molybdenum, strontium, tin, and zinc were found and compared to the previous
results of Grosse and Conway. The differences in the results are attributed '0 how the heating cycle is
Downloaded by [University of Auckland Library] at 14:48 13 October 2014

carried out and how the cycle affects the surface oxide coat.

I. INTRODUCTION Te,;t, which is defined as the lowest initial surface

In the past decade, the use of metals as a chemi-
cal fuel in rocket propulsion devices has stimulated
new interest in the combustion and ignition of
pure metal species. Investigation showed that in
particular early quantitative modeling of ignition
processes was applicable to a few limited cases
(Mellor, 1967). A qualitative model of hetero-
geneous ignition, postulated by Mellor (1967),
[see also Glassman et al. (1970)], has been used to
explain much of the phenomena inherent to the
ignition of nearly all metals. Unfortunately,
neither a quantitative extension of this model, nor
any other quantitative work, can be verified, due
to the limited data available on the ignition tem-
perature of various metals. The present investiga-
tion attempted to fill this need via an experimental
determination of the bulk ignition temperature of
ten common non-toxic metals in a pure oxygen
atmosphere.
II. THEORETICAL BACKGROUND
The general model of heterogeneous metal igni-
tion has been discussed at length by Mellor (1967)
and modified to a degree by Laurendeau (1968).
This work was reviewed by Glassman, et al.
(1970). Only those qualitative concepts useful in
the present investigation are repeated here.
As in other heterogeneous systems, metals are
known to be capable of self-heating to ignition in
an oxidizing atmosphere, under the proper cir-
cumstances. The model of Mellor (1967) showed
that an unstable equilibrium surface temperature,
characteristic of the self-heating potential of a
particular metal particle, could be defined. This
temperature is the so-called critical temperature,
4
temperature from which the surface may self-heat
to reach the steady-state combustion configuration.
Ted t is commonly called the spontaneous ignition
temperature in the literature, but here is labeled
the critical temperature in order to avoid confusion
with the experimental ignition temperature. The
ignition temperature, Ti g n , is experimentally de-
fined to be that temperature at which there occurs
the most rapid rate of change with time of both
light intensity and sample temperature, i.e., the
flame appears. This distinction between the critical
temperature and the ignition temperature is made
to allow for the possibility of the existence of a
self-heating or ignition delay time.
Metal ignition is inherently more complicated
than the heterogeneous ignition of other simple
fuel-oxidizer systems due to the formation of solid
phase products on the surface during the pre-
ignition process. Isothermal oxidation experiments
have shown that, in general, the metal oxide film is
protective at lower temperatures, and non-protec-
tive at higher temperatures. This phenomenon
usually is explained by assuming that the oxide
film has either become porous or has cracked and
hence offers no protection at higher temperatures to
further oxidation of the surface by the surrounding
oxidizing environment. The temperature at which
the oxide surface becomes non-protective is called
the transition temperature, T t m ns . Below this
temperature, simple low temperature metal oxida-
tion occurs.
Usually, the non-protective nature of the oxide
film is characterized by an isothermal surface
reaction rate independent of both time and, hence,
the amount of metal previously consumed in the
reaction. Thus, Tt,ans can also be defined as the
 78 N. M. LAURENDEAU AND I. GLASSMAN
lowest temperature above which the metal-oxidizer
system is controlled by a time-independent oxida-
tion rate that persists until metal ignition occurs.
The transition temperature is usually assumed to
be a characteristic temperature of a particular
metal-oxidizer complex and is usually attributed to
stress or thermal cracking of the oxide film or
perhaps melting of the oxide. Laurendeau (1968),
following a suggestion by Kuehl (1965), has shown
experimentally, however, that Tt m " , (and, hence,
T l o ,,) of both zinc and aluminum is pressure
dependent. The transition temperature is controlled
by the vapor pressure of the metal, which acts to
Downloaded by [University of Auckland Library] at 14:48 13 October 2014
break the oxide shell by ind ucing a sufficient pres-
sure differential across its radial thickness (Glass-
man et al. (1970) and Laurendeau (1968».
For any particular metal, the transition temper-
ature may be greater or less than the critical tem-
perature. If Tt,m" > Tn'ib then T;o" >T tm",
and the ignition temperature of the metal is called
transition temperature controlled; if Tn,!t > Tt m " "
>
then T l o " Tn'lt and the metal is called critical
temperature controlled. Most metals are critical
temperature controlled and a few, such as aluminum
and beryllium are thought to be transition temper-
ature controlled.
III. EXPERIMENTAL DESCRIPTION
Bulk ignition temperatures were obtained through
the use of an induction furnace. In the context
used throughout this paper, bulk infers small
surface area to volume ratio. This heating method
strongly duplicates pre-ignition surface oxidation,
since the resistance of the metal surface to an in-
duced current determines the bulk temperature of
the sample. Moreover, induction heating allows
the use of a nearly room temperature environment,
in contrast to previous measurements in a resistance
furnace. Practically, this type of furnace system
allows uniform, rapid heating and attainment of
higher temperatures.
Induction heating has a disadvantage, however,
in that there are unknown consequences upon the
surface reaction rate of the so-called skin effect, i.e.,
the concentration of the heating process upon the
surface of the sample. Nevertheless, this effect
may be negligible, since Mellor (1967) studied
temperature variations in metals with induction
heating, and found; (I) thermocouples placed at
various positions in the sample simultaneously
indicated ignition at essentially the same tempera-
ture; (2) bulk ignition temperatures did not change
as the heating rate was varied over a reasonable
range (10-200 °C/min).
Most of the present results were obtained using
a 4t turn, 2 in. diameter, copper, water-cooled
work coil. The coil carried a high frequency cur-
rent (0.5-0.7 MHz) with a high impedance, low
voltage circuit powered by a radio frequency
generator, model 10 KW-2DFCT/LA, built by
McDowell Electronics, Inc. The furnace was
designed to establish automatic control of the
heating process at a specific preset value of the
sample heating rate.
A schematic of the apparatus is depicted in
Figure I and the heating configuration is shown in
Figure 2. All crucibles were made of Alundum.
A chromel-alumel thermocouple protected with
double bore Alundum tubing was used in all
experiments. The thermocouple was placed in the
center of the sample and calibrated whenever pos-
sible by measuring the sample freezing point. The
average experimental error in these investigations
was on the order of 5°C.
All runs were made in atmospheres of pure oxy-
gen (99.5% purity) at pressures of 300 torr, I atm.,
and 5 atm. Mellor (1967) previously showed that
the effect of heating rate on T;o" was nearly negli-
gible in the regime of 10 to 200°C/min for bulk
temperature measurements in oxygen atmospheres.
Hence, the present investigation used heating rates
of 75 and 150 DC/min, the faster rate was used for
metals which ignited above 1000 DC.
All metals were obtained in rod form from
A. D. MacKay, Inc., and were cut to a surface to
volume ratio (S/ V) of 0.24-0.36 mm". This value
..-
M'~ING
C~A"'8EFI
4100 cu. IN.
INDUCTION FURNACE FACILITY TEST APPARATUS SCHEMATIC
FIG. 1. Induction furnace facility lest apparatus
schematic.
 IGNITION TEMPERATURES OF METALS IN OXYGEN ATMOSPHERES 79

IV. RESULTS AND DISCUSSION

~----P:===:::J _WATER IN
FIRE BRICK
SCHEMATIC OF EXPERIMENTAL CONFIGURATION
FOR INDUCTION HEATING
Downloaded by [University of Auckland Library] at 14:48 13 October 2014
Table II lists the ignition temperatures to the
nearest 5 degrees of the metals investigated.
Considering the unknown effects of certain envi-
ronmental factors, a scatter of ±25 is considered
satisfactory.
A. The effect of ambient pressure
The present investigation was not expected to
demonstrate a large variation in ignition tempera-
ture with pressure since the pressure range studied
TABLE II

Metal Bulk Ignition Temperatures

FIG. 2. Schematic of experimental configuration
for induction heating. Ignition Average ign.
Metal Pressure temperatures ('Cl temp (OC)

Ba 300 torr 550, 560, 620, 630, 590 ± 45

of S/ V coincides with the middle of the bulk range I atm 480, 510, 570, 650 550 ± 90
as determined by Mellor (1967). Table I lists 5 aim 535, 540, 600 560 ± 30
Bi 300 torr 780, 805, 810, 825 805 ± 25'
alphabetically all ten metals used in the present I aim 715, 735, 750, 750 735 ± 20
investigation, along with their purity, average 5 atm 715,735,760 735 ± 25
geometrical dimensions, and average surface to Ca 300 torr 790, 795, 800, 800 795 ± 5
volume ratio (S/ V). I atm 785, 785, 805 790 ± 10
Before all tests, most metal samples were washed 5 atm 760, 775, 805 780 ± 20
Fe 300 torr 1310, 1320, 1330 1320 ± 10
in hexane and allowed to dry and degas in a room I atm 1300, 1310,1340 1315 ± 20
temperature environment for 24 hrs. The three 5 atm 1285, 1300,1315 1300 ± IS
metals, barium, calcium, and strontium, which Ph 300 torr 845, 850, 860 850 ± 5
oxidize quickly at room temperatures, were stored I atrn 845, 855, 860 850 ± 5
5 atm 810,830,840 825 ± 15
and machined under mineral oil. I n early experi- Mg 300 torr 630, 635, 635 635 + 5
ments, they were washed in hexane for one hour I atm 630, 640, 640 635 ± 5
at room temperature and then degassed in a vacuum 5 atm 620,620,620 620
desiccator for at least 24 hrs. In later experiments, Mo 300 torr 795, 795, 810, 810 800 ± 10
each sample was put into a vapor degreaser using I atm 780, 785, 785 780 ± 5
5 atm 740, 765, 765, 785 765 ± 25
liquid freon for approximately three minutes just Sr 300 torr 985, lOIS, 1160 1055 ± 85
prior to the experimental run. I atm 935, illS, 1175 1075 ± 120
5 atrn 1125,1150,1165 1150 ± 20
Sn 300 torr 975,1005, 1015 1000 ± 20
TABLE I I atm 910,945,965 940 ± 25
5 atrn 910, 955, 990, 1000 965 ± 45
Simple Dimensions of Experimental Metals Zn 300 torr 815,835,840,880 840 ± 30
I atm 895,905,920 905 ± 15
Diameter Length 5 atm 1090, 1140, 1150, 1165 1135 ± 35
Metal Purity (%) (em) (em) S/V (0101-1)

Ba 99.99 2.14 1.83 0.239 was restricted experimentally to one order of mag-
Bi 99.999 1.23 2.57 0.365 nitude. An exception was zinc whose ignition
Ca 99.5 2.37 1.0 0.365 temperature varied with pressure due to the effect
Fe 99.9 2.52 1.0 0.264
Ph 99.999 1.27 2.60 0.357
of the boiling point (Glassman, et al. (1970),
Mg 99.96 2.38 1.0 0.285 Laurendeau (1968». Large variations in T j g n may
Mo 99.95 1.59 2.06 0.306 certainly occur over a large pressure range, however.
Sr 99.0 1.64 1.75 0.309 For example, titanium is reported to have a T j g n
Sn 99.999 1.24 2.58 0.366
Zn 99.9 1.90
of 1300-1600 DC in the 15-200 psia range, and a
1.71 0.277
r.; of 850-1300 DC in the 200-700 psiz range.
 80 N. M. LAURENDEAU AND I. GLASSMAN

As for titanium, most metals are expected to TABLE III

show a decrease in ignition temperature as oxidizer Comparison of Bulk Ignition Temperatures-
pressure is increased, since the surface reaction
Present Temple Research
rate would be expected to increase. In the present Metal results (T °C) Institute results' Other results
study, this trend is observed only in certain metals.
A TIm". controlled metal (zinc), which always Ba 550 ± 90 175
exhibits a protective oxide coating, or any metal Bi 735 ± 20 775
Ca 790 ± 10 550 805', 704-743 d
producing an extremely thick oxide coat (stron- Fe 1315 ± 20 930
tium), may not be influenced by oxidizer pressure, Pb 850 ± 5 870
or may have the opposite behavior. Although the Mg 635 ± 5 623 640', 623-630-
present data are not conclusive, to a degree they do Mo 780 ± 5 750
Sr 1075 ± 120 720
support the hypothesis that critical temperature Sn 940 ± 25 865
controlled metals have ignition temperatures that Zn 905 ± 15 900
Downloaded by [University of Auckland Library] at 14:48 13 October 2014

generally decrease with increasing pressure. (Laur-

endeau (1970) discusses the support given by
Mellor's model to these conclusions.) Thus, one
may conclude here that the variation of the ignition
temperature with pressure may be the result of
whether a particular metal is critical or transition
temperature controlled.
B. Effect of heating technique
The bulk ignition data obtained would appear
to be consistent with what one suspects in com-
parison with other data when the procedures for
obtaining the data are evaluated in the context of
the simple model described earlier. Table II I
lists the present results and other results. Except
for the work at the Temple Research Institute very
little other data are available. The Temple results
were obtained by using a resistance furnace at an
ambient gas temperature of one atmosphere. The
results were reputed to be reproducible to within
±5°e. However, the metals in this case were
• 1 atm pressure, all temperature in "C.
e Conway and Kirschenbaum (1954), Grosse and Conway
(1958).
c Mellor (1967).
d Reynolds (1959).
, Fassell et al. (1951).
heated in an inert gas atmosphere to a specific
temperatures, and then exposed to a flowing oxygen
stream. Thus, the oxide buildup is a minimum, if
any, and the ignition temperature more closely
corresponds to the critical temperature.
··..1n . the present experiments and in the others
reported in Table II I, there is slow heating in an
oxygen atmosphere and there can be a buildup of
an oxide layer. Jt is in the understanding of the
character of this oxide layer that one can explain
the differences between the data in Table 3. As a
convenience for the explanation to follow, specific
data about the metals used are accumulated in
Table IV.

TABLE IV
Fundamental Temperatures of Interest for Metals."
Metal oxide
Metal Metal melting melting Metal boiling Metal boiling Transition
Metal oxide (TOC) point (TOe) point (TOC) point (TOe) point (TOe) temperature (TOe)
Ba BaO 710 t923 1527 2000 17
Hi Bi.O, 271 860 1470 1890
Ca CaO 848 2580 1240 2850 400
Fe FeO 1536 1420 2872 1200
Pb PbO 328 897 1753 1516 550
Mg MgO 650 2800 1105 3600 450
Mo MoO. 2620 795 4507 1155 700
Sr SrO 774 2430 1366 3000
Sn SnO, 232 1127 2260 1850 475
Zn ZnO 419 1975 907 700
• Taken and extrapolated from Mellor (1967), JANAF (1965), Kubaschewski and Hopkins (195]), Hodgman (1964), Kage
and Laby (1966), Kofstad (1966), and Hauffe (1965).
Boiling points are for 760 torr.
 IGNITION TEMPERATURES OF METALS IN OXYGEN ATMOSPHERES
Consider first those metals for which the ignition
temperatures from the two primary investigations
reported in Table III are, within experimental error,
the same. These include bismuth, lead, magnesium,
molybdenum, and zinc. Zinc is easily explained
through its dependence on total pressure via the
metal boiling point. The other materials have a
very thin oxide coat that is non-protective at lower
temperatures due to a combination of low metal
melting point, low Tim"" and low oxide melting
points, which limit the protective qualities of the
oxide shell (see Table IV).
Now, the fact that a particular metal has a thin
porous oxide coat explains why the ignition tem-
Downloaded by [University of Auckland Library] at 14:48 13 October 2014
perature for such metals are in excellent agreement.
This type of oxide layer does not prevent the natural
diffusion of oxygen to the surface of the parent
metal. Thus, no matter whether heating is accom-
plished in an inert or oxidizing atmosphere, the
oxide coat cannot have any influence on the results.
This observation, along with the nearness of the
melting point of the oxide to the measured ignition
temperature in some cases, accounts for the good
agreement between the present work and Temple
work for bismuth, lead, magnesium, and molybde-
num. Indeed, other results obtained by heating in
an oxygen atmosphere with a resistance furnace
(Fassell, et al. (1951)) indicate that magnesium has
an ignition temperature that is very reproducible
under varying environmental conditions.
Consider now those metals for which the ignition
temperatures listed in Table 111 are different.
These include the alkaline earth metals, barium,
calcium, strontium, and iron and tin. All of these
metals, when heated in an oxidizing environment,
either develop a highly protective oxide coat (iron)
under the conditions of the experiment, or their
oxide layers are so thick that they hinder the igni-
tion process by allowing only a small fraction of the
needed oxygen to the metal substrate, and thus
delay the actual ignition of the metal (tin, strontium,
especially). In addition, the above metals, excluding
iron, undergo a large amount of self-heating when
suddenly exposed to an oxygen atmosphere. This
characteristic alone could easily account for the
disagreement in the two investigations, especially
for barium and calcium. Based on these observa-
tions, any differences in the ignition temperatures
between the two sets of data may perhaps be attrib-
uted solely to whether an inert or oxidizing atmos-
phere was used in the metal heating cycle of the
ignition process.
The oxidizing environment in the present inves-
81
tigation leads to higher ignition temperatures for the
five metals discussed above (see Table III). Tin
and strontium have thick oxides which hinder
ignition and cause large variations in the measured
ignition temperature. The oxide layer in the
strontium runs is so thick, that it supports molten
strontium, as would a crucible. Barium and calcium
undergo an extraordinary amount of self-heating.
Hence, the Temple measurements must be very
near the critical temperature for these metals.
Barium is particularly susceptible to the instabilities
of the critical temperature, and thus gives rise to
large variations in the measured ignition tempera-
ture.
The results for calcium are quite reproducible
because of the consistency of its oxide layer in
different experimental runs. The present results
compare well with the data of Mellor (1967)
who found an average ignition temperature at
I atm. of 805°C. Reynolds' results (1959) in a
flowing stream of air also give comparable ignition
temperatures over 700°C. His data, although
lower due to the removal of the room temperature
oxide scale, are significant, for they indicate a
higher ignition temperature for calcium when
heated in an oxidizing atmosphere in a completely
different type of ignition environment.
The above results, especially for calcium, indicate
that a consistent bulk ignition temperature can be
defined for most metals, independent of the method
of heating, but dependent on ambient pressure and
the type of oxidizing environment.
C. The relation between ignition and combustion
Visual observations of the ignition and subse-
quent combustion of the above metals generally
substantiated Glassman's criterion (Glassman,
1959, 1960). If the boiling point of the metal oxide
is greater than that of the parent metal, then com-
bustion occurs on the metal surface. Barium,
calcium, magnesium, strontium, and zine all
burned in the vapor phase, while the rest burned on
the surface. Bismuth (see Table IV) proved the
only exception to the above combustion criterion,
but its initial burning appeared to be in the
vapor phase with subsequent degradation to the
surface.
There appears to be little correlation between
the type of combustion (surface or vapor-phase)
and whether a particular metal is critical or transi-
tion temperature controlled. Other visual obser-
vations are discussed in detail by Laurendeau
(1968).
 H2 N. M. LAURENDEAU AND I. GLASSMAN
This work was supported by the National Aero-
nautics and Space Administration under NAS
Grant NGR 3\-001-129 and was monitored by the
Propulsion Branch, Applied Materials and Physics
Division, Langley Research Center.
REFERENCES
Conway, J. B. and Kirshenbaum, M. S. 1954. Ninth
Progress Rept., Contract N9-onr-87301, Res. Inst.
Temple Univ., Ad-45, 649. .
Fassell, W. M., Jr., Gulbransen, L. B., Lewis, J. R. and
Hamilton, J. H. 1951. Ignition Temperatures of Mag-
nesium and Magnesium Alloys, Journat of Metals 3,
522-28.
Glassman. I.. Mellor, A. M., Sullivan. H. F., Laurendeau,
Downloaded by [University of Auckland Library] at 14:48 13 October 2014
N. M. 1970. A Review of Metal Ignition and Flame
Models, in AGARD Conference Proceedings No. 52,
Paper 19.
Glassman, I. 1960. Combustion of Me tats. Physical Consid-
erations, in Solid Propellalll Rocket Research, Academic
Press. New York, 253-258.
Glassman, I. 1959. Metal Combustion Processes, Arner.
Rocket Society. Preprint 938-59.
Grosse. A. V. and Conway, J. B. 1958. Combustion of
Metals in Oxygen, Ind. Eng. Chem. 50,663-672.
Hauffe, K. 1965. Oxidation of Metals, English Edition,
Plenum Press, New York.
Hodgman, C. D. 1964. Editor, Handbook o.fCh~mistry and
Physics. 46th Ed., Chemical Rubber Publlshrng Co.,
. Cleveland, Ohio.
JANAF Thermochemical Tables 1965. The Dow Chemical
Co., Midland, Michigan.
Kaye. G. W. C. and Laby, T. H. 1966. Table of Physical
and Chemical Constants, Wiley. New York.
Kofstad, P. 1966. High-Temperature Oxidation of Metals,
Wiley, New York.
Kubaschewski, O. and Hopkins, B. E. 1967. Oxidation or
Metals and Alloys, Second Revised Edition, Butter-
worths, London.
Kuehl, D. K. 1965. Ignition and Combustion of Aluminum
and Beryllium, AIAA Journal 3, 2239-2247.
Laurendeau, N. M. 1968. The Ignition Characteristics of
Metals in Oxygen Atmospheres, Princeton U. AMS
Rept. No. 85 I.
Mellor, A. M. 1967. Heterogeneous Ignition of Metals:
Model and Experiment, Ph.D. Thesis, Princeton U.,
Dept. of Aerospace and Mech. Sciences.
Reynolds, W. C. 1959. Investigation of Ignition Tempera-
tures of Solid Metals, NASA TN 0-182.
Received February 4, 1971.