SAND2012-9937C

THERMAL ANALYSIS OF MIXTURES CONTAINING Al POWDER UNDER OXIDIZING

ATMOSPHERES: ANALYZING THE POTENTIAL IMPACT OF PROPELLANT FIRES NEAR

LAUNCH SITE

Eric N. Coker, Frank van Swol, Walt Gill and Burl Donaldson
Sandia National Laboratories
Albuquerque, New Mexico

ABSTRACT

The interaction of Al powder with environmental samples harvested at or near launch-pad

17A at Cape Canaveral has been studied at high temperature. The environmental samples were
sand/soil, concrete, Martyte™, and asphalt. Thermogravimetric analysis with simultaneous
differential scanning calorimetry (TGA/DSC), or with differential thermal analysis (TGA/DTA) was
used to characterize the mixtures under oxidizing conditions at temperatures up to 1500 °C.
For binary mixtures containing Al powder, exposure to air, CO2, and/or H2O at elevated
temperature resulted in a large exotherm and the sample mass increased rapidly. This is
assigned to the oxidation of liquid Al to alumina, accompanied by the reaction of alumina and
silica to yield mullite (Al6Si2O13). All of the environmental samples interrogated were found to
contain SiO2. Other reactions may also contribute to the overall energetics of the system, e.g.,
thermite reactions between Al and SiO2 or Al and Fe2O3. When heating up under either inert or
oxidizing conditions, more than one exotherm associated with the reactions were often identified,
suggesting that different components of the environmental samples reacted with liquid Al at
different temperatures, or at different rates. The exotherms measured by DSC upon exposure to
air at 1350 °C of 1:1 (mass) mixtures of Al powder and environmental sample corresponded to
energy release ranging from 1100 J g-1 (Al + Martyte™) to over 4000 J g-1 (Al + concrete).
Increasing the temperature of exposure to oxidant generally produced an increase in the energy
released.

INTRODUCTION

Powdered aluminum is a key component in most solid rocket propellant formulations.

There are two principal reasons for its inclusion: 1) to increase the energy content and specific
impulse of the propellant, and 2) as a suppressant of combustion instability [1]. The performance
boost offered by including powdered aluminum, however, presents its own problems. The
extreme temperatures and chemical reactivity produced by such propellants can present a threat
in the event of a rocket launch accident. The consequences of such an accident are particularly
severe when considering future deep-space missions employing plutonium as a persistent
(nuclear) fuel source; the possibility of dispersion of plutonium into the environment from a rocket
launch accident prompts a thorough risk assessment model to be developed. A large body of
literature exists which describes the oxidation and ignition properties of aluminum powder and
aluminized rocket propellant (see, e.g., [2], [3], and [4]), however little data exists on the reaction
between aluminum powder and materials which it may contact if a launch accident were to occur.
The purpose of the present study was to evaluate the interaction at moderately high
temperature and under oxidizing conditions of aluminum powder with specimens of material with
which it is most likely to come into contact in the case of a rocket launch accident. The results of
this study are being used to develop a launch accident risk assessment model. To evaluate the
energetics of reaction between the propellant and environmental samples, differential thermal
analysis (DTA) and differential scanning calorimetry (DSC) were employed, while

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thermogravimetric analysis (TGA) provided insight into off-gassing and oxidation phenomena.
Three oxidizing environments were used: air/Ar, CO2/Ar, and H2O/CO2/Ar, at reaction
temperatures up to 1500 °C. Comparisons are drawn between the reaction energetics of
aluminum powder with the various environmental samples.
Energetically, the major anticipated contribution to the heat generated upon interaction of
Al propellant with environmental materials is the so-called thermite reaction, wherein a metal
(here: Al) reacts with a metallic or a non-metallic oxide to form a more stable oxide (here: Al2O3)
and the corresponding metal or nonmetal of the reactant oxide. This reaction can be generalized
as follows:
A + BO → AO + B + ΔH
where the energy released (ΔH) can be quite significant. Numerous metal-oxides or non-
metal oxides can participate in the reaction; for instance, two of the most relevant thermite
reactions for the current work are those involving SiO2 and Fe2O3.
-1
4Al + 3SiO2 → 3Si + 2Al2O3 ΔH = -2.15 kJ g
-1
2Al + Fe2O3 → 2Fe + Al2O3 ΔH = -3.95 kJ g
The thermite reaction between Al and SiO2 has an adiabatic temperature of 1487 °C, [5]
however, for the reaction to occur without an initiator, a temperature considerably in excess of
1500 °C may be required. In all cases where a thermite reaction does occur, the resulting
reduced metal or non-metal is expected to re-oxidize under the oxidizing environment at high
temperature forming, in the case of the two examples given above, SiO2 and Fe2O3, respectively.

Another possible reaction pathway giving rise to the observed exotherm and mass
increase is the oxidation of Al to Al2O3 and reaction of Al2O3 with SiO2 to form mullite:
2Al + 3CO2 → Al2O3 + 3CO
3 Al2O3 + 2SiO2 → Al6Si2O13 ΔH ~ -30 to -40 kJ mol-1
At the temperatures of the present work, the rate of mullite formation is appreciable [6],
and the energy output is modest [7] compared to the thermite reaction.

EXPERIMENTAL DETAILS

MATERIALS

The aluminum powder was obtained from Valimet, Inc., grade H-95, 99.7% pure (nominally 95
μm particles), and was used as received. The environmental samples were consisted of
concrete, asphalt, Martyte™,1 and a mixture of sand and soil. Each environmental sample was
individually ground in a mortar and pestle, and then sieved to recover the particles in the size
range 90 – 180 μm which was close to the size range of the Al powder. Some additional tests
were performed using aluminum powder with a smaller particle size (Valimet, Inc., grade H-10,
nominally 10 μm particles); environmental samples were ground to < 45 μm for combination with
the H-10 powder. In some tests, ⅓ of the aluminum powder (by mass) was replaced by alumina
powder of similar particle size to the aluminum.

1
Martyte™ is a ceramic filled, amine-cured epoxy compound used as an ablative thermal barrier
coating typically applied to metal structures. It was developed by Martin Marietta.
THERMOGRAVIMETRIC ANALYSIS, DIFFERENTIAL THERMAL ANALYSIS AND

DIFFERENTIAL SCANNING CALORIMETRY

The quantities of material used in the TGA/DSC and TGA/DTA studies were intentionally
kept small (typically 100 mg or less) in order to avoid excessive heat evolution which may pose a
safety risk and damage equipment. In addition, the thermite reaction was moderated in this work
due to the presence of other non-reactive or weakly-reactive diluents present in the
environmental samples such as calcium oxides, or intentionally added diluents, e.g., alumina.

The mass ratio of aluminum powder to environmental sample was kept constant at 1:1 for
these experiments, except for experiments in which ⅓ of the aluminum powder (by mass) was
replaced by alumina powder (in such cases, the mass ratio of (Al + Al2O3) to environmental
sample was kept at 1:1). The specimens were characterized under inert atmosphere (argon) and
oxidizing atmosphere (air, CO2, H2O, or mixtures thereof) with TGA/DSC (Netzsch STA 449-F3),
or TGA/DTA (Netzsch STA 409 CD) during heating to a pre-determined temperature, and
oxidizing at that temperature for a set amount of time. In all experiments, a heating rate of 20 °C
min-1 was used from ambient to 600 °C, and from 700 °C to the final oxidation temperature. In
the range 600 to 700 °C a rate of 5 °C min-1 was used to enable accurate monitoring of the Al
melting temperature (used as an internal temperature standard). Total gas flow rates were
maintained at 160 sccm, including a constant protective gas (Ar) flow rate of 40 sccm through the
balance. During experiments where the sample was heated under inert atmosphere to the
desired oxidation temperature, once that temperature was reached the temperature was allowed
to stabilize under flowing inert gas for 15 min prior to initiating the flow of oxidant.

All TGA/DSC and TGA/DTA data have been corrected by baseline subtraction. In order
to do this, blank experiments were run under exactly the same conditions as the experimental
runs, and the blank data was then subtracted from the experimental data. Prior to starting each
TGA/DSC or TGA/DTA experiment where the oxidation temperature was reached under inert
conditions, the instrument was evacuated and back-filled with inert three times, then allowed to sit
idle under the gas flow conditions to be used in the experiment for at least 15 minutes to ensure a
clean, consistent atmosphere and stable balance and thermocouple readings at the start of each
run.
By calibrating the DSC signal using high-purity materials with known enthalpy of melting,
it was possible to quantify the energy output measured during oxidation of materials. Several
DSC experiments were repeated with the DTA instrument, allowing a crude calibration of the DTA
signal to be made based upon the calibrated signal from the DSC. To do this, the peak areas of
the exotherms in the DTA plots for each binary mixture were plotted against the calibrated energy
output for the same binary mixtures in the DSC plots. The resulting trend fit, with the exception of
one outlier, on a 2nd order polynomial curve passing through the origin with R2 = 0.9999; this
polynomial function was then used to convert the measured DTA peak areas into values of J g-1.

CHEMICAL ANALYSIS THROUGH X-RAY FLUORESCNCE SPECTROSCOPY

Quantitative chemical analysis of all materials was achieved with X-ray Fluorescence
Spectroscopy (XRF) using a Bruker Tornado M4 XRF. Samples were characterized in the
crushed and sieved form without further treatment. Element-specific maps were generated for all
elements discovered, and elemental compositions were quantified using Bruker’s standard XRF
factors in M-Quant. Note that XRF is insensitive to elements lighter than sodium, so carbon,
nitrogen, oxygen, etc. are not included in the quantification.

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STRUCTURAL ANALYSIS THROUGH X-RAY DIFFRACTION

Quantitative structural analysis of materials was achieved using powder X-ray Diffraction
(XRD) using a PANalytical X’Pert PRO diffractometer with Cu Kα radiation. Individual
components were characterized as fine powders without further treatment, and the binary
mixtures were characterized by XRD after thermal treatment in the TGA/DSC or TGA/DTA.
Peaks in the XRD patterns were assigned to specific chemical components where possible using
Jade software.

RESULTS AND DISCUSSION

QUANTITATIVE CHEMICAL ANALYSIS – X-RAY FLUORESCENCE

The XRF data is summarized in Table 1; only elements present at 0.1 atomic-% or
greater are included in the table. In short, the Al powder is 99.9% pure, and all environmental
samples contain significant levels of calcium and silicon. The sand/soil also contains moderate
levels of aluminum and iron, while Martyte™ has a significant content of magnesium. The other
elements detected (not included in Table 1) constitute less than 0.3% for all samples.

Table 1. Elemental analysis of the Al powder and environmental samples

determined by XRF.
Element / Aluminum
Asphalt Concrete Martyte™ Sand-Soil
atomic-% a H-95
Aluminum 99.86 1.04 2.6 0.98 8.38
Calcium 84.08 79.6 18.92 50.83
Chromium 0.36
Iron 0.13 1.39 4.21 0.36 11.05
Magnesium 0.24 0.21 12.59 0.61
Manganese 0.27 0.18
Phosphorus 0.27
Potassium 0.38 0.33 0.42 0.87
Silicon 10.67 11.86 66.11 23.93
Sulfur 1.33 0.44 0.1
Titanium 0.24 0.55 0.17 2.98
Zinc 0.67
Total: 99.99 99.73 99.8 99.82 99.87
a
Only elements heavier than sodium in the periodic table are detectable. Atomic-%
represents the percentage of that element as a total of all elements detected (i.e., not including
oxygen, carbon, etc.)

THERMOGRAVIMETRIC ANALYSIS – DIFFERENTIAL SCANNING CALORIMETRY

The TGA/DSC runs performed on the individual components Al, sand/soil, concrete,
Martyte™, and asphalt with exposure to air at 1350 °C are summarized in Figure 1. The Al
powder showed virtually no change in mass upon heating to 1350 °C under Ar, while an almost
imperceptible, slow rate of mass increase occurred upon exposure to air at that temperature, in
agreement with experiments carried out using high-purity Al foil. [8] The DSC trace showed a
sharp endotherm on melting of Al (on-set at 656.9 °C, theoretical 660.3 °C for pure Al), as well as
a small, sharp exotherm on first exposure to air at 1350 °C. Alloying of Al with other metals is
known to decrease the melting point; the lower melting point of the Al powder compared to pure
Al indicates that there are probably some impurities present; as seen in Table 1, about 0.13
atomic-% iron was detected by XRF in the aluminum. All other environmental samples showed
significant mass loss during heating to 1350 °C under Ar, details of which are given in Table 2.
Asphalt, concrete, and, to a lesser extent, sand/soil all exhibited an endothermic event at just
above 700 °C coinciding with their major mass loss steps. A similar, but broad endotherm can be
discerned for Martyte™ at around 400 °C, also consistent with its major mass loss step. All
environmental samples, except sand/soil, showed small, sharp exotherms upon first exposure to
air. None of the environmental samples increased in mass significantly during exposure to air at
1350 °C.

1.5 Exotherm ↓
D
1.0 C
DSC signal / μV mg-1

0.5
A
B
0.0
E

-0.5
105 1400

100 1200
E
95 A
D 1000 asphalt
B
Residual mass / %

Temperature / °C
90 martyte
800
C concrete
85
600 D sand/soil
80 C E Al
400
75 temperature
A
70 200
B
65 0
0 50 100 150 200
Time / minutes

Figure 1. TGA (lower) and DSC (upper) results for individual components heated
under Ar to 1350 °C, then exposed to air (at dashed vertical line).

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 Table 2. Summary of TGA data for individual environmental samples and Al
powder heated under inert atmosphere to 1350 °C then exposed to air at 1350 °C for 2 hr.
Mass loss during Temperature range / Mass gain on
Sample
inert ramp / % °C oxidation / %
Aluminum H-95 0.25 25 – 1350 0.61
7.53 25 – 775
Sand/soil 0.40
1.48 775-1350
19.32 25-795
Concrete 0.20
2.1 795-1350
24.3 25-490
Martyte™ 1.14 490-600 0.19
3.82 600-1350
6.5 25-505
Asphalt 19.43 505-830 0.61
2.24 830-1350

The mass changes observed during heating of (Al + environmental sample) mixtures
under inert atmosphere were qualitatively similar to those of the individual components, and
scaled to the amounts of each component present, i.e., the mixture behaved as two non-
interacting solids (Figure 2). Upon exposure to air at 1350 °C, a rapid increase in mass was
observed for all binary mixtures, which was not a combination of TGA responses for the individual
components, i.e., in the presence of air at high temperature the components do interact. There
was no discernible reaction between components at the same temperature under inert
atmosphere prior to introduction of air. The mass change data is summarized for the binary
mixtures in Table 3. Considering now the DSC data, one sees the melting of Al as an
endothermic peak as before, and the integrated area of the peak scales to the amount of Al in the
mixture. Other features of the DSC curves during the inert portion of each experiment are again
qualitatively the same as those in Figure 1. Once air was introduced, a large, almost
instantaneous exotherm was recorded for each binary mixture, corresponding to the on-set of the
mass increase (oxidation of Al to Al2O3 with formation of mullite, or thermite reaction
accompanied by re-oxidation of Si or other reduced metal that was produced). As can be seen in
the inset figure, the exothermic peak is in all cases actually a composite of at least two peaks;
one sharp initial peak that is similar for all samples, and one broader feature that is sample-
dependent. The breadth of the exotherm correlates loosely with the magnitude of the initial mass
increase during the first few minutes of exposure to air, e.g., in order of increasing broadness:
Al/Martyte™ < Al/sand-soil < Al/asphalt < Al/concrete. The fact that a mixture of Al powder with
an environmental sample was required for the exotherm and mass increase to be observed upon
exposure to oxidant shows that interaction must occur between the Al and SiO2 (or other
compounds), which points to a thermite-type reaction rather than oxidation of Al to Al2O3 and
mullite formation. Referring back to Figure 1, we recall that the oxidation of Al (in the absence of
environmental sample) is virtually undetectable at 1350 °C. Even though the thermite reactions
do not involve gaseous oxygen as written, it is interesting that an oxidant was required at 1350 °C
for the reaction to be initiated. One possible explanation for this behavior is that the introduction
of oxygen at 1350 °C initiates a re-crystallization of the alumina layer that covers the Al particles
from a less dense to a more dense phase, resulting in the opening of small cracks in the alumina
coating which enabled better contact between the molten Al (or its vapor) and the environmental
sample. In the absence of an environmental sample (Figure 1) the alumina shell heals quickly in
the presence of the oxidant, whereas in the presence of the environmental sample interaction of
Al liquid or vapor with SiO2 (or other compound) is rapid and acts as a sink for oxygen, slowing
the healing of the alumina shell.
Post mortem characterization of the oxidized samples using XRD revealed that the major
identifiable compounds present were alumina, silica, aluminum and silicon, as well as calcium
aluminate in samples containing a large fraction of calcium. The observance of elemental silicon
confirms that a thermite-type reaction must have occurred to some extent. Elemental silicon was
not observed in any of the individual components prior to oxidation. The presence of metallic Al
and Si attests to the fact that oxidation/reaction had not gone to completion; indeed the TGA
curves in Figure 2 show continued increase in mass at the termination of the oxidation step.

Table 3. Summary of TGA/DSC data for binary mixtures (1:1 by mass) of Al powder
and environmental samples heated under inert atmosphere to 1350 °C then exposed to air
at 1350 °C for 2 hr.
Sample added Mass loss Mass gain upon Energy output
Temperature
to Al H-95 during inert exposure to air / upon exposure
range / °C
powder ramp / % % to air / J g-1
Sand/soil 4.83 25-775 21.93 2380
Concrete 8.00 25-805 25.49 4117
12.38 25-485
Martyte™ 0.64 485-615 9.77 1140
1.49 615-1350
3.37 25-500
Asphalt 26.67 3363
9.91 500-830

1.0
Exotherm ↓ D B A
0.5
0.0 C
1.0
DSC signal / μV mg-1

-0.5
0.0
-1.0
96 97 98 99 100 101
-1.5 -1.0 B D A C
-2.0 -2.0

-2.5 -3.0
-3.0 -4.0
-3.5
-4.0
120 1400

115 C 1200
D
A
110
1000
A Al/asphalt
Residual mass / %

Temperature / °C

105
800 B Al/martyte
100 C Al/concrete
B 600
95 D Al/sand-soil
400 temperature
90

85 200

80 0
0 50 100 150 200
Time / minutes

Figure 2. TGA (lower) and DSC (upper) results for binary mixtures of (Al +
environmental sample component) heated under Ar to 1350 °C, then exposed to air (at
dashed vertical line). The inset in the DSC plot is an expansion of the exotherm region
upon initial introduction of air.

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ALUMINUM POWDER - CONCRETE; EFFECT OF OXIDATION BY AIR AT VARIOUS

TEMPERATURES

In this series of experiments, Al/concrete mixtures were heated under inert atmosphere to 1250,
1350, or 1450 °C before exposure to air. The behavior during the temperature ramp under inert
gas was similar for all samples. The results summarized in Table 4 show the effect of varying the
oxidation temperature. The energetics of reaction and the magnitude of the accompanying mass
change due to oxygen uptake increase with oxidation temperature.

Table 4. TGA and DTA results for a 1:1 by mass mixture of (Al + concrete) heated under Ar
to 1250, 1350, or 1450 °C, then exposed to air for 2 hr.
Mass gain during Energy output upon exposure
Oxidation temperature / °C -1
oxidation / % to air / J g
1250 18.8 3630
1350 26.7 4108
1450 41.1 10627

TGA/DTA USING CARBON DIOXIDE AS OXIDANT

The TGA/DTA runs were performed on binary mixtures of (Al + environmental sample)
under an inert ramp to the desired oxidation temperature, followed by exposure to CO2 at 1350 or
1500 °C. The oxidation by CO2 is expected to lead to formation of CO, and this was verified
during a TGA/DTA experiment by analyzing the vent gas using gas chromatography. Carbon
monoxide was detected upon exposure of the sample at high temperature to carbon dioxide, and
the evolution of CO continued as long as there was an increase in mass of the sample.
Analysis of mass increases during oxidation, magnitude of oxidation exotherm, and rates
of reaction were determined for each combination of reactants under each set of experimental
conditions, as summarized in Table 5. The exotherm areas were converted to J g-1 using the
DSC-DTA calibration factor described earlier. An example of a set of data from TGA/DTA is
given in Figure 3, where the input values in Table 5 have been identified. In some cases, it was
not possible to deconvolute an “initial exotherm” from the overall DTA signal. The terms H-95
and H-10 refer to two batches of Al powder with nominally 95 and 10 micron mean particle size,
respectively. Environmental samples were ground to appropriate size ranges for the different Al
powder batches (see experimental section). Note that a high degree of variation was noticed in
the behavior of concrete-containing mixtures when comparing the different particle size ranges.
For instance, the total mass increase after full oxidation by CO2 varied between 13 wt.-% (H-10
series) and 43 wt.-% (H-95 series); the rates of reaction showed a similar trend. This variance is
attributed to the macroscopically inhomogeneous nature of concrete. To illustrate this, three
separate specimens were taken at random from the same concrete sample, were ground to a fine
powder, and then interrogated using XRF to quantify their chemical composition. The results
showed that between the three specimens there are wide variations in the quantities of Si and Ca
(the two major constituents of concrete) that were detected. In future experiments, therefore, a
more rigorous sampling technique should be used for ensuring a representative and reproducible
sampling of concrete.
Post mortem characterization using XRD of the samples oxidized at 1500 °C under CO2
revealed that the major identifiable compounds present were alumina and mullite where the
sample contained a large fraction of silica, as well as calcium aluminate in samples containing a
significant amount of calcium. These reactions generally proceeded to completion in the 2 hr
oxidation step, thus only oxidized products were detected by XRD.

TG /% DTA /(µV/mg)
[2.4] Area: -358.8 µVs/mg [2.4]
130 ↓ exo 0.5
[2.4] [2.5]
[2.5]

Area: -95.23 µVs/mg

125 0.0

120 -0.5

115 -1.0

110 Mass Change: 41.11 %

-1.5

105 -2.0

100 -2.5
Secondary rate [Δ(mass) / Δ(time)]
95 -3.0
Mass Change: 8.81 %

90
Initial rate [Δ(mass) / Δ(time)] -3.5
[2.4]

85 -4.0
100 105 110 115 120 125 130 135 140
Main 2012-10-11 11:42 User: encoker
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Figure 3. An expanded view of a representative TGA/DTA data set where the input
values for Table 5 have been identified. Note that there is an inflection point in the mass
curve, shortly after mass increase begins. The “initial mass increase” value is the
increase in mass measured from just before CO2 exposure to the inflection point, and the
“initial rate” is also calculated from this near-linear portion of the mass-increase curve.
The “secondary rate” is taken from the gradient of the mass curve shortly after the
inflection point. The areas of the exotherm are as indicated: “initial exotherm” = hashed
area; “total exotherm” = hashed + striped areas.

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 Table 5. Summary of TGA/DTA data for CO2-oxidation of mixtures containing Al
powder, environmental sample, and optionally, alumina. The exotherm quantities are
normalized to the total sample mass; for mixtures containing added alumina Al metal
constitutes ⅓ of the mass, and for all other mixtures Al metal is ½ of the mass.

Initial Initial Total Secondary

Temperature Initial Total
mass rate / mass rate /
Sample of exposure exotherm exotherm
increase mass-% increase mass-%
to CO2 / °C -1 / J g-1 -1 / J g-1
/% min /% min

H-95 +
1350 2.584 12.502 27.44 4.4106 1041.3
Asphalt
H-95 +
1350 3.495 14.047 472.6 28.56 5.3343 1180.4
Concrete
H-95 +
1350 7.274 15.559 14.89 2.2878 531.0
Martyte™
H-95 +
1350 1.594 9.388 29.67 3.0767 351.5
Sand-soil

H-95 +
1500 9.47 18.655 358.7 42.522 4.3631 1729.8
Asphalt
H-95 +
1500 4.619 14.886 162.0 42.929 3.7966 2517.6
Concrete
H-95 +
1500 15.036 18.857 24.826 2.4235 882.2
Martyte™
H-95 +
1500 5.073 14.474 339.6 41.837 3.3916 2636.0
Sand-soil

H-95 +
Al2O3 + 1500 7.46 15.761 495.1 27.757 3.8717 1379.0
Asphalt
H-95 +
Al2O3 + 1500 7.365 15.632 28.584 4.4194 1336.1
Concrete
H-95 +
Al2O3 + 1500 18.586 19.95 2.4812 733.5
Martyte™
H-95 +
Al2O3 + 1500 14.778 26.445 3.069 959.0
Sand-soil

H-10 +
1500 21.92 17.033 1114.5 39.794 14.69 2071.4
Asphalt
H-10 +
1500 3.485 2.2229 13.482 2.0729 220.6
Concrete
H-10 +
1500 25.08 19.728 1542.9 35.705 16.536 1940.3
Martyte™
H-10 +
1500 29.424 20.899 1629.4 42.127 17.079 2504.2
Sand-soil

H-95 +
Concrete 1500 1.19 5.0 118.0 37.32 2.3 1617.0
flake
H-95 +
Al2O3 +
1500 1.80 3.0 87.1 25.86 2.2 1172.3
Concrete
flake
ALUMINUM (H-95) + CONCRETE FLAKE; EXPOSURE TO CO2 AT 1500 °C.

Since powdered environmental samples represent a “worst case” scenario in determining the
energetics and rate of reaction with Al propellant, some experiments were also conducted using
fragments of concrete block in place of the concrete powder. Figure 4 summarizes the TGA/DTA
data for Al (H-95) surrounding a piece of bulk concrete (flake) during heating under argon to 1500
°C, then exposing the sample to CO2. Data for powdered concrete is included for comparison.
As expected, the lower available surface area of the concrete flake resulted in a lower overall rate
of reaction with Al powder, as reflected in the slower increase in mass and broader exotherms
upon exposure to CO2 than the corresponding powdered concrete mixtures. The total mass
increases of the flake samples after 2 hours of exposure to CO2 approach those of the powder
samples, indicating that over time the reaction front is able to proceed into the bulk of the flake.

DTA /(µV/mg)
TG /% Temp. /°C
[1] ↓ exo 0.5
140 [2] [4]
[1]
[3]
[1]
[2] [4]
[3]

[2] 0.0 1400

130
[4] -0.5 1200

[1]
[4]
[3]
[2] -1.0
[1]
1000
120
[3] -1.5
800
-2.0
110 [1] Al-alumina-concrete 1500-CO2 DTA-low.ngb-dss
TG 600
DTA
Temp.
[2] Al-concrete 1500-CO2 DTA-low.ngb-dss
-2.5
104 106 108 110 112 114 116 118
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DTA
Temp. 400
100 [3] Al-alumina-concrete-flake 1500-CO2.ngb-dss -3.0
TG
DTA
Temp.
[4] Al-concrete-flake 1500-CO2.ngb-dss 200
TG -3.5
DTA
Temp.
90
-4.0 0
0 50 100 150 200
Main 2012-10-02 16:53 User: encoker
Time /min
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Figure 4. TGA/DTA data for a series of experiments comparing concrete powder to bulk
concrete (flake) during heating under argon to 1500 °C, then exposing the sample to CO2.
Curves 1 and 2 show concrete powder with either Al + alumina (1), or Al only (2), and
curves 3 and 4 show the corresponding samples where a piece of concrete flake replaces
the concrete powder. All mass curves have been normalized at the point just before CO2
was introduced. Exposure to CO2 coincides with the rapid mass increase and exotherm at
105 minutes into the experiment. The inset figure is an expansion of the first 15 minutes
of the exothermic peaks, normalized at the point just before CO2 exposure.

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ALUMINUM (H-95) + CONCRETE; LIMITED EXPOSURE TO CO2 AT 1500 °C.

Figure 5 summarizes the TGA/DTA data for Al (H-95) intimately mixed with concrete, during
heating under argon to 1500 °C, then exposure to CO2 for either 2, 4, or 8 minutes followed by
120 minutes soak under flowing argon. Data for a sample including added alumina at 4 minute
exposure to CO2 is included for comparison. Figure 6 shows the linear relationship between the
total CO2 exposure during the 1500 °C soak and the sample mass increase and exotherm area.
The best fit line does not cross through the origin of the graph, and this is a consequence of the
experimental setup wherein there is a consistent delay between the time CO2 flow is commanded
by the software and when the CO2 flow actually begins. The calculated CO2 exposure in Figure 6
is based upon the software-commanded flows, not actual flows.
The conclusions from Figure 6 are that CO2 is responsible for the oxidation of reactants (i.e., not
background oxygen, or other species), and that the reaction exotherm is proportional to the total
amount of CO2 to which the specimen is exposed. If one considers the reaction sequence to
involve a thermite reaction, then it seems that, at the temperatures studied, the extent of the
thermite reaction that occurs is mediated by the capacity to re-oxidize the products of the thermite
reaction. (CO2 acts to initiate the thermite reaction, but does not participate in the thermite
reaction itself). On the other hand, if the reaction sequence is one involving oxidation of Al to
Al2O3 and mullite formation through reaction with SiO2, then a correlation of the reaction exotherm
to the amount of CO2 is to be expected.

DTA /(µV/mg)
TG /% Temp. /°C
[10] ↓ exo 1600
[10]
[11]
[8]
[9] 0.2
106 [11] 1400
[8]
[9]
[10]
0.0

104 1200
-0.2

102 1000
[8] Al-concrete 1500-CO2-2min.ngb-dss [11]
TG
-0.4
DTA
Temp.
100 [9] Al-Al2O3-concrete 1500-CO2-4min.ngb-dss
800
TG
DTA
-0.6
Temp.
[10] Al-concrete 1500-CO2-4min.ngb-dss
TG
98 DTA -0.8 600
Temp.
[11] Al-concrete 1500-CO2-8min.ngb-dss
TG
DTA
96 Temp.
[9] -1.0 400
[10]

-1.2 200
94

[8]
-1.4
92 0

0 50 100 150 200

Main 2012-10-02 17:47 User: encoker
Time /min
Created with NETZSCH Proteus software

Figure 5. TGA/DTA data for a series of experiments using concrete powder mixed with Al
(curves 8, 10, and 11) or Al + alumina (curve 9) where the sample was exposed to CO2 at
1500 °C for limited periods of time. All mass curves have been normalized at the point just
before CO2 was introduced. Exposure to CO2 coincides with the rapid mass increase and
exotherm at 105 minutes into the experiment. Curve 8: 2 min exposure; curves 9 and 10: 4
min exposure; curve 11: 8 min exposure to CO2.
Regardless of the reactions occurring, it is to be expected that alumina and silica will be formed
upon oxidation at high temperature. Under the conditions of these experiments, and depending
on the stoichiometry of Al2O3 to SiO2, mullite will be formed to some extent; this has been verified
by X-ray diffraction of mixtures of Al powder and environmental sample recorded after the
TGA/DTA experiments described above.

120
Mass increase × 10 / %; exotherm area / μV s mg-1

100

80

60

40

20 mass increase
exotherm area
0
0 10 20 30 40 50
Total CO2 exposure / ml

Figure 6. Summary of total mass increase data and total exotherm area data from the
TGA/DTA experiments of Figure 5. The total CO2 exposure takes into account CO2
concentration, flow rate, and time of exposure. The mass increase and exotherm area
values are normalized to the total sample mass.

Similar variations in mass increase and exotherm area were observed when exposing the
samples to air or to water vapor in CO2 for limited periods of time.

The heat of reaction (ΔH) as a function of temperature, and the free energy of reaction
(ΔF) as a function of temperature for various thermite reactions were obtained from tabulated
data [9] of the heat of formation and the heat capacity as a function of temperature. These data
are shown in Figure 7. Reference [9] provides the coefficients for simple polynomial expressions
that (piecewise) cover a large range of temperatures. Steps in the calculated data are a
consequence of discontinuities in the tabulated data, and/or phase transitions in the materials. It
can be concluded from Figure 7 that the driving force for the iron thermite reaction is higher than
that for the silica thermite reaction, and that the former has potential to release significantly more
energy, particularly at temperatures above 1500 K.

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Figure 7. Free energy (ΔF) and enthalpy (ΔH) of the thermite reaction between Al and SiO2,
Fe2O3, or ZrO2 in the presence of oxygen as a function of temperature.

SUMMARY AND CONCLUSIONS

This brief report summarizes an initial study of the interaction of Al powder (simulating
solid rocket propellant) with environmental samples harvested at or near launch-pad 17A at Cape
Canaveral, Florida. The environmental samples were sand/soil, concrete, Martyte™, and
asphalt. Thermogravimetric analysis with differential scanning calorimetry (TGA/DSC), or TGA
with differential thermal analysis (TGA/DTA) was used to evaluate decomposition and oxidation
reactions as well as the energetics of reaction. Two series of experiments were conducted where
the specimen was heated to the desired oxidation temperature and allowed to thermally stabilize
under inert atmosphere before introducing air: 1) individual components, and 2) binary mixtures of
Al powder + one environmental sample.
When investigating the individual environmental samples, mass losses were recorded
upon heating up under inert atmosphere, and exposure to air at 1350 °C caused insignificant
change in mass compared to inert atmosphere at the same temperature. The mass of the Al
powder remained constant during heating to 1350 °C under inert atmosphere and increased only
slowly when exposed to air at 1350 °C, in agreement with data from a study of oxidation of Al foil
at various temperatures discussed elsewhere.[8] For the binary mixtures, the behavior during
heating under inert atmosphere was as predicted from the superposition of the individual Al
powder and environmental sample data, however once exposed to air a large exotherm was
recorded and the sample mass increased rapidly. There are two possible reaction sequences
considered here which may account for the observed results: 1) a thermite reaction between
liquid Al and silica (4Al + 3SiO2 → 2Al2O3 + 3Si) which is highly exothermic, followed by oxidation
of the produced Si back to SiO2; 2) oxidation of Al to Al2O3, and partial reaction of the formed
alumina with silica to form mullite (e.g., 3Al2O3 + 2SiO2 → Al6Si2O13). All of the environmental
samples interrogated were found by XRF to contain SiO2. Some other components of the
samples may also contribute to the overall exothermicity of the reaction due to other thermite
reactions, e.g., iron oxides, and other metal oxides. More than one exotherm were often
identified, suggesting that different components of the environmental samples reacted at different
temperatures, or at different rates. The observation by XRD of elemental silicon in sample
residues after oxidation in the TGA confirms that a thermite-type reaction did occur, even at the
low temperature of 1350 °C, and that reactions did not go to completion in the course of the 2 hr
oxidation.
The exotherms measured by DSC upon exposure to air at 1350 °C of binary mixtures of
Al powder (H95 grade) and environmental sample (1:1 mass ratio) have been converted to
energy released by calibration of the DSC signal. The energetics ranged from about 1100 J g-1
(Al + Martyte™) to over 4000 J g-1 (Al + concrete). The DTA data, although not as precise,
showed a similar trend to that from DSC when running under the same conditions as the DSC
experiments.
Binary mixtures of Al and environmental sample, and ternary mixtures including alumina
were exposed to oxidant (air, CO2 or H2O) at 1500 °C. Comparison of reaction exotherms with
sample composition from XRF suggests that the iron thermite reaction may be the dominant
energy source at 1500 °C under CO2 without added alumina. Furthermore, limiting the exposure
time to oxidant at 1500 °C of mixtures of Al powder and concrete demonstrated that the overall
energy output was proportional to the number of moles of oxidant the sample was exposed to.
This suggests that either 1) the extent of thermite reaction occurring, under these conditions, is
limited by the amount of oxidant available, i.e., the thermite reaction (e.g., 4Al + 3SiO2 → 2Al2O3
+ 3Si) and the subsequent re-oxidation of reduced species (e.g., Si + 2CO2 → SiO2 + 2CO) may
be linked rather than two independent reactions, or 2) the reaction sequence involves oxidation of
Al to Al2O3 and formation of mullite. The reaction of Al powder with low surface area concrete
flakes was also investigated. In comparison with concrete powder, rates and extents of reaction
were lower for the flakes, however, after 2 hours of exposure to oxidant the mass increases due
to oxidation approached those of the powder samples indicating that a reaction front will progress
through bulk concrete, given sufficient reaction time.
The rates of reaction with CO2 at 1500 °C, as reflected in the change of mass of the
mixture, showed a distinct inflection point going from a faster initial rate to a slower subsequent
rate. While the initial fast rate was similar among most mixtures, the secondary rate was found to
be strongly dependent on the average size of propellant and environmental sample particles, i.e.,
smaller particles resulted in a faster rate of reaction.

ACKNOWLEDGMENTS

Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin

Company, for the United States Department of Energy’s National Nuclear Security Administration
under contract DE-AC04-94AL85000.

REFERENCES

[1] Price, E. W. and Sigman R. K., “Combustion of Aluminized Solid Propellants,” Chapter 2.18 of
Solid Propellant Chemistry Combustion and Motor Interior Ballistics, AIAA Progress in
Astronautics and Aeronautics, Vol. 185, V. Yang, T. B. Brill, and W-Z Ren, eds., 2000.
[2] Trunov, M.A., Schoenitz, M. and Dreizin, E.L., “Effect of polymorphic phase transformations in
alumina layer on ignition of aluminium particles,” Combust. Theory Model., 10(4), 602-23, (2006).
[3] Levitas, V.I., Pantoya, M.L., Chauhan, G. and Rivero, I., “Effect of alumina shell on the melting
temperature depression for aluminum nanoparticles,” J. Phys. Chem. C, 113, 14088-96, (2009).
[4] Levitas, V.I., Pantoya, M.L. and Dikici, B., “Melt dispersion versus diffusive oxidation
mechanism for aluminum nanoparticles: Critical experiments and controlling parameters,” Appl.
Phys. Lett. 92, 011921, (2008).
[5] Wang, L.L., Munir, Z.A. and Maximov, Y.M., “Thermite reactions: their utilization in the
synthesis and processing of materials,” J. Mater. Sci., 28, 3693-708, (1993).
[6] Chen, Y.F., Wang, M.C. and Hon, M.H., “Transformation kinetics for mullite in kaolin–Al2O3
ceramics,” J. Mater. Res., 18(6), 1355-62, (2003).

Approved for public release; distribution is unlimited.

[7] Gerardin, C., Sundaresan, S., Benziger, J. and Navrotsky, A., “Structural investigation and
energetics of mullite formation from sol-gel precursors,” Chem. Mater. 6, 160-70, (1994).
[8] Coker, E.N., “The oxidation of aluminum at high temperature studied by thermogravimetric
analysis and differential scanning calorimetry” SAND report, Sandia National Laboratories, in
preparation.
[9] Handbook of Chemistry of Physics, 69th edition, CRC press, Boca Raton, FL, (1988-1989).