Ind. Eng. Chem. Res.

1993, 32, 3117-3122 3117

Supercritical Fuel Deposition Mechanisms

Tim Edwards*
USAF Wright Laboratory, WL/POSF Bldg 490, 1790 Loop Rd N, Wright-Patterson AFB, Ohio 45433-7103

Steven Zabarnick
300 College Park, KL463, University of Dayton Research Institute, Dayton, Ohio 45469-0140

Jet fuel is the primary coolant used in high-speed aircraft. A decrease in surface deposition (fouling)
is often seen as jet fuels and pure hydrocarbons are heated above approximately 370 °C, as measured
by the wetted wall or film temperature. This temperature is near the critical temperature of most
jet fuels. Two explanations have been offered for this decrease in deposition under supercritical
conditions. One explanation is that the decrease reflects the temperature where hydroperoxide
precursors to solids formation are depleted by thermal decomposition, interrupting the radical
chain reactions forming solids. Another explanation is that the solvent properties of the fuel become
enhanced under supercritical conditions, with the surface deposition reduced essentially by keeping
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

the solids in solution. In single-tube heat exchanger tests with pure hydrocarbons and jet fuels of
widely varying critical temperature, it was found that the deposition decrease is insensitive to fuel
critical temperature but very sensitive to residence time/heating rate, indicating that the deposition
decrease is a fuel chemistry effect rather than an effect of the supercritical nature of the fuel.
Downloaded via ONERA on March 7, 2023 at 09:07:05 (UTC).

Introduction Table I. Critical Properties of Current Jet Fuels (Martel,

1978) and n-Paraffins for Reference*
Development of thermally stable jet fuels has been TC,8F O Pc, psia Pc, atm
recognized as a critical research area because an aircraft’s
fuel is the only practical means of absorbing dramatically JP-4 (Cg.sHie.s) 550-690 288-365 500-400 34.0-27.2
JP-5 (C11.9H22.2) 720-780 382-415 300-280 20.4-19.0
increasing on-board heat loads. The thermal stability of JP-7 (C12.1H24.4) 760 405 270 18.4
a fuel is a measure of its tendency to cause fuel system JP-8 (C10.9H20.9) 700-760 370-405 350-275 23.8-18.7
problems, such as surface deposits or filter plugging, upon n-CsHig 564 296 365 24.8
heating during aircraft operation (Hazlett, 1991). Indeed, 726 386 263 17.9
the limited thermal stability of current fuels must be n-CieH34 836 447 200 13.6
overcome in order to fully realize the system capabilities “
Critical temperatures for fuels were calculated from the specific
of advanced aircraft. The current practice for Air Force gravity and boiling curve of the fuels by the method outlined in
engine designers is to limit the fuel to 163 °C (325 °F) bulk ASTM D2889. Fuel critical properties are listed as a range because
temperature and 205 0C (400 0F) wetted wall temperature. of varying boiling curves for different samples. Commercial Jet A
This “rule-of-thumb” is based on engine fouling experience. (C11.6H22.0) and Jet A-l fuels are similar to JP-5 and JP-8. Fuel

In the long term, the heat management requirements of
future Air Force aircraft are expected to be sufficiently
demanding that the aircraft fuel system will need to operate
at much higher temperatures. The goal for this long term
fuel is to increase the thermal stability temperature limit
to480°C (900°F) (Edwards, 1993). This high temperature
is above the fuel thermodynamic critical temperature,
which typically ranges from 370 to 415 °C (700-780 °F)
for current jet fuels (Martel, 1978). Typical fuel system
pressures are approximately 34-68 atm (500-1000 psia),
well above the fuel critical pressure. Calculated critical
data for typical fuels are shown in Table I. The physical
and chemical properties of supercritical fuels are expected
to be dramatically different from gases and liquids. There
is little information available on the properties of fuels
when operated at supercritical conditions (Edwards, 1993).
One area of concern for fuels operating at high tem-
peratures is their thermal decomposition and the formation
of insoluble products that deposit onto metal surfaces
(fouling). This area has been studied in heated metal tubes
(simulating aircraft nozzles and heat exchangers) by
various investigators (Hazlett, 1991; Hazlett et al., 1977;
Bradley et al., 1974; TeVelde and Glickstein, 1983;
Marteney and Spadaccini, 1986; Taylor, 1974; Faith et al.,
1971; Chin and Lefebvre, 1992). These high-temperature
tests cover a wide range of flow rates and residence times.
The residence time of a given fuel molecule inside the
heated tube is typically on the order of seconds, while the
test time (or the amount of time the metal surface is
0888-5885/93/2632-3117$04.00/0
composition data from (Martel, 1988).
exposed to heat and fuel flow) is on the order of hours.
Most researchers have seen a peak in surface deposition
near 370 °C (700 °F) when the deposition is plotted as a
function of wetted wall or film temperature. This is
illustrated in Figure 1 for two sets of data from different
test devices (Taylor, 1974; TeVelde and Glickstein, 1983).
The peak disappears if the dissolved oxygen in the fuel,
typically about 65-75 ppm (w/w) in air-saturated fuel, is
removed (Bradley et al., 1974; Taylor, 1974). One goal of
our work is to investigate the source of this deposition and
determine ways to reduce, avoid, or eliminate it without
resorting to removing the dissolved oxygen from the fuel.
The decrease in deposition above approximately 370
°C has been given both physical and chemical explanations.
According to Taylor (1974), “the sharp drop in autoxidative
deposit formation rates... would appear to reflect an effect
of the transition between the liquid phase and the
supercritical vapor phase.” Hazlett (1977) prefers a
chemical explanation: “The deposit rating decreases above
385 °C. Since hydroperoxide is depleted at this temper-
ature, the tie-in between hydroperoxide decomposition
and deposit formation is reinforced.” Similarly, Marteney
and Spadaccini (1986) state “the sudden decrease in
deposit formation at temperatures above 645 K [372 °C]
may be indicative of a depletion of oxygen in the fuel,
related to the known decomposition of hydroperoxides at
elevated temperatures.”
© 1993 American Chemical Society
3118 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993
Figure 1. Surface deposition data for JP-5 in UTRC single-tube
heat exchanger test (TeVelde and Glickstein, 1983) and in Esso
Advanced Kinetic Unit (AKU) (Taylor, 1974). UTRC conditions: 28
atm, 570 mL/min (60 lb/h, inlet Re = 3000), 2.4-m-long, 2.16-mm-i.d.
316 SS tube, 480 °C (900 °F) fuel outlet temperature, 19 h test
duration. AKU conditions: 69 atm, 10 mL/min (inlet Re = 64), 122
-cm-long, 2.1-mm-i.d. 304 SS tube, 4 h test duration.
The research described in this paper was motivated by
a desire to discover if the decrease in surface deposition
above about 370 °C, which creates the deposition peak, is
indeed due to supercritical fuel properties. Although other
investigators have studied a wide variety of conditions,
most ofthefuelsand hydrocarbons tested had very similar
critical temperatures. One of the approaches of this work
was to investigate several similar hydrocarbons (e.g., the
normal paraffins) with widely varying critical tempera-
tures, but presumably similar deposition chemistry, to
determine the effect of fuel critical temperature on the
deposition behavior. A second approach was to test the
effect of fuel flow rate on the deposition-temperature
behavior above 370 °C. The flow rate affects the wall/fuel
temperature d ifference, the residence time, and the heating
rate. Pure hydrocarbon fuels are fairly expensive, so JP-7
was used in most of the tests as the baseline hydrocarbon
fuel. JP-7 (MIL-T-38219) is the Air Force’s highest
thermal stability fuel and consists mainly of paraffins and
cycloparaffins. Finally, a representative Jet A-l fuel was
studied for comparison to the JP-7 and pure hydrocarbon
results. These results will be used to develop computa-
tional fluid dynamic and chemistry (CFDC) models of
fuel system components (Katta and Roquemore, 1993).
Experimental Section
The apparatus used in this study is shown in Figure 2.
The fuel is air-sparged to assure air saturation of the fuel.
The flow system is initially purged with nitrogen prior to
fuel introduction to remove any air present. The fuel is
pumped through the system with a high pressure liquid
chromatography pump. An initial 0.45-/im filter is used
to remove any particulates present from fuel handling and
to maintain a consistent filtration level between fuels. The
test section consists of an 89-cm-long, 3.2 mm (0.125-in.)
o.d., 1.4-mm (0.055-in.) i.d. 304 stainless steel tube passing
through a Lindbergh laboratory furnace. The tube makes
a 180° bend inside the furnace, thus passing through the
30-cm (12-in.) actively heated portion of the furnace twice.
After exiting from the furnace, the products are cooled to
room temperature and filtered before passing through a
back pressure valve which regulates the system pressure.
A 5-Mm filter is used to prevent particulates from fouling
the back pressure valve; the filter also gives a visual
assessment of particulates formed in the heated section.
A three-way valve downstream of the back pressure valve
allows the product flow to be diverted to a sampling system
where the liquid products are analyzed (off-line) at ambient
conditions. The stainless steel test section is cut into 5-cm
(2-in.) sections and analyzed by carbon burnoff (Leco
surface carbon analyzer) to measure carbon deposition.
The tube wall temperature distribution is measured by
K-type thermocouples spot-welded to the outside of the
tube. The fuel temperature at the furnace outlet is
measured by a thermocouple inserted into the flow.
Pressure was measured between the filter and the back
pressure valve and also at the pump. The fuel temperature
distribution is estimated with a heat transfer program
(Edwards, 1992; Edwards and Anderson, 1993) from the
measured wall temperature distribution, fuel flow rate,
and the initial temperature of the fuel entering the furnace
(20 °C). The fuel properties (density, thermal conduc-
tivity, viscosity, heat capacity) vary significantly through-
out the tube in a given test where the fuel temperature
might vary from 20 to 620 °C (70-1150 °F) (Edwards,
1993), so the calculation uses temperature-dependent fuel
properties. It is found that test times on the order of
10-20 h are required for JP-7 and pure hydrocarbons to
give reproducible deposition results above the measure-
ment background. For more typical (lower thermal
stability) fuels, deposition amounts are much larger and
test times can be shorter.
Results and Discussion
A typical result of a JP-7 experiment is shown in Figure
3. As described in the Introduction, the data is reduced
by plotting the deposition (scaled by the tube surface area
and the total fuel flow) as a function of wall temperature,
excluding points of decreasing wall temperature after the
tube exits from the furnace. Thus, the deposition is
reported as ng of deposit carbon/(g of fuel fed-cm2), or
ppm/cm2. The deposition-wall temperature results for
several 12 mL/min flow rate experiments are shown in
Figure 4. Various tests are shown spanning different
ranges of wall temperature. The decrease in deposition
near 440 °C (825 °F) is very similar to the behavior shown
in Figure 1, although the deposition decrease begins at a
temperature significantly higher than the fuel critical

©— WalJT.C
S— Fuel T, C (calc) 0 C deposition, pg
-X— Fuel T, C (meas)
Figure 3. Experimental results from 12.0 mL/min test. Air-sparged
JP-7 fuel, 69 atm, 21 h.
Figure 4. Combined results from 12 mL/min tests covering various
wall temperature ranges. Air-sparged JP-7 fuel, 69 atm. Residence
times and Reynolds number of bulk fuel at peak deposit location
calculated with temperature-dependent fuel properties. Lines connect
points in order of axial distance.
temperature of 400 °C (760 °F). The dependence of this
deposition decrease on residence time/flow rate was
investigated by running similar tests at 33.5 and 3.1 mL/
min flow rates. The results of these tests are shown in
Figures 5 and 6, respectively. It is immediately apparent
that the autooxidation deposition decrease has shifted
significantly with the varying flow rates and residence
times. As fuel flow rates are increased, the difference
between the fuel and wall temperature increases, a simple
result of the increasing heat-transfer requirements to heat
up the increasing amount of fuel. Thus, the fuel tem-
perature at the peak has also changed. If the deposition
decrease is a simple consequence of the enhanced solid
solubility of the fuel under supercritical conditions, the
peaks in Figures 4-6 should occur at the same wall
temperature (since the deposit would be dissolved by the
fuel near the wall which should be at a temperature near
that of the wall). The bulk fuel temperature at the point
where the deposition decrease begins is well below the
critical temperature for most tests. Since the deposition
decrease occurs at differing temperatures at different flow
Ind. Eng. Chem. Res., Vol. 32, No. 12,1993 3119
Figure 5. Results from 33.5 mL/min tests. Air-sparged JP-7 fuel,
69 atm.
Figure 6. Results from 3.1 mL/min tests. Air-sparged JP-7 fuel, 69
atm.
rates, the deposition-temperature behavior is more likely
a result of a chemical, rather than a physical (supercritical)
process.
It is notable in Figures 4-6 that the background
deposition levels are highest for the shortest test times.
For short test times (< 10 h), it is found that the deposition
results at temperatures above and below the autooxidative
peak were sufficiently close to background detection levels
that the data are fairly scattered. This can be seen in
Figure 4 (test 5/92-2) and Figure 5 (test 4/92-3). Apparent
background levels varied somewhat for the various tests,
but typical levels were on the order of 7 fig/cm2. Recent
tests with lower stability fuels have shown an induction
time, or delay before the initiation of deposition, of about
3 h under conditions similar to Figure 4 (Edwards and
Liberio, 1994).
The results for the varying flow rates are summarized
in Table II. In addition to the change in deposition peak
location, the deposition (expressed as ppm) decreases with
increasing flow rate. The only published results for varying
flow rates at high temperatures were those of UTRC
(TeVelde and Glickstein, 1983; Marteney and Spadaccini,
1986). UTRC examined a wider range of flow rates in
their heated tube tests. For inlet Reynolds numbers
ranging from 400 to 21 000, the deposition rate (in fig/
(cm2*h) appeared relatively constant in the 225-325 °C
(435-615 °F) wall temperature range (Marteney and
3120 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993

Table II. Autoxidation Deposition Peak (Averaged over

5-cm Tube Segment) Parameters for JP-7 as a Function of
Flow Rate*

parameters for flowrate, mL/min

autooxidation deposition peak 3.1 12.0 33.5
wall temperature, °C 390 441 523
fuel temperature, °C 294 266 225
residence time to peak, s 7 2 0.8
Reynolds number at peak 200 700 1500
peak deposition, ppm/cm2 0.0060 0.0037 0.0036
peak deposition, ng/(cm2-h) 1 2 5

Deposition values reported are for longest test reported, with

0

background (7 ng/cm2) subtracted.

Spadaccini, 1986). Expressed as ppm/cm2, the UTRC

deposition levels decrease with increasing flow rate. The
tests were not carried out to high enough wall temperatures
for the lowest and highest flow rates to determine if the Wall temperature, 'C
deposition decrease shifted with varying flow rate. Aside Figure 7. 12 mL/min deposition results for n-hexadecane and JP-7.
from the UTRC data, no published results for varying Air-sparged fuels, 69 atm.
flow rates were found which would confirm this shift in
the autooxidative peak location. However, recent work at
Southwest Research Institute has produced similar results
(Moses, 1992).
Focusing on the wall temperature alone is an obvious
oversimplification, since the deposition (as a chemical
process) is also a function of bulk fuel temperature and
residence time. Flow velocity may also be important for
deposit erosion. The importance of other parameters is
apparent in results obtained by Shell Development (Faith
et al., 1971), where two deposition peaks (autooxidative
and pyrolytic) are seen in a heated tube test where the
wall temperature is relatively constant at 650 °C (1200
°F), but the fuel temperature increases from 260 to 510
°C (500-950 °F). It seems likely also that deposition peaks
could form in tests with constant fuel and wall temper-
atures, where the peaks would arise from consumption
and/or exhaustion of reactive species. Nozzle fouling
simulations are usually performed with preheated fuel
flowing through hot metal tubes at relatively constant Figure 8. 3.1 mL/min deposition results for n-octane and JP-7.
temperature. Under these conditions, a deposition peak Air-sparged fuels, 69 atm.
may be absent (Chin and Lefebvre, 1992; Hazlett, 1991).
Another way of testing the supercritical solvency hy-
pothesis is to test fuels of similar structure but varying
critical temperature. This was done by testing n-octane
(Tc = 296 °C (564 °F)) and n-hexadecane (Tc = 447 °C
(836 °F)) under conditions similar to those for the JP-7
tests. The results are shown in Figures 7 and 8. Again,
it can be seen that the critical temperature of the fuel does
not appear to control the deposition behavior in these
tests. The deposition decrease occurs at essentially the
same temperature (both fuel and wall) for all of the
hydrocarbons, regardless of their critical temperature. The
deposition levels for the pure hydrocarbons are very similar
to that of JP-7.
The deposition rates of typical fuels are much higher
than that of JP-7 or pure hydrocarbons (Bradley et al.,
1974; Taylor, 1974; Frankenfeld and Taylor, 1980). The
thermal stability of an aircraft fuel can be assessed by the
temperature at which it fails the specification jet fuel
thermal stability test (the Jet Fuel Thermal Oxidation Figure 9. Deposition results for various fuels. Air-sparged fuels, 12
Tester (JFTOT), ASTM 3241). This is referred to as the mL/min, 69 atm.
breakpoint temperature. Thus, Taylor measured a dep-
osition of 0.4 ppm/cm2 for a JP-5 (274 °C breakpoint) Figures 4-8. In Taylor’s test, the total carbon deposit in
(Taylor, 1974) and UTRC measured a deposition of 0.04 the tube from JP-5 was 10 times that of JP-7 (Taylor,
ppm/cm2 for another JP-5 (breakpoint 270 °C) (TeVelde 1974). The results in the present test for a Jet A-l fuel
and Glickstein, 1983), as shown in Figure 1. These (333 °C breakpoint) and JP-7 are shown in Figure 9. The
deposition levels are an order of magnitude larger than deposition level is similar to that reported by Taylor for
the levels seen in JP-7 and the pure hydrocarbons in a JP-5 fuel at a similar flow rate (Figure 1). More extensive
 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993 3121
Table III. Results of Gas Chromatographic Analysis of radicals is favored as the secondary C-H bond strength
n-Octane and n-Hexadecane after Thermal Stressing is 3 kcal/mol less than the primary C-H bond. There are
GC area % three possible sec-CgHn radicals that can be formed by
n-octane test n-hexadecane test
H-atom abstraction from n-octane. These three sec
species
radicals can recombine to yield six possible Cs dimers.
propane and propylene 0.125
The fact that we found six dimer species as products further
1-butene and n-butane 0.241/0.274 0.052
1-pentene 0.352 0.056 confirms their identity.
n-pentane 0.328 0.089 The major products found, the homologous series of
1-hexene 0.448 0.109 alkanes and alkenes, are similar to those observed for GC
n-hexane 0.048 0.101 analyses in the low-temperature (160-180 °C) reaction of
1-heptene and n-heptane 0.188 0.197/0.106 n-dodecane (Zabarnick and Striebich, 1992), and in the
1-octene 0.182
n-octane 0.119 pyrolytic cracking of alkanes at high temperature. It is
n-octane and impurities 97.65 thought that these alkanes and alkenes are products of
1-nonene 0.178 the decomposition of alkyl hydroperoxides (Reddy et al.,
n-nonane 0.125 1988) at temperatures below 480 °C (900 °F) and from
l-decene 0.180 pyrolysis reactions above 480 °C (Hazlett, 1977). The alkyl
n-decane 0.129
1-undecene 0.207
hydroperoxides are produced from the autooxidation chain
n-undecane 0.130 mechanism, where the reactant alkane, RH, is converted
1-dodecene 0.196 to the alkyl hydroperoxide, ROOH:
n-dodecane 0.126
1-tridecene and n-tridecane 0.314
R + 02 —* R02
1-tetradecene 0.150
n-tetradecane 0.148 R02 + RH -> ROOH + R
1-pentadecene 0.107 The R radicals are initially produced by some poorly
n-pentadecane 0.066 understood initiation mechanism that is thought to involve
Cs dimers 0.275
n-hexadecane and impurities 95.99 oxygen and surface catalysis. These alkyl hydroperoxides
other unidentified products 0.071 0.94 are known to be produced in air-saturated hydrocarbons
at temperatures as low as «=95 °C (200 °F). The alkyl
tests with various fuels and pure hydrocarbons are hydroperoxides decompose by the following path:
underway (Edwards and Liberio, 1994). ROOH — RO + OH
RO RCHO + R or RRCO + R
—

Chemical Analysis of Products

Gas chromatographic (GC) analyses were performed on
samples of stressed n-octane and n-hexadecane for de-
termination of the reaction products. The products were
identified by a mass spectrometer detector interfaced to
the GC and quantified using a flame ionization detector
(FID). The n-octane sample was subjected to maximum
fuel and wall temperatures of 480 and 540 °C (900 and
1000 °F), respectively (Figure 8). The n-hexadecane was
subjected to maximum fuel and wall temperatures of 470
and 620 °C (875 and 1150 °F), respectively (Figure 7). The
product yields were estimated by assuming that the FID
sensitivity to individual compounds is proportional to the
number of carbon atoms present in the molecule. There-
fore at small conversions of the parent alkane to products,
the integrated areas of the GC peaks can be related to the
fraction of the carbon atoms in the original alkane that
react. The products observed for these two experiments
are shown in Table III. The data in the table indicate the
3-4 % of the carbon of the reactant alkane has reacted and
the primary products observed are a series of alkanes and
alkenes, with shorter carbon backbones than the parent
alkane. For n-octane, a series of six peaks that appear to
be dimers of CgHn radicals, that is isomers of Ci6H34, are
also found. The mass spectra of these peaks do not yield
the molecular ion; identification as Cj6 species was obtained
by comparison of GC retention times with other alkanes,
comparison with mass spectra of other large alkane isomers,
the prominent C3Hi7 mass spectral peak, and the number
of isomers found as discussed below. For n-hexadecane
the corresponding C32H66 species was not found, although
this could be due to these species not eluting from the
chromatographic column due to their expected very high
boiling points under the chromatographic conditions used
for these analyses.
The C16H34 isomers result from the recombination of
sec-CsHi7 radicals. The formation of secondary alkyl
RO + RH -*• ROH + R
R + RH -* alkane + R
R -* alkene + R
Thus, the alkyl hydroperoxides decompose to alkoxy
radicals and an OH radical. This alkoxy radical can
decompose unimolecularly to aldehydes or ketones and
alkyl radicals, or abstract an H-atom from a fuel molecule
to form an alcohol and an alkyl radical. Alkanes and
alkenes are produced from H-atom abstraction from the
fuel and unimolecular decomposition, respectively. An-
other possible pathway for the formation of alkenes is the
intramolecular isomerization of alkylperoxy radicals to
hydroperoxyalkyl radicals (QOOH), which can then de-
compose to yield an alkene and an HO2 radical (Fish, 1970):
R02 -* QOOH —*• alkene + H02
The alkyl hydroperoxide mechanism also predicts the
formation of alcohols, aldehydes, and ketones, none of
which was found in the GC analysis of the whole stressed
fuel. At this time it is not clear why oxidized products
were not found, although oxygenated products with the
same carbon chain length as the original alkane would
likely be masked by the very large alkane peak in the
analysis. Separation and concentration of the low con-
centration oxidized products using solid-phase extraction
with subsequent GC/MS analysis of the extract (Reddy
et al., 1988; Schulz, 1992) was successfully used to
qualitatively identify the oxidized products from the
hexadecane. The oxidized products included the aldehyde,
alcohol, and ketone derivatives of the n-paraffins listed in
Table III, such as the n-decane derivatives decanal,
2-decanone, and 1-decanol. The elution region near the
oxidized hexadecane products was crowded with C15-C17
primary and secondary alcohols, ketones, and aldehydes,
as well as products identified as substituted dihydrofura-
nones.
3122 Ind. Eng. Chem. Res., Vol. 32, No. 12,1993
The chemical processes that result in deposit formation
are poorly understood. The absence of oxygen greatly
reduces deposit formation (Taylor, 1974; Bradley et al.,
1974; Hazlett, 1991). Hazlett (1977,1980) proposed alkyl
hydroperoxides as precursors to deposits due to the
observation that hydroperoxide depletion appeared to
correlate with tube deposit rating in a JFTOT. More
recently, evidence has appeared demonstrating an inverse
correlation between the ability of a fuel to form peroxides
with its deposit-forming tendency (Heneghan and Zabar-
nick, 1992). Efforts are underway to incorporate oxygen
consumption and solid deposition reactions into compu-
tational fluid dynamic models of fuel system components
(Katta and Roquemore, 1993).
Summary
The results presented in this paper indicate that surface
deposition from supercritical hydrocarbon fuels is con-
trolled by chemical processes in the fuel, rather than by
supercritical solvent properties of the fuel. The primary
deposition property of interest was the decrease in
deposition usually seen at temperatures above approxi-
mately 370 °C (700 °F). The deposition decrease was
shown to be independent of fuel critical properties in two
ways. First, it was demonstrated that the deposition
decrease seen at high temperatures at a given flow rate
could be shifted significantly in temperature by varying
the fuel flow rate. Thus, the deposition decrease is not
solely a temperature effect, as it would be if supercritical
fuel properties were controlling the deposition. Second,
tests with fuels and pure hydrocarbons of widely varying
critical temperatures yielded very similar deposition-
temperature behavior, again demonstrating the high-
temperature deposition decrease is not primarily related
to fuel supercritical properties.
Acknowledgment
This work was supported by the Air Force Office of
Scientific Research (AFOSR). Julian Tishkoff was the
AFOSR Program Manager. The authors wish to thank
Bill Schulz for his separation and analysis of the hexa-
decane oxidation products.
Literature Cited
Bradley, R.; Bankhead, R.; Bucher, W. “High Temperature Hydro-
carbon Fuels Research in an Advanced Aircraft Fuel System
Simulator on Fuel AFFB-14-70”; AFAPL-TR-73-95; Air Force
Aero Propulsion Laboratory: Wright-Patterson AFB, OH, April
1974.
Chin, J. S.; Lefebvre, A. H. Experimental Techniques for the
Assessment of Fuel Thermal Stability. J. Propulsion 1992,8 (6),
1152-1156.
Edwards, T. “Deposition During Vaporization of Jet Fuel in a Heated
Tube”; AIAA Paper 92-0687; AIAA: Washington, DC, January
1992.
Edwards, T. “USAF Supercritical Hydrocarbon Fuels Interests”;
AIAA Paper 93-0807; AIAA: Washington, DC, January 1993.
Edwards, T.; Anderson, S. D. “Results of High Temperature JP-7
Cracking Assessment”; AIAA Paper 93-0806, AIAA: Washington,
DC, January 1993.
Edwards, T.; Liberio, P. D. The Thermal-Oxidative Stability of Fuels
at 480 °C (900 °F). Paper be presented at Symposium on Distillate
Fuel Auto-Oxidation Chemistry, ACS National Meeting, San
Diego, CA, March 1994.
Faith, L. E.; Ackerman, G. H.; Henderson, H. T. “Heat Sink
Capabilities of Jet A Fuel: Heat Transfer and Coking Studies”;
NASA CR-72951; NASA Lewis Research Center: Cleveland, OH,
July 1971.
Fish, A. Rearrangement and Cyclization Reactions of Organic Peroxy
Radicals. In Organic Peroxides; Swern, D., Ed.; Wiley-Inter-
science: New York, 1970; Vol. I, pp 141-198.
Frankenfeld, J. W.; Taylor, W. F. Deposit Formation from Deoxy-
genated Hydrocarbons. 4. Studies in Pure Compound Systems.
Ind. Eng. Chem. Prod. Res. Dev. 1980,19, 65-70.
Hazlett, R. N. Fuel Radical Reactions Related to Fuel Research. In
Frontiers of Free Radical Chemistry; Pryor, W. A., Ed.; Academic
Press: New York, 1980; pp 195-223.
Hazlett, R. N. Thermal Oxidation Stability of Aviation Turbine
Fuels; ASTM Monograph 1; American Society for Testing and
Materials: Philadelphia, 1991.
Hazlett, R. N.; Hall, J. M.; Matson, M. Reactions of Aerated
n-Dodecane Liquid Flowing Over Heated Metal Tubes. Ind. Eng.
Chem. Prod. Res. Dev. 1977,16, 171-177.
Heneghan, S. P.; Zabamick, S. Oxidation of Jet Fuels and the
Formation of Deposits. Fuel 1993, in press.
Katta, V. R.; Roquemore, W. M. A Numerical Method for Simulating
the Fluid-Dynamic and Heat Transfer Changes in a Jet Engine
Injector Feed Arm Due to Fouling. J. Thermophys. Heat Transfer
1993, in press.
Martel, C. R. Air Force Aviation Fuel Thermal Oxidation Stability
R&D. In Jet Fuel Thermal Stability; NASA TM 79231; Taylor,
W. F., Ed.; NASA Lewis Research Center: Cleveland, OH,
November 1978; pp 41-52.
Martel, C. R. Molecular Weight and Average Composition of JP-4,
JP-5, JP-8, and Jet A. Unpublished Results from Air Force Fuel
Surveys. Unpublished memo, Air Force Aero Propulsion Labo-
ratory, July 15,1988.
Marteney, P. J.; Spadaccini, L. J. Thermal Decomposition of Aircraft
Fuel. J. Eng. Gas Turbines Power (ASME Trans.) 1986,108,648.
Moses, C. Southwest Research Institute. Unpublished work on NASA
Grant NAG 3-1342, 1992.
Reddy, K. T.; Cemansky, N. P.; Cohen, R. S. Modified Reaction
Mechanism of Aerated n-Dodecane Liquid Flowing over Heated
Metal Tubes. Energy Fuels 1988, 2, 205-213.
Schulz, W. D. Oxidation Products of a Surrogate JP-8 Fuel.
Prepr.—Am. Chem. Soc., Div. Pet. Chem. 1992, 37 (2), 383-392.
Taylor, W. F. Deposit Formation from Deoxygenated Hydrocarbons.
1. General Features. Ind. Eng. Chem. Prod. Res. Dev. 1974,13,
133-138.
TeVelde, J. A.; Glickstein, M. R. “Heat Transfer and Thermal
Stability of Alternative Aircraft Fuels, Vol. I”; NAPC Report
NAPC-PE-87C, November 1983, AD A137 404.
Zabarnick, S.; Striebich, R. Unpublished results, 1992.
Received for review May 10,1993
Revised manuscript received September 7,1993
Accepted September 20,1993*
• Abstract published in Advance ACS Abstracts, November
1, 1993.