r RD-Ai49 934 OXIDATION ANN GUM FORMATION IN JET FUELS(U) SRI /

INTERNATIONAL MENLO PARK CA F R MAYO 16 NOY 84

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Interim Technical Report 1
Oxidation and Owm Formation in Jet Fuels

7. AUTHOR(a) II OTATO RN uBRa

Frank It.Mayo AG2-4-06

*S. PERFORMING ORGANIZATION NAME AND ADDRESS 1.PORMEEET RJC.TS
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* SRI International N/IA
333 Ravenswood Ave.
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U. S. Army Research Office November 16, 1984
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IS. SUPPLEMENTARY NOTES

* The view, opinions, and/or findings contained in this report are
* those of the author(s) and should not be construed as an official
Department of the Army position, policy, or decision, unless so
designated by other documentation.
IS. KEY WORDS (Continue an reverse side It necessary and Identify by block mnube.)

'Oxidation,gum, deposits, hydrocarbons, jet fuels, metals, metal surfacS,

2&0,A9*rRACr (=ma ai toersoa otl If mnem mi fdeatir by block numtboe)

Chapter 6 in the Ruissian book by E. T. Denisov and 0. 1. Kovalev,
rbOxidation and Stabilization of Jet Fuels"', is reviewed. It deals with
the effects of many metal and alloy surfaces on gum and deposit formation
from a stable jet fuel (T-6) produced by lkhydrodearomatizaton. The metals
affect oxidations mostly by assising or retarding the Initiation of a
* subsequent homogeneous oxidation. The effects of the metals and the difference
"asmuthem are smallI to moderate. \C I\r Cr- %-C4 VA
W ,\

*DO , jam 1473 19DOOorI 110V [email protected]

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NI",
 November 16, 1984

jOXIDATION AND GUM FORMATION IN JET FUELS

Interim Technical Report No. 1

By
Frank R. Mayo

U. S. ARMY RESEARCH OFFICE

Contract No. DAAG 29-84-K-0161

SRI INTERNATIONAL A 'n For....-

333 Ravenswood Avenue -- ; -I

Menlo Park, California 94025

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DISTRIBUTION UNLIMITED

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 OBJECTIVE

One of the objectives of my present contract with the ARO is to

determine the effect of metal surfaces on fuel stability. However, a
book has recently appeared that treats this subject competently, "The
Oxidation and Stabilization of Jet Fuels" by E. T. Denisov and G. 1.
Kovalev l . The book has been translated but not published by NASA; 2 both
versions have a very limited availability in the U. S. Chapter 6 in the
book deals with relative rates of oxidation and gum formation in the
presence of many metal and alloy surfaces. The object of this Interim
Technical Report is to review this chapter, draw some conclusions, and
consider whether and how the direction of my contract research should be
altered.

BACKGROUND

The first five chapters of the book consider in great detail the
kinetics and mechanism of oxidation of hydrocarbons and some jet
fuels. They make available in one place the extensive and detailed
Russian work in this field but I found little that is new in
principle. However, I am not aware of much other work on the effects of
metal surfaces.

Denisov's experiments used 0.5 g of metal powder in 50 g of T-6 jet

fuel. This fuel was produced by hydrodearomatization. It contains no
significant quantities of 0, N, and S has a low tendency toward deposit
formation in fuel systems. Some properties are: <10% boiling below
220-C, >98% below 315oC; density at 20°C, 840 g/L; <221 aromatic
hydrocarbons, <1.5% bicyclic aromatic hydrocarbons. Oxygen absorption
was measured over an unstated period at 150oC and presented as the
quotients of the rates of oxygen absorptions with and without metal. At
6the ends of the experiments, solid products and soluble gum were
determined. These are presented as milligrams of material/100 g fuel

1 Khimiya Press, Moscow, 1983.

2 NASA Technical Memorandum 77490, 1984.
1
 and also as the quotients of these weights in the presence and absence
of metal surfaces. Denisov treats these gum data as if they were rates
over the same periods as the corresponding oxygen absorptions and I
shall treat them the same way.

RESULTS

Table 1 summarizes the results in Denisov's Table 6.3 on pages 208-

209 of his book. I have added code letters and arranged the relative
rates of oxidation in order of decreasing rates. These relative rates
range from 8 times to one-seventh the rate in the absence of metal (q).
Th' second column of figures gives the relative rates of gum formation
!n order of decreasing rates; the code letters are repeated because the
orders in the two columns, though similar, are not identical. The
spread in rates of gum formation is small, from one-half to twice the
rate in the absence of metal. The third column of figures shows the
quotients of the same code numbers in the first two columns, arranged in
order of decreasing magnitude. The larger numbers at the top of this
column show that more oxygen is required to produce a milligram of gum
with these metals; the small numbers at the bottom show that these
metals give the most Sum for the oxygen absorbed.

Denisov and Kovalev conclude that the principal effect of the metal
surfaces is to affect the rate of homogeneous oxidation by decomposing
hydroperoxides on the metal surface. If this decomposition produces
free radicals, the oxidation is accelerated; if it does not, the
oxidation is retarded because the hydroperoxide is wasted.

CONCLUSIONS

My Figure 1 is a revision of Denisov's Figure 6.2 on page 210. The

straight line corresponds to his correlation of the data. His line has
the advantage that it comes close to the blank with no metal (q), but
the disadvantage that it predicts considerable gum formation without any

oxidation. My curve put a different emphasis on the data. It says that

for many metals, * to h, there is a close proportionality between rates
*.2

S.
 Table I
Oxygen Absorption and Gum Formation by T-6 Jet Fuel

Code Metal Surfaces Relative Relative Relative

Letter Rob RgC Ro/R
a 100 Cr 8.12 a no datum a no datum
b Cu +20 Pbe 5.16 d 2 .16 d c 2.54
c Cu +11 Pb +10 Sn 5.16 b 2 .0 4 d b 2.53
d 100 Pb 5.08 c 2.03 d 2.35
e Cu +11 Alf 3.12 f 1.76 e 1.91
f 65 Cu +33 Zn + 2 Pb 3.10 e 1.63 g 1.90
g Cu +10 Alg 3.02 g 1.59 p 1.84
h Cu + 6.2 Sb 2.57 h 1 .5 1 d o 1.77
i 100 Cu 2.51 i 1.49 f 1.76
J Stainless Steel 1.96 w 1.44 a 1.75
k 60 Cu + 40 Zn 1.86 J 1.31 h 1.70
1 Fe + 12 Cr 1.86 k 1.18 i 1.68
m 100 Fe 1.56 1 1.13 1 1.65
n 100 Al 1.55 1.000 k 1.58
0 100 Sn 1.47 n 0.99 n 1.57
p Low-Ni stainless 1.42 m 0 .8 9 d s 1.56
no metal 1.000 x 0.88 j 1.50
r 100 Zn 0.88 u 0.86 r 1.09
s 100 Ho 0.78 0 0.83 q 1.000
t 100 Nb 0.78 v 0.81 t 0.99
u 100 Mg 0.70 t 0.79 w 0.81
v 100 Ni 0.24 p 0.77 v 0.39
w 100 V 0.14 v 0.62 x 0.16
x 100 V 0.14 s 0.5 0 d w 0.097

a Hejal powder, composition in weight Z, with a surface area of about 300

cm IL. Hrwever, a, a, n, r, t, and v apparently have surface areas up to
19000 cm /L.
b (Rate of oxygen absorption with metil)(late of oxygen absorption without
metal). Latter rate was 1.97 X 10 - H '/sec.
c (Gum + deposit with metal)/(gum + deposit without metal). Latter number
is 57.0 mg /OOg fuel.
d Deposit noted. e +3 each Zn, Sb. f +5.5 each Fe, Ni. 9 +3 Fe + 1.5fu.
3

*~4~> :( :
 ti

* Id
2 Denisov relation a

C
0

S OW
*~
E
*1-4

Ci2
C

''0

0 2

relotion Relatiy

I I I
o 2 46
Relative Rates of Oxidrt~on

Figure 1, Corantsrison of Reletive Rates of Oxrdtion r nd

*um Formation

of oxidation and Sum formation and that when there is no oxidation,

there is no gum formation. The place of sample q, without any metal,
then suggests that the metals on or near the line have accelerated
oxygen absorption more than gum formation. Points that lie above my
line, especially w (V) and x (W), then accelerate gum formation more
than oxygen absorption. The metals that cause the fastest oxidations
(b, c, d) give relatively less gum formation than the metals that fit

4
 the straight part of the line. Chromium (a), which causes the fastest
oxidation, does not appear in Figure 1 because no gum data are
available.

. I conclude that the effects of metal surfaces on rates of oxygen

absorption and gum formation are not now a promising field for
investigation. Even with 300 cm2 of surface per L of fuel, the effects
of the metals and alloys tested are small to moderate and the effects in
larger containers would be less. My own data suggest that differences
among fuels are greater than the differences among effects of metals.
Although W and V are outstanding gum formers in Figure 1, gum is formed
no faster than on several other metals, but the rate of oxygen
absorption is so small. Further, they are unlikely to appear in fuel
systems. Use of the proper stabilizers (e.g., BHT, Ionol) will probably
essentially eleiminate the effects of metals on the homogeneous
reactions.

IMPLICATIONS FOR FURTHER WORK

The missing effect of a chromium surface on gum formation should be

checked to see if it is interesting.

The results cited here were obtained with a stable jet fuel. A few
results might be checked with a stable U. S. fuel (diesel and/or jet) to
see if results are analogous, and then a few experiments might also be
done with an unstable fuel. A few oxidation and gum experiments might
be done with dissolved metals. The effects of the soluble metals might
be larger but the pattern should be the same, assuming that both
dissolved metals and surfaces mostly affect peroxide decomposition and
free radical production.

Metals seem to be necessary to convert soluble gums to hard

deposits. The effects of dissolved metals and surfaces on this reaction
should be checked. This field could be the most important remaining
problem in fuel stability.

5
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