Designation: D 6468 – 99 An American National Standard

Standard Test Method for

High Temperature Stability of Distillate Fuels1
This standard is issued under the fixed designation D 6468; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 4625 Test Method for Distillate Fuel Storage Stability at

1.1 This test method covers relative stability of middle 43°C3
distillate fuels under high temperature aging conditions with D 5452 Test Method for Particulate Contamination in Avia-
limited air exposure. This test method is suitable for all No. 1 tion Fuels by Laboratory Filtration4
and No. 2 grades in Specifications D 396, D 975, D 2880, and 3. Terminology
D 3699 and for grades DMX and DMA in Specification
D 2069. It is also suitable for similar fuels meeting other 3.1 Definitions of Terms Specific to This Standard:
specifications. 3.1.1 adherent insolubles—material that is produced in the
1.2 This test method is not suitable for fuels whose flash course of stressing distillate fuel and that adheres to the
point, as determined by Test Methods D 56, D 93, or D 3828, glassware after fuel has been flushed from the system.
is less than 38°C. This test method is not suitable for fuels 3.1.2 filterable insolubles—material that is produced in the
containing residual oil. course of stressing distillate fuel and that is capable of being
1.3 The values stated in SI units are to be regarded as the removed from the fuel by filtration.
standard. 3.1.3 inherent stability—the resistance to change when
1.4 This standard does not purport to address all of the exposed to air, but in the absence of other environmental
safety concerns, if any, associated with its use. It is the factors such as water, reactive metal surfaces, and dirt.
responsibility of the user of this standard to establish appro- 3.1.4 storage stability—the resistance of fuel to formation
priate safety and health practices and determine the applica- of degradation products when stored at ambient temperatures.
bility of regulatory limitations prior to use. 3.1.5 thermal stability—the resistance of fuel to formation
of degradation products when thermally stressed.
2. Referenced Documents
4. Summary of Test Method
2.1 ASTM Standards:
D 56 Test Method for Flash Point by Tag Closed Tester2 4.1 Two 50-mL volumes of filtered middle distillate fuel are
D 93 Test Methods for Flash Point by Pensky-Martens aged for 90 or 180 min at 150°C in open tubes with air
Closed Cup Tester2 exposure. After aging and cooling, the fuel samples are filtered
D 396 Specification for Fuel Oils2 and the average amount of filterable insolubles is estimated by
D 975 Specification for Diesel Fuel Oils2 measuring the light reflectance of the filter pads. The 100 and
D 1500 Test Method for ASTM Color of Petroleum Prod- 0 % extremes of the reflectance rating range are defined by an
ucts (ASTM Color Scale)2 unused filter pad and a commercial black standard, respec-
D 2069 Specification for Marine Fuels2 tively.
D 2274 Test Method for Oxidation Stability of Distillate 5. Significance and Use 5
Fuel Oil (Accelerated Method)2
D 2880 Specification for Gas Turbine Fuel Oils3 5.1 This test method provides an indication of thermal
D 3699 Specification for Kerosine3 oxidative stability of distillate fuels when heated to high
D 3828 Test Methods for Flash Point by Small Scale Closed temperatures that simulate those that may occur in some types
Tester3 of recirculating engine or burner fuel delivery systems. Results
D 4057 Practice for Manual Sampling of Petroleum and have not been substantially correlated to engine or burner
Petroleum Products3 operation. The test method can be useful for investigation of
operational problems related to fuel thermal stability.
5.2 When the test method is used to monitor manufacture or
storage of fuels, changes in filter rating values can indicate a
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
4
D02.14 on Stability and Cleanliness of Liquid Fuels. Annual Book of ASTM Standards, Vol 05.03.
5
Current edition approved Nov. 10, 1999. Published January 2000. Henry, C. P., “The du Pont F21 149°C (300°F) Accelerated Stability Test,”
2
Annual Book of ASTM Standards, Vol 05.01. Distillate Fuel Stability and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P.
3
Annual Book of ASTM Standards, Vol 05.02. Henry, Eds., ASTM, 1981, pp. 22-33.

Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.

1
 D 6468
relative change in inherent stability. Storage stability predic- 6.6 Reflection meter, Photovolt Model 577 Digital Reflec-
tions are more reliable when correlated to longer-term storage tion Meter, complete with search unit Y with a green filter and
tests, for example, Test Method D 4625, or other lower polished black glass standard.7
temperature, long-term tests. When fuel samples are freshly NOTE 3—Other reflection meters or search units, or both, can be used,
produced, aging for 180 min, instead of the traditional 90-min but they are likely to provide only similar (not identical) results. For
interval, tends to give a result correlating more satisfactorily example, Photovolt Model 577 digital reflection meter equipped with
with the above methods (see Appendix X2). search unit W usually gives somewhat lower percent reflectance values.
5.3 The test method uses a filter paper with a nominal Correlation of these values is discussed in Appendix X1.
porosity of 11 µm, which will not capture all of the sediment NOTE 4—Older reflection meters, including but not limited to Photovolt
formed during aging but allows differentiation over a broad Model 670 analog meter, are satisfactory.
range. Reflectance ratings are also affected by the color of
7. Reagents and Materials
filterable insolubles, which may not correlate to the mass of the
material filtered from the aged fuel sample. Therefore, no 7.1 Purity of Reagents—Reagent grade chemicals shall be
quantitative relationship exists between the pad rating and the used in all tests. Unless otherwise indicated, it is intended that
gravimetric mass of filterable insolubles. all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
6. Apparatus such specifications are available.8 Other grades may be used,
6.1 Aging Tubes, 253 200 mm, heavy wall test tubes made provided it is first ascertained that the reagent is of sufficiently
of borosilicate glass. high purity to permit its use without lessening the accuracy of
6.2 Heating Bath, with liquid heating medium, thermostati- the determination.
cally controlled to maintain the sample in the aging tube within 7.2 Acetone, reagent grade. (Warning—Extremely flam-
1.5°C of 150°C. It must be large enough to hold aging tubes mable.)
immersed in the heating liquid to a depth above the level of 7.3 Adherent Insolubles Solvent (Trisolvent or TAM), a
samples in the tubes. The bath and its location shall be such to mixture of equal parts by volume of reagent grade toluene
enable shielding of the samples from direct light during aging. (Warning—Flammable. Vapor harmful.), acetone
The volume of bath and its heat recovery rate shall be such that (Warning—see 7.2), and methanol (Warning—Flammable.
the temperature of the medium does not drop more than 5°C Vapor Harmful. May be fatal or cause blindness if swallowed
when the maximum number of aging tubes are inserted, and or inhaled. Cannot be made nonpoisonous.).
recovery to 150°C shall not require more than 15 min. 7.4 Hydrocarbon Solvent, 2,2,4-trimethylpentane (iso-
(Warning—The flash point of the liquid heating medium must octane), 99.75 % purity minimum (Warning—see 7.2).
be at least 180°C. Bath vapors and oil sample vapors shall be NOTE 5—Heptane is a satisfactory alternative hydrocarbon solvent.
properly vented. Exposed hot surfaces on the apparatus and hot However, small differences may be seen due to slightly different solubility
heating medium can cause severe burns.) characteristics. Iso-octane is specified to be in agreement with the
6.3 Thermometer, either glass or digital, whose accuracy in hydrocarbon solvent used in other middle distillate stability test methods
such as Test Methods D 2274 and D 4625.
the 140 to 160°C range is certified or traceable to a certified
thermometer. Use to monitor the temperature of the heating 7.5 Filter Paper (Filter Pad), Whatman No. 1, 47-mm
bath in 6.2. diameter, or equivalent.
6.4 Membrane Filter Holder, to fit 47-mm membrane filters, NOTE 6—Filter papers of 42.5 or 55-mm diameter are technically
fitted to a heavy-walled 500-mL or 1-L vacuum flask. satisfactory. Filters with a diameter of 47 mm permit a small unused
NOTE 1—Several types of membrane filter holders are available. To margin for identifying the sample and fit all filtration apparatuses.
reduce electrostatic hazards, an all metal filter holder equipped with
grounding cables is recommended.6 Such an apparatus and correct 8. Sampling
grounding practices are described in Test Method D 5452. A fritted glass 8.1 When samples of a fuel batch are obtained to determine
filter holder is less preferred because of a tendency to become partially stability, obtain samples in accordance with Practice D 4057.
clogged during use so that filter pads that do not have uniform deposits are Use only epoxy-lined cans or borosilicate glass bottles. Shield
obtained. Glass filter holders that use a 75-µm (200-mesh) screen to
clear glass bottles from sunlight to prevent photochemical
support the filter are available; however, since the screen can be an
unbonded electrostatic charge collector, these are not recommended for reactions.
use with flammable liquids. 8.2 When samples are from a fuel or component rundown
line, exercise care to ensure that the sampling line and valving
6.5 Vacuum Source, that limits the maximum vacuum to 27
are thoroughly flushed with current mainstream sample.
kPa (200 mm Hg) below atmospheric pressure. The vacuum
should rise to 27 kPa within 10 to 15 s after the sample is added
to the filtration funnel.
7
Available from UMM Electronics Inc., Photovolt Instruments, 6911 Hillsdale
NOTE 2—Use of reduced vacuum improves retention of particulate on Court, Indianapolis, IN 46250-2062.
8
the relatively porous filter media. Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6
A suitable filter holder is available from Millipore Corporation, 80 Ashby Rd., and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Bedford, MA 01730; Catalog No. XX20 047 20. MD.

2
 D 6468
8.3 Because stability of some fuels, as determined in this NOTE 9—Where practical, filter a fuel sample larger than 100 mL. This
test method, changes over time, the sampling date shall be will reduce the possibility that the paper may absorb trace materials that
recorded; record time and date if sample is from a fuel or affect stability.
component rundown line. Samples should be stored at tem- 11.3 Place the uncapped sample tubes in the heating bath for
peratures below 5°C. If storage for more than a few days is 90 6 3 min, or 180 6 5 min. Place the tubes in the bath in the
expected, oxygen should be removed from the fuel by subsur- same order in which they are to be removed. (Warning—Fuels
face purging with a stream of nitrogen; for example, by will be heated above their flash points. There is a possibility
bubbling nitrogen for 1 min/L of sample. that certain light fuels such as kerosine will boil under
9. Preparation of Apparatus conditions of the test. Both situations raise the risk of fire when
9.1 Cleaning Aging Tubes—Clean new tubes using adherent an ignition source is present. Fuel samples that may contain
insolubles solvent, then with a mildly alkaline or neutral gasoline or other volatile components should not be tested.)
laboratory detergent, followed by copious rinsing with deion- NOTE 10—The severity of the test is increased by aging for longer times
ized or distilled water to remove all traces of detergent. Then at 150°C. The selection of the aging time depends on application and
rinse with acetone and air dry. Rinse used tubes with adherent should be established by correlation with other tests or with application
insolubles solvent, dry, then clean as above for new tubes. requirements.
Visually inspect tubes before use, and reclean or reject if there 11.4 Remove the samples from the heating bath and allow to
is the slightest trace of contamination. cool gradually in air to 20 to 25°C over a period of 90 min to
9.1.1 Because of the small sample size and the high surface 4 h. Cool in the dark to prevent photochemical reactions. Do
to volume ratio in this test method, carefully avoid carry-over
not accelerate cooling by immersing in a cooling bath as this
from past tests or from cleaning agents. There are especially
can result in small particle size and a lower pad rating. If
strong effects from traces of copper, strong acids, and strong
samples are allowed to stand more than 4 h before filtering,
bases.
insoluble gum may adhere to the aging tubes, resulting in
9.2 Cleaning Membrane Filter Holder—Rinse with adher-
erratic data. (Warning—The hot samples can cause severe
ent insolubles solvent, acetone, and air dry.
burns. Use protective equipment.)
10. Calibration and Standardization 11.5 Prepare a filtration assembly with a new filter paper,
10.1 Turn on the reflection meter and allow at least 30 min and attach all grounding clips to ground. Filter one of the two
for warm-up. The gain should be set in LO position for search aged fuel samples.
unit Y with green filter. 11.6 While maintaining vacuum, wash the aging tube with
10.2 Follow the manufacturer’s instructions to carry out a three small portions, about 15 mL each, of iso-octane and filter
two point calibration of the reflection meter, using the black through the filter paper. Wash the inside of the filter assembly
standard and standard plaque supplied with the search unit. with iso-octane, and remove the funnel portion of the assembly.
NOTE 7—The calibration procedure ensures that the instrument is While still maintaining vacuum, use a gentle stream of iso-
working properly. It also indirectly sets a nominal 100 % reflectance octane from a squeeze bottle to wash the filter clean of any
setting that is subsequently reset in 10.3. traces of fuel oil, and allow to dry under vacuum for 1 or 2 min
10.3 Place a new filter paper on top of a stack of at least ten (see Note 11). Shut off vacuum, and remove the filter from the
unused Whatman No. 1 filters of the same size. Place the assembly with forceps. When multiple tests are carried out, the
search unit on the center of the filter, and adjust the meter margin of the pad may be used for identification after drying.
reading to 100 %, using the sensitivity control. If the deposit on the filter pad is not evenly distributed, reject
the pad and rerun the test after cleaning the membrane filter
NOTE 8—Such adjustment, which sets the test method 100 % reflec-
holder (see 9.2).
tance point, alters the reflectance scale; as a result, the reflection meter will
no longer read the recited reflectance of the standard plaque. NOTE 11—Some laboratories may contain sufficient airborne contami-
10.4 Place the search unit on the center of the black glass nation to change results if the air drying period is prolonged.
standard, and (if necessary) adjust the meter reading to 0 %, 11.7 Place the test filter on the stack of at least ten unused
using the ZERO control. Recheck the 100 % adjustment filter pads, center the search unit on the filter, and record the
against the new filter paper, and continue adjustment until the meter value as percent reflectance filter pad rating to one
meter reads both 0 % with the black glass standard and 100 % decimal place.
with the new filter pad.
11.8 Repeat 11.5-11.7, using the second of two aged fuel
11. Procedure samples.
11.1 Adjust the heating bath to a temperature of 1506 1.5°C
(see 6.3). 12. Report
11.2 Assemble the filter apparatus with a new filter paper.
12.1 Report the following information:
Filter at least 100 mL of the fuel sample through the paper. Use
the inline vacuum regulator so that the maximum vacuum is 27 12.1.1 Sampling date and date of test (see 8.3).
kPa (200 mm Hg). Measure two 50 6 2-mL volumes of filtered 12.1.2 Aging time at 150°C.
fuel and decant into each of two aging tubes (see Appendix 12.1.3 Percent reflectance filter pad rating as the average of
X3). duplicate determinations, to the nearest whole percent.

3
 D 6468
9
13. Precision and Bias where:
13.1 Precision—The precision of this test method as deter- x 5 the average of two results in percent reflectance.
mined by statistical examination of interlaboratory results is as 13.1.2 Reproducibility—The difference between two inde-
follows: pendent test results, obtained by different operators working in
different laboratories on identical test material, would in the
13.1.1 Repeatability—The difference between two test re- long run, in normal and correct operation of the test method,
sults, obtained by the same operator with the same apparatus exceed the following values in only one case in twenty:
under constant operating conditions on identical test material,
Aging Time Reproducibility
would in the long run, in normal and correct operation of the 90 min 44.04 - 0.4281x
test method, exceed the following values in only one case in 180 min 34.11 - 0.3034x
twenty:
where:
Aging Time Repeatability x 5 the average of two results in percent reflectance.
90 min 22.42 - 0.2130x
180 min 22.55 - 0.2145x 13.2 Bias—Since there is no accepted reference material for
determining the bias for this test method, bias cannot be
determined.
14. Keywords
9
Supporting data have been filed at ASTM Headquarters. Request RR:D02- 14.1 distillate fuels; fuel insolubles; high temperature sta-
1463. bility; storage stability; thermal stability

APPENDIXES

(Nonmandatory Information)

X1. INTERPRETATION OF RESULTS

X1.1 Test results should be correlated to actual storage or statement for its use was developed (see RR:D02-1463).
use conditions, or equipment operation, to have maximum However, because the result and difference between results
utility. In the case of storage stability, results should be checked over the percent reflectance range varies when obtained with
against longer term, less accelerated test methods. the two search units, it was agreed that only one should be
specified in the test method, to enable generation of compa-
X1.2 For internal, contractual, or industry specification rable results, especially comparable laboratory-to-laboratory
purposes, satisfactory results are partly defined by age of the results. Further, the data suggest that the bias between the two
sample at time of testing, by anticipated storage needs, or by search units is not uniform, so a bias correction cannot be
equipment needs; all of these vary and may reflect more or less recommended. Other reflection meters can be used, but in that
conservative approaches. case, the use of a different instrument should be reported, and
X1.3 Table X1.1 shows an interpretation of test results, it should also be reported that a modified test method was used.
which appears to be generally accepted. Rankings are with It would also be appropriate to generate a new table, such as
respect to relative performance in the test; relevance to use Table X1.1, which establishes the relevance of the results.
applications requires interpretation and judgment. X1.5 When the fuel is very dark, the filter pad may be
stained a dark color, yet microscopic examination shows little
X1.4 The Y search unit with green filter has a different
or no particulate matter is present. Fuel color does not
spectral response than the W search unit, and on average, gives
necessarily correlate with performance; however, dark-colored
a higher result. Because the sediments on filter pads vary in
fuels frequently have oxidation sediment associated with them
color, the difference between results varies.
and may form sediment if commingled with fuels having poor
X1.4.1 During the precision program on this test method, solubilizing properties (for example, when a dark light cycle
some laboratories used the W search unit, and a precision oil is commingled with a paraffinic fuel). Staining alone will
typically not give filter pad ratings with less than 50 %
TABLE X1.1 Interpretation of Results reflectance.
Y Search Unit W Search Unit
Relative Stability with Green Filter X1.6 The test method can be used to determine the relative
% Reflectance % Reflectance performance of additives under conditions of the test. Because
100-90 100-85 results depend on the history of the fuel sample, relative
89-80 84-71 performance is best determined by carrying out comparison
| 79-70 70-62
Decreasing 69-60 61-53 tests in a single batch of samples, prepared and aged together.
Stability 59-50 52-32
↓ 49-0 31-0 X1.7 The test temperature may simulate conditions that
exist in some equipment where fuel is exposed to temperatures

4
 D 6468
from 100 to 150°C, or higher, then recycled back to a storage over time. Substantial changes can signal a fuel quality
tank. excursion. The test method can also be used to verify that
stabilizing additives have been appropriately added to distillate
X1.8 This test method is effective to monitor the relative fuels with marginal stability.
thermal stability and possible change in storage stability at a
production site where crude source and process conditions vary

X2. FACTORS WHICH AFFECT THE TEST METHOD

X2.1 Due to the high test temperature and the lack of X2.2.1 The test method tends to give results that amplify the
oxygen feed to the test specimen during aging, there is a benefits of some stabilizer additives. The benefit of metal
tendency of the test method to give better results with fresh fuel deactivator additive, when fuel contains dissolved copper,
than with the same fuel after it has aged at ambient temperature correlates well with less accelerated tests. Effects of dispersant
with oxygen exposure. When tests are carried out on freshly additives are also well correlated.
produced fuel, the aging period can be increased to 180 min, or X2.2.2 Some additives exhibit effects on samples aged in
more stringent standards can be imposed on the pad rating to accordance with this test method, which are not found in other
better reflect change in properties that may result from distri-
tests where samples are aged at 100°C or lower. For example,
bution and storage.
many fuels will give worse results if alkyl nitrate cetane
X2.2 Additives can have positive or negative effects in this number improver is present. The relevance of these findings is
test, which may or may not be observed in actual storage or not entirely clear.
use.

X3. FUEL COLOR

X3.1 Diesel fuel natural color ranges from water white temperatures, is not a reliable measure of fuel quality. None-
(colorless) to dark amber, reflecting the crude oil or the refinery theless, some fuel technologists believe that measurement of
process streams from which the fuel is produced, or both. Color fuel color before and after aging provides useful information.
per se, as determined by Test Method D 1500, does not
necessarily reflect suitability of the fuel for its intended use. X3.3 Practitioners of this test method who insist on
There is also no agreement on how to measure fuel color when measuring Test Method D 1500 color before and after aging
dye is present. should measure unaged fuel color (initial color) after filtration
in 11.2 and carry out aged fuel color measurement on the
X3.2 Change in fuel color (darkening) alone, during storage filtrate generated in 11.5 that has been decanted from the
at ambient temperatures or upon accelerated aging at elevated vacuum flask before use of any iso-octane.

The American Society for Testing and Materials takes no position respecting the validity of any patent rights asserted in connection
with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such
patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your
views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at
610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website (www.astm.org).