Beruflich Dokumente
Kultur Dokumente
Designation: D 6971 – 04
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D 6971 – 04
NOTE—x-axis = time (seconds) and y-axis is current (arbitrary units). Top line in Fig. 1 is voltammogram of a fresh R&O turbine oil showing valley
indicators before and after antioxidant valleys.
FIG. 1 Aromatic Amine and Hindered Phenol Voltammetric Response in the Neutral Test Solution with Blank Response Zeroed
the applied potential produces an electrochemical reaction 4.1.1 This test method is applicable to non-zinc type of
having a rate so slow that virtually no current flows through the turbine oils as defined by ISO 6743 Part 4, Table 1. These are
cell. As the voltage is increased, as shown in Fig. 1, the refined mineral oils containing rust and oxidation inhibitors,
electro-active species (for example, substituted phenols) begin but not antiwear additives.
to oxidize at the working electrode surface, producing an 4.2 The test is also suitable for manufacturing control and
anodic rise in the current. As the potential is further increased, specification acceptance.
the decrease in the electro-active species concentration at the 4.3 When a voltammetric analysis is obtained for a turbine
electrode surface and the exponential increase of the oxidation oil inhibited with a typical synergistic mixture of hindered
rate lead to a maximum in the current-potential curve shown in phenol and aromatic amine antioxidants, there is an increase in
Fig. 1. the current of the produced voltammogram between 8 to 12 s
(or 0.8 to 1.2 V applied voltage)4 for the aromatic amines, and
4. Significance and Use an increase in the current of the produced voltammogram
4.1 The quantitative determination of hindered phenol and between 13 and 16 s (or 1.3 to 1.6 V applied voltage)4 for the
aromatic amine antioxidants in a new turbine oil measures the hindered phenols in the neutral acetone solution (Fig. 1: x-axis
amount of these compounds that has been added to the oil as 1 s = 0.1 V). Hindered phenol antioxidants detected by
protection against oxidation. Beside phenols, turbine oils can voltammetric analysis include, but are not limited to, 2,6-di-
be formulated with other antioxidants such as amines which tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol; and 4,4’-
can extend the oil life. In used oil, the determination measures Methylenebis (2,6-di-tert-butylphenol). Aromatic amine anti-
the amount of original (hindered phenol and aromatic amine) oxidants detected by voltammetric analysis include, but are not
antioxidants remaining after oxidation has reduced its initial limited to, phenyl alpha naphthylamines, and alkylated diphe-
concentration. This test method is not designed or intended to nylamines.
detect all of the antioxidant intermediates formed during the 4.4 For turbine oil containing only aromatic amines as
thermal and oxidative stressing of the oils, which are recog- antioxidants, there will only be an increase in the current of the
nized as having some contribution to the remaining useful life produced voltammogram between 8 to 12 seconds (or 0.8 to
of the used or in-service oil. Nor does it measure the overall 1.2 V applied voltage)4 for the aromatic amines, by using the
stability of an oil, which is determined by the total contribution neutral acetone test solution (first peak in Fig. 1).
of all species present. Before making final judgment on the 4.5 For turbine oils containing only hindered phenolic
remaining useful life of the used oil, which might result in the antioxidants, it is preferable to use a basic alcohol solution
replacement of the oil reservoir, it is advised to perform
additional analytical techniques (as in accordance with Test
Methods D 6224 and D 4378; see also Test Method D 2272), 4
Voltages listed with respect to reference electrode. The voltammograms shown
having the capability of measuring remaining oxidative life of in Figs. 1 and 2 were obtained with a platinum reference electrode and a voltage
the used oil. scan rate of 0.1 V/s.
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D 6971 – 04
NOTE—x-axis = time (seconds) and y-axis is current (arbitrary units) with top line in Fig. 2 showing the fresh oil.
FIG. 2 Hindered Phenol Voltammetric Response in Basic Test Solution with Blank Response Zeroed
rather than the neutral acetone solutions, as there is an increase 5.4 Solvent Dispenser, or equivalent, capable of delivering
in the current of the produced voltammogram between 3 to 5 volumes of analysis solution (see 6.3) required in the test
seconds (or 0.3 to 0.6 V applied voltage)4 in basic alcohol method, such as 3.0 and 5.0 mL.
solution (Fig. 2: x-axis 1 second = 0.1 V) in accordance with 5.5 Glass Vials, with caps, 4 or 7 mL capacity and contain-
Test Method D 6810. ing 1 g of sand. White quartz suitable for chromatography,
within the size range of 200 to 300 µm 6 100 µm.
5. Apparatus
6. Reagents
5.1 Voltammetric Analyzer5—The instrument used to quan-
tify the hindered phenol and aromatic amine antioxidants is a 6.1 Purity of Reagents—Reagent-grade chemicals shall be
voltammograph equipped with a three-electrode system and a used in all tests. Unless otherwise indicated, it is intended that
digital or analog output. The combination electrode system all reagents shall conform to the specifications of the Commit-
consists of a glassy carbon disc (3 mm diameter) working tee on Analytical Reagents of the American Chemical Society,
electrode, a platinum wire (0.5 mm diameter) auxiliary elec- where such specifications are available.7 Other grades may be
trode, and a platinum wire (0.5 mm diameter) reference used, provided it is first ascertained that the reagent’s purity
electrode, as described in Test Method D 6810. The voltam- suffices to permit its use without lessening the accuracy of the
metric analyzer applies a linear voltage ramp (0 to -1.8 V range determination.
with respect to the reference electrode) at a rate of 0.01 to 0.5 6.2 Purity of Water—Unless otherwise specified, references
V/s (0.1 optimum) to the auxiliary electrode. The current to water that conforms to Specification D 1193, Type II.
output of the working electrode is converted to voltage by the 6.3 Analysis Materials:
voltammetric analyzer, using the gain ratio of 1 V/20 µA, and 6.3.1 Acetone Solution (Neutral)—Proprietary Green Solu-
is outputted to an analog or digital recording device (0 to 1 V tion,8 Acetone solvent (1:10 distilled water/acetone solution)
full scale) as shown in Figs. 1 and 2. containing a dissolved neutral electrolyte. (Warning—
5.2 Vortex Mixer,6 with a 2800 to 3000 rpm motor and a pad Corrosive, poisonous, flammable, and a skin irritant. Harmful
suitable for mixing test tubes and vials. if inhaled.)
5.3 Pipette, or equivalent, capable of delivering sample 6.3.2 Alcohol Solution (Basic)—Proprietary Yellow Solu-
volumes required in the test method, from 0.10 to 0.50 mL. tion,8 Ethanol solvent (1:10 distilled water/ethanol solution)
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Reagent Chemical, American Chemical Society Specifications, Am Chemical
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Voltammetric Analyzers specifically designed to perform antioxidant determi- Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
nations of turbine oils are commercially available from Fluitec International, American Chemical Society, see Reagent Chemicals and Standards, by Joseph
Dayton, OH and Koehler Instrument Company, Bohemia, NY. Rosin, D. Van Nostrand Co., Inc., New York, NY, and the United States Pharma-
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Vortex mixers suitable for mixing the prepared standard and sample solution copeia.
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are available from Barnstead/Thermolyne (Dubuque, IA), Fisher Scientific Co. Voltammetric solutions are available from Fluitec International, Dayton OH,
(Pittsburgh, PA). and Koehler Instrument Company, Bohemia, NY.
3
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D 6971 – 04
containing a dissolved base electrolyte. (Warning—Corrosive, 8.3 Voltammetric Reading—After the operator has selected
poisonous, flammable, and a skin irritant. Harmful if inhaled.) the valleys before and after the antioxidant peaks (as shown in
6.3.3 Alcohol Cleansing Pads—70 % isopropyl alcohol Fig. 1), the software (R-DMS9) will automatically identify and
saturated cleansing pads (alcohol prepared skin cleansing pads, calculate the area above the baseline between the two valley
for the preparation of the skin prior to injection (antiseptic)). indicators. This calculated area is then used for the sample
reading (used oil), which will be established by comparing the
used oil area to its standard (see Fig. 3) and make remaining
7. Sampling
antioxidant calculations (see Section 9).
7.1 Obtain the sample in accordance with Practice D 4057. 8.4 Calibration (Blank Reading) Procedure—Pipette 5.0
mL of analysis solution into a 7 mL vial or other suitable
8. Procedure container containing 1 g of sand. Insert the electrode of the
voltammetric analyzer into the analysis solution to wet the
8.1 The voltammetric analyzer used in this test method
bottom surface of the electrode, remove, and rub dry the
gives linear results between 2 to 50 mmol for hindered phenols bottom electrode surface with a lint free paper towel. Insert the
and aromatic amines using an oil sample size of 0.40 mL and electrode into the vial so that the bottom of the electrode is
5.0 mL of the analysis solvent. The corresponding range of submerged in the analysis solution without resting on the sand
mass % depends on the molecular weight of the hindered layer on the bottom of the vial. Place the vial/probe upright into
phenol and aromatic amine, and the density of the base oil. For rack or foam block for testing. Perform the voltammetric
instance, the mass % range of 0.044 to 1.1 is equal to 2 to 50 analysis (see 5.1). Record the voltammetric reading in the
mmol/L for a hindered phenol containing one hydroxyl group voltage range of aromatic amines, 0.8 to 1.1 V4 and the
and with a molecular weight of 220 g/mol (2,6-di-tert-butyl- phenols, 1.3 to 1.6 V4 in neutral test solution (Fig. 1). Remove
4-methylphenol) and an oil density of 1 g/mL. Below 2 mmol, the combination electrode from the blank solution and rub dry
the noise to signal ratio becomes large, decreasing the accuracy the bottom surface of the electrode with a lint free paper towel.
of the measurements. For measurements below 2 mmol or for Run at least two tests of the analysis solution to ensure the
fresh oils with high noise to signal ratios, the sample size electrode is clean and the minimal blank value has been
should be increased to 0.60 mL and the volume of analysis obtained.
solvent decreased to 3.0 mL. 8.4.1 Calibration Frequency—Recalibration with freshly
prepared blank solution shall be performed before each testing
8.2 General Voltammetric Test Procedure—The test proce-
session.
dure for voltammetric analysis will consist of the blank reading
8.5 Standard and Used Oil Sample Preparation Procedures
(calibration), followed by a standard reading, and finally the 8.5.1 Steps:
sample (used oil) reading. 8.5.1.1 Preparing Solution Step—Remove seal and cap of
8.2.1 Blank Reading—(0 mmol/L = 0 mass %). the test solution vial. Pipette 5.0 mL of analysis solution into a
8.2.1.1 The blank reading (voltammetric number) is a mea- 7 mL vial or other suitable container containing 1 g of sand.
surement of the analysis solution by itself. The blank measure- Pipette 0.40 mL of the selected oil sample also into the 7 mL
ment gives a reference number with no antioxidant present (the vial.
zero baseline). 8.5.1.2 For measurements below 2 mmol or fresh oils with
high noise-to-signal ratios, the sample size should be increased
8.2.2 Standard Reading—(30 to 150 mmol/L—mass %
to 0.60 mL and the volume of analysis solvent decreased to 3.0
dependent on density of fresh oil and molecular weight of
mL.
antioxidant). 8.5.1.3 Shaking Solution Step—Cap the vial and shake
8.2.2.1 The standard reading is a measurement of a fresh, vigorously using a vortex6 mixer for 20 s or by hand (between
unused oil (containing hindered phenol and amines antioxi- 50 and 60 shaking cycles/min.), until sand is thoroughly mixed.
dants) mixed with an appropriate analysis solvent. This mea- Place the prepared oil solution upright in a rack or perforated
surement gives you a voltammetric reading (standard reading) foam block for a minimum time of 30 s to allow the sand to
that indicates the voltammetric response for the concentration settle on the bottom of the vial with the oil.
hindered phenol and aromatic amines antioxidants being ana- 8.5.1.4 Cleaning Electrode Step—Prepare the electrode for
lyzed for the oil being tested. analysis by cleaning it. Use an alcohol-cleansing pad to wet the
8.2.3 Sample (Used Oil) Reading. bottom surface of the electrode. The bottom of the electrode
must be dried immediately with a clean lens tissue (lint free
8.2.3.1 The sample reading is a measurement of a fresh or
paper towel). The glassy carbon surface should always have a
used oil mixed with the same type of analysis solvent as the
polished look before running a test. A glazed or cloudy look
standard. This measurement will provide voltammetric read- indicates the presence of a chemical film. If the probe tip is not
ings that normally range between the blank and standard cleaned properly, voltammetric readings can be distorted.
measurements, and reflect the concentration of hindered phenol 8.5.1.5 Running Test Step—Insert the electrode into the vial
and aromatic amine antioxidant present (fresh oil) or remaining so that the bottom of the electrode is submerged in the analysis
(used oil) in the oil sample. Voltammetric readings for used oils
will decrease as hindered phenol and aromatic amine antioxi-
dants are depleted. 9
R-DMS is a software package available from Fluitec International, Dayton OH.
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D 6971 – 04
solution without resting on the sand layer on the bottom of the 9. Calculations
vial. Place the vial/probe upright into a rack or foam block for 9.1 Percent Hindered Phenol and Aromatic Amine Antioxi-
testing. Perform the voltammetric analysis (see 5.1) for hin- dant Calculation—If the hindered phenol and aromatic amine,
dered phenolic and aminic antioxidants. Record the valley to antioxidant present in the oil sample is known, then the percent
valley antioxidant readings in the voltage range of the amines, hindered phenol and aromatic amine antioxidant in the sample
0.8 to 1.1 V4 and the phenols, 1.3 to 1.6 V4 in neutral solution can be calculated as follows:
(Fig. 1). Remove the combination electrode from the oil
% of antioxidant
solution and repeat the cleaning procedure of the electrode. sample reading 2 blank reading
Run at least two tests (cleaning the electrode and shaking the 5 standard reading 2 blank reading 3 % antioxidant of standard ~%!
standard for 10 s between tests) of the standard or used oil (1)
sample to ensure the value is stable and repeatable.
8.5.1.6 Make all measurements within 5 min after the initial where:
mixing of the analysis solution, selected sample, and sand. reading = valley to valley area (see 8.3) for antioxidants
8.5.2 When the manufacturer of the oil is known, and the peaks between 0.8 to 1.6 V4
uninhibited base oil is available, use it to prepare the standards 9.2 Molar Concentration of Hindered Phenol and Aromatic
(mmole or mass % antioxidant calculations). Prepare a stan- Amine Antioxidant Calculation—If the hindered phenol and
dard containing in the range of 30 to 150 mmol/L of oil (0.5 to aromatic amine antioxidant in the oil sample is unknown, then
3.0 mass %) of the selected phenolic and aminic antioxidant the millimoles of hindered phenol and aromatic amine antioxi-
dissolved in an uninhibited base oil. The concentration should dant in the sample can be calculated as follows:
be selected to span the expected concentrations of the new and concentration of antioxidant, mmole/L of oil
used oils. sample reading 2 blank reading
5 standard reading 2 blank reading
8.5.3 Standard readings should be updated whenever new
3 antioxidant concentration of standard ~mmol/L of oil! (2)
batches of lubricants are stocked, and checked periodically to
monitor the amount of natural oxidation occurring in the stock where:
during storage. reading = valley to valley area (see 8.3) for antioxidants
8.5.4 For fresh or used oils of unknown origin, use a typical peaks between 0.8 to 1.6 V4
fresh turbine oil as the standard (100 % remaining antioxidant 9.3 Percent Remaining Hindered Phenol and Aromatic
calculations). Amine Antioxidant Calculation—Calculate the percent remain-
8.5.5 The analysis solution and scan time should be the ing antioxidant in an used oil using the fresh oil as the 100 %
same for the blank, standard, and used oil sample. standard with the following calculation:
5
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D 6971 – 04
sample reading 2 blank reading operation of the test method, exceed the following values only
% remaining antioxidant 5 standard reading 2 blank reading 3 100 %
in 1 case in 20: The repeatability standard deviation has been
(3) determined to be = 1.5094 · (x + 8.6662)0.46390 %, where x
where: denotes mean value.
reading = valley to valley area (see 8.3) for antioxidants 10.1.2 Reproducibility—The difference between two single
peaks between 0.8 to 1.6 V4 and independent results, obtained by different operators work-
ing in different laboratories on identical test material, would, in
10. Precision and Bias the long run, and in the normal and correct operation of the test
10.1 Statement of Precision—The precision of this test method, exceed the following values only in 1 case in 20: The
method as obtained by statistical analysis of interlaboratory test reproducibility standard deviation has been determined to be =
results should be used for judging the acceptability of results 3.0067 · (x + 8.6662)0.46390 %, where x denotes mean value.
(95 % of confidence).10 10.2 Statement of Bias—No information can be presented
10.1.1 Repeatability—The difference between concurrent on the bias procedure in Test Method D 6971 since the result of
test results obtained by the same operator with the same this test is defined only in the terms of this test method.
apparatus under constant operating conditions on identical test 11. Keywords
materials, would, in the long run, and in the normal and correct
11.1 2,6-di-tert-butyl-4methylphenol; 2,6-di-tert-
butylphenol; alkylated diphenylamine; aromatic amine antioxi-
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Supporting data have been filed at ASTM Headquarters and is available as dant; hindered phenol antioxidant; linear sweep voltammetry;
Round Robin Research Report ASTM D02-1548. phenyl alpha naphthylamine; turbine oil
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