EPA-650/2-74-061
July 1974
Environmental Protection Technology Series
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EPA-650/2-74-061
DETERMINATION OF EFFECT
OF PARTICULATE EXHAUST
EMISSIONS OF ADDITIVES
AND IMPURITIES IN GASOLINE
by
James E. Gentel, Otto J. Manary, and Joseph C. Valenta
Dow Chemical Company
Midland, Michigan 48604
Contract No. 68-02-0332
ROAP No. 26AAE-10
Program Element No. AA003
EPA Project Officer: John E. Sigsby, Jr.
Chemistry and Physics Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
July 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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TABLE OF CONTENTS
Paqe
page
FORWARD
ABSTRACT 2
I. INTRODUCTION 3
II. GENERAL CONCLUSIONS 6
III. PROPOSED METHODOLOGY 8
A. Equipment 10
B. Procedure 12
C. Particulate Analyses 14
IV. EXPERIMENTAL PROCEDURES 15
A. Particulate Generation 15
1. Engine Dynamometer Studies 15
2. Chassis Dynamometer Procedures 17
B. Particulate Collection 22
1. Dilution Tube 22
C. Condensate Collection 27
D. Analytical Methods 28
1. Fuels 29
2. Oils 30
3. Diluent Air 30
4. Exhaust Gases 30
a. Analytical Equipment 30
b. Sampling 31
c. Standardization 31
d. Operation 31
e. Data Reduction 32
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5. Oxides of Nitrogen '32
a. Equipment 32
b. Calibrating Gases 34
c. Procedure 34
6. Exhaust Particles 34
a. Carbon and Hydrogen 35
b. Benzo-a-pyrene 36
c. Trace Metals 38
1) Emission Spectrometry 39
2) Atomic Absorption. .- 45
3) Scanning Electron Microscopy
(SEM) and X-Ray Fluorescence .... 48
7. Condensate Analyses 51
a. Aldehydes 51
b. Ammonia 55
V. EXPERIMENTAL RESULTS
A. Specific Conclusions 58
B. Fuel and Additives 68
C. Test Procedures 68
1. Engine Dynamometer 68
2. Vehicle Tests 72
D. Data -76
E. Discussion of Results 76
1. Vehicle Particulate Emissions 76
2. Engine Stand Particulate Emissions 77
3. Particulate Composition 77
4. Particulate Mass-Size Distribution 102
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Page
5. Particulate Morphology as Studied by
Scanning Electron Microscope. . . 102
VI. FUEL ADDITIVE SURVEY.* 113
A. Dyes 113
B. Antioxidants 114
C. Metal Deactivators 115
D. Surface-Active Agents 116
1. Rust Preventing Additives 116
2. Gasoline Detergents 117
3. Intake Manifold Deposits. 117
4. Deicing Additives 118
E. "Canned" Additives 118
F. 2-Cycle Engines 119
G. Summary and Conclusion 119
VII. CONDENSATE COLLECTION AND ANALYSES 121
APPENDIX A 132
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LIST OF TABLES
Page
1. New Engine Break-In Procedure ............. 15
2. Vehicle Test Procedure - Chassis Dynamometer ...... is
3. Blowby Test Procedure ................. 20
4. DSQ Value - Andersen Model 0203 ............ 27
5. Analytical Techniques for Exhaust Species ....... 29
6. Concentration of Impurity Addition .......... . 41
7. Analytical Line Pairs ................. 41
8. Representative Precision and Accuracy of
Emission Spectroscopy ........ ......... 46
9. Gasoline Analyses ................... 69
10. Fuel Additives ..................... 71
11. Particulate Analysis, Base Fuel, Engine Stand ..... 79
12. Particulate Analysis, Additive A, Engine Stand ..... 82
13. Particulate Analysis, Additive B, Engine Stand ..... 85
14. Particulate Analysis, Base Fuel, Chassis
Dynamometer ...................... 88
15. Particulate Analysis, Additive A, Chassis
Dynamometer ...................... 92
16. Particulate Analysis, Additive B, Chassis
Dynamometer ...................... 96
17. Mass Medium Equivalent Diameter Engine Stand Runs . . .
18. Mass Medium Equivalent Diameter Vehicle Runs ...... -101
19. Scanning Electron Microscope Analysis ......... 103
20. HCHO and NH_ Analyses of Exhaust Condensate ...... 122
21. Particulate Analysis, Three Fuels, Engine Stand . . . .123
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LIST OF FIGURES
Page
1. Blowby Measurements 21
2. Blowby Test Apparatus 23
3. Flow Diagram for Engine Exhaust Particulate
Collection 25
4. Typical Gas Chromatography Analysis 33
5. Polarographic Determination of Aldehydes 53
6. Polarographic Determination of Aldehydes 54
7. Polarographic Determination of Aldehydes 54
8. Apparatus for Determination of NH_ 56
9. Blowby Measured, Baseline, Engine Stand 60
10. Blowby Measured, Additive A, Engine Stand 61
11. Blowby Measured, Additive B, Engine Stand 62
12. Grams Per Mile Particulate Vs. Mileage Accumulation
on ICFM Glass Fiber Filter, Three Fuels, Federal
Cycle Cold Start, Chassis Dynamometer 63
13. Grams Per Mile Particulate Vs. Mileage Accumulation
on ICFM Glass Fiber Filter, Three Fuels, 60 mph
Steady State, Chassis Dynamometer 64
14. Grams Per Mile Particulate Vs. Mileage Accumulation
on Andersen Seperator Plus Backup Filter, Three
Fuels, 60 mph Steady State, Chassis Dynamometer 65
15. Grams Per Mile Particulate Vs. Mileage Accumulation
on Andersen Separator Plus Backup Filter, Three
Fuels, Federal Cycle Cold Start, Chassis Dynamometer . .66
16. PPM Unburned Hydrocarbon Vs. Mileage Accumulation,
Three Fuels, Federal Cycle Cold Start, Chassis
Dynamometer 67
17. PPM Unburned Hydrocarbon Vs. Mileage Accumulation,
Three Fuels, 60 mph Steady State, Chassis
Dynamometer 73
18. Grams Per Mile Particulate on ICFM Glass Fiber
Filter, Three Fuels, Federal Cycle Cold and Hot
Start, Engine Stand 74
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19. Grams Per Mile Particulate on Andersen Separator
Plus Back-Up Filter, Three Fuels, Federal Cycle
Cold and Hot Start, Engine Stand 75
20. Baseline, Cold Start, SOOOx, Plate 2,
Andersen Separator 105
21. Baseline, Cold Start, SOOOx, Plate 2,
Andersen Separator 105
22. Baseline, Cold Start, 2000x, Plate 2,
Andersen Separator 106
23. Baseline Cold Start, 2000x, Plate 2,
Andersen Separator 106
24. Additive A, Cold Start, 2000x, Plate 2,
Andersen Separator 107
25. Additive A, Cold Start, 2000x, Plate 2,
Andersen Separator 107
26. Additive A, Cold Start, 10,000x, Plate 2,
Andersen Separator 108
27. Additive A, Cold Start, 10,000x, Plate 2,
Andersen Separator 108
28. Additive A, Cold Start, 10,000x, Plate 2,
Andersen Separator 109
29. Additive B, Cold Start, 2000x, Plate 5,
Andersen Separator 110
30. Additive B, Cold Start, 10,000x, Plate 5,
Andersen Separator 110
31. Additive B, Cold Start, 2000x, Plate 5,
Andersen Separator Ill
32. Additive B, Cold Start, 2000x, Plate 5,
Andersen Separator Ill
33. Additive B, Cold Start, SOOOx, Plate 5,
Andersen Separator 112
34. Mass Distribution, Run No. 254A 126
35. Mass Distribution, Run No. 254B 127
36. Mass Distribution, Run No. 255A 128
37. Mass Distribution, Run No. 255B 129
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38. Mass Distribution, Run No. 256A 130
39. Mass Distribution, Run No. 256B 131
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FORE WARD
This report was prepared by the Transportation Chemicals
Research Group, Ag-Organics Department, The Dow Chemical
Company, Midland, Michigan, under Contract 68-02-0332.
The work reported herein was administered under the direction
of the Office of Air and Water Programs, Environmental
Protection Agency, with John E. Sigsby, Jr., serving as
Project Officer.
The report covers work performed from June 1, 1972, to
July 31, 1973.
The authors of this report are James E. Gentel, Otto J.
Manary, and Joseph C. Valenta.
The authors wish to acknowledge the significant contributions
of the following individuals.
S. M. Sharp R. E. Mansell
W. B. Tower p. P. North
J. D. McLean N. J. Smith
R. B. Nunemaker K. Schmeck
C. E. Van Hall M. J. Baldwin
H. H. Gill R. Matalon
S. W. McLean J. F. Bartel
T. A. Killer
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ABSTRACT
This report describes work carried out to develop a method-
ology for the determination of the effect of fuel additives
on exhaust particle size, concentration, and composition,
from light-duty vehicles.
In order to determine the best methodology, particulate emis-
sions were examined using a 350 CID Chevrolet engine, and
several 350 CID Chevrolet vehicles. The engines and vehicles
were operated under steady-state cruise conditions, and under
the federal 23-minute cycle. Particulate mass measurement
techniques have included tailpipe measurement methods and
air dilution sampling methods using impaction separators,
and filters.
Two different fuel additives as well as a baseline fuel were
used to determine the validity of the methods employed. The
engine dynamometer runs were correlated with vehicles using
the same fuel and additives. Engine runs were made using
both manufacturer's suggested and higher than suggested addi-
tive concentrations.
The data collected suggests that the methods employed do
allow the determination of any adverse effects on particulate
emissions due to the inclusion of an additive in the fuel.
In addition, a study was made of probable trends in fuel
additive chemistry.
An additional task of this study was the collection and anal-
yses of exhaust gas condensate, to be used in animal health
studies.
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I. INTRODUCTION
The use of fuel additives has been shown to have an
effect on the size, quantity, and composition of parti-
culate matter emitted from light duty gasoline engines.
Work involving particulate measurements primarily on
leaded and unleaded fuel has been reported in EPA-R2-72-
066. The purpose of the study covered in this report
was to determine methodology for assessing the effect on
particulate emissions of other types of fuel additives.
This study, performed from December 1971 to July 1973, is
part of a fuel additive study program which was developed
by EPA to determine the total range of fuel additive
effects on emissions, and to develop methodology, where
appropriate, to assist in the generation of data which is
required by EPA for fuel additive registration. Other
contracts in the fuel additive program include studies
on the effect of fuel additives on the composition of
the hydrocarbon exhaust portion (Bureau of mines), the
effect of fuel additives on catalyst performance (The Dow
Chemical Co.), the effect of fuel additives on exhaust
visibility (Cornell aeronautics lab) and development of
a model for fuel additive emissions determinations (Dow
Chemical Company).
As a result of this study, and prior work done on the
collection and analyses of particulate emissions, reproduci-
ble generation, collection and analysis techniques have 'been
developed. The additives used in this study were a poly-
buteneamine and methylcyclopentadienyl manganese tricarbonyl.
Both additives were used at the levels recommended at the
time by the manufacturer, and also at 3 times the manufacturer's
recommendation. The polybuteneamine, designated additive A, in
this study was used at 1.87 grams/gal, and at 5.61 grams/gal. The
manganese additive, designated additive B, was used at
.25 grams/gal, measured as manganese, and at .75 grams/gal.
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The manufacturer's recommendation for the concentration of
this additive has since been reduced*
The engines used on the dynomometer were broken in accord-
ing to a specified break in procedure and were conditioned
for 75 hours using repeated 23 minute federal cycles.
Particulate sample was collected from the diluted exhaust
(approximately 12 to 1 air/exhaust dilution at a flow rate
of 550 cfm diluted). Four filter systems were used to
collect particulate from the dilution tube: an Andersen
impactor with a 142mm millipore back-up filter at 1 cfm, a
47 mm glass fiber filter at 1 cfm, and two 142 mm glass
fiber filters at 1 cfm.
Collections for analyses were made from the dilution tube
under steady state (60 mph) conditions, and also using
the 23 minute Federal cycle. Collected particulate was
analyzed for the following:
Total particulate mass emissions
Mass/size distribution
C, H, N content
Benze-a-Pyrene
Trace elements
In addition, aldehydes, measured as HCHO, and NH_ were
measured from condensed exhaust gas. Specific studies on
particulate size and composition were made on selected
particulate samples using a scanning electron microscope.
Standard gaseous analyses for CO, No and unburned hydro-
X
carbons were made on the raw exhaust, primarily as an
engine performance monitor.
In addition to the engine dynamometer tests, three vehicles
were operated for approximately 17,000 miles on the base-
line and the two additive fuels. These vehicles were
driven by employees in their normal fashion, and were .
rotated periodically to eliminate operational variables.
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Before active testing was begun on either engine stand or
vehicles, an attempt was made at surveying the current
fuel additive technology, with hopes of identifying what,
if any, future trends were developing. On balance, this
attempt was basically unsuccessful. Most research in this
area was treated as proprietary, and questions on future
additive trends were unvariably answered with "We don't
know". A summation of the information which was gathered
is in Section VI.
Midway through the contract, an addition was granted for
the collection of exhaust gas condensate samples for use
in animal health studies. These samples were sent to
Dr. Schubik of the Eppley Institute for Research in Cancer,
University of Nebraska Medical Center, and were used for
research on the effects of exhaust gas on the lung tissue
of animals. The condensate samples collected were analyzed,
and the data is reported in Section VII.
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II. GENERAL CONCLUSIONS
1. Under the conditions used for vehicle and engine stand
tests, described in section V, additive concentrations of
three times the manufacturer's recommended dosage, when run
for 75 hours of repetitive 23-minute Federal cycles, showed
the same trend toward increased particulate in the case
of additive B as seen in the vehicles using the additive at
the recommended level for approximately 17,000 miles. Addi-
tive A showed essentially the same trend in the engine
runs and in the vehicles, which was no noticeable increase
compared to the baseline.
2. The use of repetitive 23-minute Federal cycles on the
engine stand with additive fuels did not show significant
differences compared to the baseline fuel, with respect to
grams/mile particulate, when the additive was used at the
recommended dosage. The 75-hour conditioning period is
equivalent to approximately 1,500 miles. When total grams/mile
particulate were less than .1, any variation beneath that
point is considered insignificant since the collection and
weighing precision is poor below that level.
3. Chemical analyses (C,H&N) of collected particulate from both
the engine stand and vehicles showed variations to the
extent that no meaningful conclusions as to the
organic content of the particulate can be drawn.
In many cases the sample size was so small that any differences
could be due solely to the inherent imprecision.
4. In general, the manganese-containing additive, methyl-
cyclopentadienyl manganesetricarbonyl, (Additive B) gave
higher grams/mile of emitted particulate than did the
polybuteneamine (Additive A) and baseline fuel, in both
engine stand and vehicle tests. The increase was from 50%
to 100% above the baseline. Additive A was not significantly
different from the baseline.
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5. Additive A, a metallic additive in general, gave larg-er
particles than the baseline, while Additive B a nitrogenous
additive in general gave particulate smaller than the baseline.
use of 3 times the recommended concentration did not
significantly change the mass medium equivalent diameter,
when compared to the recommended concentration.
6. As a result of this study, and prior studies on
particulate emissions, a methodology has been developed
which can be used to reproducibly generate, collect and
analyze particulate emissions. It must be recognized however,
that any particulate collection system will entail equipment
and technique not currently used for other emissions studies,
In addition, any quantitative or qualitative analyses of
particulate will require instrumentation and techniques
which may not be readily available.
It also must be recognized that any particulate collection
system different from the one described in this study may
be quite satisfactory for the intended purpose, but cannot
be used to compare with particulate mass emissions or
particulate size data generated under this study, since
the collection system geometry and conditions themselves
define the particulate. Comparisons of data generated in a given
system should be made with a baseline measured in the same system.
7. The use of the Federal Cycle, 23 minutes or 41 minutes,
with unleaded fuel under the conditions described, in
general gives such small amounts of collected particulate
that qualitative analyses are often meaningless, if not
impossible. Steady state conditions (60 mph, collected
for 2 hours) will give larger amounts of collected parti-
culate which can be analyzed more thoroughly. The effect
of other collection parameters such as temperature, filter
face, velocity and collection time is discussed in detail
in EPA report APTD-1567, titled "Characterization of
particulates and other non-regulated emissions from mobile
sources and the effects of exhaust emissions control devices
on these emissions".
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III. PROPOSED METHODOLOGY
The basic purpose of this study was to build on existing
particulate collection and analyses technology, and from
this and the additional studies run under this contract,
develop a methodology which could be used to generate
data for use in fuel additive registration. Under current
regulations, the EPA can request data from suppliers of
fuel additives relative to the effect of a given fuel
additive on emissions. However, in order to allow EPA to
make meaningful decisions as to the future registration
of these additives, a test protocol must be issued so that
data can be generated in a consistent and repeatable
fashion. An attempt was made in this contract to build a
logical, relatively inexpensive, but thorough method of
generating and collecting exhaust particulate emissions,
which would allow an effect on particulate emissions due
to an additive to be identified.
The details of the particulate collection system which
has been set up are covered in section IV, experimental
procedures, as well as in previous reports on particulate
studies. (APTD-1567: "Characterization of Particulates
and Other Non-regulated Emissions from Mobile Sources and
the Effects of Exhaust Emission Control Devices on these
Emissions". EPA-R2-72-066: "Effect of Fuel Additives on
the Chemical and Physical Characteristics of Particulate
Emissions in Automotive Exhaust". EHS 70-101: "Development
of Particulate Emission Control Techniques for Spark
Ignited Engines.)
The engine stand testing in this study consisted of
repetitive 23 minute federal cycles. The particulate
collection was made during one 23 minute segment, both
cold start and hot start. Since the gross amount of
particulate collected during one 23 minute cycle is low,
the precision of both the mass emission figures and the
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analytical data is low. In addition, the same engine was
used for all the testing and only one 75 hour series of
tests was run for each additive concentration. Because
of the scatter in data points experienced under normal
conditions, the statistical significance of the data is
low as far as being representative of an absolute
grams/mile figure. However, based on previous work it
is felt that the method used for particulate collection
is reproducible enough so that any trends which developed
as a result of a fuel additive effect are legitimate,
even though a statement on the magnitude of the trends
would lack statistical significance. An example of a
trend which is felt to be meaningful is the increase in
particulate mass emissions noted with Additive B after
17,000 miles on the vehicles, and also the increase noted
with Additive B when used at 3X the recommended level in
the engine stand tests.
Some key conclusions concerning the proposed methodology
are as follows:
1. The cost involved in setting up a particulate study
such as the one described in this report will be somewhat
less than the cost of setting up to do CVS gaseous emissions
analyses. Assuming that a suitable structure exists
housing either an engine or chassis dynamometer, the cost
for setting up the collection system will range from
$10,000-$20,000. The most critical cost factor will
involve the analyses of the particulate for the various
chemical species which might be of interest.
2. A correlation does appear to exist between the engine
stand runs of 75 hours continuous 23 minute cycles at 3 x
recommended additive concentration, and the 17,000 vehicle
tests. Statistically speaking however, this correlation
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is of little impact. More statiscally significant is the
trend noted in the 17,000 mile vehicle tests.
3. Ambient conditions have a definite effect on particulate
emissions collection. Since the operating and collection
conditions can be controlled easier for engine tests than
they can for vehicle tests, engine stand tests would tend
to give data with less scatter. However, a statistically
significant fleet test can be set up utilizing 8-10 total
vehicles and the scheduling of tests can be made in such
a way that only one collection system would be necessary.
The effect of different ambient conditions would then be
somewhat lessened in a comparison of test vehicles against
a baseline.
Following is a discussion of ways in which the tests can
be run and equipment necessary to gather the appropriate
data. More detail on procedures and techniques is in
section IV.
A. EQUIPMENT
The equipment which was used in the experimental work by
Dow is described in Section IV. The key parts of the equip-
ment package needed for this methodology are the dilution
tube and sampling devices. In general, the geometry of the
dilution tube is not critical, although the total flow through
the tube should be about 550 cfm. The diameter of the
tube should be from 16-18 inches. With a smaller diameter
the residence time in the dilution tube will be low,
velocity high, and the temperature will be so high that
particulate measurements of any meaning will be difficult.
For consistent and reliable particulate sampling, the fol-
lowing steps must be observed:
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1. Four sampling probes, each sized to allow a 1 cfm sampling
rate of dilute exhaust from the dilution tube, should be in-
stalled. The four probes allow to check repeatability within
the same test and also permits the use of different types of
filter media within the same test run. In addition four filters
give more particulate for analytical purposes.
2. The sample probes must be water jacketed to allow the temper-
ature of the dilute exhaust to be maintained at 100°F at the filter,
3. The filters to be used are described in detail in Section III-B
along with a description of the Andersen samplers.
4. The filter media used, both Gelman glass fiber and milli-
pore, should be from the same batch for any series of runs.
The~millipore filter is used for mass emission measurements,
as well as true metal analyses. The glass fiber media is
for organic measurements.
5. A baseline for the measured patticulate must be estab-
lished using the same engine, base stock fuel, and filter paper
batch each time an additive is to be tested.
The engine used for this testing was a 1972 Chevrolet 350
CID V-8. Although a variety of engines could undoubtedly be
used, assuming a consistent baseline is established, it is recom-
mended that the 350 Chevrolet be specified. This will allow
for easier correlation of data between testing facilities.
The engine should be broken in using the procedure outlined
in Table I, Section IV. Low lead gas was used to insure that
during the break-in procedure the engine was given enough
octane valve lubricity.
After break-in, the engine should be partially dismantled, any
combustion chamber deposits removed, and the condition of the
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valves and cylinders noted. The engine was then reassembled
according to manufacturer's specifications.
Before any testing is to be done, the engine must be subjected
to a blowby test as described in Table 3 Section IV. If the
CFM blowby, after conversion to standard conditions, is higher
than an established baseline, a standard leak-down test should
be conducted, and the engine should be corrected to meet manu-
facturer's specifications before proceeding with the testing.
To eliminate any variables, during the engine stand studies,
an original equipment exhaust system should be used. This
consists of the crossover pipe, exhaust pipe, muffler, and a
length of straight tail pipe corresponding to the length of
tail pipe used in the vehicles included under this study.
For testing purposes, the engine must be equipped with the same
turbo-hydromatic 350 automatic transmission, which is the unit
used in vehicles containing the 350 CID Chevrolet engine. This
reduces any variables which might result from transmission
differences.
Any dynamometer with the capability of handling the'loads neces-
sary in the 23 or 41-minute Federal cycle can be used. The
important aspect of the dynamometer is its ability to run con-
tinuous 23-minute cycles. During the Dow work, a mode monitor
system manufactured by Northern Ampower Corporation, was used to
control the dynamometer. The Federal cycle was transcribed from
the Federal register onto Mylar computer tape. The program was
written such that after one 23-minute cycle the engine would
idle until the computer had reset itself to run another cycle.
B. PROCEDURE
In attempting to develop a screening technique for fuel add-
itives which could be run on an engine stand, in a relatively
short period of time, and would correlate to a mileage accu-
mulation of about 15,000 on a vehicle, the idea of running
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continuous high speeds on the engine stand for one week or
more was ruled out since this type of operation would be
non-typical of normal driving. In addition, seven days of
around the clock operation at 60 mph would only be 10,000
miles. The approach finally settled on was to take the Federal
23-minute cycle, which contains all commonly encountered
modes of operation and continuously cycle the engine. From
prior work it had been determined that about 75 hours was
sufficient to reach a stabilized situation with respect to
particulate emission, for a given additive. As a result
of the experimental work reported in Section V, the pro-
cedures outlined below are suggested as a screening technique
for fuel additive effect on particulate emissions.
1. The continuous 23-minute cycles are to be run for 19
hours each day. This was done by starting the engine at
10:00 a.m. on a given day, and shutting it down at 5:00 a.m.
the following morning. A cold start test is to be run when
the engine is restarted at 10:00 a.m. After four 19-hour
cycling periods, the engine is to be allowed to stand for
12 hours before running the final cold start. After the
final cold start, two or more hot starts are to be run.
If the amount of particulate collected during the hot or
cold start is too low for detailed chemical analyses, a
2-hour 60 mph steady-state run should be made following the
last hot start.
2. The test sequence should involve a baseline run of 75
hours for each additive tested, unless several additives
are to be done within a short time period. If this is the
case, baseline runs should be interspersed between the addi-
tive runs as follows:
Additive at recommended concentration
Additive at 3 times recommended concentration
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Engine tear-down, clean-off deposits, then baseline
run
Additive at recommended concentration
Additive at 3 times recommended concentration
If three or more additives are to be tested, each additive
series should be separated by a baseline run.
3. The runs involving additive concentrations three times
the recommended level are necessary to amplify the effect
of the additive on particulate emissions. While it was recog-
nized that using a given additive at greater than recommended
levels could cause other exhaust abnormalties, the experi-
mental work on the two additives in question showed that
the vehicles correlated well with the increased additive
concentration.
C. PARTICULATE ANALYSES
The analytical procedures described in Section IV should
be used to determine the basic chemical make-up of the par-
ticulate. In addition, the grams/mile emission rate should
be calculated as described in Section IV.
It is recognized that additives of varying chemical compo-
sition can be expected to give particulate emissions contain-
ing those chemicals, of modifications. This is especially
true for additives with inorganic components. Specific
analytical techniques for the determination of the quantity
and form of these elements are necessary. No attempt was
made in this contract to develop techniques for compositions
other than those outlined in Section IV and discussed in
Section V.
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IV. EXPERIMENTAL PROCEDURES
A. PARTICLE GENERATION
1. Engine Dynamometer Studies
The test engine was completely disassembled, cleaned and
reassembled according to manufacturer's specifications.
It was then mounted on the dynamometer bed plate and attached
to a fully instrumented General Electric dynamometer. Appro-
priate control and sensing devices were attached to the
engine. A 1972 350 CID Chevrolet engine was used for all
engine tests. It was equipped with standard emission control
devices for that model and year. The following procedure
(Table 1) was then employed to run-in the new engine, using
Indolene .5 cc TEL/gal. fuel.
TABLE I
NEW ENGINE BREAK-IN PROCEDURE
(28 hours)
1) Warm up engine to 180°P coolant outlet temperature at
1000 rpm, no load, set spark advance, timing, and idle
according to manufacturer's specifications.
2) Run one hour at 1500 rpm, no load, automatic spark
advance and fuel flow. Shut down, retorque cylinder
heads, drain and change lubricating oil.
3) Run Cycle 1
RPM Man. Vac. (In. Hg) Time (hr.)
1500 15.0 1.0
2000 14.0 1.0
2400 14.0 1.0
2600 14.0 1.0
2000 11.0 1.0
5.0
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4)
Run Cycle 2
RPM
1500
2000
2500
3000
2000
Man. Vac. (In. Hg)
7.
7,
7,
7,
7.0
Time (hr.)
0.2
0.6
.0
,0
1.
1,
0.2
3.0
5)
Repeat Cycle 2.
6) Run Cycle 3
RPM
2000
2500
3000
3500
2800
Man. Vac. (In. Hg
WOT*
WOT
WOT
WOT
WOT
*WOT - wide open throttle
Time (hr.)
1.
1.
1.
0.
0.5
4.0 x 4 cycles
16 hours
7) While engine is hot, run motoring compression and conduct
leak-down check.
The engine was removed from the dynamometer, drained, par-
tially dismantled, cleaned, reassembled, and placed back
on the dynamometer stand. A typical vehicle exhaust system
for the specific test engine was attached to one bank of
cylinders. The other bank of cylinders was attached to the
dynamometer cell exhaust system. Suitable engine monitors
were attached to the engine in order to provide continuous
monitoring of oil pressure and temperature, coolant temper-
ature, carburetor air flow rate (using a Meriam Laminar Flow
Element 50MC-2-45F) and temperature, etc.
After the break-in procedure, the engine was run, with trans-
mission, using repetitive 23-minute Federal cycles. The
-------
- 17 -
engine was operated for approximately 75 hours, with one
5-hour shut-down in each 24-hour period. The engine was
monitored during this period by performing gaseous analyses,
sampled from the Dow dilution tube, during the course of
one 23-minute cycle.
At the termination of the test run, the engine was removed
from the dynamometer stand, dismantled, and samples for anal-
ysis were removed. The engine was completely cleaned, reas-
sembled, and reinstalled on the dynamometer stand.
Subsequent tests did not require the break-in procedure noted
in Table 1 unless a new engine was used. If the same engine
was used again, the next test series began with the running
of the repetitive 23-minute cycles discussed above.
2. Chassis Dynamometer Procedures
A Clayton CT-200-0 chassis dynamometer with a variable iner-
tia flywheel assembly was used in all tests conducted under
this program. A Chelsa direct-drive Model PLDUP-200A fan
was located in front of the test vehicle, and operated at
1750 rpm providing 18,750 scfm air flow. In these tests,
the vehicle was operated under approximately 60 mph road-
load cruise conditions (2250 rpm - 17" Hg manifold vacuum)
and under cyclic conditions of the Federal Test Procedure
(1970) and LA-4 (1975) procedure driven by a vehicle opera-
tor following the cycle on a strip-chart recorder driver
aid.
Table 2 indicates specific procedures employed to prepare
each vehicle for test run.
-------
- 18 -
TABLE 2
VEHICLE TEST PROCEDURE - CHASSIS DYNAMOMETER
1) General Vehicle Inspection
Exhaust System;
a) Inspect for holes or cracks, dents, and collapse
b) Inspect for leaking joints
Engine check
a) All fluid levels
b) All coolant hoses
c) Air pump fan, power steering, and belts
d) Check heat riser (if applicable) for fullness
of operation
e) Check automatic choke operation and adjustment
2) Engine Analysis and Tune-up
Leak-Down Test
a) Remove all spark plugs
b) Determine percent leak-down of each cylinder
c) Install recommended, new, and gapped spark
plugs, points, and condenser
Scope Check
a) Start engine and allow to warm up for at least
15 minutes
b) With engine running at fast idle, check
.Spark plugs
.Spark plug wires
.Distributor cap and rotor
.Coil output
.Points
c) With engine running at idle, check
.Dwell
.Timing
d) With engine running at 1500 and 2400 rpm, check
.Timing advance
e) Carburetor Adjustment
.Tighten intake manifold and carburetor
.Install new air cleaner element
.With engine running at specified idle speed,
adjust air to fuel ratio to specifications
.Make final adjustment on idle speed
f) Recheck all scope patterns for normal appearance
-------
- 19 -
3) Instrumentation and Equipment Installation
Thermocouples - install thermocouples in
a) Engine oil - dipstick
b) Coolant - upper radiator hose engine out
c) Garb air - air filter element
Vacuum and rpm monitors
a) Attach tachometer to ignition coil
b) Connect "U" tube monometer to intake manifold
c) Install throttle cable (if running under cruise
mode)
Wheels
a) Remove rear wheels
b) Install test tires and wheel assemblies to
insure safe operation
4) Procedure for Cold, Hot Starts, and Engine Temperature
Stabilization
Cold Start
a) Place vehicle on the dynamometer rolls, set inertia
weights for specific vehicle, and go through the
preparation for test as well as the tune-up procedure.
b) Allow at least a 12-hour soak period.
c) Connect vehicle tailpipe to dilution tube.
d) Start the vehicle and proceed with the individual
test.
Hot Start
The hot start procedure is the same as for the cold start
except that the vehicle was warmed up and allowed to sit
for 10 minutes before starting.
Engine Temperature Stabilization
Upon completion of the tune-up procedure (Step 2) the vehicle
is started cold and driven a total of 32 highway miles
at 60 mph to allow the engine temperature to stabilize.
The vehicle was then driven on-to the dynamometer rolls (Step 3)
and prepared for the test during which time the engine
idles for approximately five minutes. When preparation
has been completed, the vehicle was placed in gear and
the speed was increased to 2250 rpm and the intake mani-
fold vacuum was set at 17.0" Hg by controlling the amount
of load imposed on the drive wheels. At the time, when
-------
- 20 -
the load and the speed become stabilized, the tailpipe
is connected to the dilution tube inlet pipe and sampling
is started.
Table 3 is a description of the blowby test procedure used
to ascertain that proper piston ring and valve guide seating
is occurring.
TABLE 3
BLOWBY TEST PROCEDURE
Clayton CT-200 Chassis Dynamometer Used
1) Thermocouples installed as follows to record accurate
temperatures:
a) Top radiator hose
b) Carburetor venturi
c) Oil pan
d) Ambient air
e) Blowby gas flow tube
2) Close oil dip stick tube
3) Close rocker cover vent to carburetor (right side on
350 CID Chevrolet)
4) Install tube from PCV (left side) to sharp orifice
meter intake (1/4" port) Figure 1
5) Install Vernier band throttle
6) Place wind fan in front of car
7) Connect accurate tachometer
8) Connect blowby apparatus as follows (see diagram for
details) :
a) Use cooling water to maintain 75-85°F blowby
b) Connect condensate trap to tube from PCV
c) Connect outlet from condensate trap to sharp
orifice meter (use 1/4" orifice)
d) Connect incline water monometer across orifice
meter
e) Connect mercury monometer to engine vacuum
-------
Figure 1. BLOWBY TEST APPARATUS
H Sharp Orifice Meter
J
Cooling
Water
Condensate Trap
Exhaust Blowby
Incline Manometer
Blowby from Engine
-------
- 22 -
9) All test run at 2000 rpm
10) Collect the following data at each load condition:
a) MPH
b) RPM (maintain at 2000)
c) Load
d) Intake manifold pressure
e) Ambient air
f) Carburetor air
g) Coolant temperature
h) Oil temperature
i) Barometer reading
j) Wet and dry bulb temperatures
k) Blowby temperature before orifice meter
1) Pressure drop observed across water monometer
m) Observed cfm blowby - read from sharp orifice
meter chart relating pressure drop to cfm
11) CFM at standard conditions is calculated using a cfm
correction factor to compensate for barometric pressure
and a standard conversion factor to bring the final result
to cfm at standard conditions.
12) The initial reading is taken at the lowest horsepower
load measurable. Subsequent readings at multiples of
10 hp.
13) See attached data collection sheet for an example of
one blowby run.
B. PARTICLE COLLECTION
Exhaust particles were collected after air dilution of the
exhaust in the large dilution tube described below. During
the engine stand studies, one-half of the engine exhaust
was fed into the tube while the other half was exhausted
through the dynamometer cell exhaust system. With vehicles,
the entire exhaust stream was diluted.
1. Dilution Tube
Air dilution and cooling of the exhaust was accomplished
by a dilution tube 16 inches in diameter and 27 feet in
-------
BLOW BY MEASUREMENTS
Figure 2
- 23 -
SHEET NO.
OBSERVER
LOT-
DATE
. 33"Jl
VEHICLE MAKE C K fe.V
MILES ON VEHICLE
IGNITION TIMING
TRANSMISSION
£*
DISPL.
AT
VAC. IDLE
HP
BAROMETER IN Hg
at
WET BULB
°F DRY
CORRECTED BAROMETER (DRY )
INERTIA WEIGHT 4*-5"(OQ
. 7p at 28.5°F ABS . HUMIDITY
LBS
VALVE COVER PRESSURE + p"
SPARK PLUG TYPE ^ V */ T DWELL
REMARKS: CO**. W«'
YEAR /??&> ' NUMBER
'& NO. OF CYL. f&
RPM GARB /^ P
BBL
RPM
7 Q
GR/LB
6A
HP
RPM
SPEED
RPM
LOAD
_2_QOQ_
3>V
2000
2000
2000
2000
10
20
an
CO
w
K
W
(X,
X W
CQ EH
S W
O EH
J 2
CQ W
W
CO
<
W
s
VAC.
/7.
AMB. AIR
90
9*
GARB. AIR
//r
/JLO
WATER
OIL
O.V6
BLOW- BY AIR
S
85-
55"
OBS. PRESS DROP
.*£>
/.a*
2.OO
OBS. CFM
Ag/
CFM CORR. FACTOR
CORR CFM
X3VJT
STD. CONV. FACTOR
/.Q78
A
/
CFM at STD COND.
. 497
-------
- 24 -
length constructed of extruded polyvinyl chloride (PVC),
except for a 6* stainless steel inlet Section, in several
sections with butt joints which were taped during assembly
prior to each run (Figure 3). The diluent air coming into
the tube is filtered by means of a Dri-Pak Series 1100
Class II PIN 114-110 020 untreated cotton filter assembly.
This filter assembly is 24" x 24" and has 36 filter socks
which extend to 36 inches in length. This filter will
pass particles 0.3y in size and smaller. Pressure drop
at 600 cfm flow rate was minimal.
Exhaust was delivered to the tube via a tailpipe extension
which was brought into the bottom of the tube downstream
of the dilution air filter assembly. The extension was
bent 90 degrees inside the tube, thus allowing the introduction
of the exhaust stream parallel to the tube axis. Within
the dilution tube, along the perpendicular plane of the
end of the exhaust extension was a mixing baffle which has
an 8-inch center hole and was attached to the inside
diameter of the tube. The baffle presented a restriction
to the incoming dilution air in the same plane as the end
of the exhaust extension and performed three essential
functions.
a. Provided a turbulent mixing zone of exhaust gas and
dilution air.
b. Eliminated engine exhaust pulsations in the tube.
c. Caused the tube to perform as a constant volume device
over a wide range of engine exhaust output volumes.
2. Sampling Devices
The particulate sampling zone for particles smaller than
15ja was located at the exhaust end of the dilution tube.
Four isokinetic sample probe elbows are located in the ex-
-------
Figure 3.
Flow Diggrom for Engine Exhoust
Particulcte" Collection
t
Air
out
F ilter <
Instrument
r TCJ and
Engine Room W Control Room
Air
in.
Eng ine
Dynamometer
I?
Eng ine
. .
ix ing
Part iculate
Gravimetric Fallout
Flow
Control
!
X t /
Sampling Slits
Tail Pipe
Standard Muffler
Scott Research ins,
NO and N02
Analysis
> Fisher Gas Partitioner
CO, C02, N2, 02
Beckman 109A
Total Hydrocarbon
Analyzer
Anderson
Separator
Millipore
Filter
Flow Meter
Air
Pump
Vacuum
Pump
en
I
Manometer
I
Exhaust P ipe
-------
- 26 -
haust-air stream. One probe is connected to an Andersen
Impact Sampler Model 0203, a filter assembly, and a vacuum
pump, in that sequence. The probes are 0.754 inch ID stain-
less steel tubes which are located as shown in Figure 1.
A mercury manometer was connected between the dilution tube
probe and the exhaust side of the filter assembly, to mea-
sure the pressure drop across the filter. A flow meter was
used to monitor and regulate the flow through the Andersen
Sampler during the course of each run. Two other sample
probes, each were connected to 1 cfm Millipore filter
holders (142 mm) fitted with Gelman Type A glass fiber
filter pads and vacuum pumps. The fourth filter was a 47
mm, 1 cfm glass fiber.
Prior to use, all the filters were stored in the instrument
room which was temperature- and humidity-controlled. The
filters were placed on the tray of the Mettler Analytical
Balance, allowed to reach equilibrium, and then weighed out
to 0.1 milligram (mg).
After the test, the filters were removed from the holders
and again allowed to reach equilibrium, noted by no further
change in weight, and then weighed to 0.1 mg. This was done
in the same room in which the papers were stored. The Milli-
pore filter pads used were 142 Type AAWP 0.8p. The glass
fiber filter pads used were Gelman 0.3y Type A. It is
extremely important that all filters used in a given sequence
of tests be from the same batch. Variations in batch lots
have been found to lead to gross differences in collected
particulate.
Andersen Sampler Model 0203 with a back-up 142 mm Millipore
filter was used as the basic particle collection device for
determining mass size distribution. Sample probes sized
to deliver an isokinetic sample from the dilution tube were
connected to the Andersen Sampler through which a proportional
sample was drawn at 1 cfm. The D cut-off values for the
-------
- 27 -
Andersen stages are listed in Table 4. The D,-n value is
the size at which 50% of those particles are collected, while
the remaining 50% pass on through to be collected on the
next stage.
TABLE 4
D5Q VALUE - ANDERSEN MODEL 0203
Stage 1 DS(J 9y
Stage 2 DSQ 5.45y
Stage 3 DSQ 2.95y
Stage 4 DBQ 1.55y
Stage 5 D^Q 0.95y
Stage 6 D^Q 0.54y
Preweighed glass collection plates were used in this study.
Back-up filters were either Millipore Type AAWP 0.8y or
Gelman 0.3y Type A 142 mm diameter. Gelman glass fiber
filters were routinely used while the Millipore filters
were used for special analytical applications. Particulate
larger than 15y was collected as gravimetric fallout in the
dilution tube.
C. CONDENSATE COLLECTION
Exhaust gas condensate was collected for aldehyde and NH3
analyses. A tap was placed into the raw exhaust gas stream,
as close to the tailpipe of a vehicle as practical (about
12 inches in most cases) and 8 feet from the muffler in an
engine run. Raw exhaust was drawn through a three-stage
cold trap at the rate of 1 cfm. The cold trap consisted
of three flasks connected in series containing 40 grams
each of DI water, immersed in an ice water bath. The ex-
haust gas flow bubbles through the water in the flasks.
Condensate was collected for 41 minutes during a modified
Federal cycle cold start, and for 23 minutes during a Federal
cycle hot start. Sampling was terminated at 25 minutes during
a steady-state run.
-------
- 28 -
The condensate from the exhaust gas was analyzed for ppm
of HCHO and NH.,. It was felt desirable to express this anal-
ysis in volume percent to compare to the other components
analyzed in the exhaust gas. The procedure for this calcu-
lation is as follows:
The "Ideal Gas Law" was used
PV = n RT
V = n RT
P
The total liters of exhaust that was put through the conden-
ser is known, the liters of the aldehyde can be calculated
from the formula above, so the volume percent can be calcu-
lated. This volume percent is reported as volume parts per
million in the exhaust.
D. ANALYTICAL METHODS
Collected exhaust particles have been analyzed for both phy-
sical and chemical character. Many analytical techniques
have been employed in the past, some of which provide very
similar data in the interest of correlating trends observed.
This section reviews the basic analytical concepts applied
to each of the many test components from fuels to exhaust
particles. Detailed descriptions of the specific analytical
procedures employed are then presented. Table 5 is a summary
of the techniques used on the exhaust emissions.
-------
- 29 -
TABLE 5
ANALYTICAL TECHNIQUES FOR EXHAUST SPECIES
02, N2, CO, CO2 Fisher Gas Partitioner
Total Hydrocarbons Beckman Model 109A Flame
lonization Detector
Oxides of Nitrogen Beckman UV and IR Analyzer
C, H Pyrolysis
BenzoTcQp-yrene Chromatograph, Fluorescence
Trace Metals Emission Spectroscopy,
Atomic Absorption
Aldehydes Polarography
NH.. Steam Distillation, Titration
1. Fuels
Each test fuel was analyzed to verify concentrations of addi-
tives under study. Additionally, complete physical analyses
were determined on the base stock test fuel. These analyses
include distillation, octane numbers, fluorescence indicating
analysis (FIA) composition, Reid vapor pressure (RVP), and
trace metals. The test fuel was Indolene 0, and was
from the same batch for all engine and vehicle runs.
The additive blending was done in a large batch, and the
fuel was then drummed off for future use.
-------
- 30 -
2. Oils
Engine oils were examined for trace metals both before and
after test runs. Compliance of physical properties with
specifications was verified. The oils were only checked
on the engine stand runs, not on vehicles.
3. Diluent Air
Mass and composition of the filtered diluent air particulate
was determined with the engine or vehicle operating in the
air pick-up zone as during a test run. This data was neces-
sary to provide a correction factor applicable to the mass
emission rates determined during a test run.
4. Exhaust Gases
Engine exhaust gases were analyzed routinely several times
during the conditioning sequence and during sampling runs.
Schematically, exhaust gas sample points are as shown earlier
in Figure 1. The engine exhaust gas was analyzed for oxygen,
nitrogen, carbon monoxide, carbon dioxide, and total unburned
hydrocarbons. The hydrocarbons were broken down into satur-
ates and unsaturates. These analyses were done by gas chroma-
tography, chemical absorption, and a total hydrocarbon ana-
lyzer. Data reduction was via an IBM 1800 computer through
a Bell Telephone ASR 33 Teletype interface.
a. Analytical Equipment
A Fisher Gas Partitioner was used for the analysis of oxygen,
nitrogen, carbon monoxide, and carbon dioxide. The partition
column consisted of a 6-foot section containing hexamethyl
phosphoramide and a 6 1/2-foot section containing 13x molec-
ular sieves in series.
-------
- 31 -
Total hydrocarbons were obtained from a Beckman Model 109A
Total Hydrocarbon Analyzer. The concentration of unsaturated
hydrocarbons was determined by passing the sample through
an absorption tube (1/2" x 8") filled with 30-60 mesh pink
Chromosorb impregnated with 50 percent mercuric perchlorate.
The output of the gas chromatograph was coupled with a Hewlett-
Packard Model 3370A Digital Integrator which has an ASCII
coded output to drive an ASR 33 Teletype and punch paper
tape.
b. Sampling
A Neptune Dyna-Pump was used to pull the sample from the
exhaust pipe sampling point through 1/4" OD stainless steel
tubing and transfer it to the total hydrocarbon analyzer
and the gas sampling valve of the gas chromatograph through
1/8" OD stainless steel tubing. A manifold system was pro-
vided to allow the operator to calibrate the equipment with
the appropriate standards.
c. Standardization
A gas mixture containing known concentrations of oxygen,
nitrogen, argon, carbon monoxide, carbon dioxide, and
n-hexane was used as a reference standard for the total
hydrocarbon analyzer and the Fisher Gas Partitioner.
d. Operation
The operator typed the proper computer code and program num-
ber on the teletypewriter, injected the reference standard,
and pressed the integrator start button. As the peaks emerged,
-------
- 32 -
the time and area information was encoded and stored on punched
paper tape. Each succeeding exhaust gas was identified along
with the total hydrocarbon level, and run in the same manner
as the standard. When the series was finished, the punched
tape was sent to the computer by teletype over regular tele-
phone lines.
e. Data Reduction
A typical output format for the gas analysis is shown in
Figure 2. Identification of the components in the standard
was based upon each peak size in descending order. Esti-
mated retention time was the updated time of each peak in
the standard. Retention time windows are 4 seconds plus
2 percent of the retention time. Actual percent is a direct
ratio of the area counts in the unknown sample to the area
counts in the standard times the volume percent in the stan-
dard. The total percent actual will normally be 97-98 per-
cent since water is removed from the saturated sample after
the sampling valve.
A correction for the unresolved argon in oxygen was made
based upon response factors and the amount of argon found
in a number of exhaust gas samples by mass spectroscopy.
The actual percent was normalized to 100 percent in the next
column on a moisture-free basis, and an Exhaust Gas Analysis
report was issued (Figure 2) . The air-to-fuel ratio was"
calculated from this analysis, the total hydrocarbon content,
and the percent carbon in the fuel.
5. Oxides of Nitrogen
a. Equipment
Beckman Ultraviolet Analyzer
Beckman Infrared Analyzer
-------
- 33 -
Figure 4
G. C. ANALYSIS - TEC3;;JICAL DATA -
CSV RUN 23 CCT 16
CYCLE 2 72.9 HOURS
KC 620.
PEAK TIKE
NO. ACT. EST«
PC?. V3L.
ACTUAL N3RM*
10-16-70
IDENTIFICATION
1 22
2 59
3 C3
4 104
5 107
21.
59 .
83.
107.
. IRC.
0.000
12.003
1.493
0.900
81.033
1.626
97.0(SO
2.940
2.940
0.000
12.366
1.530
0.927
83.492
1.675
100.000
COMPOSITE
CAR DON DIOXIDE
CXYGEU
ARG3N
NITROGEN
C ARSON 'K3N0X1DE
TOTALS
BALANCE DY DIFFEHZriCE
TOTAL CCiJTAMINATICM LEVEL
EXHAUST GAS
GOV RUN 23 OCT 16
CYCLE 2 72 o 9 HOURS
KC 620.
ANALYSIS
10-16-70
TIME PERCENT IDEFJTIFICATICN
83. 0.9 ARG'il
107. C3.5 HITSJGuN
C3. 1.5 OXVC-rJ.'l
ICO. 1.63 CAJ^-N tr.JMOXIDE
59. 12.4 CAH3GM DIOXIDE
ICOoO TOTAL
FRACTION CAR3SM IN FUEL O.G'625
TOTAL HYDROCARnCN COMTEHT" 620. PPM.
AIR/FUEL RATIO 14.S
-------
- 34 -
Recorder - Texas Instrument Company
The above pieces of equipment were in a single, self-contained
unit built by Scott Research Labs Inc., San Bernardino, Cali-
fornia.
b. Calibrating Gases
Nitric oxide (3545 ppm in nitrogen)
Nitrogen dioxide (862 ppm in nitrogen)
These standard gases were purchased from Scott Research Labs
Inc.
\
Nitrogen was used as zero calibrating gas.
c. Procedure
Before making NO, N0~ measurements, the paper filters (What-
man #3) to each analyzer were changed and the Drierite dryer
in the exhaust sample line was replaced. Both analyzers
were standardized using the appropriate calibrating gas at
a constant flow. The zero standardizing was done using nitro-
gen as the calibrating gas and using the same flow rate.
After the instrument was standardized, the exhaust gas was
passed through the analyzer using the same flow rate as in
the standardization step. The NO, NO2 values were recorded
by the dual pen Servo-riter recorder. Figure 3 indicates
the source of the exhaust gas sample.
6. Exhaust Particles
The collection and classification techniques employed allow
the calculation of mass emission rates in grams/mile of ex-
-------
- 35 -
haust particulate. Additionally, cumulative mass distribu-
tion data can be calculated. Several collection methods
were used, and have been discussed previously in Section III-B,
page 13.The specific techniques for chemical analysis of
this particulate matter are discussed in this section.
a. Carbon and Hydrogen
The percentage of carbon and hydrogen in the particulate
was determined by pyrolysis and collection of the combustion
products. An entire 142 mm glass fiber filter containing
the particulate was placed in a large platinum boat. The
boat was then transferred to a combustion tube, and the
sample was combusted at 1100°C for 3/4 hour. Carbon dioxide
and water were absorbed in micro absorption tubes and weighed
in the conventional manner. The C and H values were then
calculated from the increase in weight using the given weight
of the particulate.
In general, this technique is quite accurate for carbon and
hydrogen analysis. However, the small sample sizes generated
in a 23-minute cycle or from vehicles or engines operating
on unleaded fuel make it difficult to obtain precise results.
For example, the 142 mm Gelman glass fiber filters have a
blank of approximately 7 mg for hydrogen and a spread of
nearly 1 mg. For carbon the blanks are over 2 mg with a
spread of 0.5 mg. It is not uncommon to have sample sizes
of less than 2 mg; therefore, the inherent inaccuracy of
weighings (even using a 5-place balance) plus the large blank
size make the results of a small sample only meaningful in
a gross comparative sense.
This technique can be used on samples collected on the Ander-
sen Sampler plates by careful transfer of the particulate
to the combustion chamber. However, even with the best hand-
ling techniques the transfer of particulate is only about
-------
- 36 -
30 percent. In general, engine runs in which very little
sample was collected on the filter pads also gave very little
on the Andersen Sampler Plates.
Nitrogen can also be determined by pyrolysis, but due to
the small sample size no meaningful results have been ob-
tained in nitrogen content.
b. Benzo-g-pyrene
Samples of exhaust particulate were collected on Gelman
142 mm glass fiber filter pads in a Millipore filter holder
operating at 1 cfm. Particulate weights gathered in this
fashion ranged from 0.2 to 35 mg. The samples on the glass fiber
filter pads were analyzed for benzo-a-pyrene in the following
manner.
Mien available a sample of at least 10 mg (on either one
or two filter papers) was used for analysis. The filters
were folded and rolled with the particulates toward the
inside of the roll and tied with copper wire. The rolls
were Soxhlet extracted for at least 6 hours (with siphoning
four to six times per hour) with 75 ml of benzene. The
extracts were evaporated under a stream of filtered air at
room temperature to approximately 3 ml. This concentrate
was filtered through a M-fritted glass filter into a tared
vial. The flask and filter were washed three times with
approximately 2 ml of benzene for each wash. The combined
filtrates were evaporated to dryness at room temperature
with a stream of filtered air.
The residues obtained from both sample and blank filters
were weighed and the difference between them designated
"benzene soluble weight" for each sample. The residue was
dissolved in 0.2 ml of methylene chloride and a 10-40 yl
aliquot was spotted in 2 yl increments on a pre-conditioned
Alumina TLC plate along with a known standard of benzo-a-
-------
- 37 -
pyrene in methylene chloride. The TLC plates were condi-
tioned by heating at 120°C for 1.5 hours and desiccating
overnight in a 45 percent relative humidity chamber (satu-
rated aqueous zinc nitrate). The TLC plate was developed
in an unsaturated tank containing 20 ml of ethyl ether in
200 ml of n-pentane to a height of 15 cm (approximately 45
minutes).
The benzo-a-pyrene spots were identified by comparison of
R,:' s with that of the standard spot under an ultraviolet
lamp. The spots, marked with a pencil, were circumscribed
with a #15 cork borer and scraped from the plate into vials.
All TLC work was performed as much as possible in a dimly
lighted area to avoid decomposition of the benzo-a-pyrene.
Five ml of 5 percent acetone in n-pentane was added to the
alumina in the vial and it was agitated for 15 minutes on
a mechanical shaker. The slurry was filtered through an F
sintered glass filter into a vial, washing the alumina four
times with approximately 2 ml of 5 percent acetone in n-pen-
tane with a 45-second soak period between each wash. The
combined filtrates were evaporated to dryness at room tem-
perature using a stream of filtered air. The benzo-a-pyrene
residue was taken up in 2.0 ml of concentrated sulfuric acid.
This solution was evacuated for five minutes to remove trapped
air bubbles and its fluorescence was measured in a one-cm
cell at 540 nm while exciting at 470 nm on an Amino-Bowman
Spectrophotofluorometer using a #4 slit arrangement and a
sensitivity of 30.
Standard and blanks were carried through the entire TLC pro-
cedure. The blanks were subtracted from all fluorescence
readings and the net fluorescence values for each sample
were used to calculate the amount of benzo-a-pyrene present.
Throughout all steps in the procedure the samples were refrig-
erated when not actually being processed and exposure of
the samples to light was kept at a minimum.
-------
- 38 -
c. Trace Metals
Both emission spectrometry (ES) and atomic absorption (AA)
were used for determination of metals in the particulate.
Atomic absorption was primarily used for lead determination.
Trace metals were determined by ES on Millipore filters while
lead was determined as a percent of the particulate collected
on the 142 mm, 1 cfm fiberglass filter.
1) Emission Spectrometry
a) Principle
Organic matter in the sample is destroyed by wet ashing in
sulfuric, nitric and perchloric acids. The resulting solu-
tion is taken to dryness and the residue is taken up in a
spectroscopic buffer solution containing the internal refer-
ence element, palladium. A portion of the solution is dried
on pure graphite electrodes. The electrodes thus prepared
are excited in an a.c. arc discharge and the spectrum is
photographed. The intensity ratios of selected lines are
determined photometrically and the concentration of each
element is read from an analytical curve relating intensity
ratio to concentration.
b) Apparatus
(1) Excitation. Excitation is obtained by the use of a
2400 volt a.c. arc discharge - Jarrel-Ash Custom Varisource,
or equivalent.
(2) Spectrograph - Baird 3 meter grating spectrograph.
Reciprocal dispersion is 5.55 A/mm in the first order.
-------
- 39 -
(3) Developing equipment - Jarrel-Ash Company. Plates are
developed in a thermostatically controlled developing machine,
washed and dried over heat in a stream of air.
(4) Densitometer. Spectral lines are measured with a non-
recording projection-type densitometer. Densitometer Com-
parator, Baird Associates Inc.
(5) Calculating equipment. A calculating board is employed
to convert densitometer readings to log intensity ratios.
Jarrel-Ash Company.
(6) Wet ashing equipment. A micro Kjeldahl digestion rack
is used for wet ashing the organic solvents.
c) Reagents and Materials
(1) Distilled nitric and perchloric acids. Perchloric acid
is an intense oxidizing agent. Organic matter should not
be heated in perchloric acid unless in the presence of sul-
fur ic or nitric acid.
(2) Sodium nitrate, reagent grade (NaNCO .
(3) Palladium diamine nitrite, Pd(NH3)2(N02)2«
(4) Water soluble salts of the elements Al, Ca, Cu, Fe,
Mg, Mn, Ni, Pb, Sn, and Zn.
(5) Electrodes, high purity graphite, 1/4" diameter by
3/4" length. Ultra Carbon Corporation.
(6) Photographic plates - Eastman Spectrum Analysis No. 3.
(7) Kjeldahl flasks, 10 ml.
-------
- 40 -
d) Calibration
(1) 0.2182 gm of palladium diamine nitrite Pd (NH.J 2 (NO2)
were dissolved in water. 10 ml of concentrated reagent grade
nitric acid were added and the mixture diluted to volume
with water in a 100 ml volumetric flask. This solution con-
tains 1 mg Pd per ml.
(2) A buffer solution was prepared by dissolving 20 gm of
sodium nitrate in water. 5.0 ml of the palladium solution
above and 7.5 ml of concentrated reagent grade nitric acid
were added and the whole diluted to 100 ml.
(3) A stock solution containing 0.01% (0.1 mg/ml) each of
the elements Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Sn, and Zn was
prepared. Two aliquots of this solution were diluted ten-
fold and one hundred-fold to provide 0.001% and 0.0001%
solutions.
(4) Standard additions of the impurity elements were made
to Kjeldahl flasks as shown in Table 6.
(5) 0.5 ml of concentrated reagent grade sulfuric acid was
added to the Kjeldahl flasks and the solution evaporated
to dryness. After cooling, 1 ml of concentrated nitric acid
was added and the mixture was evaporated to dryness again.
The residue was taken up in 5 ml of buffer solution, warming,
if necessary, to put the salts into solution.
-------
- 41 -
Concentration
Table 6
ml. of ntandird r.ddition impurity solution
Blank
O.C0001%
0.000025%
0.00005%
0.0001%
0.00025$
O.OOO-l-'-o
O. 00075%
0.001%
0.0025%
0.005%
0.01 %
0.5 nl.
1.25 til.
o.r.o -s.i.
O.5 DA.
1.25 nl.
2.5 T:.l.
O.37£ ill.
O.5 ul.
1.25 nl.
2.5 ml.
5.0
0.0001% t
II
O O3 ^ ''
tl
II
II
0.01%
It
II
II
II
3Oll
II
II
II
II
II
II
II
II
II
II
Element
Analytical
Lino' A
Al
Ca
Cu
Fe
Fe
L"s
KS
lln
loQ
Ni -,
Ni
Pb
Pb
Sn
Sn
Zn
3032.71
3179.33
3273. 03
30.21.07
3020. G4
XG02.C9
2779.83
2C33.G3
270-1. C2
3414.77
3037. C-l
2873.32
2C33.07
3175.02
2SG3.33
33C 5. 02
TaBle 7
Analytical Liuo Fairs
Internal Standard
Lino A
y
3027.01 Pd
I
ii.
it
it
ti
it
D^clx^round
Concentration
Range %
0.000025-O.OO10
O.OOO25-0.010
O.OO001-O.OC025
O.OOO1-O.O1O
0.000025-0.C050
O.OOG025-O.CO10
O.O005-0.010
O.OC05-0.010
0.00001-0.0010
.O.COC025-O.0010
O.OO05-O.OIO
O.OO10-O.O10
O.OO005-O.OC50
O.00005-0.0050
O.O0075-O.01O
O.O001-O.O10
-------
- 42 -
(6) The end of the 3/4" graphite electrodes was polished
on filter paper and placed in a stainless steel drying tray.
A drop of kerosene was placed on the top of each electrode
to seal the porosity and the electrode allowed to dry. One
pair of electrodes was prepared for each of the standard
addition solutions by pipetting 0.03 ml of the solution onto
the end of each electrode. The electrodes were dried slowly
over micro burners in a gas drying oven and stored in a desic-
cator until run.
(7) The samples were excited in water cooled electrode
holders using the following conditions:
(a) Current, 4.0 amps, a.c. arc.
(b) Spectral region, 2150-3550 A.
(c) Slit width, 50y
(d) Electrode gap, 2 mm.
(e) Pre-burn period, 10 seconds.
(f) Exposure period, 90 seconds.
(8) The emulsion was calibrated by use of a stepped filter
or by other recommended methods described in the "Recommended
Practice of Photographic Photometry in Spectrochemical Anal-
ysis" A.S.T.M. Designation: E116, Methods for Emission
Spectrochemical Analysis, (1964).
-------
- 43 -
(9) The emulsion was processed according to the following
conditions:
(a) Developer (D19, 20.5°C), 3 1/2 minutes.
(b) Stop bath (SB-4), 1 minute.
(c) Fixing bath (Kodak Rapid Fixer), 2 minutes.
(d) Washing, 3 minutes.
(e) Drying, in a stream of warm air.
(10) The relevant analytical line pairs were selected from
Table 7 (pg 41). The relative transmittances of the internal stan-
dard line and each analytical line were measured with a den-
sitometer. The transmittance measurements of the analytical
line pairs were converted to intensity ratios by the use
of an emulsion calibration curve and a calculating board.
(11) Analytical curves were constructed by plotting con-
centration as a function of intensity ratio on log-log graph
paper. For best results, the average of at least four deter-
minations recorded on two plates were plotted.
e) Procedure
(1) The available sample was weighed directly into a Kjeldahl
flask. Sulfuric acid was not used in the wet ash procedure
because test samples usually contained a large amount of
lead which would form the insoluble sulfate. Wet oxidation
was carried out with nitric and perchloric acid only. Extreme
-------
- 44 -
caution was exercised in the use of this technique. Concen-
trated nitric acid was added dropwise, a few tenths ml at
a time, to the hot mixture to aid in oxidation. A few drops
of concentrated perchloric acid may be added to the hot solu-
tion after most of the free carbon has been destroyed, to
hasten complete oxidation. When the solution became water
clear, it was evaporated to dryness. After cooling, 0.5
ml of nitric acid was added and the mixture evaporated to
dryness. The addition of 0.5 ml of nitric acid was repeated
and the solution evaporated to dryness again. The inorganic
residue was dissolved in dilute nitric acid and the volume
adjusted to a known concentration, usually 10 mg/ml. If
the original sample size was below 30 mg, a less concentrated
solution was usually made up. Aliquots of this solution
were taken to dryness and then the buffer solution (d2) added
in an amount to give a dilution factor of lOOx. One sample
was analyzed by the direct reader while a second was examined
photographically. Some samples had to be run at factors
larger than lOOx in order to get the concentration for some
elements to fall within the range of the analytical curves.
By varying the sample to buffer ratio any number of concen-
tration or dilution factors could be achieved. A blank of
the acids used was carried through in the same manner as
the sample.
(2) Proceed as in d(6), (7), (8), (9), and (10) of the
calibration procedure. Duplicate spectra were recorded for
each sample.
f) Calculations
The intensity ratios were converted to concentration by use
of the analytical curves.
-------
- 45 -
g) Precision and Accuracy
Representative precision and accuracy of the method are
given in Table 8. Each of the twelve samples A,, A-, A.,,
B,, B2, B.J , C,, C2, C3, D,, D2, D.,, was analyzed by means
of duplicate excitation.
2) Atomic Absorption
a) Method for Lead Determination
Following nitric acid digestion, particulate samples were
washed into 50-ml volumetric flasks a-nd diluted to mark.
This normally put the concentration of lead in the flasks
between 20 and 200 yg Pb/ml. If the concentration was higher
than 200 yg Pb/ml, the sample required redilution. The sam-
ples were analyzed on an atomic absorption spectrophotometer
(Perkin-Elmer Model 303) using a hollow cathode lamp with
a lead cathode filament. Operating conditions were as fol-
lows: 10 milliamps tube current, light path slit opening -
4, ultraviolet light range, acetylene-air oxidizing flame,
one-slot burner head, wavelength - 2170 angstroms. The sam-
ple solution is aspirated into the flame where lead atoms
present absorb the light from the lead cathode filament.
The amount of absorbed light is proportional to the concen-
tration of lead. The samples were analyzed in conjunction
with the following series of lead standards: 10, 20, 40,
60, 80, 100, 150, and 200 yg Pb/ml. The concentration c?f
the standards was plotted versus their absorbance values
giving a standard curve. With the absorbance values for
the samples and the standard curve, it was possible to deter-
mine the concentration of lead in the samples. The sensi-
-------
TABLE 8
o
r-»
P.
E
d
w
A,
j.
A2
A3
B,
1
B2
B3
Cl
JL
C2
C3
Dl
A
P2
D3
*1
% Al
O.OOOO44
O.OOO052
0.000045
O.OOOO52
O.OCOQ-1
O.OOOO52
O.OOO12
0.-CCC097
O.OC0097
0 . CG0094
0 . CCG032
O.CC011
0.00023
O.C0020
O.O0020
O.c^;::3
o CO324
O.OC028
0.00074
O.OGOS4
O.CC053
O.COOG3
O.OO359
0.00053
, A 2 , and A3
KtPKhb
% Ca
0.00043
0.00050
0.00043
0.00037
O.OOO13
0.00050
O.OO1O5
O.OOC03
0. GOODS
0.00003
O.COOS.3
O.CC074
0.0023
O.C313
O.C0223
O.C02C3
O.OQ23-
0.00275
O.C07O
O.C03-1
O.GQ49
O.G057
O.CO-13
0.005O
contc.la.
hNIAl IVh VY
% Cu
O.OOOO48
O.OOO054
O.OO0046
O.OOOO-17
O.OOO050
O.OOOO48
O.OO012
O.OOO10
O.OOO099
0.000095
O.OOOOC5
O.OOOOS6
O.OOO23
O.O0020
O.CC023
O.OOO25
0 . OOO26
0.00028
_
__
~-
~- .
~-
O. OOO05% ol
(hUIblU
% Fc
O.OOO43
Q. 00055
O.O0044
0.00043
O.OOO46
O.OOO46
0.0010
0.00094
O.COODO
O.CO105
0.0010
O.OO10
0.0025
0.0030
O.C023
0.00235
O.CO275
O.G02S5
O.CDC-5
O.COC3
O.C057
O.O-339
O.C050
O.C05S
Al an4
H ANU ALL
% MB
0.00049
0.00052
0 . 0004 7
0. OCX) 50
O. OCX) 53
0.00049
0.00105
0.00095
O.C0092
0.00091
0 . 0010
O.CCO9O
O.OO23
0.0(423
0.0023
O.0024
' O.OO23
O.OO24
O.0057
0.0051
0.0048
0. 00-17
O.0045
O.O055
Cu, and 0.
URACY 0
% Mn
O.OOO46
O.OO057
O.O0051
0.00050
O.OOO49
0.00046
O.OO1O
0.0012
O.OO11
O.OOO66
O.OO086
O.OOO92
O.OO2G5
O.O0195
O.C02S5
0.00275
0.00245
O.O025
O.O059
0.0058
O.OO45
O.0048
O.O047
0.0054
OO05% of
h EMISSIO
":: Nl
O.O0047
0.00055
O.OOO45
0.00051
O . OO04 7
O.OOO48
O.OO10
0.00096
O.OO10
O.OO105'
O.OO10
0.00105
O.O0245
O.CO265
O.OO23
O.O0245
O.0026
O. 00255
O.G035
0.0058
O.GO56
0.0057
O.O05O
O.OO55
each other
N bPECTRl
% Pb
0.00056
0.00059
0.00050
O.OO051
O.O0052
O.O0053
O.OO105
O.OOO98
0.0010
0.00105
O.C010
0.0010
0.00235
0.00255
0.00245
0.0026
0.0025
O.OO245
O.OO55
O.CO15
O.OO45
O.OCW3
O.OO-13
O.OO-19
elcaent .
JSCOPY
% Sn
0.00052
O.O0059
0.00053
O.OOO50
O.OOO5O
O.O0046
0.0011
O.OO094
0.00105
0.00105
O.OOO99
O.OO10
0.00255
O.CO27
O.OO215
O.OO23
O.OO25
O.OO265
O.OO54
O.OO59
0.0053
O.0057
0.0054
0.00-19
B, , B2,
%Zn
O.OOO40
0.000-15
0.00054
O.OOO40
O.O0052
0.000-12
O.OOO94
O.OO12
0.00125
O..OO1O
o'.OOO96
O.OO115
O.OO14
0.00215
O.OO225
O.O030
O.OO30
0.0020
0.0058
O.OO50
O.O050
O.OOSO
O.O037
O.OC41
and B3 contain
i
i
t*.
CTi
1
O.OOOl?) of Al and Cu, and O.C01OJ ol each other element.
and 0.0025% of each other elecent.
eleuent.
C,, C5, and C3 contain- O.OOO25% of Al and Cu
Dfi and D3 contain O.OO05% of Al and Cu and 0.005O% of each *"
-------
- 47 -
tivity for the lead determination in an air-acetylene flame
is about 0.25 yg Pb/ml at 1 percent absorption. The detec-
tion limit is 0.1 yg Pb/ml.
b) Determination of Lead and Iron in Engine Combustion
Chamber Deposits
These samples were thoroughly ground in a mortar prior to
analysis to obtain uniform samples. The ground sample was
dissolved in nitric acid and lead determined by atomic absorp-
tion. A portion of the sample solution was also used in
the determination of iron. Iron is reduced with hydroxyl-
amine to the ferrous state, and reacted with 1,10-phenan-
throline in an acetate buffered solution (pH 5) to form an
orange-red complex. Photometric measurements were made using
a Beckman DU-2 spectrophotometer. Operating conditions were
as follows: sensitivity setting - 2, slit opening - 0.10
mm, wavelength - 510 mm, 40 mm optical cells. The concen-
tration of iron was determined from a standard curve. For
a one gram sample diluted to 100 ml, the detection limit
is about 1 ppm and the sensitivity +1 ppm.
c) Gravimetric Method for Lead Determination in Millipore
Filters
Following nitric acid digestion, concentrated sulfuric a.cid
was added to the sample to precipitate lead sulfate. The
solution was filtered, and the precipitate dried and weighed
to determine the amount of lead percent. In addition, the
filtrate was analyzed by atomic absorption for trace amounts
of lead. This analysis is included in the total amount of
lead reported for the sample.
-------
- 48 -
d) Determination of Lead and Other Metals in Glass fiber
Filters
The glass fiber filters cannot be digested completely with
nitric acid. They were cooked with concentrated nitric acid
for two hours to leach out the metals. The pulp was filtered
and washed and the filtrate analyzed by atomic absorption
for lead, and by emission spectroscopy for other metals.
3) Scanning Electron Microscopy (SEM) and X-ray Fluorescence
The Scanning Electron Microscope (SEM) was used to identify
(X-ray spectrometer) the collected exhaust particles from
the Andersen Sampler and the Millipore backup filter.
a) Instrumentation
Cambridge Stereoscan Mark 2A
Ortec Non-dispersive X-ray Detector
Nuclear Data Analyzer
Varian Vacuum Evaporator
Kinney Vacuum Evaporator
b) Work Outline
(1) Particle characterization (SEM) on plates of Andersen
Sampler
(2) Particle identification QC-ray)
-------
- 49 -
(3) Single element X-ray scan
(4) X-ray spectra on impingement area of Andersen plates
and spectra on backup filter
c) Techniques and Methods
(1) Substrates for sample collection: The most satisfactory
substrates for photomicrography were micro cover glasses,
while where X-ray analysis was employed/ ultra pure carbon
strips proved best. Silica interference from micro cover
glasses, halogens in epoxy, and thermal instability in mylar
film reduced the desirability for using these materials as
substrates where X-ray analysis was to be carried out.
(2) Storage and sample preparation: All samples were main-
tained in a dry atmosphere from collection to examination.
Both the glass cover slip and the carbon strip substratum
were attached to SEM sample stubs with conducting, silver
paint. Samples for SEM characterization were made conductive
o
with a thin layer (-200 A) of gold or gold-palladium evapo-
rated. Graphite carbon was sputtered on the samples used
for X-ray diffraction.
(3) Normal operation for the Stereoscan:
(a) Gun potential - 20 to 30 kV (depending on sample degra-
dation and resolution needed).
(b) Vacuum - -10 Torr.
(c) Sample angle - 20°.
(d) Working distance - 11 mm.
-------
- 50 -
(e) Polaroid P/N Type 55 film with 100 sec exposure.
(4) Normal operations for X-ray Spectrometer (warranted
215 ev FWHM resolution) :
(a) Gun potential - 30 kV
(b) 1024 channel - Series 2100 Nuclear Data Multichannel
Analyzer
(c) Collection time - 200 sec
(d) Count rate - ~60 c.p.s.
(e) Spectra recorded on Moseley 7035B X-Y Recorder
(f) Single channel recording
(g) Polaroid P/N Type 55 film 400 sec or 800 sec exposure
depending on concentration
d) Analys is
(1) Particle characterization and photomicrographical docu-
mentation was done with the scanning electron microscope
employing standard operational procedures.
(2) Particle identification involved elemental analysis
using the X-ray spectrometer on the scanning electron micro-
scope. This included, for multiple particles, full spectrum
elemental scan, and single element scan. Spot scans were
carried out on single particles or in specific regions of
particles.
-------
- 51 -
7. Condensate Analyses
Condensate was collected from the raw exhaust as described
in Section III-C. The condensate was analyzed for aldehydes
and NH3 using the procedures outlined below.
a. Aldehydes
The analytical method for the determination of carbonyl com-
pounds in automotive exhaust emissions employed polarographic
techniques. Samples for analysis were collected from undi-
luted exhaust effluent using ice-water cooled cold traps
and via a sample probe welded into the engine or vehicle
exhaust system. A Princeton Applied Research Model 170 Elec-
trochemistry System was used as the monitoring device. The
derivative pulse polarographic mode yielded the best combin-
ation of carbonyl compounds. A dropping mercury electrode
with a Princeton Model 172 Drop Timer was employed as the
working electrode.
Hydrazine derivatives (hydrazones) were employed for the
determination of the carbonyl compounds, since hydrazones
are easier to reduce than the free compounds, thus elimi-
nating many possible interferences.
An acetate buffer of approximately pH 4 (an equimolar mixture
of acetic acid and sodium acetate, 0.1 M in water) was used
to control pH for hydrazone formation and also acted as sup-
porting electrolyte. Hydrazine was added as a 2 percent
aqueous solution. In this system formaldehyde gave a peak
potential (half-wave potential) of -0.92 v vs. a saturated
calomel reference electrode. A platinum wire was employed
as the auxiliary electrode.
-------
- 52 -
With the above system, it is possible to distinguish between
and simultaneously determine aromatic aldehydes, formaldehyde,
higher aliphatic aldehydes, and aliphatic ketones as shown
in Figure 5.
Since aromatic ketones, e.g. benzophenone, give polarographic
response in pH 4 buffer without hydrazine, it is also pos-
sible to detect aromatic ketones. Lead and zinc could also
be determined from the samples under these conditions.
Since formaldehyde was the main carbonyl component of the
condensate samples, all results were calibrated against and
reported as formaldehyde. The upper curve in Figure 6 shows
an actual sample without hydrazine present and demonstrates
the lack of interference in the carbonyl region. The lower
curve shows the same sample after the addition of hydrazine.
Figure 7 shows the same solution after the addition of a
formaldehyde standard. These two figures clearly establish
the presence of formaldehyde in the exhaust samples.
Procedure:
Pipet 2 ml of methanol sample into a 25-ml volumetric flask.
Add 10 ml of pH 4 acetate buffer and dilute to volume with
water. Transfer this solution to a polarographic cell and
deaerate with oxygen-free nitrogen for ten minutes. Record
a derivative pulse polarogram from 0 to -1.6 v vs. SCE.
Add 2 ml of hydrazine reagent to the polarographic cell and
deaerate for 5 minutes. Again, record the polarogram from
0 to 1.6 v vs. SCE.
Lead and aromatic ketones are determined from the waves ob-
tained without hydrazine at the peak potentials listed above.
Formaldehyde, higher aliphatic aldehydes, aromatic aldehydes,
and aliphatic ketones can be determined from the second polar-
ogram with hydrazine present.
-------
- 53 -
. :"ix:T.LiiiiLL.iTi'L'iir?-
."|4-i_T.:i.._:-n
Figure 5
iji"tir ."Tj-t--f ^ 1 J: -"Pr
.;.:.|j.U j-TUtTL,-1-H--
-:-rr; ; fi H-Pol arographi c Determination of Aldehydes-j-
2T~'T! 'i-i.
_] _; |_ J._J \_i |_
I ;
M-
,-f-i
^^irn:
._^_,-T-^-^4..
-4-
_ J_L.J _; ._.
0) j.4.C
'
_1.^^^__.
_^_:_-..v£^_^.
TTT
TTT
-/I
:_i-Lj..oo_i-
J-fr-r
:,ozr
_.O i ,.
_:"<« :
nTlTimL
ft=rrJ
J~r~
^4-J-^-t-:
": I [ r |~~f i ;
r-T-t-t-
-r
-rres_\ ]'_''
-UL5£_M4-I
-4-i-
drfe-r-
jfcVU-W
ztihh
_±_ L.__J ,_J
t t ' i ' .
r~, . '", r
4:i^:L..:(:n:py;Jjjii^,^-fcr^Er
Tr-nr:-^r"ill/V^H:r^-7QJ^TH-U-|4-
H:^r
-^ _ .... _t
T^^^rrrt^-WS/^T-tH-JI-i-t-
-4TH--HTt-'W-r rrr-rr-H-r
t-tto-r^1
;- tf
i±.
H-rrt-hr
SfH'tt'J
u ,.u _i_:
:T\^Sijli:
;.-i
i-. :J.;
' ^^yI
iiiffill
v -vs ISCP
i l t- r t-
-------
Figure 6
. .' : _-_-.Po'arogrjphle Determination of AldehydesZJij
rpH7V72ce;aEe~nHiffer~:- .
L-iJ±i
., .}.. ..i.,., r
LffHJtSi
I
Ul
-------
- 55 -
All responses should be calibrated by addition of known amounts
of standard compounds to actual runs. Peak heights are linear
with concentration.
In this system, zinc has a peak potential of -1.00 v vs.
SCE, but it can be differentiated from benzophenone by the
fact that it possesses only one polarographic wave.
A blind comparison of the polarographic technique vs. the
MBTH technique was made, and the results were as follows,
expressed as formaldehyde:
MBTH Polarographic
340 ppm 300 ppm
1500 ppm 1530 ppm
430 ppm 480 ppm
105 ppm 110 ppm
150 ppm 110 ppm
b. Ammonia
Ammonia was present in the exhaust gas condensate and was ana-
lyzed in the following manner.
A 5-10 cc aliquot of condensate was added to a 50 percent
potassium hydroxide solution. This mixture was then steam
distilled into an excess of 0.010 N hydrochloric acid. The
excess acid was determined by adding potassium iodide and
iodate and titrating the liberated iodine with 0.010 N sodium
thiosulfate.
This technique is capable of determining ammonia as low as
0.3 ppm. Figure 8 is a sketch of the apparatus used for
the determination.
-------
t
Evacuated
Jacket
Not Over
From Bottom
. Tube
Length 36"
Pinch
JTube to ctarn-D
Rubber Tubing
MICRO-KJELDAHL APPARATUS
(Mount on Ring Stand)
Distlliati
--
Distilling
Flask
50 ml. Erlenmeyer
Receiving Flask
Rubber^/
^;-~-|> Stopper/
/
Rubber
Tubing
Figure 8
ZLPPARATUS FOR DETERMINATION OF NH.
Electric
Heater
-------
- 57 -
The analytical procedures given herein have been adapted
from literature sources or developed upon the basis of exper-
imental data which are believed to be reliable. In the hands
of a qualified analyst they are expected to yield results
of sufficient accuracy for their intended purposes. However,
The Dow Chemical Company makes no representation or warranty
whatsoever concerning the procedures or results to be obtained
and assumes no liability in connection with their use. Users
are cautioned to confirm the suitability of the methods by
appropriate tests.
-------
- 58 -
V. EXPERIMENTAL RESULTS
The primary goal of this contract was to develop a test pro-
cedure which would be reproducible, reasonable inexpensive,
and which could be performed in other test facilities with a
minimum of modifications to existing equipment, for the pur-
pose of evaluating any negative or positive effectives of a
given fuel additive on particulate exhaust emissions. In-
cluded in this section will be the data generated while trying
to establish a consistent testing method. The basic method
was generally described in Section III.
A. SPECIFIC CONCLUSIONS
1. Additive B, (an amine detergent) -at the then manufacturer's
recommended level, increased particulate emissions in both engine
stand and vehicle test runs, from 50% to 100% above the base-
line (Figures 9, 10, 15) when collected on the 142 mm glass
fiber filters. Increases in particulate with the use of
Additive B fuel were also noted in the Andersen separator and
back-up filter, but the increases were not as pronounced.
2. Additive A (a manganese antiknock) at the manufacturer's
recommended level, did not significantly increase or decrease
the particulate emission levels in the vehicle test runs
(Figures 9 through 12) .
3. Additive A, at the manufacturer's recommended level,
slightly decreased the particulate emissions under 23-minute
Federal cycle cold start and hot start conditions, when.
tested on the engine stand (Figures 15, 16).
4. Additive B increased unburned hydrocarbons in the raw
exhaust under both steady-state and 23-minute Federal cycle
cold start conditions, when tested in the vehicles (Figures 13,14).
-------
- 59 -
5. Additive A did not significantly increase or decrease
unburned hydrocarbons under either steady-state or cyclic
conditions when tested in the vehicles (Figures 13,14).
6. The use of Additive B, at three times the manufacturer's
recommended level, gave particulate emission increases
varying from 8 times greater than the baseline and 5 times
greater than the particulate measured at the recommended
dosage level, when tested under Federal cycle cold start
conditions (Figures 15, 16) and collected on 142 mm glass
filters. The respective increases for the Andersen plus
back up filters are 3 times the baseline and 9 times the
IX concentration.
7. The use of Additive A at three times the manufacturer's
recommended level gave no significant increase in particulate
emissions compared to the baseline or to the recommended
dosage level (Figures 15, 16).
8. Increasing the additive dosage to three times the manu-
facturer's recommended level caused the same general effect
on particulate emissions after a 75-hour cyclic conditioning
period on the engine stand, as was noted after approximately
17,000 miles of vehicle testing (Figures 9, 10, 15, 16).
9. The increase in particulate and hydrocarbon emissions
noted with Additive B in the vehicle tests was a function
of mileage and did not appear to level off until after
10,000 miles (Figures 9 through 14) .
10. The particulate emissions measured after a 75-hour
cyclic conditioning period on the engine stand using the
manufacturer's recommended dosage correlates well with the
measured particulate after 5,000 miles (break-in period
plus 1,500 miles) of vehicle testing. A 75-hour sequence
of 23-minute cycles equates to about 1,500 vehicle miles
(Figures 9, 10, 15, 16).
-------
15
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FIGURE
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9
5000
10,000
VEHICLE MILES
15,000
CTl
O
20,000
FEDERAL CYCLE COLD START, AVG. OF 2 RUNS
BASELINE FUEL
- - - - ADDITIVE A
O 0 ADDITIVE B
CHASSIS DYNOMOMETER
-------
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to
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GRAMS PER MILE PARTICULATE VS MILEAGE ACCUMULATION
ON
ICFM GLASS FIBER FILTER I42MM
FIGURE NO. 10
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60 mph Steady State, 2 hours
10,000
VEHICLE MILES
15,000
20,000
BASELINE
Air conditioner failed room temp. 96°F
ADDITIVE A
-O 0 ADDITIVE B
CHASSIS DYNOMOMETER
-------
.060
.050
GRAMS PER MILE PARTICULATE VS MILEAGE ACCUMULATION
ON
ANDERSEN SEPARATOR PLUS BACKUP FILTER
FIGURE NO.
\
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.VEHICLE MILES
60 mph Steady State, 2 hours
* Point is up for suspect did not use
** Air conditioner failed room temp. 96°F
15,000 20,000
BASELINE FUEL
' ADDITIVE A
o4 ADDITIVE B
CHASSIS DYNOMOMETER
-------
,60
50
GRAMS PER MILE PARTICULATE VS MILEAGE ACCUMULATION
ON
ANDERSEN SEPARATOR PLUS BACKUP FILTER
\
FIGURE NO. 12
40
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FEDERAL CYCLE COLD START, AVG. OF 2 RUNS
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BASELINE FUEL
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ADDITIVE B
CHASSIS DYNOMOMETER
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HYDROCARBON VS MILEAGE ACCUMULATION
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FIGURE
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1
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5,000
60 mph Steady State, 2 hours
10,000
VEHICLE MILES
15,000
20,000
BASELINE FUEL
J ADDITIVE A
0 b ADDITIVE B
CHASSIS DYNOMOMETER
-------
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FIGURE NO. 15
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Baseline
Additive
Additive
Additive
Additive
FEDERAL CYCLE COLD START FEDERAL CYCLE HOT START
ENGINE STAND
-------
,60
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ENGINE STAND
FEDERAL CYCLE HOT START
-------
- 68 -
11. Examination of the particulate by the scanning
electron microscope showed differences in size distribution
and particle shape between the baseline and the two
additives tested.
B. FUEL AND ADDITIVES
The fuel used in all of the tests was Indolene 0, to which
the additives were added in the desired amounts. Table 9
is a listing of the pertinent physical and chemical data
on the base stock fuel, as well as the physical and chemical
analyses of the fuel after the additives were blended.
The additives which were used as references for the develop-
ment of the methodology are described in Table 9. Both addi-
tives were blended into the fuel in two different concen-
trations. Additive A was used at 1.87 grams/gal., which
was the level recommended by the manufacturer, and at 3 times
the recommended level, or 5.61 grams/gal. Additive B was
used at .9988 grams/gal., which is equivalent to .25 grams/gal,
of manganese. At the time of the tests, this was also the
level recommended by the manufacturer. The recommended
usage rate has since been reduced. Engine runs were
also made with 3 times the recommended level, or .75
g/gal. of manganese.
The vehicle tests were carried out using only the recommended
levels of additives, while engine dynamometer studies were
carried out with both concentrations.
C. TEST PROCEDURES
1. Engine Dynamometer
The engine was broken in according to the procedures outlined
in Section III-A 1. After break-in, the engine was run 19
-------
TABLE 9
GASOLINE ANALYSES
Gravity
1 BP
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
EP
RON
MON
RVP
Baseline
- 62.3
- 96
- 118
- 129
- 148
- 168
- 192
- 206
- 228
- 246
- 270
- 311
34
- 372
- 90.6
- 80.4
8.5
Additive A
59.6
94
124
138
157
179
200
218
238
252
278
312
342
395
90.8
80.2
8.4
Additive B
59.7
90
122
136
163
179
198
218
238
258
284
326
360
392
91.8
81.5
8.0
ppm
Trace
Metals Baseline
Fe <1
Ni <1
Cu .4
Al <1
Ca <1
Mg <3
Mn <1
Pb <3
Cr <1
Sn <2
Zn <3
Ti <1
%C 85.9
%H 14.0
%S .046
ppm P <.05
A
7
1
<.2
<1
<1
<3
<1
<3
1
<2
<3
<1
86.0
13.6
.047
.20
B
1
<1
<1
<1
<3
61
<3
<1
<2
<3
1
85
13
.3
.9
.6
.048
.11
NOTE: "Less than" means that none of the material in question was detected,
and denotes the lower level of sensitivity for atomic absorption
under the conditions of the analyses.
-------
- 70 -
hours a day, with a 5-hour shut-down period, until approxi-
mately 75 hours had been accumulated. At the start of each
19-hour segment a gaseous exhaust analysis was run to deter-
mine the point at which the engine stabilized. Based on
prior particulate loads, it was felt that in all cases, full
stabilization was reached prior to 75 hours.
The 75-hour runs consisted of repeated 23-minute Federal
cycles. These cycles were controlled by the mode monitor
system described in Section III-A 1. At the end of 75 hours,
particulate measurements were made using a single 23-minute
Federal cycle. Both cold starts (12-hour room temperature
soak period) and hot starts were run for particulate collec-
tion. The procedures used for collection and analyses are
described in Section III-B, C, and D.
The engine tests were run in the following sequence:
1. Additive A at 1.87 g/gal. See Table 10.
2. Additive A at 5.61 g/gal.
3. The engine was then disassembled, deposits were cleaned
out, new exhaust was installed.
4. Additive B at .25 g/gal. of manganese. The engine was
again dissambled, deposits were removed, and new exhaust
system installed.
5. Baseline fuel, with no additives. Engine disassembled,
deposits cleaned, and new exhaust installed.
6. Additive B .75 g/gal. of manganese
-------
TABLE 10
FUEL ADDITIVES
Name
Code
A
B
Chemical
Polybuteneamine
Methylcyclopentadienyl
Manganesetricarbonyl
Function
Deposit Modifier
Octane Improver
Use Level gm/gal
Ix 3x
1.87
0.25
5.61
0.75
-------
- 72 -
It was felt, that the baseline run would be more meaningful
if it were run at some point in the middle of the tests,
rather than at the beginning, since any changes in the engine
due to the use of the additive at 3 times the concentration
would be noted. The use of additive A at recommended levels
was not expected to have any negative effects on the engine,
while the 3x effect was unknown. Additive B, containing
an inorganic functional group, was expected to give more
engine deposits, and therefore the 3x concentration was run
last.
2. Vehicle Tests
Three 1972 Chevrolets, equipped with an automatic transmis-
sion, air conditioning, and a 350 CID engine, were used for
mileage accumulation studies for each additive and a baseline,
The additive concentrations used in the vehicle fuels were
at the manufacturer's recommended level, or .25 g/gal. of
manganese for Additive B and 1.87 g/gal. of Additive B.
All of the vehicles were operated on baseline fuel for 2,000
miles, after which the two additive cars were switched to
their respective fuels.
Blowby tests (Section III-A) were run every 1,000 miles until
it was determined that the engine had stablilized. Figures
17,18, 19 show the measured blowby at three different points
in each vehicle's life. It is apparent that all three vehi-
cles stabilized relatively quickly, with no abnormalities
showing up in the blowby results.
The vehicles were driven by Dow employees in normal driving
situations. Some care was exercised in ascertaining that
the vehicles were not driven for prolonged periods of time
above 70 mph, the maximum posted speed limit on Michigan
highways. The vehicles were periodically rotated between
drivers so that each vehicle had a somewhat similar opera-
ting history.
-------
- 73 -
Figure 17
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Figure 18
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-------
- 76 -
D. DATA
Tables 11, 12, 13 are a compilation of the data generated
during the 75-hour engine runs. The particulate measure-
ments and analyses were made on individual 23-minute Federal
cycles at the conclusion of the 75-hour conditioning. Tables
14, 14, and 16 are compilations of the data generated over
the lifetime of the vehicles under test.
E. DISCUSSION OF RESULTS
The primary purpose of this contract was to develop an engine
stand method which would determine any effect of a given
additive on the particulate phenomena noted in a yehicle
operating on fuel using that additive. The purpose was not
to determine whether the two additives under test were good
or bad. Any conclusions drawn from the data presented herein
are done so solely for the purpose of validating the proposed
method.
1. Vehicle Particulate Emissions
By approximately 17,000 miles, the vehicles began to show a
definite pattern as to the grams/mile emission measured from
each one. Figures 9 and 10 (pg. 60 & 61) show graphically
the particulate emission rate as a function of miles. Additive
B appeared to cause a substantial increase in particulate
emissions, while Additive A caused neither an increase nor
decrease compared to the baseline. The 142 mm, 1 cfm filter
-------
- "11 -
gave the most consistant results, while the Andersen impactor
plus Millipore (Figures 11 and 12) gave more scatter (pg. 62 & 63)-
2. Engine Stand Particulate Emissions
The particulate emissions measured at the conclusion of the
75-hour conditioning sequence are shown graphically in Fig-
ures 15 and 16 (pg. 66 & 67) .
The 23-minute Federal cycle is equivalent to about 7.5 miles
of driving. Therefore, 75 hours of continuous 23-minute
cycles represent only about 1,500 miles of vehicle operation.
The particulate emission increases noted using Additive B
at recommended levels in the vehicles showed up to a lesser
degree in the engine runs, as was to be expected. However,
when the additive concentration was tripled, the increased
particulate which showed up with Additive B in the vehicle
tests was duplicated in the engine runs, while the particu-
late levels of Additive A were not significantly different
from the baseline.
3. Particulate Composition
The particulate emissions generated under both the engine
and vehicle test programs were analyzed for trace metals,
C, H, N, Benzo-a-pyrene, and benzene solubles. This data
is included in Tables 11 through 16. Some significant con-
clusions from the analyses are as follows:
a. As might be expected, the manganese containing Additive
B gave particulate high in manganese. Additive B showed
a lower percentage of C, H, and N in the particulate, and
in general, lower benzene solubles, than the baseline or
the Additive A. However, in total there appeared to be more
organic particulate present using Additive B since the total
mass was larger.
-------
- 78 -
b. Additive A showed higher Benzo-a-pyrene in the particu-
late from the engine runs and from the engine deposits taken
from the vehicles, while the exhaust particulate Benzo-a-
pyrene compared to the baseline vehicle run was inconclusive.
Additive B showed lower ppm of Benzo-a-pyrene, as would be
expected since the total mass was larger.
c. In general, the analyses for C, H, and N showed wide
variations. It is difficult to make any meaningful conclu-
sion, per se, since the precision of the technique used is
so dependent on sample size, and since the sample sizes in
general were so small.
d. The carbon content of the particulate collected from
the 60 mph steady state vehicle runs decreased from 36%
to 8% for the baseline fuel over the 17,000 mile test
period/ while remaining virtually constant at around 20%
for Additive B over the same mileage. Additive A showed
an initial increase from 40% to 78% carbon, with a subse-
quent decrease to 25%. Although the carbon content decreased
for the baseline, the total particulate mass emissions under
these conditions remained relatively constant. The Additive
B mass emissions increased, while the carbon content
remained constant.
e. The correlation between the engine runs and the vehicle
tests with respect to C, H, and N analyses of the particulate
is not good. The most important factor contributing to
this is the small sample size collected under the Federal
Cycle. The steady state collection on the vehicles gave
enough sample for relatively precise analyses, but the
23 minute cycle generally produced such small amounts of
collected particulate that analytical precision was low.
No steady state collections were made on the engine runs.
-------
TABLE 11
ENGINE DYNAMOMETER TEST
ENGINE TYPE: 1972 Chevrolet 350 CID
FUEL: Indolene # 15214
Grains per Mile Particulate
Additive
Type Cone.
aseline
none
none
Conditioning
Hours
75
75
i
i
i
1
Test Mode
FCCS
FCHS
.
1
'; j
Andersen
Sampler
.1246
.0268
Millipore
Filter
.0293
.0146
: i
Andersen +
Millipore
.1539
.0414
Glass I
1 cfm
.0696
.0440
'ilter
47 mm
.0146
.0146
Run
No.
240A
240C
i
i
-------
TABLE 11 Con't.
EXHAUST GAS ANALYSIS
Run #
240 A
240 C
co2
13.0
12.9
% by
°2
1.5
1.8
Volum
N2
84.0
84.1
g
CO
.59
.38
I
H.C.
200
170
>arts pe
N02
r Millioi
NO
1100
1090
i
N0x-Nx
297
332
Exhaust
Condensate
PPM PPM
HCHO NH3
PPM HCHO
in. exhaust
i
00
o
1
-------
TABLE 11 Con't.
ANALYSIS OF EXHAUST PARTICULATE
Run #
240A
240C
Engine .
Deposits
Head
Piston toj
I. Valve
Used
Engine Oi!
Unused
Engine Oil
Fe
40
33
.6
.4
.6
.8
.000:
Ni
1.0
1.5
<.OOI
<.00<
. .005
<.oo;
<.0003
Cu
<2.5
< .4
.01
.5
.03
.05
,OOo6
Al
5
3.2
.07
1.5
.07
.07
.0001
Ca
4.5
8.3
.3
.8
1.0
4.
.0011
Mg
2.0
0.5
.4
1.5
2.0
6
1.36
%
Mn
< .2
< -2
.5
.3
.3
<.2
.0001
on Millipore
Crj Sn Zn
1.0
0.7
__
(.00]
<.oo3
.07 --
.07
.000]
.0001
<.5
<-4
.5 <
1.3,
1.0 -
.2
2.43
Filter
Ti Pb
2.0
.08
T005
?005
£005
.005
.0001
.5
^08
2.0
2.0
1.0
.4
.oooe
%c
54.21
10. 1
%H
6.28
5.16
%N
2.86
0.58
benzene
solubles
51
PPM
BAP
28
i
00
h-1
1
-------
TABLE 12
ENGINE DYNAMOMETER TEST
ENGINE TYPE: 1972 Chevrolet 350 QID
FUEL: Indolene # 15214 plus Additive A
Grams per Mile Particulate
Additive
Type Cone .
A
A
ii
l.X
l.X
l.X
3.X
3.X
3.X
Conditioning
Hours
75
75
75
75
75
75
i
I
i
i
i
Test Mode
FCCS
FCHS
FCHS
FCCS
FCHS
FCHS
j
i
:
Andersen
Sampler
.0374
.0244
.0300
.0586
.0171
.0171
Millipore
Filter
Nill
Nill
.0132
.0220
.0122
.0171
1
t
i
Andersen +
Millipore
.0374
.0244
.0432
.0806
.0293
.0342
Glass I
1 cfm
.0322
.0070
.0282
.0464
.0268
.0353
'ilter
47 mm
.0366
.0122
.0146
Run
No.
234 A
234 B
234 C
238 A
238 B
238 C
i
00
ro
1
-------
TABLE 12 Con't.
EXHAUST GAS ANALYSIS
Run #
234A
234B
234C
238A
238B
238C
co2
13.1
12.7
12.3
% by
°2
2.0
2.0
2.8
Volum<
N2
83.8
84.3
83.7
2
CO
V
.15
.03
.21
I
H.C.
155
190
160
'arts pe
N02
r MilliO]
NO .
i
N0x-Nx.
Exhaust
Condensate
PPM PPM
. HCHO . NH3
408
267
127
237
185
165
PPM HCHO
ia exhaust
i
00
u>
1
-------
TABLE 12 Con't.
ANALYSIS OF EXHAUST PARTICULATE
iii .1 .^
% on Millipore Filter
Run #
234A
234B
234C
238A
238B
238C
Engine
Deposit
Head
Piston top
I. Valve
Used
Engine Oil
Unused
Engine Oi'.
Fe
13. C
5.6
3.7
1.4
3
1.2
.6
.09
.02
..ooo:
Ni
.09
.2
.26
<.l
.009
.007
.002
.0001
<.000)
Cu
<.5
<.5
.24
.93
.056
.2
.,015
.002
.00001
Al
4.6
1.8
1.1
.4
.05
.2
.007
.0018
.OOO/
Ca
8.1
7.4
15.9
6.9
.18
.22
.02
.06
.0011
Mg
.5
.9
4.3
1.5
.2
.3
.01
.1
1.36
Mn
< .2
.4
.18
.05
.013
.008
:ooi
.0008
.0001
Cr
.02
.4
.40
.17
.01
.01
:oo7
.001
.6001
Sn
.28
<.l
.008
.03
.001
.00:
.0001
Zn
<.5
<.5
>.5
.8
.003
.5
.'065
.10
2.43
Ti
.04
.05
.22
.08
.02
,02
003
.poo/
.0001
Pb
0.1
0.2
.9
.8
.1
01
.0006
%C
16.8
38.48
37.08
-
43.3
%H
0.66
7.25
2.95
4.84
%N
__
0.92
5.70
.01
1.59
benzene
solubles
30%
67%
61%
PPM
BAP
__
r~
700
10 0
4.80
'
00
*>
1
-------
TABLE 13
ENGINE DYNAMOMETER TEST
ENGINE TYPE: 1972 Chevrolet 350 ClD
FUEL: indolene #15214 plus additive B
Grams per Mile Particulate
Additive
Type Cone .
B
B
II
II
.
:
l.X
l.X
l.X
3.X
3.X
3.X
Conditioning
Hours
75
75
75
75
75
75
Test Mode
FCCS
FCHS
FCHS
FCCS
FCHS
FCHS
Andersen
Sampler
.0440
.0195
.0171
.3740
.0464
.0366
Millipore
Filter
.0073
.0293
.0244
.1246
.0757
.0733
Andersen +
Millipore
.0513
.0488
.0415
.4986
.1221
.1091
Glass I
1 cfm
.1100
.0696
.0708
.5433
.1588
.1344
'ilter
47 mm
.0440
.0366
.0366
.5280
.1197
.0944
Run
No.
239 A
239 B
239 C
241 A
241 B
241 C
00
7
-------
TABLE 13 Con't.
EXHAUST GAS ANALYSIS
Run #
239A
239B
239C
241A
241B
24 1C
co2
12.7
12.9
13.0
12.8
12.7
12.9
% by
°2
1.7
2.0
2.0
1.9
2.2
2.0
Volum<
N2
83.7
83.8
83.7
83.8
83.9
84.2
a
CO
V. V
.81
.43
.38
.60
.35
.03
I
H.C.
390
340
345
520
465
475
'arts pe
NO 2
r Millioi
NO .
1
N0x-Nx
1040
1108
1040
1224
1138
1180
Exhaust
Condensate
PPM PPM
HCHO NH3
497
422
940
927
1061
PPM HCHO
in. exhaust
i
00
a\
I
-------
TABLE 13 Con't.
ANALYSIS OF EXHAUST PARTICULATE
% on Milllpore Filter
Run #
239A
239B
n QX-»
241A
241B
241C
Oil. Tube
Sweepings
Engine
Deposits
Head
Piston to]
I. Valve
Used
Engine Oi.
Unused
Engine Oi
Fe
8.7
1.2
1.0
3.2
1.6
2.0
.6
. .01
.5
.7
..ooo;
Ni
.15
.11
.06
.1
.07
.01
.005
.005
.02
.000^
.000 /
Cu
1.7
.59
<.l
< .08
<.08
.03
401
.02
.03
.02
CWDI
Al
1.4
.41
1.0
1.3
0.3
.2
.05
.2
.04
.05
.000 1
Ca
17.7
3.5
2.9
2.1
1.3
.15
.4
.4
.4
4
.0011
Mg
3.3
.98
.2
'.1
.1
1.2
.4
.5
1.5
6
1.36
Mn
20.2
34.1
.7
3.2
3.3
10.0
10
1.5
7.0
8
.0001
Cr
.35
.09
.1
.1
.03
.05
,001
,001
.05
.06
.OOO/
Sn
.16
.11
.
--
^ "
.OOO/
Zn
1.5
.7
.1
.08
.08
1.5
.5
.5
.6
.04
2.43
Ti
.3
.07
.02
.01
.01
.005
.005
.005
.005
.005
Pb
.5
.5
.4
.2
2
2
.09
.02
.0006
%C
29.1
28.0
13.9
16.4
18.9
%H
1.1
3.26
1.22
1.3
1.75
%N
.63
.36
1.57
1.07
1.03
benzene
solubles
25.%
23.%
on a
J U t>
5.2
10.4
9.2
PPM
BAP
83
53
If)
O U
72
28
-------
TABLE 14
CHASSIS DYNAMOMETER TEST
VEHICLE No.: 0-2547
FUEL: Indolene #15214 No-Lead 91 Octane
00
oo
GRAMS PER MILE PARTICULATE
Run #
208A
208B
208C
213A
213B
213C
218A
218B
218C
227A
227B
227C
233A
233B
233C
244A
244B
244C
250A
250B
250C
253A
253B
253C
Additive
Type Cone .
Baseline Ix
Ix
Ix
Ix
Ix
" Ix
" Ix
Ix
" Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
" Ix
Ix
Ix
Ix
Ix
Vehicle
Miles
2,886
2,886
2,886
4,250
4,250
4,250
6,517
6,517
6,517
8,592
8,592
8,592
10,739
10,739
10,739
12,642
12,642
12,642
14,792
14,792
14,792
17,051
17,051
17,051
Test
Miles
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
14,792
14,792
14,792
-
Test Mode
60 mph
FCCS
FCCS
FCCS
FCCS
60 mph
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
FCCS
60 mph
Andersen
Sampler
.0092
.1027
.1467
.1247
.1833
.0058
.1173
.0031
.2199
.0586
.0051
.0659
.1100
.0025
.1100
.0513
.0043
.0586
.0659
.0029
.0733
.13199
.13933
.00704
Millipore
Filter
.0030
.0146
.0806
.0367
.0879
.0066
.0513
.0108
.0439
.0953
.0102
.1173
.0366
.0109
.0440
.1026
.0287
.1990
.0733
.0086
.0659
.19066
.16133
.0044
Andersen +
Millipore
.0122
.1173
.2273
.1614
.2712
.0124
.1686
.0139
.2638
.1539
.0153
.1832
.1466
.0134
.1540
.1539
.0330
.1685
.1392
.0115
.1392
.3226
.3006
.01144
Glass Filter
14 7mm
.0049
.0293
.0659
.0367
.0769
.0042
.0366
.0066
.0403
.0513
.0067
.0696
.0386
.0060
.0626
.0879
.0082
.0916
.0549
.0095
.0623
.08066
.07333
.00778
, 1 cfm
47mm
None
0146
0366
0220
0219
0019
0220
0015
0146
0219
0219
0219
0293
0018
0293
0293
0043
0293
0293
0037
0219
02933
02933
00482
Run #
208A
208B
208C
213A
213B
213C
218A
218B
218C
227A
227B
227C
233A
233B
233C
244A
244B
244C
250A
250B
250C
253A
253B
253C
-------
TABLE 14 Con't.
EXHAUST GAS ANALYSIS
Exhaust
Condensate
% by Volume
Run #
208A
208B
208C
213A
213B
213C
218A
218B
218C
227A
227B
227C
233A
233B
233C
244A
244B
244C
250A
250B
250C
253A
253B
253C
CO 2
13.5
None
13.1
12.7
13.0
13.4
12.8
13.8
13.1
12.9
13.2
12.8
12.9
14.6
12.7
12.3
13.4
12.3
12.5
13.4
12.7
12.8
12.7
13.0
©2
2.7
3.0
4.1
3.8
1.45
3.3
2.25
2.8
3.2
1.9
3.2
3.2
2.0
3.1
2.8
1.7
2.8
2.1
1.3
1.7
1.6
1.9
.85
82
82
82
82
82
82
82
82
82
83
81
82
83
82
83
83
83
83
84
83
83
83
83
2
.6
.4
.2
.4
.2
.2
.9
.3
.1
.3
.8
.3
.0
.2
.4
.7
.0
.3
.1
.3
.4
.3
.38
CO
.10
.53
.03
.03
1.48
.92
.08
.90
.85
.70
1.35
.72
.10
1.10
.60
.20
.96
1.20
.28
1.40
1.33
1.15
1.88
H.C.
80
100
80
120
85
120
65
110
115
75
118
90
90
175
170
75
167
180
82.5
190
190
170
185
Parts
NO 2
65
120
300
300
7
370
48
315
160
40
240
300
33
210
per Million ppm
NO
1650
290
275
190
1300
275
2350
220
365
2600
360
125
2300
230
39
-
29
350
1680
432
NOX-NX HCHO
336
104
129
159
192
180
106
184
100
160
183
150
27
294
53
315 162
>2000 232
307 189
388 72
1793 246
481 84
260 108
275 86
1100 119
.1
.5
.8
.9
.2
.4
.0
.7
.8
.0
.0
.0
.63
.31
.58
.02
.24
.94
.4
.3
.6
.6
.7
.3
ppm
NH3
w
-
-
_
-
_
-
10.4
26.6
14.1
17.5
30.8
31.5
23.66
34.19
13.10
3.3
6.7
4.0
6.94
6.13
19.98
ppm HCHO
in exhaust
.0026
,00021
,000153
,00034
,00053
,00043
,00050
I
00
00021
-------
TABLE 14 Con't.
ANALYSIS OF EXHAUST PAKTICULATE
% on Millipore Filter
Run i
208A
208B
208C
213A
213B
213C
218A
218B
218C
227A
227B
227C
233A
233B
233C
244A
244B
244C
250A
250B
250C
253A
253B
253C
Engine Deposits
C. Chamber
I. Valve
Fe Ni Cu Al Ca Mcj_ Mn CrSta Zn Ti Pb %_C
% H
% N
benzene ppnt
Solubles BAP
2.0
1.0
4.0
2.0
0.4
2.0
.62
.53
1.4
.3
.7
.1
.8
.8
.2
.7
.3
.3
.6
1.1
.4
.15 .6
.04 .12
.04 .7
.05 .4
.03 .09
.03 .08
.1 .62
.1 .32
.1 .4
<.l .1
<.05 .2
<.005 .06
<.05 .5
<.05 .4
<.l .2
<.l .5
<.l .3
<.l .3
<.l 1.2
<.01 .03
<.01 .03
1.0
.09
.3
.4
.04
.4
.2
.1
.8
.1
.2
.05
.2
.4
.2
.4
.2
.1
.3
.09
.02
24.0
6.0
14.0
15.0
3.0
14.0
4.8
2.6
4.6
1.1
2.9
.5
6.2
5.3
2.3
5.7
1.9
2.4
4.7
.1
.1
8.0
2.0
7.0
7.0
1.8
8.0
1.13
.53
1.3
.4
.8
.2
1.0
1.1
.5
1.1
.3
.5
1.1
.9
1.8
.3
.06
.2
.14
.02
.08
.1
.1
<.04
<.04
.1
.06
.09
<.l
< .1
<.l
<.05
<.05
.1
.01
.01
.5 <.03
.09 <.05
.14 .007
.07 .07
.16 .03
.1 .1
.1 .1
<.l <.l
<.l < .1
.1 <.05
.02 <.05
.1 <.05
.1 <.l
<.l < .1
.1 <.l
<.l <.l
<.l < .1
<.l <.l
.01 .05
.01 .03
_
-
.3
.32
.5
<.3
.3
< .1
15.0
.3
<.3
.3
.4
.8
2.0
1.5
2.9
.03
.005
.03
.02
.002
.04
.1 2
.1 3
3
<.l
-------
Date: 7/9/73 - 91 -
Vehicle No. = D-2547
Fuel Used = Base Fuel No Additive
TABLE 14 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor No deposits but a very light coating
that was black in color.
Throat
Butterfly
2) Intake Manifold No deposits but black in color.
3) Exhaust Manifold Normal deposits black to gray in
color.
4) Intake Valves Back side of valve had heavy black
deposit above normal.
5) Exhaust Valves No deposit but dark brown in color.
6) Combustion Chamber Very few deposits. Surface was
dark tan to black in color.
7) Spark Plugs Very few deposits. Surface was dark tan
to black in color.
NOTES: The only thing that seemed to be abnormal was the amount
of deposit on the back side of the intake valve. Other-
wise a very clean engine.
-------
TABLE 15
CHASSIS DYNAMOMETER TEST
VEHICLE No.: D-2548 .,.,.
FUEL: Indolene #15214 No-Lead 91 Octane + Additive A
GRAMS PER MILE PARTICIPATE
Additive
±\u.n ff *jfsr*~
209A A
209B "
209C
215A
215B "
215C "
224A
224B "
224C "
236A
236B "
236C
242A "
242B
242C
245A "
245B
24 5C
24 9A
24 9B
249C "
257A "
257B "
257C
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Ix
Vehicle
Miles
3,436
3,436
3,436
5,748
5,748
5,748
7,050
7,050
7^050
9,100
9,100
9,100
10,990
10,990
10,990
13,069
13,069
13,069
15,080
15,080
15', 080
17,440
17,440
17,440
Test
Miles Test Mode
0
0
0
2,000
2,000
2,000
3,302
3,302
3,302
5,352
5,352
5,352
7,242
7,242
7,242
9,633
9,633
9,633
11,332
11,332
11,332
13,692
13,692
13,692
60 mph
FCCS
FCCS
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
FCCS
60 mph
FCCS
60 mph
FCCS
Andersen
Sampler
.0118
.0807
.1614
.1613
.1613
.0101
.0879
.0659
.0052
.1100
.0660
.0033
.1246
.0028
.0880
.0733
.0026
.1099
.1393
.0879
.0051
.19066
.00931
011733
Millipore
Filter
.0024
.0220
.0293
nil
nil
.0007
.0879
.0219
.0052
.0733
.0660
.0048
.0733
.0047
.1613
.1026
.0020
.1246
.0659
.0733
.0096
.0806
.00969
.19066
Andersen +
Millipore
.0142
.1027
.1907
.1613
.1613
.0108
.1758
.0878
.0104
.1833
.1320
.0081
.1979
.0075
.1906
.1759
.0046
.2345
.2052
.1612
.0147
.27126
.0190
.3079
Glass Filter, 1 cfm
147mm
.0054
.0513
.0623
.0660
.0440
.0066
.0806
.0513
.0068
.0476
.0550
.0090
.0535
.0099
.0586
.0843
.0094
.1099
.0659
.0659
.0079
.07333
.00833
.10633
47mm
.0024
.0220
.0293
.0440
.0220
.0077
.0366
.0219
.0026
.0220
.0220
.0022
.0146
.0244
.0293
.0439
.0026
.0439
.0366
.0366
.0031
.0220
.00349
.0366
Run #
209A
209B
209C
215A
215B
215C
224A
224B
224C
236A
236B
236C
242A
242B
242C
245A
245B
245C
249A
249B
249C
257A
257B
257C
-------
TABLE 15 Con't.
EXHAUST GAS ANALYSIS
Exhaust
Condensate
% by Volume
Run #
209A
209B
209C
215A
215B
215C
224A
224B
224C
236A
236B
236C
242A
242B
242C
245A
245B
245C
249A
249B
249C
257A
257B
257C
CO 2
13.1
14.3
None
11.9
13.1
14.1
13.1
13.5
13.5
12.5
12.2
12.4
12.6
13.2
12.5
11.9
12.4
12.7
11.0
12.7
13.1
12.7
13.07
12.9
02.
3.1
1.4
-
5.6
3.1
2.3
2.8
2.2
2.7
2.3
2.4
2.7
2.1
2.2
2.3
1.6
1.7
1.7
4.5
1.9
.8
2.2
.90
1.7
N£
82.3
83.2
-
81.4
82.2
82.7
82.4
82.8
82.8
84.2
83.7
83.9
83.2
83.9
83.2
84.5
85.0
83.3
82.4
83.3
83.6
83.6
83.4
83.5
CO
.55
.32
-
.19
.72
.04
.82
.65
.03
.03
.76
.03
1.12
.03
1.12
1.17
.030
1.38
1.25
1.24
1.65
.50
1.66
.99
H.C.
125
100
-
80
120
55
205
155
55
170
140
55
190
60
190
230
55
220
205
200
170
165
162
260
Parts per Million
NO 2
230
7.5
225
290
380
40
225
180
48
X
X
X
_
-
_
-
NO
280
2100
230
250
245
2500
300
375
3100
X
X
X
_
-
460
>2000
537
213
466
2000 T
ppm
NOX-NX HCHO
141
455
310
562
2000
614
552
>2000
618
337
519
2000 T
334
1487
385
149
136
138
65
73
126
76
-
168
127
121
340
99
197
125
130
232
137
119
109
152
97
142
56
.9
.4
.8
.4
.4
.9
.9
.8
.1
.4
.7
.3
.8
ppm ppm HCHO
NH3 in exhaust
.00013
.00007
29.2
35 .00042 '
28.0 w
25.7 '
21.8 .00047
20.4
23.4 .00014
13.5
4.6
8.8 .00039
3.5
1.2
2.8
8.3 .00030
1.9
5.9 .00020
4.5
-------
TABLE 15 Cqn't.
ANALYSIS OF EXHAUST PARTICULATE
% on Millipore Filter
Run 8
Fe
Ni
C
Al
' Ca
Mn
Cr
' Sn
Zn ' Ti
Pb
% C
% H
benzene ppm
Solubles BAP
209A
209B
209C
215A
215B
215C
224A
224B
224C
236A
236B
236C
242A
242B
242C
245A
245B
245C
249A
249B
249C
O C *T *
257A
257B
257C
Engine Deposits
C. Chamber
I. Valve
3.0
3.0
5.0
.9
2.0
.9
1.0
3.0
.6
-
.52
.96
.29
.9
.7
IT
.1
.3
.2
1.2
1.1
.06
.05
.18
.02
.03
.1
.1
.005
.0008
-
.02
.07
.02
1.7
<-|
1
<~\
. 1
<.l
.02
.35
.35
1.8
.5
.4
.4
.5
.3
.05
-
.92
1.4
.50
.4
.4
.
.3
.2
.2
.07
.4
.6
1.5
.4
.4
.3
.3
2.0
.5
.12
.28
.08
.4
.3
.2
<.l
.2
.03
21.0
21.0
71.0
8.0
5.0
3.7
3.6
9.0
10.0
-
2.6
5.9
2.0
2.2
5.2
2ft
.0
5-7
* /
1.8
1.5
.4
.3
"
8.0 .
12.0
25.0
4.0
4.0
3.8
1.1
.2
.08
-
.63
1.5
.46
.8
.9
1t\
.U
.4
<.3
.9
.2
.1
.1
.8
.05
.04
.05
.04
.1
.02
-
.03
.37
.07
<.l
".1
<*.05
<.05
.09
.02
.4
.3
.5
.1
.09
.1
.1
.3
.03
-
.09
.23
.07
<.l
!i
<.i
.01
.01
.01
.01
.2
.004
.05
.1
.1
_
-
-
.41
1.0
.29
<.l
<.l
<.l
.1
.1
.01
.05
.05
.01
.007
.6 .1
.6 .1
.5 .05
.08 .006
- -
.08
.17
.06
<.3 <.l
.5 <.l
<.3 <.l
3.0 .02
1.0 .01
<5
<4
<8
_
1.3
.05
.008
-
2.5
2.^
2.1
.3
<.3
> J
50
o
2.5
4.5
6.2
.8
39.8
33.9
50.2
35.6
78.1
27.07
20.56-
15.52
16.33
26.2
17.95
19.75
14.2
co n
OZ v
25*. 3
17.4
48.2
72.2
6.0
6.0
5.2
5.16
11.9
9.57
5.47
8.15
8.15
7.32
9.77
10.2
16.22
15 fi
!.£. O
11 Q1
J.X . y 1.
12.2
13.5
3.7
7.8
.01
5.08
2.04
2.35
.70
20.18
11.23
17.20
22.30
27.3
1 fl "\7
XO . J £,
2C.C.
D D
2.70
2.81
2.26
3.06
52
23
28
57
24.1
17.3
22
58
58
Ad
*t u
29
17
310
180
30 '
VD
140 *>
32 '
44
<50
140
127
31
3500
5500
-------
Date: 7/12/73 - 95 -
Vehicle No. = D-2548
Fuel Used = Additive A
TABLE 15 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor Clean, bare metal. No deposits or
discoloration.
Throat
Butterfly
2) Intake Manifold Clean with no deposits or discoloration
but the surface was wet with a film
coating.
3) Exhaust Manifold Light coating-of black carbon with no
buildup of deposits.
4) Intake Valves Some buildup of a black deposit that had
a gooey consistancy was present on the
back side of all valves.
5) Exhaust Valves A thin reddish coating was present on
the back side of valve while the tops
were whiteish.
6) Combustion Chamber Thin deposit brown to black in color,
Coating was equal on all cylinders.
7) Spark Plugs No deposits with a dark brown color.
Appeared cleaner than normal.
NOTES: In general it appeared to be the cleanest engine- of
the three with no heavy deposit buildup.
-------
TABLE 16
CHASSIS DYNAMOMETER TEST
I
<£>
VEHICLE No.: D-2549
FUEL: Indolene #15214 No-Lead 91 Octane + Additive B
251D
258A
258B
258C
*NOTE:
GRAMS PER MILE PARTICULATE
Additive
Run # Type
207A B
207B
207C "
216A
216B
21 6C
230A
230B
230C "
237A
237B
237C "
24 3A
243B "
243C
251A
251B
251C
Cone.
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
lx
Vehicle
Miles
3,529
3,529
3,529
6,051
6,051
6,051
8,015
8,015
8,015
10,026
10,026
10,026
11,890
11,890
11,890
14,030
14,030
14,030
Test
Miles
0
0
0
2,000
2,000
2,000
3,964
3,964
3,964
5f975
5,975
5,975
8,361
8,361
8,361
9,979
9,979
9,979
Test Mode
FCCS
FCCS
60 mph
FCCS
60 mph
FCCS
FCCS
FCCS
60 mph
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
FCCS
60 mph
FCCS
Andersen
Sampler
.0073
.1099
.0105
.2493
.0074
.2053
.0440
.0587
.0050
.0660
.0050
.0733
.0659
.0035
.1026
.0879
.0078
.1393
Millipore
Filter
.0366
.0513
.0019
.0293
.0089
.0219
nil
nil
.0192
.1026
.0465
.1100
.1833
.0362
.1833
.4913
.0905
.3960
Andersen + Glass Filter, 1 cfm
Millipore
.0439
.1612
.0214
.2786
.0163
.2272
.0440
.0587
.0242
.1686
.0515
.1833
.2492
.0397
.2859
.5792
.0983
.5353
147mm
.0623
.0586
.0071
1.444
.0202
.1026
.0807
.0807
.0196
.0953
.0265
.1633
.0953
.0218
.1539
.1796
.0412
.1759
47mm
.0293
.0293
.0023
.3666
.0124
.0293
.0367
.0367
.0132
.0513
.0166
.0880
.0733
.0132
.1173
.0953
.0282
.0953
Run #
207A
207B
207C
216A
216B
216C
230A
230B
230C
237A
237B
237C
243A
243B
243C
251A
251B
251C
lx 14,030 9,979
(New Spark Plugs)
60 mph .0034 .0386
,0420
0214
lx
lx
lx
16,407
16,407
16,407
12,356
12,356
12,356
FCCS
60 mph
FCCS
.1760
.00779
.2795
.08067
.01113
.2860
.2566
.01892
.5655
,0134
.0550 .0440
.01614 .0129
.2240 .1320
For Runs 258A and B: Air conditioner in dilution tube room was off temperature of 96°F in room.
Normal temperature of 75°F - possibility of a low particulate collection due to temperature of
dilution tube starting off above normal. Run 258C = 78°F.
251D
258A
258B
258C
-------
258A
258B
258C
TABLE 16 Con't.
EXHAUST GAS ANALYSIS
Exhaust
Condensate
% by Volume
Run #
207A
207B
207C
216A
216B
216C
230A
230B
230C
237A
237B
237C
243A
243B
243C
251A
251B
251C
CO 2
n.g.
13
14.3
13.1
13.9
13.1
12.9
n.g.
13.8
12.1
13.5
12.6
11.9
13.4
12.0
11.6
12.7
12.0
OjL
3.2
1.5
2.8
2.4
2.9
2.8
-
2.2
2.4
1.5
1.8
1.9
1.6
2.0
3.0
2.53
1.9
N*
82.2
83.1
82.3
82.7
82.3
82.1
-
83.0
83.3
84.0
83.3
82.8
83.9
82.6
82.6
83.3
83.9
CO
*
1.
-
1.
1.
2.
2.
1.
2.
7
16
82
74
74
31
03
3
17
38
88
20
45
93
45
26
H.C.
140
100
225
155
240
320
-
90
380
190
370
500
245
555
980
1354
500
Parts per Million
N02 NO
90 185
280 310
15 2000
300 300
28 625
260 250
170 250
- -
65 2800
220
2000
360
402
342
229
1660
293
NOX-NX
465
2000
440
382
2000
371
275
1639
314
ppm
HCHO
142
160
161
195
478
246
310
219
297
347.
702.
271.
173.
703.
223.
385.
337.
271.
06
29
95
83
4
51
2
8
2
ppm
NH3
20.6
23.7
53.0
26.3
35.9
23.7
23.42
60.76
18.02
3.0
14.0
3.9
251D 13.3 1.45 83.8 .48
12.7
13.0
12.1
1.5
1.15
2.1
83.4
82.8
82.9
1.48
2.18
2.04
(New Spark Plugs)
295 1862 1909
355 273
447 1170
450 261
196.7
301.2
126.2
9.59
6.79
9.09
ppm HCHO
in exhaust
.00011
.00037
,00052
,0012
,0014
0006
.00035
-------
TABLE 16 Con't.
ANALYSIS OF EXHAUST PARTICUIATE
% on Millipore Filter
Run >
207A
207B
207C
216A
216B
216C
230A
230B
230C
237A
237B
237C
243A
243B
243C
251A
251B
251C
251D
258A
258B
258C
Fe N_i Cu Al Ca Mg Mn Cr Sn Zn Ti
Engine Deposits
C. Chamber
I. Valve
10.0 .06
4.0 .06
4.0 .18
3.0 .17
10.0 .1
.22 .05
.1 <.l
.6 <.l
.7 <.l
.1 <.l
.5 <.l
.1 <.l
.03 <.01
.1 <.l
.07 <.01
.7 <.l
.3 <.l
.2 <.l
.3 <.01
1.0 .02
.3
.3
.35
.45
.10
.14
.1
.5
.3
.1
.3
.09
.02
.11
.05
.6
.2
.2
.02
.08
.4
.3
.6
.8
.02
.05
<.l
'.2
.2
<.l
.2
<.l
!02
<.l
.02
.4
.1
<.l
.06
.07
16.0
9.0
18.0
20.0
.58
.88
.5
3.2
2.3
.5
1.8
.8
.2
.9
.4
5.2
1.7
1.3
.4
.9
9.0
7.0
5.0
5.0
.30
.40
.3
1.1
.6
.2
.6
.2
.1
.2
.2
1.1
.6
.3
2.2
1.4
.6
.1
40.0
60.0
.22
25.9
12.3
11.5
4.3
14.2
7.1
1.4
5.5
2.8
8.0
6.8
26.9
4.5
11.7
4.1
.3
.2
.4
.3
.1
.05
<.l
<.l
.1
< .1
<.l
<.l
<.01
< .1
<.01
<.l
<.l
<.l
.01
.01
Sn 2n
:.oi
i:S
.1 .6
.05 .22
:!i !e
:.i .3
:!i !s
:.i .3
:.oi .1
:.i .3
:.oi .2
:.i .4
:.i .3
:.i 4.o
:.i 3.0
Ti Pb
.03
.02
.05
.05
.1 2.0
.05 3.0
3.1
<.l 3.0
<.l <0.75
<.l 2.6
-<.l 3.3
<.l 4.6
<.01 2.8
<.l 6.0
<.01 5.8
<.l 3.8
<.l 2.4
<.l 4.2
<.01 10.9
<.01 5.4
% C
97.0
<5
47.0
23.1
18.79
18.2
29.32
18.55
24.79
9.59
34.45
9.59
17.1
39.3
20.2
0.2
28.13
41.72
% H
16.7
<2
-
1.78
5.3
10.31
3.27
6.78
3.95
5.97
4.63
4.05
25.6
5.5
6.4
2.04
3.37
% N
-
3.5
1.6
2.41
.45
.77
1.93
.25
8.76
3.58
7.01
6.88
9.6
3.68
1.5
0.65
1.49
benzene
Solubles
28
32
2.4
13
38
18
20.0
11.9
35
12
19
13
38
9.5
16
ppm
BAP
25
250
4
12.5
45 1
36
00
-------
Date: 7/11/73 - 99 -
Vehicle No. = D-2549
Fuel Used = Additive B
TABLE 16 Con't.
ENGINE DEPOSITS RATING SHEET
1) Carburetor Dark gray color, clean with no deposit
buildup, considered normal.
Throat
Butterfly
2) Intake Manifold Black color, clean and dry with no
deposits, considered normal.
3) Exhaust Manifold Black color, carbon coated but dry,
considered normal.
4) Intake Valves Considerable buildup. Black deposit
was present on the back side of all
intake valves.
5) Exhaust Valves Were tan in color with a thin black
coating. There were no deposits as
such.
6) Combustion Chamber The quantity of deposits appeared
to be normal although some cylinders
had more deposits than others.
7) Spark Plugs The deposits were tan in color and below
normal in amount.
NOTES: Deposits in the combustion chamber were tan in color.
When the deposits were scraped from the piston tops,
most of the deposit or coating would come off, leaving
the bare aluminum.
Some spark plug fouling was noted.
-------
- 100 -
TABLE 17
MASS MEDIUM EQUIVALENT DIAMETER ENGINE STAND RUNS
cutoff %
Run #
239 A
239 B
239 C
241 A
241 B
241 C
240 A
240 C
234 A
234 B
234 C
238 A
238 B
238 C
Additive
B
B
B
B
B
B
Baseline
Baseline
A
A
A
Cone,
IX
IX
IX
3X
3X
3X
IX
IX
IX
IX
3X
3X
3X
Mode*
CS
HS
HS
CS
HS
HS
CS
HS
CS
HS
HS
CS
HS
HS
50%
1.5
< .5
< .5
.9
< .5
< .5
1.1
< .5
1.0
1.6
1.0
.9
.55
< .5
80%
3.7
1.4
1.0
2.3
1.0
.7
1.6
2.3
4.3
4.0
3.2
3.0
4.1
2.2
* CS = Cold Start, 23 minute Federal cycle
HS = Hot Start, 23 minute Federal cycle
All % cutoff values in microns
-------
TABLE 18
MASS MEDIUM EQUIVALENT DIAMETER VEHICLE RUNS
Baseline
Run #
208 A
208 B
208 C
213 A
213 B
213 C
218 A
218 B
218 C
227 A
227 B
227 C
233 A
233 B
233 C
244 A
244 B
244 C
250 A
250 B
250 C
253 A
253 B
253 C
Mode*
60
CS
CS
CS
CS
60
CS
60
CS
CS
60
CS
CS
60
CS
CS
60
CS
CS
60
CS
CS
CS
60
50%
1.3
.9
< .5
1.4
.6
< .5
.6
< .5
1.2
< .5
.5
< .5
.7
< .5
.7
< .5
< .5
< .5
< .5
< ,5
< .5
< .5
< .5
.55
80%
3.8
5.0
1.5
4.0
3.5
2.0
2.0
.55
3.3
1.3
1.0
1.8
2.5
< .5
2.3
2.0
< .5
1.5
1.8
.7
2.0
1.1
2.1
3.0
Run #
209 A
209 B
209 C
215 A
215 B
215 C
224 A
224 B
224 C
236 A
236 B
236 C
242 A
242 B
242 C
245 A
245 B
245 C
249 A
249 B
249 C
257 A
257 B
257 C
Additive A
Mode*
60
CS
CS
CS
CS
60
CS
CS
60
CS
CS
60
CS
60
CS
CS
60
CS
CS
CS
60
CS
60
CS
50%
1.0
.9
1.0
1.0
1,6
1.3
< .5
.8
< .5
< .5
.5
< .5
.6
< .5
< .5
< .5
< .5
< .5
.55
.55
< .5
.9
< .5
< .5
80%
4.2
2.5
3.0
2.3
3.8
3.2
1.7
3.0
2.5
1.8
1.1
3.7
2. B
1.0
1.1
2.0
2.5
2.0
1.8
2.6
.6
3.3
1.7
1.7
Additive B
Run #
207 A
207 B
207 C
216 A
216 B
216 C
230 A
230 B
230 C
237 A
237 B
237 C
243 A
243 B
243 C
251 A
251 B
251 C
258 A
258 B
258 C
Mode*
CS
CS
60
CS
60
CS
CS
CS
60
CS
60
CS
CS
60
CS
CS
60
CS
CS
60
CS
50%
< .5
.55
1.2
.7
< .5
1.1
1.3
1.2
< .5
< .5
< .5
< .5
< .5
< .5
< ,5
< .5
< ,5
< .5
.6
< ,5
< .5
80%
3.0
1.5
3.2
2.0
1.5
2.4
3,8
3.6
< .5
1.8
.5
.7
.7
< .5
1.0
< .5
< .5
< .5
3.0
1.4
2.1
I
M
O
\->
I
* CS = Federal cycle 23 minute cold start
All % cutoff values in microns
60 = 60 mph steady state, 2 hours
-------
- 102 -
4. Particulate Mass-Size Distribution
The mass medium equivalent diameter (MMED) for the engine
stand and vehicle tests are summarized in Tables 17 and 18.
Cut-off values of both 50% and 80% are used. In general,
the particulate mass-size distributions range from Additive
B, giving the smallest particles while Additive A gave the
largest, with the baseline in between. The 50% cut-off was
quite inconclusive since most 50% values fell below the
smallest measured separation (.55vi). The 80% cut-off showed
much more of a trend toward the conclusion drawn above. The
mass distribution plots are found in Appendix A, in order of
run number.
It does not appear that using the additive at 3 times the
recommended levels caused any noticeable difference in MMED.
The complete set of MMED graphs are in Appendix A.
5. Particulate Morphology as Studied by Scanning Electron
Microscope
Samples collected from the vehicles were studied using the
scanning electron microscope to determine if there were dif-
ferences in the physical or chemical nature of the indivi-
dual particles. Several conclusions were drawn, as follows:
a. Additive B tends to produce a very fine particle size
with no evidence of flakes, rods, crystals, or flower-like
material.
b. The base fuel tends to produce more spherical particles
and little crystalline or rod-like material.
c. Additive A tends to produce more crystalline material,
porous rod-like material, and flower-like clumps.
d. A flake-like material, never previously encountered in
exhaust particulate photographs, was observed in the base
fuel and with Additive A.
-------
- 103 -
e. The particulate encountered using Additive A was high
in sulfur, while Additive B gave particulate high in manganese.
The data reported as a result of the SEM work must be con-
sidered incomplete because of a lack of individual particu-
late identification. In order to chemically identify the
individual particles and correlate chemistry with morphology,
it is essential that the material be collected on a substrate
that will interfere neither with the chemical nor morpholog-
ical analyses. The most appropriate substrate for use in
the Andersen sampler is thin, flat, polished, and pure graph-
ite. Unfortunately, the irregular topography of the graphite
substrates used prevented the measurement of representative
particle morphology. As a consequence, the morphological
studies were carried out on Au-Pd coated particulate collected
on glass cover slips which precluded accurate chemical anal-
yses. The chemical analyses were carried out on aggregates
of particles scraped from the collection plates onto the
graphite substrates, a process which prevents chemical identi-
fication of individual particles.
The complete results of the qualitative chemical analyses
of the aggregates of particulate are summarized in the at-
tached table and the predominant differences in chemistry
are as follows:
TABLE 19
Element Base Fuel Additive A Additive B
Pb high none high
Br low none none
Zn none low low
Ca low low low
S low high low
Mn none low high
-------
- 104 -
The data implies that Additive A somehow reduces or eliminates
Pb from the auto exhaust particulate, since the base fuel
in all series contained Pb. The Additive B does not produce
this effect. Br was only found in the base fuel particulate.
Both additives lead to low Zn content in the particulate
(none in base fuel particulate). Additive A gives particulate
relatively high in S, while Additive B produces particulate
high in Mn. Mn was not found in the base fuel particulate
and was only present at a low level in one other sample.
The only difference in chemistry between plates would appear
to be a slight tendancy for higher concentrations of some
elements (Si, S, Ca) to be found in the particulate on Plate 5
(pg 110,111,112). Another nebulous effect is an apparent in-
crease in Pb and S when progressing from a cold to a 60 mph start,
The morphological variations are so large within a particu-
lar sample that it is somewhat hazardous to compare samples
and generalize. The scanning electron micrographs are at-
tached and documented in Figures 20 through 33. Compared
to the base fuel sample Additive A appears to produce more
crystalline material, more of the porous rod-like material,
and perhaps more of the flower-like clumps. The base fuel
sample appears to produce more spherical particles and some
crystalline or rod-like material. The 60 mph steady-state
baseline exhibits a small particle size with a relatively
uniform particle distribution. Additive A and the baseline
both contain some thin, flake-like material not previously
encountered. The series of Additive B samples exhibit a
finer particle size than the baseline or Additive A with
no evidence of flakes, flower-like material, crystalline
material, or rods. Additive B Federal cycle cold start par-
ticulate appears more electron-transparent than the other
samples.
-------
- 105 -
Figure 20
Baseline, Cold Start, SOOOx
Plate 2, Andersen Separator
Figure 21
Baseline, Cold Start, SOOOx
Plate 2, Andersen Separator
-------
- 106 -
Figure 22
Baseline, Cold Start, 2000x
Plate 2 Andersen Separator
Figure 23
Baseline, Cold Start, 2000x
Plate 2 Andersen Separator
-------
- 107 -
Figure 24
Additive A, Cold Start, 2fiOOx
Plate 2 Andersen Separator
Figure 25
Additive A, Cold Start, 2000x
Plate 2 Andersen Separator
-------
- 108 -
Figure 26
Additive A, Cold Start, 10fOOOx
Plate 2 Andersen Separator
Figure 27
Additive A, Cold Start, 10,00Ox
Plate 2 Andersen Separator
-------
- 109 -
Figure 28
Additive A, Cold Start, 10,000x
Plate 2 Andersen Separator
-------
- 110 -
Figure 29
Additive B, Cold Start, 200Ox
Plate 5 Andersen Separator
Figure 30
Additive B, Cold Start, 10,000x
Plate 5 Andersen Separator
-------
- Ill -
Figure 31
Additive B, Cost Start, 2000x
Plate 5 Andersen Separator
Figure 32
Additive B, Cold Start, 2000x
Plate 5 Andersen Separator
-------
- 112 -
Figure 33
Additive B, Cold Start, SOOOx
Plate 5 Andersen Separator
-------
- 113 -
VI. FUEL ADDITIVE SURVEY
Part of the effort in this contract involved a study of the
trends which might be apparent concerning the type and usage
rate of future fuel additives. Bay refineries, Leonard
Oil Co., American Oil, Phillips Petroleum, and Union Oil
Co, were contacted in April, 1972, and the subject of new
additives was discussed in detail. In addition, a survey
of the available current literature was made. Most sources
were quite reluctant to discuss additives other than those
currently available, in any but the most general terms.
It appears that most research in this area is guarded
quite closely, since any development of a new additive can
be of more benefit to the developer if it remains propri-
etary as long as possible. Questions concerning trends of
future additive research were invariably met with the
response "we really don't know".
Following is a summary of discussions on currently used
fuel additives, segregated by functionality of the additive.
None of the companies contacted were willing to speculate
on the future of antiknock additives, assuming that lead
alkyls will be prohibited. No discussion of antiknocks
is made for that reason.
A. DYES
Dyes have for years been added to gasoline at the recommen-
dation of the Surgeon General. The color serves as a warning
that the gasoline contains lead. Oil soluble solid dyes
are generally azo compounds and amino and oxygenated aro-
matics, such as benzene, naphthalene or anthracene deriva-
tives. Thus, other than carbon and hydrogen, the only other
-------
- 114 -
elements present in gasoline dyes are oxygen and nitrogen.
Liquid dyes are currently becoming more popular because of
their ease of handling in automatic in-line gasoline blending.
We are not familiar with the chemistry of liquid dyes but
believe that they are quite similar to the solid dyes. Dyes
are added to gasoline at the 1-6 ppm range. Suppliers are
Morton Chemicals, Du Pont and Ethyl. Some examples are
Du Pont Red B Liquid and Du Pont Orange Liquid. In the
future dyes may well be used to a lesser extent than they
are currently. In an EPA proposal for removing lead from
gasoline (Federal Register, February 23, 1972) refiners would
be required to supply by 7/1/74, an unleaded gasoline which
contains no dye. Even though dyes are expensive, people
in the petroleum industry, especially those in Marketing
and Transportation, have gotten accustomed to having gasoline
dyed. The color is helpful as a means to distinguish between
the different grades of gasoline and midbarrel products.
Thus, barring legislation against them, dyes will probably
continue to be used.
B. ANTIOXIDAHTS
Other than lead alkyls, antioxidants were the first addi-
tives used in gasoline. Antioxidants became necessary when
cracking methods were introduced into refining. Olefins,
which are formed during the cracking process, are suscep-
tible to liquid-phase oxidation. One of the products of
the oxidation process is an insoluble gum. The gum can clog
fuel filters and lines, carburetor jets, intake manifolds,
and valve ports and can add to intake valve tulip area de-
posits. As this oxidation takes place via a free radical
mechanism, materials which donate a hydrogen atom can ter-
minate the formation of the intermediate peroxy radicals.
-------
- 115 -
Thus aromatic amines and phenols are good gasoline anti-
oxidants. The most commonly used materials are N,N'-di-
sec-butyl-p-phenylenediamine, N-n-butyl-p-aminophenol, and
2,6-di-tert-butyl-4-methylphenol. Antioxidant dosages range
from 8-40 ppm. The phenylenediamine type inhibitor is pop-
ular because it also acts as a catalyst for sweetening gaso-
line. Over the years the percentage of olefins in gasoline
has decreased and thus the amount of antioxidants required
has decreased. However, as the olefin content has gone down
the percentage of higher octane aromatics has gone up. Aro-
matics can also form peroxides. Although the aromatic per-
oxides do not contribute to gum formation, they do react
with the lead alkyls. The result is hazy fuel and sometimes
precipitates of lead salts. Thus antioxidants are still
required, although at lower concentrations than for gum pre-
vention. In the future as lead alkyls are removed from
gasolines, the need for antioxidants will be even less.
There are many suppliers of antioxidants such as Du Pont,
Hercules, Productol, Ethyl, Koppers, Shell, and Eastman.
C. METAL DEACTIVATORS
Trace quantities of metals in gasoline, especially copper,
catalyze the oxidation of the fuel. As little as 0.1 ppm
copper can be troublesome. Copper gets into the gasoline
through either a copper sweetening process or merely from
copper or brass fittings used in refining and distribution.
Copper can be deactivated by the use of a chelating agent.
The most common chelating agent is N,N'-disalicylidene-
1,2-diaminopropane. This material is sold by several addi-
tive suppliers under as many different trade names. Examples
are Du Pont DMD-2, Ethyl MDA, Tretolite Kuplex 60, and East-
man Tenemene 60. Another metal deactivator which is used
is Du Pont Metal Suppressor, a carboxylic acid salt of
-------
- 116 -
1-salicylalaminoquanidene. Metal deactivators are used at
concentrations of 1-12 ppm in conjunction with antioxidants.
Many refiners no longer use metal deactivators, as the trace
metals content of their gasolines may be below the level
necessary to act as a catalyst. Also, as with antioxidants,
as the olefins content of gasoline decreases, the need for
a metal deactivator diminishes.
D.. SURFACE-ACTIVE AGENTS
Surface-active agents (surfactants) are the newest type of
additives to be used in gasoline. At very low concentra-
tions these additives can prevent fuel system corrosion,
prevent and remove carburetor deposits, prevent and remove
intake manifold deposits, and prevent carburetor icing.
1) Rust Preventing Additives
Extremely low concentrations of certain surfactants are very
effective in preventing corrosion in wet gasoline systems.
Water, the result of tank breathing, is almost always present
in gasoline terminal storage tanks, gas station tanks and
vehicle fuel tanks. Materials which contain a polar group
and a long hydrocarbon chain can be absorbed in a close-
packed monomolecular layer on metal surfaces. If the film
is impervious to water, then rust protection is achieved.
Carboxylic acids, alcohols, amines, sulfonates, and phos-
phoric acid salts of amines are all effective rust inhibitors,
Commercial rust inhibitors include Du Pont AFA-1, Apollo'
PRI-19, Nalco 5400, Vanderbilt Nasul LP, Tretolite Tolad
T-245, UPO Unicor PL, Edwin Cooper Hitec E-534, and Lubrizol
541. These surfactants are quite effective in the range
4-40 ppm. As it is almost impossible to completely elimi-
nate water from liquid fuel systems it is most likely that
the use of surfactant type rust inhibitors will continue
for some time.
-------
- 117 -
2) Gasoline Detergents
Some surfactants are very effective in preventing and removing
deposits which form in the throttle bore area of a carburetor.
Such deposits have been a problem since the widespread use
of 2-barrel carburetor V-8 engines began in 1955. In current
automobiles with their many emission control devices the
accumulation of deposits has become even more severe. Deter-
gent additives have been in use for almost 20 years. The
most effective ones are amines and amine phosphate salts.
Extensive research efforts have been directed toward finding
more effective detergents. The recent trend has been to
higher concentrations of polyamine materials. Unless legis-
lation forces the removal of nitrogen containing additives
from use in gasoline, it appears that because these types
of additives are so effective they will continue to be used.
Current highly effective detergent additives include: alkyl
amine phosphates, e.g. Du Pont DMA-4, Ethyl MPA-90, and Gulf
Agent 724; alkyl amines, e.g. Union Oil NR-76, Enjay Para-
dyne 55, and Humble HTA-71; polybutene polyamines, e.g. Amoco
575, Lubrizol 8101, and Oronite OGA-472. Detergent concen-
trations range from 15 to 150 ppm.
3) Intake Manifold Deposits
Some surfactants, primarily the high molecular weight polymer
dispersants, are effective in preventing and removing intake
system deposits. In this case the cleaning action of the
surfactant is not a result of coating the metal surface but
appears to be the result of softening the deposits so that
they then slough off. A more effective means of removing
and preventing the formation of these deposits is through
the use of an effective dispersant plus a high concentration
(0.05-0.5 volume %) of a low volatility lubricating oil.
In this case the dispersant softens the deposits and the
top cylinder oil serves as a flux to "wash" the metal surface
-------
- 118 -
clean. Examples of dispersant gasoline additives are:
Lubrizol 580 and 8101, Enjay Paradyne 501,.Amoco 575, and
Oronite OGA-472. In the past two years there has been a
trend towards the use of dispersant additives and a smaller
yet significant trend towards the use of top cylinder oils.
4) Deicing Additives
Two types of icing occur in automobiles; freezing of water
in the fuel and carburetor icing. Ice formation in the fuel
can be eliminated through the use of freeze point depressants
such as alcohols, glycols or dimethylformamide. These mater-
ials are added to the gasoline. However, because they are
more soluble in water they move into the aqueous phase and
lower its freezing point. Freeze point depressants are used
at concentrations up to 2 volume %.
Carburetor icing occurs in cool, damp weather when moisture
in the air freezes on metal surfaces in the carburetor throat
and on the throttle blade. Stalling because of carburetor
icing can be reduced through the use of surfactant additives.
Such materials coat the throttle plate and carburetor walls
so that ice crystals will not adhere. The surfactants can
also interfere with ice crystal growth causing a snow-like
ice which is easily blown off of the metal surfaces. Effec-
tive surfactant deicers included Du Pont DMA-4 and Ethyl
MPA-90. These deicers are effective in the 20-100 ppm range.
Because engines in late model cars are designed to heat the
intake air rapidly, the problem of stalling because of car-
buretor icing will not be as critical in the future as it
has been in the past. Thus, additives which function only
as deicers will probably not be used much in the future.
E. "CANNED" ADDITIVES
"Canned" additives, those which are offered for sale in
service stations and retail stores, are a multi-million
-------
- 119 -
dollar per year business. Though many of these additives
claim reduced pollution, increased mileage, higher horse-
power, etc., in most cases these claims are unfounded. The
majority of "canned" additives are top cylinder oils or sol-
vents or both. Those which contain surfactant materials
are similar to the additives mentioned above, although gen-
erally surfactants, if present at all, are present at ex-
tremely low concentrations. However, because there is obvi-
ously a market for these additives, it seems reasonable to
assume that their use will continue.
F. 2-CYCLE ENGINES
Lubrication of 2-cycle engines takes place via the gasoline.
Therefore, gasolines for 2-cycle engines contain the lubri-
cating oil additives. These additives are a combination
of materials which consist mostly of either a calcium sul-
fonate or amine-type dispersant. Examples are Lubrizol 981
and Oronite 340K, respectively. The concentration of lubri-
cating oil in gasoline varies from 2 to 4 percent. The con-
centration of additive in the gasoline is in the 0.1 to 0.4
percent range. Because of recent water pollution legisla-
tion the lubricating oil concentration will soon be reduced
to 1%. Also in the future the calcium sulfonates may be
replaced altogether by the amine-type ashless dispersants.
G. SUMMARY AND CONCLUSION
Extensive research efforts by several companies over many
years have resulted in the gasoline additives which are
currently in use. Research is continuing in an effort to
find even more effective additives. However, current tech-
nology still indicates that the amine, amine phosphate and
amine polymer surfactants are the most effective additives
for controlling many of the problems associated with today's
internal combustion engines. As new applications for addi-
tives are sought possibly a new and different type of addi-
tive will be found. An example of a new use for additives
-------
- 120 -
is Humble's HTA-71. This additive is claimed to control
surge, a problem which is becoming more common in today's
leaner running engines. Here again HTA-71 is an alkyl amine
surfactant. Thus for the naturally aspirated internal com-
bustion engine, we believe that gasoline additive types
currently in use will remain in use for some time.
-------
- 121 -
VII. CONDENSATE COLLECTION AND ANALYSES
A modification to Contract 68-01-0332 included the genera-
tion and collection of exhaust gas condensate samples for
use in biological studies. The condensate was collected
and analyzed using techniques discussed in Sections III-C,
and III-I 7 a,b, respectively. A 1972 350 CID Chevrolet
engine was used. This engine had previously been broken
in and operated on continuous 23-minute Federal cycles.
The conditions of operation for the collection of the con-
densate samples was identical to that used for the particu-
late studies. Half of the samples were taken using both
cold start and hot start 23-minute cycles, while half were
taken at 60 mph steady-state conditions. The runs were made
using the Indolene baseline fuel and fuel containing 1.87
g/gal. of Additive Af and .25 g/gal. of Additive B, based
on manganese. Standard gaseous analyses were made, as well
as particulate measurements and analyses. The condensate
analyses data is reported in Table 20, and the particulate
data is in Table 21. Mass size distribution is shown in
Figures 34 through 39.
The samples were sent to the University of Nebraska
for use in animal health studies.
-------
TABLE 20
ECHO and NH3 Analyses of Exhaust Condensate
Sample #
98G
99G
100A
100B
100C
100D
100E
100F
100G
100H
1001
101G
102G
103A
103B
103C
103D
103E
10 3F
103G
103H
1031
104G
107A
107B
107C
107D
107E
107F
107G
107H
1071
108G
Additive
none
none
none
none
none
none
none
none
none
none
none
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
OGA-
472
472
472
472
472
-472
472
-472
-472
-472
-472
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
CI-2
Test Mode
FCCS
60 mph
FCHS
60 mph
FCHS
60 mph
FCHS
FCCS
60 mph
FCHS
60 mph
FCCS
60 mph
FCHS
60 mph
FCHS
60 mph
FCHS
60 mph
60 mph
FCHS
60 mph
FCCS
60 mph
FCHS
60 mph
FCHS
60 mph
FCHS
60 mph
FCCS
60 mph
FCHS
ppm HCHO
453
263
340
252
434
352
349
385
304
403
315
226
351
330
274
403
278
209
334
195
420
295
437
441
472
345
498
402
422
616
465
541
414
ppm NH3
10.4
15.6
12.0
12.8
13.6
15.8
8.4
12.0
12.0
12.0
11.6
6.8
7.2
10.0
12.0
8.4
11.2
11.2
9.2
'9.6
8.8
11.6
7.6
12.0
13.2
15.2
13.6
14.4
16.0
14.4
17.6
14.4
13.6
Run #
254A
254B
255B
255A
to
N)
256A
256B
-------
TABLE 21
ENGINE DYNAMOMETER TEST
ENGINE TYPE: 350 CID Chevrolet
FUEL: Indolene 0, 91 Octane
GRAMS PER MILE PARTICIPATE
Additive
Run # Type
254A
254B
255A
255B
256A
256B
none
none
OGA-472
OGA-472
CI-2
CI-2
Cone. Test Mode
1.87
1.87
.9988
.9988
g/gai
g/gal
g/gai
g/gal
FCCS
60 mph
60 mph
FCCS
FCCS
60 mph
Anderson
Sampler
.1833
.0149
.0099
.2933
.1687
.0185
Glass
Filter
.1613
.0026
.0116
.2200
.1687
.0270
Anderson +
Glass
.3446
.0175
.0215
.5133
.3373
.0465
Glass Filter, 1 cfm
142 mm
.1797
.0162
.0195
.3399
.1760
.0291
47 mm
.0513
.0041
.0050
.1332
.1613
.0110
Run #
254A
254B
255A
255B
256A
256B
N)
CO
-------
TABLE 21 Con't.
EXHAUST GAS ANALYSIS
Exhaust
Condensate
% by Volume
Run #
254A
254B
255A
255B
256A
256B
CO 2
10.0
9.9
10.0
10.0
9.9
9.8
22
6.1
6.9
6.8
6.2
6.5
6.9
82.3
82.3
82.2
82.2
82.3
82.2
CO
.64
.03
.03
.76
.42
.08
Parts
H.C. NO2
130
70
70
250
150
100
per Million
NO NOX-NX
726
1100
1400
1027
873
1080
ppm
HCHO
453
263
226
251
437
414
ppm ppm HCHO
NHs in exhaust
10.4
15.6
6.8
7.2
7.6
13.6
-------
TABLE 21 Con't.
ANALYSIS OF EXHAUST PARTICULATE
% on Millipore Filter
Run t
254A
254B
255A
255B
256A
256B
Fe Ni Cu
.8 <.]
.5 <.]
.6 <.]
.6 <.]
.2 <.]
.1 <.]
L .3
L .2
L .3
L .1
L .1
L .06
Al
.4
.2
.3
.1
<.l
<«1
Ca
2.6
2.6
3.0
1.1
1.5
.7
Mg
.7
.6
.7
.3
.3
.1
Mn Cr
.4 <.l
.03 <.l
.02 <.l
.05 <.l
6.0 <.l
4.2 <.l
Sn Zn Ti
<.3 1.7 <.l
<.3 1.0 <.l
<.3 1.0 <.l
<.l 0.4 <.l
<.l 0.7 <.l
<.l 0.8 <.l
Pb
1.2
1.8
1.5
0.2
0.3
<.3
% C
19.37
18.74
15.74
11.78
12.28
24.30
% H
5.5
8.9
6.1
6.5
4.3
9.9
benzene ppm
% N Solubles BAP
4.4
3.5
3.7
3.2
2.8
4.2
420
50
82
2400
795
160
1
M
M
Ul
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES ..or IN .»... .
40
c
o
i.
o
t.
ra
D-
KEUFPEL ft ESSCR CO.
10 "-9' 99.9 99.8 99 98 95 90 80 70 60 50 40 > 1 20 10 5 21 0.5 0.2 0.1 0.05
p - 1 - -1 r-T TTT T 1 ! 1 1 1 1 1 1 1 t 1 1 1 1 1 r I , , ' 1 1 1 1 1 1 - ' 1 1 . '. 1 i 1 r- ^^ 1-^ 1 1 1 i 1 i 1 1 1 1 1 1 r^ 1 1 1 1 i
9...
8
7
6
5
4
3
9
1
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n No,,
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fffe
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I " jj-i
rhiffi
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BUTION
34
254A
i
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te fe HI ask s^
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E;E;EEE* = :=-^::|:r..||^r
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H- -tt1; r::ti"' tttlt tTlT HPT| p I!
% Total in Particles of Diameter
^
-------
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9 ,
8
7
6-
5
4
3
V)
O
E
A «
a
. 5-_
J_
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99.99 99.9 99.8 99 98 95 90 80 70
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No
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1
0.1 0.2 0.5
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35
. 2f
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1
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54B
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% Total in Particles of Diameter
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES MAOC IN u.i.«. .
KEUFFEL & ESSER CO.
to
o
o
r
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O
+J
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0)
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1-
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Q.
0.2 0.1 0.05 0.01
MASS DISTRIBUTION
Figure 36
Run No. 255A
Total in Particles of Diameter
-------
mm mm mm
^^^^OA^? ^W^ffBKBIUI^^^^^
rVS X 2 LOG CYCLES
543
X 2 LOG CYCLES HADC IK U.S.A. .
KEUFFEL ft ESSER CO.
0.01
o
S-
u
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£
«
a
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r-
s-
D.
M
VD
1.
0.01 0.05 0.1 0.2
99
99.8 99.9
99.99
-------
13
X Z LOG CYCLES ..DC ,* .].«.
KEUFFEL * ESSER CO.
10
8. .
7
6
5
4
3
9
1
. 8.
. 7 .
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* *-
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99.99 99.9 99.8 99 98 95 90
=
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No.
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38
256A
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1
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% Total in Particles of
' ! 1 ' . M 1 M l!l 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 t 1 1 1 1 1 1
0
r
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t
^
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c
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o
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E
Q
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES HADE in U.S.A. .
KEUFFEL ft ESSER CO.
10
9
8
7
6.
5.
4
3
9
1 .
. 7
. 5...
. 3
2
. 1
99.99 99.9 99.8 99 98 95 90
L_l 1 1 1 I .'II II 1 1 1 l 1 1 II 1 M II i . 1 1 1 1 1 1 . n-h
i
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% Total in
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10
20
30 40 50 60 70
80
90
95
98 99
99.8 99.9
99.99
-------
APPENDIX A
-------
K.W- PROBABILITY 46 8O43
V£ X 2 LOG CYCLES HADE IN U.S.*. .
KEUFFEL ft ESSER CO.
in
9. .
8
7.
6.
5
4
3
to
C
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99.99 99.9 99.8 99 98 95 90
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LT " "TT 1
% Tot
1 ! 1 1 . .-1 1,1
80
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al in
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70 60
w
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(/
1
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Diameter
-------
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° .7
o
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. 2 J
Kt«S PROBABILITY 46 8O43
£ X 2 LOG CYCLES «ADE IN U.S.A. .
KEUFFEL ft ESSER CO.
99.99 99.9 99.8 99 98 95 90 80 70 60
'-
1
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% Total in
so
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mrH
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7
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20
= ::::::
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T :i;3
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5
. J J !
Particles of Diameter
-------
PROBABILITY
X 2 LOG CYCLES
46 8O43
MADC IN U.S.A.
KEUFFEL & ESSER CO.
0.5 0.2 0.1 0.05 0.01
I
U)
!
001 0.05 0.1 0.2 0.5 1 2
99
99.8 99.9
99.99
-------
K.
B
46 8043
MADE IN U.S.A.
KEUFFEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
99.99
0.2 0.1 0.05 0.01
c
o
t-
u
O
l_
E
-------
M-
PROBABILITY
99.99
46 8043
X 2 LOG CYCLES »ADE in U.S.A.
KCUFFEL & ESSER CO.
0.01
co
I
001 0.05 0.1 0.2 0.5 1
98 99
99.8 99.9
99.99
-------
_K»
£
99.99
CO
C
o
i.
-------
K-C PROBABILITY 46 8O43
V£ X 2 LOG CYCLES .ADI IN u.s.n. .
KEUFPEL » ESSER CO.
m 99.99 99.9 99.8 99 98 95 90 80 70 60
" 1 1 l=i^=d==fc=i==g=t=====t=====i==i= = S}4=3₯===:^S=^== = = = == = =
9.
8
7.
6.
5
4-
3
to
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r-
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J-
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+J 1
-------
PROBABILITY
X 2 LOG CYCLES
99.99
I/)
c
o
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o
0)
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d)
E
(O
S-
-------
K(g PROBABILITY 46 8O43
£ X 2 LOG CYCLES HADE IN U.I.A
KCUFFEL ft ESSER CO.
in 99.99 99.9 99.8 99 98 95 90 80
i-uiivii ii i i I mill I'll i -;-t i i i 1 1 |TrrtriitH-t^j
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% Total in Particles of Diameter ! 1
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2 5 10 20 30 40 50 60 70 80 90 95 98 99 99.8 99.9 99.99
10
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8
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4
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8
7
6
5
4
3
2
1
-------
99.99
c.
o
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£
to
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<0
O-
PROBABILITY 46 8O43
X 2 LOG CYCLES HADE IN U.S.A.
KEUFFEL ft ESSER CO.
0.05 0.01
MASS DISTRIBUTION
Total in Particles of Diameter
-------
IWdtS PROBABILITY 46 SO43
y\vS X 2 LOG CYCLES .ADC IN U.S.A. .
KEUFFEL. & ESSER CO.
,n 99.99 99.9 99.8 99 98 95 90 80 70
8.
7
6
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3B
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1
60
50
P - - 1
1
40 30
1
I
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Particles
1 i ' ' ' ' i ' i i ' U
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f
i
of
k
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20
rn
jlW:::::
ft
10
m
.1
^ : 1 1 !
Diameter
-------
PROBABILITY
X 2 LOG CYCLES
46 8O43
MADE IN U.S.A.
KeUFPEL a ESSER CO.
10
9
8
7
6. .
5
4
tide Diameter (D), microns
I [- f» W
1 r r r r 1 1 !
-^ 3
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES M,DE IH u.l.».
KEUFFEL & ESSER CO.
10
9. .
8
7.
6.
5-
4 I
3
C
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1
99.99 99.9 99.8 99 98 95 90 80 70
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% Total in Particles of Diameter
-------
10
9. .
8
7
6
5.
4
rticle Diameter (D), microns
- f» «»
r r r r r 1 J
TO
°- .4
. 3
2 '_
. i
KC PROBABILITY 46 8O43
£ X 2 LOG CYCLES -.or in u.i.«. .
KEUFFEL » ESSER CO.
99.99 99.9 99.8 99 98 95 90 80 70
L
1
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T--J-J- {
>.!.
001 0.05
MS!
...
F
D
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S
t
i
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i
TRIB
No.
~ tf -
T"
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TT
"T-
iji
1 -r - -
0.1 0.2 0.5 1
UTION
215B
m
i
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1 i
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L
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1
i
I
% Tota
2 _
U_ L
1 in F
It! 11 1
60
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iii iii i
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99 98 95 90 80 70 60 50 40 30 20
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KC PROBABILITY 46 8O43
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KEUFFEL ft ESSER CO.
10
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20
30 40 50 60 70 80
90 95
98 99
99.8 99.9
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-------
PROBABILITY
X 2 LOG CYCLES
46 8O43
.ADC IN U.,.A.
KEUFFEL ft ESSER CO.
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K_^ PROBABILITY 46 SO43
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KEUFFEL & ESSER CO.
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0.01
MASS DISTRIBUTION
Total in Particles of Diameter
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2 LOG CYCLES »»oe IN U.S.A.
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99 98 95 90 80 70 60 50 40 30 20
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K_«- PROBABILITY
v£ X 2 LOG CYCLES
46 8O43
MADE IN U.S.A.
KEUFFEL ft ESSER CO.
10
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PROBABILITY 46 SO43
X 2 LOG CYCLES N.DE m u.l.t. .
KEUFFEL & ESSER CO.
10
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-------
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PROBABILITY
46 8043
X 2 LOG CYCLES M.ot in U.S.A.
KEUFPEL & ESSER CO.
99.9 99.8
99 98
95 90
80 70 60 50 40 30 20 10
1 0.5 0.2 0.1 O.OS 0.01
10
MASS DISTRIBUTION
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PROBABILITY 46 8O43
X 2 LOG CYCLES ».DI .» u.s... .
KEUFFEL ft ESSER CO.
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6
5
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meter (D), microns
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K.P PROBABILITY 46 8O43
V£ X 2 LOG CYCLES M.DE IN U.S.A. .
KEUFFEL & ESSER CO.
99.99 99.9 99.8 99 98 95 90 80 70 60 50 40
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I
1
1
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*£ X 2 LOG CYCLES M.OE
DON u.s... .
KEUFFEL & ESSER CO.
10
9
8
7
6
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99.99 99.9 99.8 99 98 95 90 80 70
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234A
T~i~rT| I
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i
% Total in Particles of Diameter
-------
K.C PROBABILITY 46 8O43
*£ X 2 LOG CYCLES M.of IN U.S.A. .
KKUFPEL ft ESSER CO.
,n 99.99 99.9 99.8 99 98 95 90 80 70 60
9. .
8.
7. .
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in Particles
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mt
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of
1 1 I I 1
2
20
y
10
i
Diameter
-------
X 2 LOG CYCLES
KEUFFEL & ESSE
.ot IH u >.«.
10
9
8
7
6
5.
4
3
9
1
09
08.
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0.01 0.05 0.1 0.2 0.5 1 2
10
20 30 40 50 60 70 80 90 95 98 99
99.8 99.9
99.99
-------
PROBABILITY
46 8O43
99.99
to
c
o
o
p-
E
&
o
©
o
t-
(3
D.
X 2 LOG CYCLES »,D[ ,. U.S.A. .
KEUFCEL & ESSER CO.
O.OS 0.01
MASS DISTRIBUTION
Total in Particles of Diameter
-------
3BABILITY 48 8O43
X 2 LOG CYCLES IKDF to u.l.«. .
KEUPPEL & ESSER CO.
10_ 99.99 99.9 99.8
99 98
95 90
80 70 60 SO 40 30 20
10
1 0.5 0.2 0.1 O.OS 0.01
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6.
5
3
9
1
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08
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-------
PROBABILITY 48 8O43
X 2 LOG CYCLES MADE IN u.i...
10
9_
8
7.
6
5. .
4
3
to
c
o
fc «-J
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% Total in Particles of Diameter
-------
10
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6.
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K.C PROBABILITY 46 8O43
*£ X 2 LOG CYCLES «,ot IN u.l.«. .
KEUFFEL a ESSER CO.
99.99 99.9 99.8 99 98 95 90 80 70 60 50 40 30 20 10 5
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1
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236A
1
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% Total in Particles of Diameter
-------
46 8043
MADE Itt U.S.A.
KEUFFEL ft ESSER CO.
PROBABILITY
X 2 LOG CYCLES
10
9
8
7.
6
4
3
to
O
b *-\
r
E
«l
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at
4-1 1
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99.99 99.9 99.8 99 98 95 90
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001
0.05 0.1 0.2 0.5 1 2
10
20 30 40 50 60 70
80
90 95
98 99
99.8 99.9
99.99
-------
PROBABILITY
46 8O43
X 2 LOG CYCLES HADE IN U.I.A. .
KEUFFEL & ESSER CO.
99.99 99.9 99.8
I MB
99 98
95 90
80 70 60 50 40 30 20 10 5 21 0.5 0.2
0.01
1
001 0.05 0.1 0.2 O.S 1
98 99
99.8 99.9
99.99
-------
J/^^wf
X 2 LOG CYCLES
KEUFFEL ft ESS
8
MADE IN U.S.*.
99.99
0.01
in
c
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O
s-
10
001 0.05 0.1 0.2 0.5 1
98 99
99.8 99.9
99.99
-------
K
w
PROBABILITY 46 8O43
X 2 LOG CYCLES »»D[ IN u.i.». .
KEUFFEL a ESSER CO.
10
9
8
7-
6- _
5.
4
3
CO
c
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99.99 99.9 99.8 99 98 95 90 80 70
N -i 1 1 1 1 i ! 1 1 M 1 1 1 ' 1 1 1 M 1 i II 1 ,- 1 1 1 i 1 1 1 , M-l-ill+l-M-4444-n
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-------
_ £ 8
2 LOG CYCLES M.DE IN u.TTTT
10
8
7
6
5
4
3
to
c
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E
O
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E °9
fa ° B
Q 7
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-------
^^£
._'ao4^
X 2 LOG CYCLES M«DE IN U.S.A. o
KEUFPEL & ESSER CO.
10
9
8
7
6.
5
4
3
f?
1
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39.99 99.9 99.8 99 98 95 90
L_ 1 1 1 HiUI 1 I I I I Mill 1 III! | -i 1 1 1 i !|Ug
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7
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r
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-------
PROBABILITY 46 8O43
X 2 LOG CYCLES H»DE IN U.S.A. .
KEUFFEL a ESSER CO.
10
9 _
8
7. .
6
5
4
3
C
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99.99 99.9 99.8 99 98 95 90 80 70
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2
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1
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r-r
-------
PROBABILITY 48 8O43
X 2 LOG CYCLES H.DE IN U.S.*. .
KEUFFEL » ESSER CO.
99.99
0.5 0.2 0.1 0.05 0.01
40
C
o
b
£_
-------
2 LOG CYCLES ».DE IK U.S.A. .
KEUFFEL » ESSER CO.
10
9. .
8.
7
6.
5
4
3
C
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a
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99.99 99.9 99.8 99 98 95 90 80 70 60 5
L. 1 1 1 l-i . JH II 1 . 1 ! 1 1 II II 1 1 1 i . 1 1 1 i 1 l+T-t-M-M-l-H-M-l 1 1 i 1 1 i ITTTTq
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1
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1
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^
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0 40 30 20 10 S
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% Total in Particles of Diameter
3
7
6
5
3
2
1
9
7
6
5
4
3
»
1
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES XAOC IN U.S.A. .
KEUFFEL & ESSER CO.
99.99
crons
(_
0)
E
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n)
1 0.5 0.2 0.1 0.05 0.01
U-
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98 99
99.8 99.9
99.99
-------
10_
9..
8_
7..
6..
5..
99.99
K-
"
46 8043
».DE in U.S.A.
KCUFPEL & ESSER CO.
PROBABILITY
X 2 LOG CYCLES
99.9 99.8
99 98 ' 95 90 80 70 60 50 40 30 20
10
2 1 0.5 0.2 0.1 0.05 0.01
DISTRIBUTION
No. 240A
4
V)
c.
0
b
i.
1
9
. 9
7
0)
+>
s_
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES «ADE IN U.S.A.
KEUFPEL a ESSER CO.
10
9- -
g
7
6.
5
4
3
9
1
08-
oO -
o 8-
o 2 -
0 1
99.99 99.9 99.8 99 98 95 90
=
i
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1 1
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1
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240C
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tzi :
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p
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L_
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80
fHj+H-
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rn
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% Total
i i ; M i ' n n i
i
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r-
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U
7C
u
50 5
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:==:(
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Particles
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
)
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1
of
1 1 1 1
30
r
/(
20
m
m
- t t---
'!«=».
: °I
10
-\
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=1
i
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-
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1
Diameter
-------
Kg PROBABILITY 46 8O43
/£ X 2 LOG CYCLES ».DE IN U.S.A. .
KEUFFEL & ESSER CO.
in 99.99 99.9 99.8 99 98 95 90 80 70 60 50 40 30
9. .
8.
7.
e
5
4
3
10
c
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1
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0.1 0.2 0.5
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i
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mm
. j i
20
4*1
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10
S?i^
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in Particles of Diameter
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES MADI in u.j.«.
KEUFFEL & ESSER CO.
0.01
I
00
I
o ni
90
95
98 99
99.8 99.9
99.99
-------
PROBABILITY
46 8043
X 2 LOG CYCLES MODE IN U.I.A.
KEUFFEL & ESSER CO.
10
9. .
8
7. .
5
4
O
b «
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0
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£= . S
* .8
Q .7
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. 2
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99.99 99.9 99.8 99 98 95 90
1 i 1 it i i ' i| i 1 1 I I 1 1 1 1 M 1 1 1 j j H-H-Hn+r
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i
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99.99
PROBABILITY
X 2 LOG CYCLES
KEUFFEL a ESSE
46 8O43
»DC IN u.i.«.
0.01
0.01 0.05 0.1
95
98 99
99.8 99.9
99.99
-------
99.99
C.
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*
0)
-------
PROBABILITY
X 2 LOG CYCLES
KEUFFEL & ESSE
46 8O43
"ADF IN U.S.A.
0.01
001 0.05 0.1 0.2 0.5 1
99.8 99.9
99.99
-------
PROBABILITY
X 2 LOG CYCLES
KEUFFEL ft ESSE
46 8O43
».Dt , .,.,.
99.99
0.2 0.1 0.05 0.01
001 0.05 0,
95
98 99
99.8 99.9
99.99
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES «,=t IN u.J.«.
*Millipore filter seems out of line High
99.99
1 0.5 0.2 0.1 0.05 0.01
O
4-
o
S-
D-
MASS DISTRIBUTION
Run No. 244B*
Total in Particles of Diameter
-------
99.99
CO
c
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crons
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99.99
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MADE IN U. 3. A.
99.9 99.8
60 50 40 30 20
1.1 0.05 0.01
MASS DISTRIBUTION
Total in Particles of Diameter
-------
99.99
to
o
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a
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X 2 LOG CYCLES HADE IN U.S.A. .
KEUFFEL & ESSER CO.
0.5 0.2 0.1 0.05 0.01
MASS DISTRIBUTION
Total in Particles of Diameter
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES «AO[ in i). J.A.
KEUFFEL » ESSER CO.
10
8
7
6. _
5.
4._
3
9
1
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99.99 99.9 99.8 99 98 95 90
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20 30 40 50 60 70 80
90 95
98 99
99.8 99.9
99.99
-------
46 8O43
MADE IN U.S. A.
KEUFFEL a ESSER CO.
PROBABILITY
X 2 LOG CYCLES
99.99
0.01
CO
c
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I
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95
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99.8 99.9
99.99
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to
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K^ PROBABILITY 46 8O43
V4S X 2 LOG CYCLES ««OE IN U.J.A. .
10
9
8
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PROBABILITY 46 8O43
X 2 LOG CYCLES M.DE IN u.s...
KEUFFEL & ESSER CO.
0.01
1
M
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o.ni o.os o,
99
99.8 99.9
99.99
-------
PROBABILITY
X 2 LOG CYCLES
46 8O43
MADE IN U.S.A.
CO.
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99.99
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99.99
KEUFFEL ft ESSER CO.
95 90 80
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PROBABILITY 46 8O43
X 2 LOG CYCLES M»DC IN u.i.«.
KEUFFEL a ESSER CO.
99.99
c
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MASS DISTRIBUTION
Total in Particles of Diameter
-------
99.99
10
C
o
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PROBABILITY 46 8O43
X 2 LOG CYCLES MADE IN U.S.A. .
10
9. ,
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4
3
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99.99 99.9 99.8 99 98 95 90
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99.8 99.9
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PROBABILITY 46 8O43
X 2 LOG CYCLES MADE IH u.n.
KEUFFEL * ESSER CO.
99.99
CO
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98 99
99.8 99.9
99.99
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PROBABILITY 46 8O43
X 2 LOG CYCLES HADE IN U.S.A. .
KEUFFEU & ESSER CO.
0.2 0.1 0.05 0.01
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PROBABILITY 46 8O43
X 2 LOG CYCLES ..DC IN u.j.n. .
KEUFFEL & ESSER CO.
I/)
c;
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MADE IN U. S. A.
KEUFFEL & ES5ER CO.
PROBABILITY
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99.99
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98 99
99.8 99.9
99.99
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES »«DE IN u.i.«. .
KEUFFEL ft ESSER CO.
99-9?
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98 99
99.8 99.9
99.99
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10
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f\ S X 2 LOG CYCLES
KEUFFEL ft ES5ER C
99.99 99.9 99.8 99 98 95 90
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PROBABILITY 46 8O43
X 2 LOG CYCLES MADE IN U.S.A. .
10
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10
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K_\^ PROBABILITY 46 SO43
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KEUFFEL & ESSER CO.
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20 30 40 50 60 70 80 90 95 98 99
99.8 99.9
99.99
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