EFFECT OF FUEL ADDITIVES ON THE CHEMICAL
AND PHYSICAL CHARACTERISTICS IN AUTOMOTIVE
EXHAUST
John B. Moran, et al
Dow Chemical Company
Midland, Michigan
July 1970
Distributed .,, 'to foster, serve
and promote the natToh's
economic development
and technological
advancement.'
NATIONAL TECHNICAL INFORMATION SERVICE
-------
July IS'/j;
Report.
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a*.
APHK0618
Additives on tfee -.Cftpical and Physical1, ฃ' ..^,,
" laissions, ,w Autoaotlvev ^ -^
1 ' .Jo'fe^B. Mbran and Otto J. Manary ' - .-.
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aic Chemicals Department: ....-. ^;
*'jr^he'fBpw Chemical Compaiiy " '' "'
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A^r Polution; Control Adajinistration
St. Mary's Street ;
North 'Carolina, 27605
^
were "developed of generating,
75 aqurs under cycled conditions before stable,,.gaseoua,aiM''7|^;^ticu,Ja.,t6;-e
achievedT>An air dilution chamber-was designed whichr^allows ,Jpfc:-codling'''
was
arid exhaust system attached, was loaded by means of anthyl lead
{Environments
Cyclic loads
17c> CQSATI Fteld/Greปg> 13/02, 21/07, 21/02
19. Security ClesalThis
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.This report was. furnished,4tp
Pollution Control Office by the flow
Chemical Company in fulfillment of
Contract No. CPA-22-69-145.T . V
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CPA-22-69-145
EFFECT OF FUEL ADDITIVES ON THE CHEMICAL
AND PHYSICAL CHARACTERISTICS
OF PARTICULATE EMISSIONS
IN AUTOMOTIVE EXHAUST
John B. Moran
and
Otto J. Manary
Contributors
R. A. Bredeweg
Dr. W. B. Crummett
H. L. Garrett
L. P. Schloemann
L. A. Settlemeyer
J. C. Tou
Dr. V. A. Stenger
H. W. Rinn
W. B. Tower
P. A. Traylor
J. C. Valenta
Dr. C. E. Van Hall
L. B. Westover
D. F. Wisniewski
C. K. Neimi
The Dow Chemical Company
Midland, Michigan
Interim Technical Report
July 1969 to June 1970
for
Division of Chemistry and Physics
National Air Pollution Control Administration
1330 St. Mary's Street
Raleigh, North Carolina 27605
Attention: Dr. Jack Wagman
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,- FOREWORD
't *
f;
?ฃ<, This report was prepared by the Transportation Research Group,
;:! Organic Chemicals Department, The Dow Chemical Company, Midland,
;): Michigan under Contract CPA-22-69-1 45. This work was administered
K under the direction of the National Air Pollution Control
' Administration, Environmental Health Service, with Dr. Jack Wagman
- as project officer.
,*f
h This report covers work performed from 30 July 1969 to
f 30 June 1970.
i\
$
I The authors of this report are John B. Moran and Otto J. Manary.
$: The authors wish to acknowledge the significant contributions
|; of the following individuals:
R. A. Bredeweg W. B. Tower
Dr. W. B. Crummett P. A. Traylor
H. L. Garrett J. C. Valenta
L. P. Schloemann Dr. C. E. Van Hall
L. A. Settlemeyer L. B. Westover
J. C. Tou D. F. Wisniewski
Dr. V. A. Stenger C. K. Neimi
H. W. Rinn
ซ.
5
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\ ABSTRACT
\i
\-, This report describes^wpr^ carried out on a research program
to* d'eVelVp^methods^f "generating, collecting, and analyzing
particulates in automotive engine exhaust by a means suffi-
ciently accurate and reproducible to allow determination
of the effects of fuel additives on exhaust particulate size8
concentration, and composition.^ It has been determined^hat^
it is essential to condition^he clean (new) engine^w'ftF file
test fuel for a period of at feast 75 hours under cycled
conditions before stable gaseous and partjculate emissions
are achieved. An air dilution chamber hals ibeen designed
which allows for cooling, dilution, and mixing so that repre-
sentative particulate samples can be obtained at a sampling
station which is essentially equivalent to 8-10 feet downstream
of the end of the exhaust pipe on a vehicle at highway speeds.
Temperature^ of the diluted exhaust at the sampling station 4-sฐ w^
around IIO^F. - . ~
The work reported has been conducted using(a. 1970 Chevrolet
350 CID engine of 9.0:1 compression ratio with a standard
exhaust system attached?^loaded by means of an engine dyna-
mometer. Samp! ing*A*&&*~bซefl conducted with the engine operating
at 2250 RPM and 17.0" Hg manifold vacuum from 4 of the 8
cylinders. A few sampling runs hav1ff%o-eti conducted under
mild cycled conditions consisting of several cruise modes.-v,
- Special analysis techniques have-H&ee* developed for the
analysis and characterization of jixJiaiuงt,Jl9XJUฃttXal.!|s^ The
details of these techniques are "included in this report.
The dataxฃatherecL whil e substantiating the applicability of
the techniques developed', 'in "ad*dTtTorixsuggest a very significant
effect of fuel additives, primarily TEL, on exhaust particulate
size, concentration and composition. Significant differences
are observed with minor changes in other fuel additives.^..JLkese
observations emphasize the need for a study of particul
emissions from vehicles operated under simulated driving
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TABLE OF CONTENTS
Page
I. INTRODUCTION T
I II. CONCLUSIONS 4
vV'jo
\ III. TEST EQUIPMENT AND PROCEDURES 6
IV. EXHAUST GAS ANALYSIS AND SAMPLE COLLECTION 12
/., A. Exhaust Gas 12
} 1. General 12
J a. Analytical Equipment 12
I
*,: b. Sampling 13
;V c. Standardization 13
;!'; d. Operation 13
1 "h e. Data Reduction ... 14
' 2. Oxides of Nitrogen 15
'' ,s a. Equipment 15
!'. b. Calibrating Gases 15
f .ซ c. Procedures 15
1 B. Particles 16
; C. Combustion Chamber Deposits 17
r
| V. RESULTS 18
,]; A. Introduction , 18
j B. Dilution Tube 19
d 1. Temperature Profile 19
' 2. Flow Rate/Volume, Dilution Ratio 20
: 3. Sampling Zone 22
j C. Gaseous Emissions 25
:f 1. Hydrocarbons 25
I 2. Nitrogen Oxide 25
]: - D. Fuel Analysis 26
f E. Engine Oil Trace Metal Analysis 28
JO .
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i 11
G. Microscopy 30
1. Introduction 30,
2. Scanning Electron Microscopy and X-Ray
Fluorescence Analysis 31
a. Purpose 31
b. Instrumentation 31
c. Work Outline 31
d. Technique and Methods 32
e. Results 33
f. Discussion 35
3. Light Microscopy and X-Ray Characterization. 37
a. Purpose 37
b. Results 37
c. Particle Size 38
d. Particle Description 39
e. Color 40
f. Chemical Composition and Crystal Species. 40
4. Transmission Electron Microscopy
Characterization 42
H. Mass Spectrometric Analysis 44
I. Ultraviolet Fluorescence Spectra 48
1. Introduction 48
2. Procedure 49
a. Sample Handling 49
b. UV Absorption Measurements and
Calculations ป 50
c. Fluorescence Measurements and
Calculations 50
3. Discussion of Results 54
J. Particle Trace Metal Analysis 55
K. Particle Emissions 56
VI. DISCUSSION OF RESULTS ' . 60
VII. SUMMARY 65
VIII. FUTURE 69
REFERENCES 70
LIST OF TABLES 71
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-I-
:' I. INTRODUCTION
f- '. '
""I
|u This 1s an Interim report covering our first year's efforts
A-, " to develop a fundamental understanding of the nature of
'$'
^k partlculate emissions from automotive internal combustion
Mjo - '-.. ''
| . engines. In general terms, we have Investigated the effect
;| of well-defined fuel additives on the characteristics of
|j particulate and gaseous emissions from a dynamometer-loaded
| automotive engine. The study has involved proper engine
'$ conditioning to provide stable and repeatable gaseous and
4^
$ particulate emissions, the design and Installation of a suitable
''!'
f particulate collection system, and the examination of the
effect of steady-state operation versus mild cyclic operation
of the engine on exhaust emissions, both gaseous and particulate.
' ' ' ' v
A well-defined research fuel, namely Indolene HO, has been
used as the base fuel throughout these studies. An anti-
knock compound (Tetra Ethyl Lead), lead scavengers, and a
'
? detergent additive, have been investigated to date.
: '
Collection, classification, and analysis of the exhaust par-
ticulates have been the most challenging tasks in this study.
An exhaust-air dilution chamber has been used which forms
the basis for the particulates data reported herein. We attempted
., to sample the raw exhaust to obtain particulate samples. This
effort failed. It became apparent that air dilution of the
exhaust was essential in order to obtain particulate samples
which were somewhat representative of those encountered from
actual vehicles. A dilution tube was designed and installed
which provides approximately 12:1 dilution ratio of air to
exhaust gas. The tube is of sufficient length that nearly
'"' all particles 20 y and larger separated before entering the
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-2-
so that it could be easily disassembled, cleaned, and reassembled,
thus allowing collection of all particles emanating from the
exhaust pipe. Initially, the complete exhaust from the engine
was diverted through the dilution tube. However, 1t became
apparent that adequate dilution ratios to avoid condensation
in the Andersen samplers, to reduce particle agglomeration,
and obtain reasonable sampling temperature, and yet obtain
proper filtration of the diluent air could not be achieved
with such high exhaust volumes. Consequently, it was decided
to use only the four left bank cylinders of the V-8 engine
for exhaust sampling. Reduced loading of the engine was deemed
inappropriate as idle to 30 MPH cruise conditions would not
be relevant. In addition, we recognized the need for cycled
operation sampling 1n the near future.
It is apparent that the definition of an exhaust particle
is somewhat dictated by the collection system employed,
i.e., particulates are defined as those solid and liquid materials
collected in the specific device and under the specific conditions
of the sampling hardware. Several particulate sample collection
methods could have been employed. We decided to use the Andersen
Impact Sampler Model 0203 because it provided reasonably large
samples, size classification and is relatively Insensitive
to operator variables. The Andersen provides only a proportional
sample of the air-exhaust mixture. However, stable sampling
zone conditions have been achieved with the dilution system.
This report covers, in detail, the procedures employed in generating,
collecting and analyzing exhaust particulates. It is apparent that
fuel consumption, engine condition, engine loading, and collection
procedures greatly affect particulate emissions results. As
with hydrocarbon emissions,, it will be essential to define specific
procedures in order to obtain meaningful and reproducible partic-
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-3-
v, t The relevance of this study tb actual vehicles and the
51 effect mileage accumulation procedures and sampling cycle
\ฐ . will have on particulate emissions therefrom has not yet been
fปV
;!!; established. This work does, we feel, provide a sound basis
;iv from which meaningful studies in that direction can be based
.; as sound, reproducible, collection and analytical techniques
I'i have been developed.
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.4-
II. CONCLUSIONS
This interim report covers only the first phase of work in
a continuing program to develop a fundamental understanding
of particulate emissions from the automotive engine. In order
to develop sampling and analytical proficiency, it was found
necessary to limit the work to one make of V~8 engine, a well-
defined operating condition of that engine, and a well-defined
particulate sampling system. The evaluations were conducted on
an engine attached to a dynamometer programmed to simulate !
typical engine cruise conditions (60 MPH, road load). None of
the work in this phase involved complete vehicle system operation.
It was recognized that particulate emissions could be sensitive
to engine condition, operating mode, etc., as are gaseous
emissions. The particulate sampling device also somewhat defined
the particles collected for study.
Conclusions within the defined scope of study are:
1. A collection and classification system was developed which,
when combined with the analytical capabilities developed
under this study, resulted in the ability to ascertain
significant differences in exhaust particles with minor
changes in fuel additives. Thus, the basic objective of
this initial study was achieved.
2. In the series of 16 tests reported the following fuel
additive effects were noted.
A. Increased concentration of Tetra Ethyl Lead from trace
levels to 3.0 ml/gal resulted in increased particle
emissions, increased combustion chamber deposits, and
hydrocarbon emissions.
B. Increased concentration of TEL from trace levels to
1.5 ml/gal showed a disproportionate increase in
hydrocarbon emissions and combustion chamber deposits,
but an unexpectedly small increase in particulate
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>
3'
-5-
C. Lead scavengers had a pronounced effect on exhaust
particulates and emissions, and on combustion chamber
deposits. The more effectively the scavenger did
its job (lower combustion chamber deposits), the lower
were the hydrocarbon emission levels and the greater
the particulate emission levels (motor mix, EDB, and
EDC have been evaluated).
D. The use of a detergent additive to the 3.0 ml/gal
TEL motor mix base fuel , decreased deposits and hydrocarbon
emission levels, but increased particulate emissions
when compared to the base fuel.
j. E. Some experiments using cycled operation showed only
,i a slight effect on particulate emission levels compared
I to steady-state operation probably due to the fact
j' - that our cycled sequence was a combination of several cruise
^ conditions.
j] F. The percentage of organics associated with exhaust
i particulates Increased with decreasing particle size.
1 . .
'j G. The percentage of organic material associated with
i exhaust particles increased with decreasing TEL
4! concentration. ,.However7~see~page 68~
|i H. The exhaust particle size distribution was affected
;j. by TEL, scavengers, additives, and cycling.
\ I. In general, 50% of the mass of exhaust particles
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-6-
III. TEST EQUIPMENT AND PROCEDURES
The test equipment arrangement used for this study 1s as shown
schematically 1n Figure 1. The engine, dynamometer, exhaust
system, and dilution tube inlet are located in the dynamometer
cell. The cell air is filtered, and heated when necessary.
Sufficient air capacity is available to keep a positive pressure
in the room and to replace the cell air every 30 seconds.
The remainder of the dilution tube is located adjacent to the
engine cell in an air-conditioned room which also houses all
instrumentation with the exception of the NO/NOp analyzer
which is in the test cell.
The engine used for all experimental runs made during the
period of the report was a 1970 Chevrolet 350 CID engine with
the following specifications:
Displacement 350 cubic inches
Horsepower 255 @ 4800 rpm
Carburetor 2 barrel Rochester
Compression Ratio 9.0:1
Bore 4.0"
Stroke 3.48"
Spark Plugs AC R45S
Plug Gap .035"
Point Dwell 28-32ฐ
Timing 4ฐ BTC
The right bank of cylinders is attached to an exhaust pipe
which is exhausted from the room through the cell exhaust
system. The left bank of cylinders is connected to a typical
-------
F ilter
I
Air
in.
Eng ine
Dynamometer
I
Eng ine-
I
Flow Diogrom for Engine Exhoust
Particulote Collection
Air
out
n
Instrument
and
Control Room
M i x-i ng
9- P articulate
-'Gravimetric Fallout
Flow
Control
i
11
Sampling Slits
-Tail Pipe
Standard Muffler
Scott Research ins,
NO and N02
Analysis
ป Fisher Gas Partitioner
CO, C02, N2, 02
Beckman 109A
Total Hydrocarbon
Analyzer
Anderson
Separator
ipore
Filter
Flow Meter
Vacuum
Pump
Manome
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-7 -
I' cross-over heating passages under the carburetor are plugged.
|f Specific components of the exhaust assembly used for each run
'% " ' . are:
$ " Exhaust Manifold 1-5/8" ID
i? -' 20" long
| Exhaust Pipe Walker 97836
& 2-1/2" ID
| 67" long
;'j Muffler Walker 21530
]! x W5798
si? 21" long
4 Tail Pipe 1-5/8" ID
;); 76" long
4r
;j: A Meriam Laminar Flow Element Model 50MC-2-45F air flow measure-
'ff ment unit is attached to the carburetor via a flexible rubber
i|j hose for air consumption measurements. An A/C paper filter
id element is used on the Meriam to filter incoming air.
., < *
'I ' The engine-dynamometer set-up is completely instrumented to
>f
;^i- monitor and/or control coolant temperature, oil temperature,
fi* manifold vacuum, fuel flow rate, air flow rate, RPM, load,
i ' ' ' etc.
"'I!
"!;
;] Amoco 100, SAE 30 lubricating oil has been used in all experimental
{j! runs. This oil was chosen as a minimum acceptable oil with
,j a low additive package content so that contributions of the
; oil to the particulate material would be minimized. This
;; oil has the following trace metal analysis:
5 Table 1
?j' ENGINE OIL, TRACE METAL ANALYSIS
Wt. %'
Mn .0001
Pb .0006
Cr <.0001
Sn <.0001
Zn .081
Ti <.0001
P .05
M Mo <.OC01
;
i-
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-8-
and the following physical properties:
Table 2
ENGINE OIL, PHYSICAL PROPERTIES
Gravity, ฐAPI 26.4
Flash, ฐF . 450
Pour, ฐF 0
Viscosity 100ฐF 555 SUS
210ฐF 66 SUS
V.I. 95
Color, ASTM 5
Sulfated Ash, % Wt. 1.0
Carbon Residue, % Wt. 1.3
Before each run is begun, the engine is thoroughly cleaned and
inspected. The heads are removed and deposits from the heads
and piston tops from the previous run are removed for weighing
and analysis. The heads are then cleaned with solvent. Valves
are removed and inspected. Generally three runs can be made
between each valve refacing and re-seating, in which case
the valves are cleaned of deposits and only a light valve
lapping is necessary 1n order to obtain good seating and
seat width. Each valve guide clearance is checked for tolerances
and the valve end is observed for wear.
New seals are installed on each valve stem. The he-ads are
reassembled and torqued to the manufacturers specifications.
A new exhaust system, oil filter, oil, points, plugs, and
condenser are installed. The dwell and timing are checked
and set to manufacturers specifications. The fuel lines
are purged with clean dry air before the new test fuel is
pumped to the engine. The carburetor is then adjusted for
best idle vacuum.
The dilution tube is an extruded pipe made of polyvinyl
chloride. It is 16" in diameter with a 1/4" wall thickness.
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.9-
as shown 1n Figure 2. A 7 foot air Induction head which houses
, t; " the air filter assembly, exhaust inlet elbow, and mixing baffle
(. si
;, |0 is mounted in the wall between the Instrument room and the
engine test cell. The mixing baffle consists of a flat sheet
metal donut attached perpendicular to the tube axis to the
'| inside wall of the induction head which acts to force the
,'ij incoming diluent air through the 8" hole in the center of the
;j, baffle, thus mixing with the exhaust gas. The exhaust elbow
;j! enters at 90ฐ to the tube axis and is bent 90ฐ so that the
I' flow axis of the exhaust gas parallels the axis of the dilution
i tube. The exit end of the exhaust elbow is in the same plane
i*1.
ft as the baffle.
I
.|: An exhaust fan vs located at the exit end of the dilution
\ tube. A throttle plate is located in the dilution tube exit
assembly following the fan in order to allow control of flow
\ - volumes through the tube. The dilution tube consists of several
'JU sections with butt joints which are taped during assembly.
:;--: ' This construction allows for easy removal, cleaning, and
,1' inspection of the complete dilution tube after each run.
-\'. Samples swept from each tube section are designated as shown
''j inFigure2.
f; Several small slits have been cut in the bottom of the tube
:j!;I along its length. Special glass collecting plates were fabri-
: cated which are attached to the outside of the tube under
.j each slit to collect particulate samples. Such samples are
| referred to herein as "slit samples." Slit locations and
'.'? numbers are shown as short dashed lines perpendicular to the
: tube axis in Figure 2.
Initially, a simple 24" x 24" flat fiberglass air filter was
i, used to filter the diluent air coming into the tube. Particulate
: loading in the tube and sampling systems observed with diluent
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\
\
k /
>
;
\
0
' \
1
\
v
i
k
\i
O
V
N
O
~- .
* .
<
s
-K A
Scale = 5 Feet = 2"
t
~^-x
1 . 1 ." '
1 1
.- t
1
1 . 1
1
i
fi
1
To' >
G'O"
~^. / ~x
/4-<.
n -
v.
PARTICULATE SAMPLING TUBE
-------
-10-
wlth a test fuel, This caused us to look for a better filter
medium. As a result, we Installed a Dr1-Pak Series 1100 Class
II PIN 114-110-020 untreated cotton filter assembly. This
filter assembly 1s 24" x 24" and has 36 filter socks which
axtend to 36" in length. This filter will pass particles
0.3 v 1n size and smaller. Pressure drop at 600 cfm flow
rate is minimal.
The particulate proportional sampling zone is located at the
exhaust end of the dilution tube. The sample probe elbows
are located in the exhaust-air stream. Each 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"
ID aluminum tubes. These sample tubes are located as shown
in Figure 1. A Hg manometer is connected between the dilution
tube probe and the exhaust side of the filter assembly and
is used to monitor the pressure drop across the Andersen Samplers
during the course of each run. A flow,meter follows the filter
and is used to monitor and regulate flow through the Andersens
and filter during the run.
Each run consists of positioning the cleaned and washed tube,
connecting slit collection plates, and connecting the cleaned
Andersen Samplers and filter sampling equipment at the sampling
zone. The engine is started and run on the new test fuel
at idle for several minutes while temperatures, oil pressure,
etc., are observed. The engine is then switched over to a
cycling conditioning sequence. Unburned hydrocarbon levels
are closely monitored during the first two hours of cycling
which allows excellent scrutiny of engine condition.
The engine is run on the conditioning cycle for 75 hours to
stabilize engine deposits, emission levels, and engine condition.
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-11-
:;{ Table 3
i| * , TEST ENGINE CONDITIONING SEQUENCE
'I
*>
Cycle
1
2
3
4
5
RPM
800
1070
1615
2125
1070
T i me
(Min.)
2.0
13.0
20.0
13.0
12.0
Vacuum
("Hg)
18.8
16.4
17.2
14.3
16.4
Decay
ซB M
1/2 min.
1/2 min.
1/2 min.
1/2 min.
The sequence repeats after cycle 5. Unburned hydrocarbons,
oxides of nitrogen, and all engine operating conditions
are observed and recorded during the conditioning sequence
of 75 hours.
After the 75 hour conditioning sequence, the exhaust pipe
is connected to the inlet pipe to the dilution chamber while
the engine is running. The particulate sampling run is then
begun with the exhaust gas being put into the dilution chamber
and mixed with diluent air from the dynamometer cell.. Sampling
is conducted for 48 hours with the engine running at 2250
RPM at 17.0" Hg intake vacuum. During this time unburned
hydrocarbons and oxides of nitrogen are monitored and recorded
as are the engine conditions and dilution tube conditions.
In several instances, the engine was run under cycling mode
into the dilution chamber to determine the effect of cycling
on the particulate emissions. In that case, the engine
is shut down after the 48 hours steady-state run, the dilution
tube is cleaned and reassembled as are the particulate samplers.
The engine is then run under the same cycling mode as the
conditioning sequence. The exhaust is again put into the
dilution tube and samples collected as before, for 48 hours.
The dilution air flow rate is not, however, changed to hold
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-12-
IV. EXHAUST GAS ANALYSIS AND SAMPLE COLLECTION
A. EXHAUST GAS :
1. General
The engine exhaust gas is analyzed for oxygen* nitrogen,
carbon monoxide, carbon dioxide, total and individual
volatile hydrocarbons. The analysis is done by gas chromat-
ography, chemical absorption, and a total hydrocarbon
analyzer. Data reduction is by an IBM 1800 computer through
a Bell Telephone ASR 33 Teletype interface.
a. Analytical Equipment
A Fisher Gas Partitioner is used for the analysis of
oxygen, nitrogen, carbon monoxide, and carbon dioxide.
The column system consists of a 6* hexamethyl phosphoramide
and a 6-1/2' 13x molecular sieve in series.
Total hydrocarbons are obtained from a Beckman Model 109A
Total Hydrocarbon Analyzer. The concentration of
unsaturated hydrocarbons is determined by passing the
sample through an absorption tube 1/2" x 8" filled with
30-60 mesh pink Chromosorbฎ impregnated with 50% mercuric
perchlorate. . ' i
A Hewlett-Packard Model 5750 Gas Chromatograph with a
hydrogen-flame detector is used for the analysis of
individual volatile hydrocarbons. The column is a
20' x 3/16" O.D. filled with 20% Apiezonฎ L on 60-80
mesh pink Chromosorb and is programmed from 50ฐC to
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-13-
:| '.. The output of each gas chromatograph 1s coupled with a
;: ป Hewlett-Packard Model 3370A Digital Integrator which
4 has an Asc11 coded output to drive an ASR 33 Teletype
^ - and punch paper tape.,
'1.
vf b. Samp! ing
) A Neptune Dyna-Pumpฎ is used to pull the sample from the
exhaust pipe sampling point through 1/4" O.D. stainless
- steel tubing and transfers it to the total hydrocarbon
-{ analyzer and the gas sampling valves of the two gas
chromatographs through 1/8" O.D. stainless ;steel tubing.
A manifold system is provided to allow the operator to
calibrate the equipment with the appropriate standards.
(See Figure 1 for sample source information.)
-j'|
Jj c. Standardization
sj A gas mixture containing known concentrations of oxygen,
?( nitrogen, argon, carbon monoxide, carbon dioxide, and
-.'! . n-hexane is used as a reference standard for the total
-------
-14-
emerge, the time and area information is encoded and
stored on punched paper tape. Each succeeding exhaust
gas Is Identified along with the total hydrocarbon level*
and run 1n the same manner as the standard. When the
series Is finished, the punched tape is sent to the
computer by teletype over regular telephone lines.
e. Data Reduction
A typical output format for the gas analysis is shown in
Figure 3. Identification of the components in the standard
is based upon each peak size in descending order. Estimated
retention time is the up-dated time of each peak in the
standard. Retention time windows are 4 seconds plus 2%
of the retention time. Actual percent 1s a direct ratio
of the area counts in the unknown sample to the area
counts in the standard times the volume percent 1n the
standard. The total percent actual will normally be
97-98% since water is removed form the saturated sample
after the sampling valve.
A correction for the unresolved argon in oxygen 1s made
based upon response factors and the amount of argon
found in a number of exhaust gas samples by mass spectro-
scopy.
The actual percent is normalized to 100% in the next
column or a moisture free basis, and an Exhaust Gas
Analysis report is issued below. The air to fuel
ratio is calculated from this analysis, the total hydro-
-------
1
<3. C. ANALYSIS - TECHNICAL OATA -
Cu>v' SUM #18 JUNE 27 1970
CYCLE 04 78ป1 HKS
HC 620. PPrt
PEAK TIKE
iM0. ACT. EST
PCT. VOL.
ACTUAL N&RM'c
6-29-70
IDENTIFICATIuN
1
2
3
4
5
6
G3V SUN
CYCLE v
HC 620
TI.'iE
132.
146-
132.
202
75.
54. 54-
75. 75.
92. ---.
132- 132.
147* 146-
202* 202.
EXHAUST GAS
718 JUNE 27 1
A 78-1 KRS
. ??,4
PERCENT I DENT
0ซ9 ARGJN
83.7 NITx'JG
0*6 ..DXYGEN
! 90 ._CAR;33'.'ii
12 ปS CA!-?3ijiNซ
0-000 0ป000 C2iป5?-j3ITฃ
12.561 12.325 CAR33N- DIuXlOE
o.ooo o.ooo
0ซ616 0ซ6'23 3XYGEN
0-900 0.913 ARGJrt.
82*00 1 83.724 NIT^wGEN
1ป363 1*902 CAS3SN i"JOM0Xli)E
97.941 100. 000 T3TALS
2.059 BALANCE 3Y DIFFERENCE
2-059 T0TAL CONTAMINATION LEVEL
ANALYSIS 6-29-70
970
IFIC:ATION
EN.
HQNtJX'iOE
OI6XIOE
100.0 TWTAL
IN FUEL Q.S625
C3.\TEjNT 620. PPM.
AIR/FUEL .^ATId 14. I
-------
-15-
2. Oxides of Nitrogen
a. Equipment
Beckman Ultraviolet Analyzer
Beckman Infrared Analyzer
Recorder - Texas Instrument Company
The above pieces of equipment are in a single, self-
contained unit built by Scotts Research Labs Inc.,
San Bernardino, California.
b. Calibrating Gases
Nitric oxide (3545 ppm in nitrogen)
Nitrogen dioxide (862 ppm in nitrogen)
These standard gases are furnished by Scotts Research
Labs, Inc.
Nitrogen is used as zero calibrating gas.
c. Procedure
Before making NO, N02 measurements, the paper filters
(Whatman #3) to each analyzer are changed and the
Dri-Rite dryer in the exhaust sample is replaced.
Both analyzers are standardized using the appropriate
calibrating gas at a constant flow. The zero standardizing
is done using nitrogen as the calibrating gas using
the same flow rate.
After the instrument is standardized, the exhaust gas
is passed through the analyzer using the same flow rate
-------
-16.
are recorded by the dual pen Servo-riter recorder.
Figure 1 indicates the source of the exhaust gas
sample.
B. PARTICLES
Participates are sampled in such a manner that all particulates
emitted from the tail pipe are represented. The mass dis-
tribution is determined by weighing collected particulates
after 48 hours sampling at the following locations:
1. Dilution tube slit collection plates
2. Dilution tube - each section
i
3. Andersen Samplers - 6 collection plates each
4. Filter (following Andersen Sampler)
Tube slit plates are simply weighed in and out,, the difference,
being the mass of particles collected during the run. The
dilution tube is disassembled and each section is carefully
swept out with a camel hair brush onto a sheet of clean paper.
The sample is then transferred to a tared sample bottle* which
is weighed again to determine sample weight by difference.
The Andersen Sampler collection plates are weighed before
and after the run, the difference being, again, sample
weight.
Prior to use, the Millipore and fiberglass filters are stored
in the instrument room which Is temperature and humidity
controlled. The filters are placed on the tray in a Mettler
Analytical balance and are allowed to reach equilibrium, then
-------
-17-
After the test, the filters are removed from the holders and
again allowed to reach equilibrium, noted by no further change
1n weight, then weighed to fourth place. This 1s done in
' '
the same room in which the papers are stored. The Mill 1 pore
filters used are 142 mm type AAWP 0.8 y. The fiberglass filters
used are Gelman 0.3 y Type A 2" diameter. The Millipore
filters are used for most of the sample work, the fiberglass
'
for special analytical processing.
The particulate samples follow a rather involved route for
complete analysis. This is due to the fairly small quantity
. .' ;'
of particulate sample, notably in the smaller size ranges
(below 15 y) associated with the Andersen Sampler - filter
portion of the sampling system as each sampler only gets
^l/500th of the diluted stream. Three Andersens are used
at a sampling rate of 1 cfm. An additional unit operates
at 1/2 cfm and is provided to the Microscopy Lab for analysis.
This is used to facilitate Stereoscan/X-ray analysis of larger
crystals which are less impact damaged in the Andersen.
C. COMBUSTION CHAMBER DEPOSITS
The deposits in the combustion chamber and on the top of the
pistons are collected after each test tun. Head bolt and
water passage holes are taped to avoid contamination and sample
loss. The deposits are scraped off using a putty knife and
round nosed spatula into a large sheet of heavy paper. The
valves are left in the head during deposit removal. The
deposits are similarly removed from the piston tops. The
deposits collected are transferred to tared sample bottles,
which are weighed and the run number, date, and sample weight
-------
-18-
V. RESULTS
A. INTRODUCTION
Much of the data to be presented in this section of the report
bears on several topics. Mass spectrometry, for example,
provides an analysis of the effect of parficle size on the
amount of NH~, H90, HC1, and total organics present. Ultraviolet
ซ3 <. '
Analysis provides information on the relative amounts of aromatic
organics including PNA's. In order to provide a basic picture
of the results from each of these various techniques, they
will be reported and discussed separately. Comparisons will
be drawn in the Discussion Section which follows.
For convenience, all data are presented by referring to run
numbers rather than the specific test fuel used for each such
run. The test fuels are shown in table 4 on the attached fold-out
-------
-19-
B. Dilution Tube
1. Temperature Profile
I" The temperature of the exhaust gas-diluent air stream 1" into
:1 , the dilution tube at four points along the tube are shown
for all runs below in Table 5. Thermocouple location is shown
in Figure 4. Temperature in ฐF.
Table 5
Run #
3
4
5
6
7
8
9
11
13
16
TC #9
no
106
106
114
125
120
127
117
125
126
TC #10
106
103
103
104
118
115
115
113
120
115
TC #11
108
104
103
110
120
115
120
113
120
118
TC #12
107
103
103
no
120
115
115
108
120
118
Diluent*
Air
82
78
79
96
95
80
80
88
95
82
TC - Thermocouple
-------
-19-
B. DILUTION TUBE
1. Temperature Profile
The temperature of the exhaust gas-diluent air stream 1" Into
the dilution tube at four points along the tube is shown '.
for all runs below in Table 5. Thermocouple location is
shown in Figure 4. Temperature is 1n ฐF.
Table 5
DILUTION TUBE TEMPERATURE PROFILE DURING
STEADY-STATE OPERATION SAMPLING
Run #
3
4
5
6
7
8
9
11
13
16
TC #9
110
106
106
114
125
120
127
' 117
125
126
TC#10
106
103
103
104
118
115
115
113
120
ITS
TC #11
108
104
103
no
'120
115
120
113
120
118
TC #12
107
103
103
./ no
120
115
115
108
120
118
Diluent*
A1r
82
78
79
96
95
80
80
88
95
82
TC - Thermocouple
-------
OJ
V
O
xl
X.
o
Point of dilution
.-Jill
PARTICULATE SAMPLING TUBE
Scale = 5 Feet = 2'
'
-------
-20-
The tube temperature profile during cycling sampling is
shown in Table 6. Temperatures are in ฐF with the tempera-
ture range- rather than average shown.
Table 6
DILUTION TUBE TEMPERATURE PROFILE DURING
CYCLIC OPERATION SAMPLING
Cycle
2
3
4
5
2
3
4
5
2
3
4
5
TC #9
74-82
83-97
107-123
81-112
79-85
79-90
115-120
77-91
83-95
89-110
134-140
9arl03
TC #10
75-83
84-97
108-119
81-112
76-85
79-91
113-119
77-85
83-95
88-105
126-135
87-101
Flow Rate/Volume, Dilution Ra
TC #11
75-83
83-91
109-120
80-111
76-85
80-92
117-123
77-85
83-95
88-106
127-132.
86-101
tio
TC #12
75-83
83-94
105-118
80-112
76-85
80-92
116-123
78-85
83-95
88-106
126-131
90-101
69-83
69-83
14 2 79-85 76-85 76-85 76-85 78-82
78-82
78-82
78-82
17 2 83-95 83-95 83-95 83-95 77-88
77-88
77-88
77-88
2.
Sample runs have been made with sampling into the tube at .j
both steady-state (60 MPH road load) and under cycling j
conditions as per the cycling sequence described earlier. j
Flow rates and dilution ratios for all steady-state runs i
are shown in Table 7. Exhaust volume is calculated on the {
basis of fuel flow rates, air-fuel ratio, and C-H ratio of |
the fuel. These values are for mixed stream condition at ]'
-------
-21-
Table 7
DILUTION TUBE FLOW RATE AND DILUTION RATIO
f '
1 Average
;'"" Dilution Ratio
(Air to Exhaust,
Sampling Zone)
12.5:1
11.4:1
11.7:1 'v
11.9:1
12.2:1
11.9:1
12.1:1
11.8:1
12.4:1
11.6:1
Run #
3
4
5
6
7
8
9
11
13
16
Flow Rate
cfm
6.32
6.30
6.46
6.46
6.62
6.65
6.64
6.62
6.63
6.67
Cycling operation resulted in the following dilution
tube conditions:
Table 8
DILUTION TUBE FLOW VOLUME AND FLOW RATE
Run # Cycle
12 2
3
4
5
14 2
3
4
5
Flow Volume
cfm
538.9
534.9
530.0
533.1
522.7
544.7
520.7
550.0
Flow Rate
fps
6.85
6.80
6.74
6.78
6.77
6.93
6.63
-------
-22-
A Model 60 Aneraotherm Air Meter instrument is used to determine
air velocity in feet/minute in the dilution tube. The 100-1000
fpm scale is used which has a claimed accuracy of ฑ5%. Our
flow rates are typically 400 fpm (6.67 fps) which results
in an error band of 6.67 +^.33 fps. We also use an Alnor
Series 6000 Velometer for these measurements for second source
verification.
Flow volumes are,calculated on the basis of the air velocity
measurements using the following:
Q - A x V
where: Q = volume in cfm
A = cross-section area
V = average flow velocity
The 10 point traverse method for determining average velocity
was initially used. We found, however, that 13 point deter-
minations on both the vertical and horizontal axis (26 mea-
surements total) which are averaged gave similar results.
Therefore, this technique has been used in all sample runs.
The 13 point probe starts 2" inside the tube and traverses
the tube cross-section in 1" steps to 14" (2" from opposite
wall). This is repeated at 90ฐ to the original probe axis.
3. Sampling Zone
Of key importance in obtaining relevant data in the Andersen
Samplers and filters is that the sampling zone of the dilution
tube be uniformly mixed exhaust gas, particles, and dilution-
air, as we are sampling only a small fraction of the total
stream through the Andersens. Air flow and temperature profiles
have been measured at the sampling zone in both the horizontal
and vertical axis at 1" intervals, from 2" to 14" through
-------
-23-
Table 9
DILUTION TUBE SAMPLING ZONE TEMPERATURE
FLOW RATE PROFILE
Vertical Probe
Horizontal Probe
Air Flow
<*, (fpm)
410
410
410
405
400
400
400
400
395
400
405
380
390
Temperature Range
Flow Rate Range
Temp.
ฐF
170 2"
170 3"
171 4"
171 5"
171 6 "
171 7"
171 8"
171 9"
170 10"
170 11"
169 12"
167 13"
167 14"
Vertical P
Horizontal
TOTAL
Air Flow
(fpm)
385
385
390
390
405
400
395
390
400
400
405
410
420
rofile:
Profile:
Vertical Profile:
Horizontal Profile:
TOTAL
Temp.
ฐF
168
170
171
171
171
172
172
172
172
172
171
171
169
167-171ฐF
168-172ฐF
167-172ฐF
380-410 Uni
385-420 Uni
380-420
2.2%
2.2%
2.9%
ts 7.9%
ts 9.0%
10 %
Stated accuracy of the air flow devices used is +5% which
-------
-24-
Th e following table reflects the total participate sample
weight in grams collected by each Andersen Sampler for all
sample runs at 1 cubic foot per minute flow rate which
indicates the practical homogeneity of the air-exhaust
mixture in the sampling zone.
Table 10
ACTUAL SAMPLE WEIGHTS FROM EACH ANDERSEN SAMPLER
Run #
3
4
5
6
7
8
9
11
12
13
14
16
17
1Diluent Air
2Diluent Air
B
.0420
.0481
.0825
.1868
.1060
.1301
.0999
.0727
.0402
.0053
.0095
__ _
.0007
C
.0399
.1215
.0011
.0427
.0638
.1923
.0950
.1191
.1032
.0704
.0419
.0077
.0080
.0088
.0006
D
.0988
.0015
.0417
.0781
.1836
.0858
.1117
.1006
.0606
.0396
.0088
.0043
.0059
.0005
Remarks
24 hours
46 hours
,11
n
n
n
M
ii
n
n
n
H
II
II
75 hours
, cycled
, cycled
, cycled
fiberglass filter assembly on dilution tube Inlet
2Dri-Pak filter assembly
i
Calculations for each test run regarding particulate
collected in the Andersen Samplers are based upon a simple
-------
-25-
C. GASEOUS EMISSIONS
1. Hydrocarbons
Unburned hydrocarbons are measured for engine cycles
2, 3, 4, and 5 during the 75 hour conditioning sequence
with each test fuel by the method described earlier in
the Exhaust Gas Analysis Section. Figures 5 through 17
indicate the effect of the conditioning sequence on exhaust
hydrocarbons presented as parts per million, mole percent
for all test fuels used in this study. The change during
steady-state and cyclic sampling in the dilution tube is
also shown.
Figure 18 indicates the percentage increase In exhaust
unburned hydrocarbon emissions for the simple average of
cycles 2, 3, 4, and 5 at 0 hours and at 75 hours, after
the engine conditioning sequence. For example, in Run #3
(Indolene HO 30 fuel) the unburned hydrocarbons as an
average of cycles 2, 3, 4, and 5 at 75 hours* increased
76% above the 0 hour (clean engine) average emissions for
these cycles.
2. Nitrogen Oxide
Figure 19 represents the average change in nitrogen oxide
(NO) emissions in the exhaust for engine cycles 2, 3, 4,
and 5 as a result of the conditioning sequence of 75 hours.
This data represent the increase (or decrease) in NO
emissions from clean engine to fully conditioned engine
-------
NO. 3<1-5V, DIETZGEN CRAPH PAPER * '
5 X S PER HALF INCH
EUGENE DIETZGEN CO.
MADE 'IN U. S. A.
T-TOTAUHYpROCARBON vsl
OPERATION
-; 50'-rr6
__
jrsT CycTe
" " "
-------
NO. 341-S'/i DitTZGKN GRAPH PAPER1
5X5 PER HA.LF INCH
EUGENE DlETZGEN CO.
HADE IN U. S. A.
-------
NO. 341 -5V. DIETZGEN UK'APH PAPER
5 X S PER HALF INCH
EUGENE DIETZGEN CO.
MADE IN U. 5. A.
-------
NO. 341 -S'/ป DIETZGEN GRAPH PAPER
S X 5 PCR HALF INCH
EUGENE OIETZBEN CO.
MADE IN U. S. A.
hTOTAL HYDROCA
-------
NO. 341 -5Vป DIETZGEN GRAPH PAPER-
S X S PER HA.LF INCH
EUGENE DIETZGEN CO.
MADE IN U. 5. A.
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-------
ND. 341 -5
-------
NO. 341-5VJ OtETZBEN GRAPH PAPER' '
S X S PER HALF INCH
EUGENE DIETZGEN CO.
MADE IN U. 5. A.
Figure 11
-------
5X5 PCR HA.UT INCH
MADE IN U. 5. A.
-------
ND. 3-ปI-S'/a OIETZGEN GRAPH PAPER '
5 X S PER HAUF INCH
EUGENE DIETZGEN CO.
MADE IN U. S. A.
-------
NO. 3-41-5V, OIETZGEN GRAPH PAPER
5 X S> "CR HALF INCH
EUGENE DIETZGCN CO.
MADE IK U. S. A.
ii! il I
ARBON vs'.-H
UJULNiNb;
40 : 50 r:60 r H
-- ^
-------
ND. 341 -SVi DIETZGEN GRAPH PAPER1
5X5 PER HA.LF INCH
EUGENE DIETZGEN CO.
MADE IN U. 5. A.
-------
NU.
b X 5 '"L!? HALF
EUl?ENE U'tTZlSCN CO.
M/tOE IN U. S. A.
' ' ' ' ; . i '. ; j
TOTAL HYDROCARBON vs. HOURS ENGINE OPERATION
Run No.
Code
-------
NO. 341 -5V. DIETZGEN GRAPH PAPER-
S X S PER HALF INCH
EUGENE DIETZGEN CO.
MADE IN U. S. A.
i TOTAL HYDROCARBON vs'J HOURS
NGINE OPERATION
j~Tt "~H:.' "
n r-r + -rr-;
imt'
; i . i i i
-------
t-
j. : j I I I j i i ,
-------
-------
-26-
D. FUEL ANALYSIS
The following
studies:
Distillation
D86, ฐF
IBP
5
10
20
30
40
50
60
70
80
90
95
E.P.
% Recovery
% Residue
% Loss
RVP :
Octanes:x
MON
RON
FIA:
% Saturates
% Olefins
% Aroma tics
cc/gal TEL
is the physical analysis of test fuels use
Table 11
PHYSICAL ANALYSIS OF TEST FUELS
Indolene Indolene Indolene* Indolene HO+
HO HO 15 HO 30 3cc TEL/Gal .
100
126
140
165
190-
207
221
231
244
268
320
368
395
96.5
0.6
2.9
7.3
87.5
97.4
66.4
4.2
29.4
0.06
88
118
137
166
190
207
220
236
249
272
332
386
398
96.0
0.6
3.4
7.4
,92,3
101.2
63.1
4.6
32.3
1.5
92
118
132
162
190
207
218
238
250
274
326
364
404
97
0.6
2.4
8.2
96.3
103.4
65.9
3.6
30.5
3.0
90
116
130
159
190
202
220
235
249
274
328
370
394
96
0.4
3.6
i 8.5
95.6
103.2
65.1
3,2
31.7
3.0
Indolene**
HO 30
90
118
133
162
188
208
222
234
249
273
320
368
394
96.5
0.5
3.0
95.9
102.9
68.1
3.d
28.9
3.0
* 1st load I
** 2nd load I
ndolene HO 30 Fuel
-------
-27-
These are the base fuels for all runs reported. Individual
physical analysis of each additional test fuel was, therefore,
not conducted. Analysis of each fuel was conducted to verify
concentration of additives being used, however.
Trace metal analysis of the 2nd batch of Indolene HO 30 fuel
is shown below:
Table 12
TRACE METAL ANALYSIS OF INDOLENE HO 30 FUEL
Fe
Ni
Cu
Mg
Zn
Al
Ca
Mn
Sb
Ti
<1
<0
<0
<0
<3
<1
<1
<1
<1
<1
.0
.5
.2
.5
.0
.0
.0
.0
.0
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
The weight percentage of carbon (C) and hydrogen (H) in several
s*'
of the test fuels was determined by an automated 4*regl mjLcro-"';
analysis combustion technique. The fuel is: first pyrolized
in argon to avoid explosion hazard. Results are shown in
Table 13 and were used for exhaust gas volume calculations.
Table 13 \
WEIGHT PERCENTAGE CARBON (C) AND HYDROGEN (H)
IN SEVERAL TEST FUELS
Fuel Wt. % C Mt. % H
Indolene HO 30 86.4, 86.3 13.19, 12.99
Indolene HO 15 85.7, 85.9 13.11, 13.07
Indolene HO 0 86.3, 86.2 13.28, 12.91
Indolene HO 0 + Rfi . ft, , ,~ ?fi , -, .,,
-------
-28-
As these are basic fuels used for all runs reported, this analysis
was not repeated for each specific test run fuel mix.
E. ENGINE OIL TRACE METAL ANALYSIS
The following table shows results of trace metal analysis
on new and used Amoco 100 SAE 30 motor oil used in all tests
reported herein. Analysis is by Emission Spectroscopy and
results are reported in weight percent.
Table 14
TRACE METAL ANALYSIS OF NEW AND USED ENGINE OIL
Element
Fe
Ni
Cu
Al
Ca
Si
Mg
Mn
Pb
Cr
Sn
Zn
Ti
P
Mo
Amoco 100
New
.0002 wt.
<.0001
<. 00002
.0001
.0017
.0001
.089
.0001
.0006
<.0001
<.0001
.081
<.0001
.05
<.0001
Run #5*
Oil Filter
<.0001
Run #13**
Oil Filter
.0012
Run #13**
Crankcase
.012 wt. %
<.0005
.0003
<.0005
.0057
<.0005
.083
<.0005
.12
.0008
<.0005
.078
<.0005
.012 wt. %
<.0005
.0002
.0013
.0028
.0010
.084
<.0005
1.3
.0055
<.p005
.082
<.0005
.012 wt.
<.0005
.0002
.0012
.0026
.0030
.088
<.0005
1.3
.0048
<.0005
.076
f>.
<.000'5
.0011
*Indolene HO Fuel
-------
-29-
F. ENGINE COMBUSTION CHAMBER DEPOSITS
Total combustion chamber deposits from all cylinders of the test
engine for all sample runs are shown in Figure 20. Runs 11,
13, and 16 are not shown as runs 12, 14, and 17 were made
directly after these runs without cleaning or re-conditioning
the engine. Deposits are shown in grams. Each run is of
somewhat different duration notably those such as run 11/12
where steady-state and cycling sampling runs are conducted.
Total engine hours for each run are shown at the top of each
data bar.
Combustion chamber deposit analyses for these runs are shown
in Table 15:
Table 15
ENGINE COMBUSTION CHAMBER DEPOSIT ANALYSIS
Run #
4
5
6
7
8
9
12
14
Wt. %
Pb
64.6
5.9
54.9
72.0
59.8
67.9
66.4
65.6
Wt. %
Fe
0.26
1.1
0.27
0.2
.18
.217
.177
.190
Wt. %
c
5.7
55.9
12.0
11.0
7.8
7.4
6.01
6.08
Wt. %
Br
8.21
0.55
8.19
0.6
20.67
0.55
9.10
9.12
Wt. %
Cl
10.81
0.57
9.78
0.28
0.58
13.55
8.99
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-30-
G. MICROSCOPY (P. Traylor)
1. Introduction
The responsibility of the Microscopy Laboratory is to apply
light, transmission and scanning electron microscopies in
characterization of the automotive exhaust particulates
relative to:
1. Color
2. Size
3. Shape, Form
4. Fusion Characteristics
(a) Melting point
(b) Sublimation
(c) Crystallinity
5. Electron Diffraction
6. Solubility
7. Organic-inorganic Composition
8. Elemental analysis by X-ray fluorescence while in the
scanning electron microscope.
The plan of attack up to this point for the Microscopy group
included the development of sampling techniques for the charac-
terization work, developing characterization techniques
and skills, making characterizations, and establishing the
most useful parameters for future work. The immediate goal
was to become well acquainted with the exhaust particle as
rapidly as possible and be prepared to read out characteristic
changes relative to changes in fuel composition and engine
-------
-31-
The work on the exhaust particle was divided into four
parts. Submitted here will be summary reports of what
has been accomplished. Each summary report will contain
either a copy of or examples of all routine laboratory
reports submitted on the individual runs.
These summary reports deal primarily with the responsibilities
mentioned above.
2. Scanning Electron Microscopy and X-Ray Fluorescence
Analysis - (Lois Settlemeyer)
a. Purpose
To characterize (SEN!) and id-entify (x-ray spectro-
meter) the particulates in exhaust emission
collected by the Andersen Sampler or collected oh
the Millipore filter following the sampler.
b. Instrumentation
Cambridge Stereoscan Mark 2A
Ortec non-dispersive x-ray detector
Nuclear Data Analyzer
Varian Vacuum Evaporator
Kinney Vacuum Evaporator
c. Work Outline
1) Particle characterization (SEM) on plates
1, 3, and 6 of the Andersen Sampler.
2) Particle identification (x-ray).
3) Single element x-ray scan.
4) X-ray spectra on impingement area of
plates 1, 3, and 69 and spectra on final
-------
-32-
Techm'que and Methods
1) Substrates - Initial sampling for the SEM was
t
by breaking the glass collection plates used in
the Andersen sampler. This was awkward and often
resulted in loss of particulate. Because, of this
various substrata were attached to the Andersen
collection plate with double adhesive tape. Micro
cover glasses, mylar strips, epoxy with lamp black,
and ultra pure carbon strips were tried. Most
satisfactory were micro cover glasses, but the
ultra pure carbon strips proved best where x-ray
analysis was to be done. Silica interference
from the micro cover slips, halogens in epoxy,
and thermal instability in mylar film reduced
their desirability for x-ray substratum.
2) Conditions for Andersen Sampler - The initial
purpose of this analysis was to identify and
characterize individual particles (Ip.to 5Qy).
Sampling with the Andersen Sampler at a flow
rate of 1/2 CFM yielded sufficient particulate
for documentation and reduced breaking and
piling as was evidenced at 1 CFM.
3) Storage and Sample Preparation - All samples were
maintained in a dry atmosphere from collection ;
to examination. Both the glass cover slip and the
carbon, strip were attached to SEM sample stubs with
conducting silver paint. Samples for SEM character-
ization were made conductive with a thin layer
(%200 A) of gold or gold-palladium evaporated onto
under vacuum (5 x 10 Torr). Graphite carbon >
was sputtered on the samples used for x-ray
-------
-33-
4) Normal Operation for the Stereoscan -
a) Gun potential - 20 to 30 kv (depending
on degrading of sample and resolution
needed)
b) Vacuum - ^10" Torr maintained
c) Sample angle - 20ฐ
d) Working distance - 11 mm
e) Polaroid P/N Type 55 film with 100
sec. exposure
5) Normal Operations for X-Ray Detector
(warranted 215 ev FWHM resolution)
a) Gun potential - 30 kv
b) 1024 channel - analog to digital converter
c) Collection time - 200 sec.
d) Count rate - ^600 c.p.s.
e) Spectra recorded on Moseley 7035B X-Y
recorder
f) Single channel recording
Polaroid P/N Type 55 film
400 sec or 800 sec. exposure depending on
concentration
e. Results
1) Particle documentation - All particles were
classified into basic groups (1) individual
partic!e - one structural type >3y (Figures;
21, 22, and 23); (2) agglomerate - a single
mass of
-------
-------
-------
-------
A G G L 0 M E R A T E
BLANK--FLY ASH
C-ATYP, I C A L
-------
-------
The fines from one run to another and from
one tray to another differed significantly.
Two possible reasons for th,1s: 1) mass
differences, 2) different substratum. In
one case, fines collected equidistant from
an impingement point, but on different
substratum revealed different types of fines.
Some of these fines, particularly runs #5 and
#12, degrade under the beam [indicating either
the presence of organics or .highly volatile
inorganics.
2) Particle Identification (X-r.ay) - In most
cases background and variations were observed.
Characteristic of diluent blank runs (Figure 24)
were particles high in 1ron.< Several different
particle shapes would yield ;Pb:Cl:Br and likewise
some particles very similar in crystalline form
would yield different spectra. Due to the M
orbital of Pb being the same' energy as the Ka
orbital of S, positive identification of sulfur
in the presence of lead cannot be made. At
present, no correlation between shape and
chemical identification has been made.
3) Single Element X-ray Scan - This mode of
operation allowed the presence or absence of
a single element in a group of particles to be
determined. The element most often scanned was
lead. Individual particles most noticeably
! "
-------
-------
Run 11
-------
Run 12
-------
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Figure
-------
-------
Figure 32
-------
can also be identified using SEM for characterization
and electron diffraction for identification with mapping
of finder grids. Thus far the qualitative approach to
individual particles has been used. In the future a
frequency distribution w'11 make the results more
quantitative as well as qualitative.
Scanning Electron Microscope Photomicrographs and X-Ray
spectrum for several runs are shown in figures as noted
below:
Table 16
SCANNING ELECTRON MICROSCOPE PHOTOMICROGRAPHS
AND X-RAY SPECTRUM FIGURE DESIGNATIONS AND
DESCRIPTIONS
Run #7 Indolene HO 0 + 3 ml/gal TEL
Figure 32 5000X
Plate #1 Andersen Sampler
Figure 33 10.000X
Plate #1 Andersen Sampler
Figure 34 20.000X
Plate #1 Andersen Sampler
Figure 35 Various X
Plate #6 Andersen Sampler
Run #8 Indolene HO 0 + 3 cc/gal TEL + It EDB
Figure 36 10.000X
Plate #3 Andersen Sampler
Figure 37 20,OOOX
Plate #3 Andersen Sampler
Run #9 Indolene HO 0 + 3 cc/gal TEL + It EDC
Figure 38 Various X
Plate #1 Andersen Sampler
Figure 39 10.000X
Plate #1 Andersen Sampler
Figure 40 , 20.000X
-------
Figure 33
-------
Figure 34
-------
Figure 35
-------
F i gu re 36
-------
Figure 37
-------
Figure 38
-------
Figure 39
-------
Figure 4Q
-------
Run #11 Indolene HO 30, Steady-State Sampling
Figure 41 1000X and 2000X
Left side, particles plate #1 Andersen Sampler
Right side, Pb scan of same areas with x-ray
detector
Figure 42 5000X
(B) Plate fซl Andersen Sampler
(C) Pb scan (B) area
(D) Cl scan (B) area
Figure 43 10.000X and 20.000X
Plate #6 Andersen Sampler
Figure 44 X-Ray Spectra
(D) Particle Figure 55
3. Light Microscopy and X-Ray Characterization -
(Howard Garrett, S. Rinn)
a. Purpose
This part of the microscopy analysis can be divided into
two sections: (1) Documentation at low magnification to
show the particle distribution and several impingement
points on collection plates 1, 3, and 6 of the Andersen
Sampler. (2) Documentation of particle size range and
character using polarized light at 400X on plates 1, 3,
and 6 of the Andersen Sampler, plus the Millipore filter.
X-ray diffraction identifications were made on'these same
samples by H. W. Rinn of the Chemical Physics Research
Laboratory. An effort was made to correlate crystal
character (as seen by polarized light) with chemical and
physical composition.
b. Results
The main purpose of the low magnification photomicrography
was documentation. There were differences between runs
-------
-------
Figure
-------
20.000X
-------
-------
or describing some aspects of the higher magnification work.
This work also shows a rough comparison, of the amount of
material on a particular plate of different runs and compares
an actual run with a diluent air blank run.
The polarized light microscopy and the attempt to correlate
the polarized light microscopy with x-ray diffraction identi-
fications have not been as informative as was hoped for,
but nevertheless have produced some valuable information.
The x-ray diffraction identification of the crystalline
species has been invaluable as this technique has been able
to identify the different crystalline species from the
various runs and has even shown different species on the
various trays of the Andersen Sampler and Millipore filter
of a given run.
Judging from the photomicrographs (15X) there is a vast
difference in the quantity of material collected on a
sample run (Figure 45) as compared to a blank run
(Figure 46). There is considerable variation in the
amount of material and the pattern of the deposit within
the various sample runs. The remainder of the results
will be divided into several topics.
c. Particle Size
Although gross variations occur between some runss KB
can make some broad generalizations as follows:
1. The particles on plate 1 are usually in the
5-20y range.
2. The particles on succeeding plates gradually
decrease in size until plate 6 has most of
its particles in the ly range although larger
particles may be found also.
3. The Millipore filter has the finest particles
(ly and below) although Run #8 had clear
-------
Figure 45
-------
Figure 46
-------
d. Particle Description
1) Diluent Air Blank Run - This consists of a
wide variety of particles which might be
classified as dirt and contains such species as
(a) spherical, glassy fly ash particles and
(b) highly birefingent particles which are probably
calcite. Calcite may be used in scouring powders
and could originate from that source. Traces of
calcite are observed in most runs, especially on
plate 3. Such trace quantities are not detected
by x-ray diffraction.
On blank runs 6-B and 7-B lead compounds from the
engine which was being cycle conditioned in the
test cell were also detected - especially on plate 3
2) Sample Runs - The major particles varied from
single transparent crystals to translucent
agglomerates. The external morphology of the
particles is impossible to define by polarized
light microscopy but this is described under SEM
and x-ray. Although several crystalline species
have been identified by x-ray diffraction, it has
not been possible to identify these particles by
polarized light alone because of the similar
morphology of the different crystalline species.
Also a particular species such as lead chlorobromide
may appear as transparent single crystals in one
run (#11) and appear as translucent agglomerates
in the next (#12).
Black opaque particles are usually present on plates
1 and 3 and they are probably flakes of Fe30. from
-------
e. Color
The preliminary samples which were received when the
methods were being developed showed some color variations
so color film was used. However, later samples have not
shown significant color worth recording so the use of
color was discontinued after Run #4.
f. Chemical Composition and Crystal Species
This portion of the report is the work of H. W. Rinn of
the Chemical Physics Research Lab, Although some variations
do occur, we can make the following general conclusions:
1. The most common solid particulate from Indolene
HO 30 gasoline is lead chlorobromide with an
unknown species designated as UP 1875 also present.
The UP 1875 appears to be another crystallographic
form of lead chlorobromide.
2. Leaded gasoline in combination with ethylene
dibromide gives lead bromide plus a bromine rich
form of UP 1875.
3. Leaded gasoline in combination with ethylene
dichloride gives lead chloride plus a chlorine
rich form of UP 1875.
4. Leaded gasoline without scavengers produced
chiefly 4PbO-PbS04 plus some PbS04ปPb3(P04),
and Pb5(OH,X)(P04)3.
4PbO-PbS04 was also found in Run #17 along with
Pb5OH(P04)3 and lead chlorobromide.
The x-ray diffraction method is capable of identifying
only the crystalline species so there is some question
whether any non-crystalline species are present which
would not be detected. A summary of x-ray diffraction
-------
Run#
TABLE 17
X-RAY DIFFRACTION DATA
Fuel Crystalline Species Present
Indolene HO 0
+3 ml/gal TEL
+It EDB
PbBr2
UP 1875* Chief constituent on
Andersen Plate 6 and Filter
11
12
Indolene HO 0 +
3 ml/gal TEL
+ It EDC
Indolene HO 30
11 , cycled
PbCl2
UP 1875 (high Cl) and
5-10% PbCl2 on Andersen
Plate 6
UP 1875 only, Filter
Pb (Cl , Br)2
UP 1875 present (20-30%)
on Andersen Plate 6 and
Filter
Pb (Cl, Br)2
UP 1875 5-10% to 10-20%
from Andersen Plate 1 to
Filter.
13
Indolene HO 30
+ DMA-4A
Pb (Cl, Br)2
UP1875 10-20% on
Andersen Plate 6 and
20-30% on Filter
14
Indolene HO 30+
DMA-4A cycled
Pb (Cl, Br)2
UP 1875 50% on Andersen
Plate 6 and 30-40%
on Filter
-------
15 Blank Quartz
(Diluent Air) Calcite
NaCl
NH4C1
all weak lines
16 Indolene HO 0 Pb (Cl, Br)2
NH4C1
(P04)3
17 16, cycled Pb (CT, Br)2
NH4C1
Pb5 OH (P04)3
4PbO-Pb S04 (trace)
4. Transmission Electron Microscopy Characterization -
(Penn Schloemann)
The purpose of this work using the transmission electron
microscope is to characterize the particles smaller than
one micron and obtain crystallographic analysis of the
particles by means of electron diffraction.
The electron photomicrographs and diffraction patterns were
made from the exhaust particles collected on electron micro-
scope grids. The grids were placed on Andersen Sampler
collection plates 1, 3, and 6 and on the Millipore filter.
Usually no mounds or impingement points appeared on the grids,
so that the photomicrographs represent the area between these
points. The particles documented range in size from 100 to
o
1000A. Sometimes, a particle as large as 10 microns is shown.
Besides the importance of documenting the small particle, the
transmission electron photomicrographs show the difference
and similarity in particle character among the runs and also
between the runs and the blanks. For example, Blank Run #15
appears to be the most different of all the runs. The particles
-------
Run 9 was picked to study the electron grids for the presence
of organic particles. A photomicrograph was made and then
the grid was washed in the hot vapors of hexane and the same,
or a similar, area was photographed again. The only difference
observed appeared on plate 6 where some of the small particles
next to a large one were dissolved away.
Sometimes the particles undergo a change in appearance from
black to white under the electron beam. This is shown in
photos of Run 12, Plate 1, (top, Figure 49). The exact change
taking place is not known, but electron diffraction patterns show
a slightly different compound to be present after the change.
i
This has been the progress of the transmission electron work thus
far: (1) to document the particles, (2) to compare the particles
in each run, and (3) to note any peculiarities in the sample.
Progress has also been made in the area of electron diffraction
analysis.
Figures 47 through 50 are examples of the photomicrograph
for runs 9 and 12 as follows:
Figure 47:
Figure 48:
Figure 49:
Figure 50:
Run #9 Plate 1 - top half
Plate 3 - bottom half
10,000 and 60.000X
Run #9 Plate 6 - top half
Filter - bottom half
10,000 and 60.000X
Run #12 Plate 1 - top half
Plate 3 - bottom half
10,000 and 60.000X
Run #12 Plate 6 - top half
Filter - bottom half
-------
ngure a,/
-------
Figure 48
10 K
60K
-------
-------
Figure 50
k'^ *N*
-------
-44-
H. MASS SPECTROMETRIC ANALYSIS - (J. C. Tou)
Mass spectrometry was used in this project for the semi-
quantitative and qualitative comparison of the levels of
NH3, H20, HC1, and organics on the auto exhaust particulates
obtained from an engine using different types of fuels and
fuel additives and under different operating conditions.
Different mass spectrometric techniques were tried and their
advantages and disadvantages are discussed in this section.
The mass spectra were obtained at 70 ev using a standard
90ฐ magnetic sector mass spectrometer. The sample was scraped
from the trays of the Andersen Sampler, weighed and devolati1ized
in a 500 cc reservoir. The vapors were introduced into
the ion source through a 2 mil diameter molecular leak while
the inlet system was held at 200ฐC. In an attempt to avoid
the changes in the composition during sampling, the scans
were delayed one minute to assure complete volatilization
of organics. Both the masses and the intensities of peaks
were digitized automatically during scanning of the mass
spectrum. A low energy (^10 ev, uncalibrated) mass spectrum
of one sample showed the presence of intense peaks at m/e=17,
18 and 36 which could be due to NH3, H20, and HC1. These
tentative identifications were extended to other samples.
Assuming that the average instrumental sensitivity for the
components in the sample remained approximately constant
between samples, the 'following quantities were calculated
as a measure of the relative amounts of NH-, H20, HC1 and
organics respectively.
r
- 0.21
Wx
I,]
NH3,
HC1
and
I
1 8
W x St
200
i = 40
_ W x St
I,
H,0
-------
-45-
where I, is the intensity of the peaks at m/e = i, W the
weight in mg of sample loaded, $t the toluene sensitivity
of the mass spectrometer on the day when the samples were
run.
The term 0.21 I18 in the case of NH, was introduced to correct
J +
for the contribution of the fragment ion HO from HpO to
the intensity of the peak at m/e = 17. The mass spectral
profile of organics in the auto exhaust particulates was
plotted using a B-5500 computer by connecting the mass to
charge peak tops after the intensities of the peaks had been
normalized by the computer according to the following formula:
E I-
j = 25 J
j t 28, 32, 44, 36, 38
Plots were made of the data for those spectra with enough
intensity to be judged significant. The plotted profiles
allow one to make a direct comparison of the relative changes
in organic composition for the samples obtained at different
engine conditions.
The direct probe sample introduction technique was also
used in the characterization of the particulates. This
technique allows the sample to be heated up to 600ฐC in
a miniature oven located a few mm away from the electron
beam in the mass spectrometer. The mass spectra were taken
-------
-46-
of PbClBr, PbBr2 and organic components giving peaks at
m/e = 43, 55, 57, 69, 71, et al. However, the technique
did not allow one to observe the differences between samples.
A combination technique of direct probe and field ionization
mass spectrometry was also tried. Field ionization mass
spectrometry is a technique of ionizing the molecules with
O
a high electric field in the order of O.lv/A. This is a
much milder means of ionization than electron impact. Hence,
the fragmentation of a molecular ion is very much reduced
in the field ionization mass spectrum and thus the spectral
features are simplified. The field ionization mass spectra
of only one sample were obtained using a CH4B mass spectro-
meter and these were weak and complex. However, peaks 14
masses apart are clearly shown in some of the spectra. Two
series of peaks were observed: a) m/e = 92 + 14xn, where
n=0-6 or higher, b) m/e = 94 + 14xm, where m=0-4 or higher,
which might be due to the molecular ions of:
OH
s.
and
respectively. The disadvantage of not being able to observe!
the difference between samples involved in the direct probe
technique for characterizing the particulates also remains
in this approach.
l<
High resolution mass spectrometry was also used in this study
to find the accurate masses of the ions observed in the mass
spectrum within an accuracy of 5 millimass units. The accurate
masses were used for the calculation of the elementary com-
positions of the ions which should reflect the composition
of the sample to some extent. The high resolution mass spectrum
was recorded on a photo plate by using a CEC HOB high reso-
lution mass spectrometer. The data were processed with use
-------
-47-
It was found that the data obtained were extremely complex
and difficult to interpret. However, the hydrocarbon ions
were clearly shown in the high resolution mass spectrometric
data.
Table 18, as an example, indicates the relative values for
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plate and filter for each test fuel is shown graphically in
Figures 51 through 63. Figures 64 through 72 are examples of
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for run #11 (Indolene HO 30) and run #16 (Indolene HO 0).
The less the amount of sample available, the less accurate
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from the fiberglass filters were contaminated with filter
fiberglass. Hence, the calculated values on Table 18 for
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will not be affected by the presence of fiberglass.
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i...L;J_',i...L:.l, .i :...i . .'. i ;'.L .,i. rp-o-rD*
ANDEHSEIT.PLAIM NtJMBER
6
Figure
-------
4 .
tr
4 r :
i ;
~n
ooooo
IONS 17
NH.
J '
: H h-'r?
i r~1 1 i '
i oOh-H-'T-.-
F7 ' i
'W
-CO
"g!.FpJ_i"
.... ^ |~t"~|- ";""i ~~
iffiTi:
;ซ
-co
:a:
'En i
!ซ
|W
-",0
..i9t
P-,
is
: .-
...-,....-.
I , Ml I
_| i l . I i j j: i I
...nti'in "LT:'.'. "j. * ."ii
i-.-'i T-!
JLLJ-*
iiJ_LL:^-jrjU: ._l _ i
i8j " 36 - 200
H00^': HC1 * I,
\ '' 1-40
Organics
o-o-o ooo
i:L!.l:r:'
11,' * i'.
I ^L'"""": ;"
' a. I
i i ^
I r
_j.-j. ij-
__i. . .i...
Oi
LLJW
W
-t^M-r-rr
.001
" I
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I^Fi ;n".'i-j-.;
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nti-
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LH
***
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ซfl^&
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... ,. .,...:...;
-------
10.0 .,
RUN ll.TRRY 1
1.0
0.1
CAtlfOBNi' COM'UTER PRODUCTS. INC. ANAHEIM. CALIFORNIA CHAKT NO. 4OO
-------
10.0 .,
RUN ll.TRRY 2
1.0
0.1
-iti LJ" i* i M 'i'a*
'25 50 ' ' 7j ' ' '
I I I I J_l I 1 I
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CALIFORNIA COMPUTER PRODUCTS. IMC. ANAHEIM. CAUTOIWIA CHART MO. 4OO
-------
10.0 .,
1.0
0.1
RUN ll.TRRY 3
Vi ' ' ' Tdr-^-W*
CALIFORNIA COMPUTER PRODUCTS. IHC. AKAHEIM. CAUTORNU CHART NO. 4OO
-------
10.0
1.0 .
0.1
CHART NO. 40O
RUN ll.TRRY
CALIFORNIA COMPUTER PRODUCTS. INC. ANAHEIM. CALIFORNIA CHART HO. 40O
-------
10.0 _
1.0
0.1
RUN ll.TRRY 5
JTER PROOUCT5 INC. ANAHEIM CALIFORNIA CHART NO. 4OO
CALIFORNIA COKPUTIR PROOVCTS. INC.
-------
10.0 _
1.0 .
0.1
RUN ll.TRRY 6
iiie^ii i i i.j-i i i iii i t i.j.itii.j_i ii i-j.i t i
CALIFORNIA COMPUTER PBODUCTt. INC. ANAHEIM. CALIFORNIA CHART NO. 40O
-------
10.0 .,
RUN 11.FILTER
1.0
0.1
''SB ' ' ' '7J ' ' ' 'idd' ' ' 'TIS
1 ' ' '' ' '
' '
' ' '' ' ' '' ' '
'260' ' ' 'ads
CALIFORNIA COMPUTER PRODUCTS, INC. ANAHEIM. CALIFORNIA CHART NO. 4OO
-------
10.0 _
1.0 .
0.1
RUN NO-16 TRflY 1
-------
10-0 _
RUN NO.16 TRflY 4
1.0
0-1
5d
-------
-48-
Table 18
RELATIVE VALUES OF THE AMOUNT OF NH3, H20,
HC1, AND ORGANIC MATERIAL PRESENT IN ANDERSEN
AND FILTER SAMPLES BY MASS SPECTROMETRY
Run #
4
4
4
4
4
4
4
4
4
4
4
4
4
4
Pla
Sli
1
2
3
4
5
6
Fil
te
t A
B
C
D
E
F
G
ter
NH3/
mg sample
0.0017
0.003
0.03
0.03
0.03
0.03
0.03
0.013
0.013
0.017
0.051
0.143
0.247
0.258
H20/
rug sample
0.027
0.096
0.070
0.086
0.11
0.12
0.10
0.013
0.014
0.019
0.048
0.089
0.089
0.133
HC1/
mg sample
0
0
0
0
0
0
0.002
0.004
0.002
0.002
0.023
0.134
0.183
0.161
Organic
Level/
mg sample
0.020
0.11
0.066
0.093
0.066
0.066
0.060
0.084
0.109
0.131
0.387
3.120
1 .654
0.877
Sampl e
Wt.
(mg)
10.10
10.40
10.25
7.50
9.15
4.70
2.00
28.20
17.10
11 .25
5.00
4.90
3.30
4.90
I. ULTRAVIOLET FLUORESCENCE SPECTRA - (R. A. Bredeweg)
Automobile exhaust particles were extracted with cyclohexane and the
ultraviolet and fluorescence spectra were run. The absorbance
*
at 255my and the fluorescence area using an exciting wavelength
of 290my were used to calculate relative amounts of UV absorbing
and fluorescent compounds present. The total amount of absorbing
and fluorescent compounds do not seem to vary significantly
from one run to the next, however, the amount present in a given
sample weight increases with non-leaded gasoline and with the
decreasing particle size.
1 . Introduction
A quick standard procedure for the determination of
relative amounts of aromatic organic materials present in auto-
-------
-49-
available to develop separation procedures and determine
individual components, a general procedure of determining
the ultraviolet absorbance and a value for fluorescence was
used. ! These techniques detect the aromatic organics present
including the poly-nuclear aromatics. Samples were received
on Andersen glass plates and in bottles. The bottled samples
had been obtained by sweeping out the inside of a tube used
in place of the exhaust system and from trays that were
located beneath slits in the tube.
2. Procedure
a. Sample Handling
The residue from the Andersen glass plates was scraped loose
with a razor blade and transferred to a small tared watch
glass with a small camel hair brush. The sample weight
was obtained using a Mettler micro balance. The sample was
then transferred to a 15^ml screw cap centrifuge tube (the
cap of the tube should be lined with foil or Teflon) and
2-10 ml of cyclohexane (purified by passing through a silica
column) was added depending on expected organic concentration
Andersen plates with <1 mg of residue present were handled
by placing the glass filter in a petri dish and adding 5 ml
of the cyclohexane.* The dish was rotated in such a manner
as to rinse the filter thoroughly, then the solution was
transferred to a screw-cap centrifuge tube. The procedure
was repeated with 5 more ml of solvent and the solution
evaporated to 2 ml by passing a stream of nitrogen over the
solution. The sample weight was obtained by weighing the
filter before and after use.
*Run #5 - May have low results since an attempt was made
to scrape the small amount of sample from the filter
-------
-50-
Approximately 10 mg of the bottled samples were weighed in
a small porcelain boat and transferred to the 15 ml screw-
cap centrifuge tubes and 10 ml of solvent added.
The centrifuge tubes were capped tightly and the caps pre-
vented from loosening by wrapping with rubber tape. The
tubes were placed on their sides in an automatic shaker
and shaken for a minimum of 5 hours. The rubber tape was
removed and the solution centrifuged until clear and then
the liquid was decanted into screw-cap bottles.
b. UV Absorption Measurements and Calculations
A Gary Model 15 spectrophotometer was used with 1-cm silica
cells. When adequate solution was not available, a 1-cm
semi-micro cell (volume '0.5 ml) was used. The solutions
were scanned from 400-220mp, diluting when necessary to
keep the absorbance less than 2.0. All the samples gave
very similar shaped spectra with a distinct maximum at 255my
The absorbance at 255mp was used as a measure of the organic
content. A relative value of UV absorbing material present
was obtained by calculating the absorbance for 1.0 mg of
residue in 1.0 ml of solvent x 1000 (Tables 19 and 21).
An estimation of the relative total absorbing material present
on an Andersen plate can be obtained by multiplying the
sample weight in mg times the number obtained above.
i
c. Fluorescence Measurements and Calculations
An Aminco-Bowman spectrophotofluorometer equipped with a
Moseley model 135AMX-Y recorder and standard 1-cm cells,
polished on all sides, was used for the fluorescence mea-
surements. When adequate solution was not available, a
semi-micro cell (Volume -0.5 ml), polished on all sides,
-------
-51-
Table 19
RELATIVE AMOUNTS OF UV ABSORBING MATERIAL
PRESENT ON ANDERSEN PLATES
Run #
Plate #2
mg sample
Absorbance*
Plate #4
mg sample
Absorbance*
Plate #5
mg sample
Absorbance*
1
1
1
1
1
Bl
1
1
3
4
4
5
6
7
8
9
1
2
3
4
5
ank
6
7
7
24
10
0
8
15
22
15
24
'19
14
8
0
1
0
.93
.6
.8
.13
.56
.3
.7
.4
.1
.7
.9
.49
.1
.1
.9
240
520
560
810
680
720
380
730
640
370
500
300
2400
13500
8670
2.
13.
6.
0.
2.
8.
8.
7.
6.
8.
5.
4.
0.
0.
19
7
27
18'
71
73
27
86
34
55
34
44
3
6
750
850
680
360
2620
830
1000
1810
1780
860
1950
480
34400
10700
1
6
3
3
4
5
7
3
2
<0
0
1
.40
.15
.54
.92
.93
.39
.32
.38
.65
.1
.6
.0
2020
4620
1550
2940
4460
4220
2360
3440
1160
assumi ng
0.1 mg
13400
17500
6940
*Values are calculated on a basis of Absorbance @255my for 1.0 mg
of sample in 1.0 ml of solvent x 1000. A relative value for the
total amount UV absorbing material on a particular plate can be
obtained by multiplying the sample weight in mg times the above
value.
-------
Table 20
RELATIVE AMOUNTS OF FLUORESCENT MATERIAL
PRESENT ON ANDERSEN PLATES
Run #
3
4
4
5
6
7
8
9
11
12
13
14
15
Blank
16
17
Plate #2
mg sample
Fluorescence*
7.93 240
24.6 190
10.8 240
0.13 840
8.56 260
15.3 310
22.7 130
15.4 140
24.1 60
19.7 70
14.9 110
8.49 100
0.1
650
Plate #4
mg sample
Fluorescence*
2.19 570
13.7 440
6.27 350
0.18. 500
2.71 1320
8.73 470
8.27 420
7.86 280
6.34 250
8.55 180
5.34 320
4.44 230
Plate #5
mg sample
Fluorescence*
1.40 1580
6.15 1790
3.54 880
3.92 1750
1.1 290
0.9 '.1480
0.3 3570
0.6 2380
4*93 320
5.39 190
7.32 190
3.38 550
2.65 180
assuming
<0.1 0.1 mg
5400
0.6 2260
1.0 1480
*Values are calculated on the basis of area (in. x 100, with a
planimeter) for 1.0 mg of sample in 1.0 ml of solvent, with instru-
ment settings of excitation wavelength = 290mp, slits = 2mm, sen-
sitivity = 0.01, and vertical scale of recorder at a setting of 5.
A relative value for the total amount of fluorescent material on a
particular plate can be obtained by multiplying the sample weight
-------
-53-
Table 21
RELATIVE AMOUNTS OF UV ABSORBING AND FLUORESCENT MATERIALS
PRESENT IN SWEEPING AND SLIT SAMDLES
(See Notes at Bottom of Tables 19 and 20)
Relative Relative
Run #
l\ U 1 1 TT
13 - Sweeping A
B
C
D
E
F
G
Slit 1
2
3
14 - Sweeping A
B
C
D
E
Slit 1
2
Sample Wt.
in mg
9.49
9.41
9.31
8.95
8.85
7.69
12.1
11 .1
7.90
9.49
13.4
9.83
11.9
8.70
4.48
8.87
10.0
, Absorbance
Val ues
340
180
: 180
: 600
800
910
770
40
50
20
210
90
T
40
270
1010
50
30
h 1 uorebi-Kii i.
Values
320
110
110
300
350
340
290
20
30
20
160
50
30
140
510
30
-------
-54-
source and the wide portion (1 cm of solution) facing the
detector. Various excitation wavelengths were examined
(290, 330, and 353my) with 290my giving, in general, the
most detailed and intense spectra. Exceptions to this are
plate #5 from runs 9, 11, 12, 13, 14, and 16 and all of run
17, where the 353mn exciting wavelength gives a more intense
spectra (353my is used by some authors for determining poly-
nuclear aromatic compounds). The area in in.^ x 100 under
the fluorescence peaks at an excitation wavelength of 290my
was determined with a planimeter. A relative value of the
fluorescence area for 1.0 mg of residue in 1.0 ml of solvent
at a sensitivity setting of 0.01, with all slits at 2mm,
the wavelength (x) scale on the recorder set at 20 fixed
and the intensity (y) scale on the recorder set at 5 fixed
(Tables 20 and 21). An estimation of the relative total
fluorescent material present on an Andersen plate can be
obtained by multiplying the sample weight in mg times the
number obtained above.
3. Discussion of Results
The absorbance and fluorescence values tend to give similar
variations on all the samples. In general, the smaller particles
have the highest concentration of detectable organic material
present. The concentration also increases when no additive
gasolines are used; however, the total residue is also decreasing
and, therefore, the total detectable organics in a given size
range do not vary significantly with additive. The sweeping
samples indicate an increase in organics at a further distance
down the tube, while the slit samples are very low, which may
be due to the low contact with exhaust fumes. The fluorescence
curves may be the most useful in the future in correlating to
actual percentage amounts of various classes of organic compounds,
since spectra has been obtained at excitation wavelengths of
-------
-55-
J. PARTICLE TRACE METAL ANALYSIS
Trace metal analysis of participate samples from all sources
has been conducted for run #11 and #12 (Indolene HO 30 steady-
state and cycled). Analysis is by Emission Spectroscopy and
the data is presented in Table 22.
Table 22
PARTICULATES: TRACE METAL ANALYSIS
Run #11 Slit Samples
wt. :
Fe
Cu
Al
Ca
Si
Mg
Mn
Cr
Sn
Zn
Ti
Ni
Mo
Wt. 5
Fe
Cu
Al
Ca
Si
Mg
Mn
Cr
Sn
Zn
Ti
Ni
I 1 2
4.0 5.6
0.012 0.015
0.092 0.16
0.071 0.065
0.060 0.13
1.8 1.3
0.035 0.044
0.042 0.043
0.033 0.024
3.8 6.1
<0.010 <0.010
<0.010 <0.010
0.011 0.007
Andersen Tray
K 1 2
.16 .19
.018 .026
.032 .08
.13 .10
.039 .038
.066 .063
<.005 .005
<.01 .012
< . 01 < .01
.068 .059
< . 01 < .01
< . 01 < . 01
A
3.
0.
0.
0.
0.
0.
0.
0.
0.
3.
-------
-56-
Run #12 Slit Samples
Sweeping Samples
wt. %
Fe
Cu
Al
Ca
Si
Mg
Mn
Cr
Sn
Zn
Ti
Ni
Mo
1
3
0
0
0
0
0
0
0
0
4
<0
0
0
.5
.010
.080
.031
.046
.71
.074
.075
.019
.4
.010'
.017
.010
2
4
0
0
0
0
0
0
0
0
9
<0
0
0
Anders
Wt. %
Fe
Cu
Al
Ca
Si
Mg
Mn
Cr
Sn
Zn
Ti
Ni
1
.16
.038
.074
.17
.061
.086
<.005
<.01
<.01
.069
<.01
<.01
.3
.011
.062
.063
.060
.15
.060
.059
.017
.3
.010
.012
.007
en Pla
2
.14
.025
.027
.17
.03
.083
<.OG5
< . 01
< . 01
.051
< . 01
< . 01
A
3.0
0.010
0.055
0.02!5
0.039
0.33
0.036
0.054
0.010
5.4
<0.010
0.01 1
0.007
te
3
.31
.032
.044
.15
.034 <
.073
<.005 <
< . 01 <
< . 01 <
.061
< . 01 <
< . 01 <
B
4.9
0.011
0.075
0.032
0.087
0.57
0.067
0.085
0.015
7.0
<0.010
0.014
0.008
4
.39
.027
.043
.29
.025
.14
.01 <
.025 <
.025
.11
.025
.025 <
C
3.1
0.019
0.076
0.036
0.095
0.48
0.036
0.056
0.012
9.7
<0.010
0.011
0.005
5
.19
.027
.072
.27
.072
.22
.01 <
.025 <
.027 <
.11
.70 <
.025 <
D
2.5
0.016
0.13
0.088
0.084
0.65
o.io
0.13
0.016
4.2
<0.010
0.029
0.008
.
6 :
.16:
.028
.11
.29
.046 <
.20'
.01 <
.025 <
.025 <
.088
.025 <
.025 <
E
1 .6
0.009
0.063
0.078
0.13
0.46
0.015
0.043
<0.010
0.51
<0.010
<0.010
0.006
Filter
.18
.006
.010
.058
.01
.027
.005
.01
.01
.069
.01
.01
F
0.95
0.008
0.064
0.050
0.054
0.33
0.011
0.030
<0.010
0.32
<0.010
<0.010
0.004
G
1 .3
0.010
0.043
0.12
0.079
0.38
0.012
0.034
<0.010
0.41
<0.010
<0.010
0.005
K. PARTICLE EMISSIONS
Emitted particulates, as noted earlier in this report, have
been collected as four samples: i.e., tube sweepings, tube
slit trays, Andersen samplers, and a "final" filter following
the Andersen. This technique has allowed the capture and evaluation
of essentially all particles emitted from the exhaust pipe. In
general, particle sizes associated with these samples are:
tube
>100ฐ to
Andersen - 20p to 0.5y
-------
-57-
Thfc mass percentage distribution of emitted particles as
related to these sources is shown in Figure 90 for all test
fuels. Note in all cases that the tube sample, which includes
sweepings and slit samples, is small compared to the Andersen
and filter sources. Note also that the filter sample is,
generally, the largest. Figure 91 provides a little different
perspective to the data. It shows the grams/hour particles
emitted as a function of the sample source for all test fuels.
Total particle emissions are also indicated by a T above
the bars representing each test fuel.
These data can best be understood by plotting cumulative
particle size distribution curves.. Such cumulative distribution
data are represented by log-normal plots of stage D values
(equivalent diameters for unit density spheres at 50% mass
collection efficiency) against mass cumulative percent. Such
plots for all test fuels are presented in Figures 73 through 78.
Dj-g values for the Andersen samplers are as follows:
Andersen Stage D5Q y
1 9.0
?. 5.35
3 2.95
4 1 .53 ,
5 0.95
6 0.54
Similar distribution curves for percent total Pb, Cl, Br, and
organic are presented in Figures 79 through 89. Chlorine and
bromine are determined by Neutron Activation Analysis of samples
washed in a 1:1 ethanol:water solution. The sample is then
digested in nitric acid and analyzed for lead by atomic absorp-
tion. Filter samples are analyzed by the same method except for
lead which is determined gravimetrically as lead sulfate. However,
-------
PROBABIU.ci 46 8O43
X 2 LOC-. CYCLES ปซ: i.. n i ป
80 70 60 50 40 30
-ir "L- nun i2 A
Figure 73
Weight X. Particles, of Plameter
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES ปoe i>. ... s .
KEUFFEL a ESSER CO.
99.99
99.9 99.8
0.01
Legend
i Run~5
Run 11 x
-------
40 8O43
0.? 0.1 0.05
80 70 60 50 40 30
Legend
i ~
Run 13
Run I A
figure 75
rrli"H!irin
Weight % Particles of Diameter
-------
,,
-------
46 8O43
10
99.99
c.? oi o.os r.oi
_. r
-t-.-i
in
c
o
o
r-
E
s_
O)
ป->
O)
E
IB
r-
=3
O)
u
>->
s-
ro
i.
Legend
Run 7 A
height % Particles of Diameter
-------
K^C PROBABILITY
".ฃ= X 2 LOG CYCLES
46 8043
99.99
99.9 99.8
99 98
KELjrFEl. A ESSER CO
95 90 80
0.2 0.1 0.05 O.C1
10 3_-
O
S-
o
2
J_
O
-->
O)
E:
(O 1
cles of Diameter
Weight % Parti
. 3 :1 ,-t
. 2
-------
IKfl
r-rt^- =3ii_ii i ** *_? OV"*.:
X 2 LOG CYCLES <. ; * ซ
Kt-l'f F t : 6. t:b?CR (.O.
80 70 60 SO 40 30 20
10
1 0.5 0.2 O.t 005
a-i--;^EF:
r!" Figure
% Total in Particles of Diameter,
-------
PROBABILITY
X 2 LOG CVCLES
46 8O43
KEUFFEL ft ESSER CO.
99.99
99.9 99.8
99 98
-------
-* Legend
Pt
^Organic
5-.
Figure 81
Total in Particles of Diameter
-------
PROBABILITY 46 8O43
X 2 LOG CYCLES ^DI .ซ ,i . ..
99.99
99.9 99.8
99 98
80 70 60 50 40 30 20
1 0.5 0.2 0.1 0.05 0.01
Legend
FD
Br
Organic D
-------
PROBABILITY
X 2 LOG CYCLES
46 8O43
99.99
99.9 99.8
99
Total in Particles of Diameter
-------
-------
ซ C1 PROBABILITY
V'fc x 2 LOG cvctes '
4ง 4SO4.3;".''"J. v- / ;'"
99.99
99.9 99.8
99 98 95 90 80 70 60' 50. 40 30 7.0.
10
1 0.5 0.2 0.1 0.05 C's
Legend ฃ -' ;ซ
Organic !
Figure 85
*- \ -
, % Total
in Particles of Diameter
-------
46 8O43
ซปD(. IN u s t.
KEUFFEt. a ESSER CO.
PROBABILITY
X 2 LOG CYCLES
99.99
99.9 99.8
99
;-j
-------
PROBABILITY " ~46 8O43
X 2 LOG CYCLES ซvn IN u -. ซ
KEOFFtL & ESSER CO.
10
99.99
99.9 99.8
V
j
U
1)
J
80 70 60 50 40 30
1 0.5 0.2 0.1 0.05
Cl A = =
Organic
a
Total in Particles of Diameter
20 30 40 50 60 70 80
0.01 O.Ofi 0.1 0.23 0.5
-------
PARTICULATE WT. % DISTRIBUTION IN SYSTEM
Fi
gure
90
-------
IU'V.
-------
5 X 5 TO 1/2 INCH 46 O863
7 X 1O INCHES WADE >* u s. ป.
KEUFFEL& ESSCP CO.
TOTAL PARTICULATE EMITTED CORRECTED FOR .DILUENT AIR
Figure 92
TT
-j-i-i-
Rgg."
-H-
t-rtt
i
T-
--#
j-H
ff
TT<
-ii-
44-
4+H
-------
samples are not available, so tube samples have been
ignored in these distributions. In most cases, the tube
sample accounts for less than 5% of the sample mass, so the
error is slight. Distribution of the organic present in the
emitted particles is only approximate. This distribution
is based upon the organic level/rug sample determined by mass
spectrum, the details of which are discussed in an earlier
section.
Values for the mass median equivalent diameter (MMED) and the
Pb, Cl, Br, organic mass median equivalent diameter are obtained
in many cases by extrapolation of the above distribution curves.
These values are listed in Table 23.
In all cases, on an equivalent diajneter basis, 50% of the mass
of emitted particles is associated with particles smaller than
1 micron (except run 6, Indolene HO 15).
Table 23
MASS MEDIUM DIAMETER
Run #
4
6
7
8
9
11
12
13
14
15
16
17
MMED
0.10
1 .5
ซ0.10
0.65
1 .1
^0.10
^0.10
^0.10
<0,10
ซ0.10
<0.10
0.7
Pb MMED
-\-0.10
3.1
ซ0.10
0.35
2.0
^0.10
-^0.10
-v.0.10
<0.10
-
1.5
1.2
Cl MMED
ซ0.10
0.5
-
-
1.2
'x-O.lO
vO.10
'vO.lO
<0.10
-
-
_
Br MMED
<0.10
2.7
-
-vO.10
-
^0.10
vO.10
vO,10
<0.10
-
-
_
Organic MMED
0.68
0.2
ซ0.10
0.3
<0.10
<0.10
<0.10
ซ0.10
ซ0.10
-
0.4
1.5
< less than O.lOy
ซ much less than O.lOy
~ approximately
The total particulate emissions in grams/hour are shown in
Figure 92 for all test fuels. These values represent the
-------
Anricjr', on ' r;, and filters with appropriate factors applied
for proportional sampling factors, for example. (Emissions
in grams/mile can be obtained by dividing these values by
60 for all runs except 12, 14, and 17 in which case one
-------
-60-
VI . DISCUSSION OF RESULTS
The results reported herein are based upon the generation,
collection, and analyses of exhaust particles in a well-
defined system and under carefully controlled engine
laboratory conditions. Our basic aim in this first year's
effort was to develop repeatable and reproducible means of
generating and analyzing exhaust particles. This required
that one establish an operational procedure which eliminated
as many variables as possible and still was not an uncommon
mode of operation for the internal combustion engine. Basic
decisions with that in mind, dictated that the engine attached
to a laboratory dynamometer be operated under reasonable
conditions of load, speed, and stability. The "conditioning
sequence" employed allowed the engine sufficient time under
several mild load conditions with no severe acceleration
modes to form stable deposits, exhaust hydrocarbons, etc.
The particle sampling operation under air diluted conditions
at 50 mph road load provided a not uncommon operational
mode for the engine and yet allowed particle sampling under
conditions somewhat related to the actual vehicle emission
environment on the roadway. This careful control of the
engine-fuel-emissions environment and the development of
sound analytical approaches has resulted in our ability to
ascertain significant differences with minor changes in fuel
additives.
Faced with the realization that many factors could affect
particulate emissions, we chose not only to reduce as many
engine and sampling variables as possible but, in addition,
at this stage to eliminate the basic fuel composition
variable. This dictated that a single base fuel be used
for initial studies. Indolene HO was chosen as that fuel.
The first step- in assessing our ability to observe particulate
-------
levels In the base fuel as TEL is well known to emanate
from the engine particles. The first phase of the effort
then was to examine participate emissions with TEL as the
variable.
The next step was to determine the effect of TEL scavengers
on particle emissions. This variable resulted in runs with
Indolene HO plus 3.0 ml/gal TEL with no scavenger, motor mix
scavenger, and EDB and EDC each in 1 theory concentrations.
Satisfied that we could indeed discern differences with these
variations we proceeded to the addition of a very small amount
of a common detergent additive to the Indolene HO 30 leaded
fuel. Although the additive was present at a level of only
12 pounds/1000 barrels of fuel, we believe on the basis of
obviously limited data (Run 11 vs. Run 13), a significant
effect on particle emissions, engine deposits, and hydrocarbon
emissions was observed.
This quest, then, for a system capable of determining differences
in particle emissions, deposits, and hydrocarbon emissions,
has led us to the threshold of applying these techniques to
the actual vehicle under simulated road conditions. This is
the basis for our continued effort in this program.
Now that the basis upon which the data reported herein has
been established, it is appropriate to address several specific
topics.
The particle sampling system, the dilution tube, is perhaps the
key to the data generated. In reality it dictates the definition
of particulates collected and evaluated herein. Because it
is designed in several pieces, it allows the capture and
relatively simple collection of all particles emitted from the
tailpipe. Because the samples collected in the Andersen's
-------
this zone of the dilution tube be a stable and homogeneous
mixture of diluent air and exhaust particles. The tube length
(27 feet), flow rate (7 fps), and mixing baffle were designed
to accomplish this objective. Additionally, this design
results in a constant volume device noted by the small change
in flow rate (volume) when sampling under the conditioning
mode of engine operation.
Analysis of particles collected in the tube slit samples
(removed from direct contact with the air-exhaust stream)
suggested that organic levels were substantially higher
for particles within the tube than for those removed. It
is possible that adsorption of organics is occurring in
the particle collected in the tube during the 48 hour
sampling period. The significance of the organic level
associated with the exhaust particles must, at this point,
entertain this possibility. The dramatic increase in organic
associated with particles as the particle size decreases
however, (as noted by mass spectrometry, UV absorbance, and
UV fluorescence) suggests that additional factors are
involved. That the organics are associated with non-
organic particles (lead salts) is substantiated by the
Transmission Electron and Scanning Electron studies.
The determination of organics associated with particles has
been and continues to be a challenging task. The mass
spectrometry evaluations have provided a reasonable semi-
quantitative evaluation of the total level of organics
present. The trends .observed (increased organic with
decreasing particle size) seem to be clearly supported by
the UV absorbance and fluorescence studies. The use of this
data to provide cumulative organic distribution plots is
not, however, completely sound. Thus, these distribution
-------
The cumulative distribution plots of percent Pb, Cl , and
Br neglect the particles collected 1n the tube. The
percentage of the total particles collected in the tube,
however, varies from 3 to 16 percent and, in most cases,
has little effect on the MMED value. The cumulative
distribution plots and D5Q cut-off values were chosen on the
basis of work reported by Flesch, et al (1967) and Wagman,
et al (1967).
Trace metal analysis of the exhaust particles collected during
runs 11 and 12 may provide an interesting cursory insight
into the distribution of elements other than Pb, Cl, Br, and
organics. Iron (from engine wear and the exhaust system)
is clearly associated with larger particles as the percentage
drops almost two orders of magnitude from tube samples to the
filter following the Andersen. Calcium (oil) concentration
increases with decreasing particle size. Zinc (oil, exhaust
system) follows the iron trend. Silicon (air) is noted to
be fairly constant in all particles. These analyses provide
insight into the contribution of engine wear debris, fuel
composition, oil additives, and air-borne debris on the
complex composition of exhaust particles.
The frequent monitoring of the hydrocarbon emissions during
the conditioning sequence was essential in maintaining
stable engine operation. During the run with Indolene HO +
3.0 ml/TEL gallon, for example, it became necessary to change
spark plugs every 6 to 8 hours. The fouling problem
was noted before it was apparent to the engine operator by
observing an unusual and sudden increase in hydrocarbon
emissions. Following hydrocarbon emissions during conditioning
and sampling indicated that combustion chamber deposits were
not completely stable for the Indolene HO 30 fuel runs as the
hydrocarbons continually increased. This is confirmed upon
examination of the combustion chamber deposits for this fuel
in runs 3, 4, and 11/12 which show an increased deposit
-------
The generation, collection, and analysis techniques developed
and reported herein provide the basis for evaluation of
fuel additives, fuel compositions, etc., on the particle
emissions from vehicles under simulated road conditions
-------
VII. SUMMARY
A summary of test results is shown in Table 24. This summary
sheet shows particulate emissions in grams/hour and grams/mile
for samples collected in dilution tube slits and tube sections
(sweepings), the Andersen Samplers, and filter following the
Andersen. The total particles emitted for each test fuel
is also shown as grams/hour and grams/mile, and is a summation
of the individual sections. The Andersen and filter data
figures are based upon the total exhaust stream although they
are proportional sampling devices. The percentage increase
from 0 hours (clean engine) to 75 hours (conditioned engine)
for unburned hydrocarbons and NO are also summarized. Combustion
chamber deposits are presented in grams (8 cylinders) and the
total test hours for each run are shown.
Increasing the level of TEL in the fuel results in increased
particle emissions, increased combustion chamber deposits, and
increased hydrocarbon emissions during the conditioning sequence.
No clear trend is obvious as to the effect of TEL on NO emissions,
Intermediate levels of TEL (1.5 ml/gal) shows an unusual increase
in hydrocarbon emissions build-up and in combustion chamber
deposits, but a small increase in particulate emissions compared,
of course, to the trace TEL run (Indolene HO 0). TEL scavengers
have a definite effect on emissions and deposits. Runs #8 and
#9 are graphic examples and should be compared to runs #3, #4,
#11, and #12. Run #8 is the Indolene HO base fuel with 3 ml/gal
TEL plus 1 theory of EDB in place of the motor mix scavenger
package used in'the Indolene HO 30 fuel (1 theory EDC plus
1/2 theory EDB). Run #9 is with 1 theory EDC only instead of
motor mix scavenger. The results indicate that EDB does a more
efficient job of removing TEL reaction products from the
combustion chamber which results in lower chamber deposits and
-------
Table 24
TABULATION OP PARTICUMTE EMISSIONS DATA
Run No.
and
Fuel Used
3
Indolene HO 30
4
Indolene HO 30
5
Indolene HO 0
6
Blank
6
Indolene HO 15
7
Blank
T
Indolene HO 0
+3.nl/8allon
TEJ,
8
Indolene HO 0
1.0 Theory KDB
+3.nl/gallori
TEL
9
Indolene HO 0
1.0 Tteory EDC
+ 3. n I/gallon
TEL
11
Indolene HO 30
Steady State
Sampling
12
Indolene HO 30
Cycling for
Snrpllng
13
Indolene HO 30
DMAU
Steady State
Sampling
11
Indolene HO 3C
DKA4A
Cycling for
Sampling
15
Blank
16
Indolene HO 0
Steady State
Sampling
17
Indolene HO 0
Cycling for
Saspllng
Dilution Tube
Silts
r/hr
...
01182
01237
0
01155
.0
.0081
.0112
.01868
.01538
.02119
.03117
.01529
0
.0131*
.0077J
Kr/nll*
.000247
.000206
0
.000192
0
.00014
.000186
.000311
.000256
.000353
.000519
.000254
0
.000219
.000128
Sweeping
prVhr
.1809
.03340
0
.1230
0
.3525
L.0344
.4987
.4241
.4488
.7269
.2266
0
.16459
.0939
avntle
Andersen
Sena tฐr
pr/hr
1.65208
.00301 2.2405
I
.000559 -.02708
1
0
.00205
0
.00587
.01724
.00831
.00706
.00748
.01211
.00377
0
.0027
.0015
.03958
.89163
.06875
47813
.8938
.0395
.
2.3998
3.6165
2.3806
1.8725
.0043
.1675
.2206
r/rnlle
. 02751
.03734
.00045
.00065!
.01486
.00114!
.02463
. 06489
. 03399
.03999
.04360
.03967
.03120
. 00007
. 00279
.00367
5 Filter
Paper
r/hr
.106?
.16053
.17916
.79786
.28333
.90826
.3997
2.14786
4.1955
4.739ซ
5.0213
6.3233
.1420
.63091
.3029
gr/mlle
.06843*
.00267
.00298
.013297
.00472
.13180
.07332
.03579
.06992
.07899
.08368
.10538
.002366
.010515
.00504
TOTALS"
,
gr/hr {
6.5424
.17922
.21874
1.82399
.35208
9.7473
9.3385
[r/mlle
.10904
.00298
.00365
.03039
.00586
.16246
.15564
4.7046
7.03477
7.8258
8.15997
8.43776
.14633
.97617
.62518
.07841
.11725
.13043
.13599
.14063
.00244
.016.27
.0104
% Increase
75-Hour
VK. All Cycles
tiV.1
76.25
78.0
15.01
59.42
94.07
65.03
31-5
IJO.
3.65
1.76
7.05
7.14
4.37
16.07
-4.0
-nglne Di
Grans
115
143
20
96
87
135
173
1
i '
33.98
72.16
mm-~
9.22
4.4
4.28
0
186
120
20
;?03lts
Hours
Total
103.7
128.8
126.1
127.0
-
126.1
129.2
*
127.3
179.5
139.7
180.2
I
01
en
Deed filter paper uelght. froป Bun 111 (Irxlolene HO 30 repeat).
-------
As a result, the particulate emissions are substantially
increased. EDC, on the other hand, does a much less efficient
job which results in increased chamber deposits and hydrocarbon
emissions build-up, and decreased particulate emissions.
Not only are the emission levels affected, but the particulate
emissions mass distribution is quite different.
The use of TEL with no scavengers results in higher hydro-
carbon emissions and particulate emissions but lower combustion
chamber deposits. The particle distribution is much different
as most of the particles are below O.ly in size. The use of
TEL alone also resulted in severe spark plug fouling problems
which necessitated plug changes every 8-10 hours of engine >
operation.
o
The addition of a detergent type additive (DMA-4A) to the
Indolene HO 30 fuel resulted in decreased combustion chamber
deposits and hydrocarbon emissions build-up but, as noted
for the scavengers above, an increase in particulate emissions.
It is apparent that additives which effectively remove reaction
products from the combustion chamber also reduce hydrocarbon
emissions of the stable, conditioned engine but, as a result,
increase particulate emission levels.
Particulate emissions are modestly affected by the mild cyclic
operation of the engine used in these studies. Runs #11 and
#12, #13 and #14, and #16 and #17 are runs in which the first
of the pair was sampled under steady-state (60 MPH, road load)
conditions and the second under mild cycling conditions
(Table 3) which averages about 40.5'mph. The cycling sequence
is identical to the cycling sequence used in the first 75 hours
-------
however, change the particle mass distribution and resulted
,in an increase in particulate emissions of somewhat less than
10% except for Indolene HO 0 (trace TEL) in which case a
decrease was noted.
The data indicates that the fraction of organic material associated
with particles increases substantially as particle size decreases.
The amount of organic material present in the collected particles
increases with the reduction of TEL levels in the fuel. The
total organic present in all particles collected in each run
appears to be roughly the same, however. In effect, the presence
or absence of TEL and scavengers does not substantially change
the total amount of organic material present in all collected
particles, but the percentage organic is much higher for low
TEL fuel runs because the mass of particles emitted is much
lower. We believe this is due to the fact that the base fuel
-------
VIII. FUTURE
: The relationship of this study to the practical world of
the automobile is only casual at this point. It is essential
that the following studies be conducted to serve as background
information in support of proposed standards and measurement
r>
procedures for particulates.
1. Determine the effect of basic fuel composition
on the chemical and physical characteristics of
! particulate emissions.
2. Determine the impact of the new -low octane, low and
non-lead fuels and low compression ratio engines on
particulate emissions.
3. Relate these studies to the actual vehicle by conducting
similar studies with the same classification system
: developed here with vehicles loaded by a chassis
dynamometer under simulated road conditions.
It is felt that a sound technical basis has been developed in
these studies from which we can knowledgeably extend this
-------
REFERENCES
Flesch, J., Morris, C., and Nugent A., (1967), American
Industrial Hygiene Association Journal, Vol. 28, Nov.-Dec. 1967.
Wagman, J., Lee, R. E., Jr., and Axt, C. J., Atmospheric
-------
LIST OF TABLES
1 Engine Oil, Trace Metal Analysis ................ 7
2 Engine Oil, Physical Properties ................ 8
3 Test Engine Conditioning Sequence ............... 11
4 Test Fuel - Run Number Designations ............. 18
5 Dilution Tube Temperature Profile During
Steady-State Operation Sampling; by Run
Number .......................................... 19
6 Dilution Tube Temperature Profile During
Cyclic Operation Sampling; by Run Number ........ 20
7 Dilution Tube Flow Rate and Dilution Ratio;
by Run Number ................................... 21
8 Dilution Tube Flow Volume and Flow Rate
During Cyclic Operation
Sampling Runs 12 and 14 ......................... 21
9 Dilution Tube Sampling Zone Temperature and
Flow Rate Profile ............................... 23
10 Actual Sample Weights from each Andersen
Sampler by Run Number .......... ....... . .......... 24
11 Physical Analysis of Test Fuels ................. 26
12 Trace Metal Analysis of Indolene HO 30 Fuel ..... 27
13 Weight Percentage Carbon (C) and Hydrogen (H)
in Several Test Fuels ............. .............. 27
14 Trace Metal Analysis of New and Used Engine Oil.. 28
15 Engine Combustion Chamber Deposit Analysis
for Several Runs ................................ 29
16 Scanning Electron Microscope Photomicrographs ,
and X-Ray Spectrum Figure Designations and
Descriptions .................................... 36
-a
-------
-72-
18 Relative Values of the Amount of NHL, H20,
HC1, and Organic Material Present in Anaersen
and Filter Samples by Mass Spectrometry -
All Runs 48
19 Relative Amount of UV Absorbing Material
Present on Andersen Plates - All Runs 51
20 Relative Amounts of Fluorescent Material
Present on Andersen Plates - All Runs 52
21 Relative amounts of UV Absorbing and
Fluorescent Materials Present in Sweeping
and Slit Samples from Dilution Tube 53
22 Trace Metal Analysis of Particulates 55
23 Mass Medium Diameter for Total Emitted Particle
Mass and For Pb, Cl, Br, and Organics by
Run Number 58
-------
-73-
LIST OF FIGURES
1 Flow Diagram for Engine Exhaust Participate
Col 1ection
2 Participate Sampling Tube
3 Exhaust Gas Analysis - Computer Print-out
4 Particulate Sampling Tube - Thermocouple
Locations
5 Total Hydrocarbons vs. Hours of Engine
Operation - Run #3
. 6 Run #4
7 Run #5
8 Run #6
9 Run #7
10 Run #8
11 Run #9
12 Run #11
13 Run #12
14 Run #13
15 Run #14
16 Run #16
17 , Run #17
18 Total Hydrocarbon Increase During 75 Hour
Conditioning Sequence
19 Nitric Oxide Change During 75 Hour Conditioning
Sequence
20 Total Engine Deposits - Runs #3 through #17
21-23 Typical Individual Exhaust Particles -
-------
-74-
24 Agglomerate Fly Ash, Typical Exahust
Particles - SEM
25 Typical Fines - SEM
26 Pb, Cl, Br Ratios. SEM - X-Ray Fluorescence
Andersen Plates 1, 3, and 6 and Filter
Run #8
27 Run #9
28 Run #11
29 Run #12
30 Run #13
31 Run #14
32 Exhaust Particles. SEM Run #7
5000X. Andersen Plate #1
33 Exhaust Particles. SEM Run #7
TO.OOOX. Andersen Plate #1
34 Exhaust Particles. SEM Run #7
20.000X. Andersen Plate #1
35 Exhaust Particles. SEM Run #7
Various X. Andersen Plate #6
36 Exhaust Particles. SEM Run #8
10.000X. Andersen Plate #3
37 Exhaust Particles. SEM Run #8
. 20.000X. Andersen Plate #3
38 Exhaust Particles. SEM. Run #9
Various X. Andersen Plate #1
39 Exhaust Particles, SEM. Run #9
10,OOOX. Andersen Plate #1
40 Exhaust Particles, SEM. Run #9
20.000X. Andersen Plate #1
41 Exhaust Particles. SEM. Run #11
Various X. Andersen Plate #1
X-Ray Pb Scan of Areas A and C in
-------
-75-
42 Exhaust Particles. SEM. Run #11
5000X. Andersen Plate #1
X-Ray Pb Scan of Area B in Section C.
Cl Scan Area B in Section D.
43 Exhaust Particles. SEM. Run #11
Various X. Andersen Plate #6
44 X-Ray Fluorescence Spectrum. Section D,
Figure 55.
45 Run #13 - Polarized Light Photomicrograph
400X. Andersen Plates 1, 3, 6 and Filter
46 Run #15 - Polarized Light Photomicrograph
400X. Andarsen Plates 1, 3, 6 and Filter
47 Transmission Electron Photomicrographs
10,000 and 6.000X. Run #9
Andersen Plate #1 and #3
48 Transmission Electron Photomicrographs
10,000 and 60.000X. Run #9
Andersen Plate #6 and Filter
49 Transmission Electron Photomicrographs
10,000 and 60.000X. Run #12
Andersen Plate #1 and #3
50 Transmission Electron Photomicrographs
10,000 and 60.000X. Run #12
Andersen Plate #6 and Filter
51 Mass Spectra Peak Height per mg Sample/Unit
Instrument Sensitivity for Andersen Plates
#l-#6 and Filter. Relative Levels of
NH3, H20, HC1, and Organics. Run #3
52 Run #4
53 Run #5
54 Run #6
55 Run #7
56 Run #8
57 Run #9
58 Run #11
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60 Run #13
61 Run #14
62 Run #16
63 Run #17
64-72 Actual Computer Plotted Mass Spectrum of
Exhaust Particles on Andersen Plates #l-#6
and Filter for Runs 3, 4, 5, 6, 7, 8, 9, 11,
12, 13, 14, 16, 17, Plotted as Log Intensity
vs. m/e
73 Particle Diameter (D) vs. Weight % of Particle
Mass of Diameter Smaller than D. Runs 4, 11, 12
74 Runs 6, 11, 16
75 ' Runs 13, 14
76 Runs 16, 17
77 Runs 7, 8, 9, 11
78 Run 15 (Blank)
79 Particle Diameter (D) vs.. %'total Pb, Cl , Br,
and Organic in Particles of Diameter Less
Than D. Run 4.
80 Run 6
81 Run 7
82 Run 8
83 Run 9
84 Run 11
85 Run 12
86 Run 13
87 Run 14
88 Run 16
89 Run 17
90 Particulate Weight Percentage Distribution
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91 Particulate distribution in Collection
System in Grams/Hour Emitted - All Runs
92 Total Particulates Emitted. All Runs
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