-------
CHARACTERIZATION OF NINE HIGH-MILEAGE
CATALYTIC CONVERTERS FOR EPA
(Contracted through Automotive Testing
Laboratories P. O. No. 2628)
R. G. Lyben and L. M. Niebylski
September 1979-
Ethyl Corporation Research Laboratories
Ferndale, Michigan 48220
-------
FOREWARD
This study was a pilot project designed to analyze the efficiency
and condition of in-use catalysts on high-mileage vehicles. These 1975
model year vehicles were originally all public-owned and were obtained
from an earlier EPA project (Restorative Maintenance Evaluation of High-
Mileage, Catalyst - Equipped Vehicles, conducted for EPA by Automotive
Testing Laboratories, Inc., EPA Contract #68-03-2413). Tables I and II
present descriptions, miles accumulated and FTP results for these nine
vehicles from this past report.
For the current project the catalysts were removed from the vehicles
and tested for conversion efficiency and pressure drop. The catalysts
were then subjected to visual, chemical and physical analysis to provide
data on their in-use condition.
-------
Table I presents descriptions and miles accumulated for the original
nine vehicles from the earlier report.
TABLE I
High Mileage Vehicles for Catalyst Evaluation
Veh. #
511
512
513
524
525
526
537
538
539
Make
Plymouth
Dodge
Plymouth
Mercury
Ford
Ford
Chev
Chev
Buick
Model
Duster
Charger
St. Wagon
Monarch
Custom
LTD
Nova
Malibu
St. Wagon
Miles
Accumulated
138,831
75,064
71,026
103,977
. 108,238
111,512
89,691
107,979
137,751
CID
225
360
318
250
400
351
260
350
350
IW
3500
4500
5000
5000
5000
4000
3500
4500
4500
Trans
A
A
A
M3
A
A
A
A
A
Engine Family
F-RG-CII
F-LA2L-C
F-LA2-6C
2501CEF
351M/400"E"
351M/4001CET
10F13
10J23
40J43
-------
Table II presents the composite FTP emission and fuel economy
results for the high-mileage vehicles from the earlier report. Testing
was performed after emission control repair, removal of catalyst and
catalyst replacement.
Table II
FTP Composite Results for High-Mileage
Vehicles
Test Conditions:
(1) measured with high mileage catalyst after emission component
repair and vehicle maintenance.
(2) measured with catalyst removed
(3) measured after the original catalyst was replaced with a new
catalyst
Veh#
511
512
513
524
525
526
537
538
539
Test
Condition
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
HC
3.00
3.15
1.65
3.75
8.97
.93
.74
1.68
.62
1.52
2.09
.6
3.07
2.90
2.13
2.04
2.84
2.05
1.14
3.35
.64
1.90
4.07
.69
1.41
2.31
.59
g/mi
CO
22.9
29.8
20.1
16.6
16.8
21.8
4.6
28.5
14.3
8.0
20.7
4.8
35.2
17.3
14.3
11.0
10.3
8.0
7.5
9.1
5.6
12.9
21.0
7.3
11.9
21.6
8.4
NOx
2.54
2.10
1.34
2.08
1.79
.67
2.12
1.78
1.34
2.68
2.41
2.81
3.06
4.00
4.44
6.38
6.76
6.21
1.17
1.25
1.08
1.52
1.42
1.37
1.87
1.86
1.49
MPGu
17.11
18.24
17.49
11.05
12.01
11.17
11.46
11.67
11.69
17.79
18.17
17.73
6.61
10.86
9.85
11.63
11.73
11.64
17.67
18.56
18.41
13.05
12.66
12.36
12.53
11.89
11.88
-------
CHARACTERIZATION OF NINE CATALYTIC CONVERTERS
REMOVED FROM 1975 PASSENGER CARS
INTRODUCTION
This report is divided into two sections authored by two different
people. The first section deals with dynamometer tests made to obtain
relative emission data, photographs of cut-apart converter cases, semi-
\
quantitative analysis by emission spectroscopy of major elements present
on the inlet faces of the converters and quantitative lead analysis of one
converter which appeared to have been run on leaded fuel. The second
section deals with data obtained using X-ray diffraction, B. E. T. measure-
ments of surface area, differential thermal analysis, energy dispersive
analysis and scanning electron microscope analysis.
-------
SECTION I
Report by R. G. Lyben
A. Description of Dynamometer Tests
A 400-dD Ford V-8 engine equipped with an adjustable carburetor
and coupled to a dynamometer is used to supply a controlled exhaust gas
mixture to the converter under test. Table 1 gives the operating parameters
of the engine. Figure 1 is a schematic drawing of the test piping. Photos 1
and 2 show a converter attached to the engine for testing. Photo 3 shows the
emission measuring consoles used in this work.
The test procedure used is detailed below:
1. Warm up the engine with the converter installed but bypassed. The
two valves attached to the converter are closed and the valve in the
bypass line is open while the engine is brought up to equilibrium
temperature at 50 mph road-load. The air/fuel ratio is adjusted
to 16. 0 at which level 1.9 - 2. 0% oxygen is present in the exhaust
gas.
2. When conditions have stabilized, the valves to the converter are
opened and the bypass valve is closed. Temperatures, carbon-
monoxide and hydrocarbons are continuously recorded for samples
drawn from the converter inlet and outlet taps. These measurements
are continued until readings show no further change.
3. Pressure drop across the converter is measured at 50 mph road-
load and then the engine is adjusted to 3800 rpm WOT where another
pressure drop measurement is made. A 30" mercury manometer
is used to make these pressure measurements.
4. The recorded charts are then examined to determine the time and
temperature it takes to reach 50% hydrocarbon conversion. These
data can be related to warm-up time. With some of the converters,
-------
Section I --2
the.50% point is never reached. With 2% oxygen in the exhaust,
CO levels are too low to be significant and very little reduction
in CO occurs.
B. Converter Efficiency
Nine converters removed from high-mileage 1975 passenger cars were
tested. Three converters were double-biscuit monoliths removed from Chrysler
vehicles. Three single-biscuit monolithic converters were from Ford vehicles.
The Ford converters of this model year were only installed in one leg of the
exhaust system, thus only receiving one-half of the exhaust gas. When ana-
lyzing the Ford data, this should be kept in mind. The last three converters
came from GM cars. These were all 260 cubic inch containers. Two were
filled with spherical catalyst and one was filled with cylindrical catalyst pellets.
1. Chrysler Converters - The Chrysler converters have two ceramic
biscuits mounted in a single'canister. Emission data are given in
Table 2. Converters 511 and 513 gave HC reductions of 67 and 68%
at equilibrium and appear to be undamaged. Converter 512 had a
melted inlet face in the second section. This can be clearly seen in
Photo 10. Photos 3-15 show all inlet and outlet faces of the Chrysler
converters.
a. Warm-up Time - This is defined as the time required to reach
50% HC conversion. Catalyst 512 had a maximum conversion of
24% due to the melt.
Time to reach 50% Temperature °C
Cat. # HC Reduction, sees. Inlet Outlet
511 62 520 480
512 N. R.
513 50 515 400
b. Pressure Drop - As expected, catalyst 512 had the highest
pressure drop:
-------
Section I --3
Back Pressure "
50 mph 3800 rpm
Cat. # Road Load W. O. T.
511 1.6 8.0
512 2.4 11.0
513 1. 2 6. 2
2. Ford Converters - These are single-section monoliths used only
in one leg of the exhaust systems in the 1975 model year. As shown
in Figure 2, HC conversions were 55, 17 and 43%. Catalyst 525 was
cut in half to exhibit a peculiar melt which began 1/2" from the inlet.
Usually, several inches of catalyst are required to build temperatures
up to the melting point of the ceramic (see Photo 19). Other photos of
Ford inlet and outlet converter faces are shown in Phtos 16-22.
-a. Warm-up Time - Only converter 524 was active enough to reduce
hydrocarbons by 50%. This occurred in 55 seconds at an inlet tem-
perature of 515 °C and 410°C outlet.
b. Pressure Drop - Pressure drops for the Ford catalysts are given
below:
Back Pressure " Hg
General
Cat. #
524
525
526
Motors
50 mph
Road Load
Converters
0
2
0
_
8
4
6
These
3800
W. O
1
260-in. 3
5.
3.
4.
cc
rpm
. T.
1
0
6
:>m>
rer
alumina spheres or pellets. Bacause of. the greater mass involved,
one would expect longer warm-up times before conversion starts.
The GM catalysts gave conversions of 86, 57 and 74%. Converter
538 had the lowest conversion efficiency, longest 50% HC conver-
sion time and largest pressure drop of the three. Inspection of the
outlet screen showed partial plugging due to attrition of the catalyst
as shown in Photos 23-26.
-------
Section I --4
a. Warm-up Time - The times to reach 50% HC reduction are
given below:
Time to reach 50% Temperature "C
Cat. # HC Reduction, sees. Inlet Outlet
537 <30 482 75
538 150 545 440
539 75 530 240
Catalyst 537 wasrexceptionally active.
b. Back Pressure - Catalyst 538 had the highest back pressure
due to partial screen blockage.
Back Pressure " Hg
50 mph
Elemental
Cat. #
537
538
539
Analysis
Road
0.
2.
1.
of Converter
Load
8
4
0
Inlet Faces
3800 rpm
W. O.
5.
13.
6.
T.
8
8
8
cylinders
spheres
spheres
Order of magnitude analyses were made of samples removed from
the inlet faces of the monolithic converters. Aliquot samples were also
taken from the GM pellet-filled converters. Monolith samples were obtained
by drilling 3/8" holes to a depth of 1/2". All samples were ground to a fine
powder and analyzed using Emission Spectroscopy.
The source of the elements found would be mainly from the fuel and
oil. For example, unleaded fuels still contain about 0. 02 gram lead/gallon
on average. Thus in 100, 000 miles of driving on unleaded fuel, assuming 15
miles per gallon, 133 grams of lead would pass through the engine. Since
the alumina and silica catalyst supports are good adsorbents of lead halides
in the vapor state, it is not surprising to find appreciable amounts of lead
in all samples.
-------
Section I --5
1. Chrysler Converters - Table 3 lists the elements found on the
inlet converter faces. Since the Chrysler converters are double-
section monoliths, two analyses are shown for each converter.
Catalyst 512 .would appear to have been exposed to leaded fuel.
Additional analyses for lead were made on converters 512 and
513 by Atomic Absorption. Percent lead found was:
Converter 512 Converter 513
Inlet #1 29.10 2.21
Inlet #2 3.41 0.58
2. Ford Converters - The Ford converters are single-section mono-
liths and were used in only one leg of the exhaust system in the 1975
model year. Converter 525 suffered a peculiar melt that started
about 1/2" from the inlet surface. The lead content of all three inlet
faces is in the 1-10% range so it is unlikely that any of these ran on
leaded fuel. Larger amounts of calcium, copper, titanium and zinc
were found on the melted converter than on the other two. The
elemental analyses are given in Table 4.
3. GM Converters - One of the converters was filled with cylindrical
pellets while the other two contained catalyst spheres. Table 5 gives
elemental compositions for the three converters. The support material
appears to be of different composition for the cylinders. The cylinder-
filled converter (#537) also was superior in conversion of HC, warm-
up time and back pressure.
D. Conclusions
It would be difficult to reach firm conclusions on the basis of testing
only nine converters. We can, however, compare the nine converters tested.
1. The GM converters as a group were better than the Chrysler conver-
ters, which in turn were better than the Ford converters.
-------
Section I - -6
2. One each of the Chrysler and Ford converters had ceramic melts.
This occurs when ignition malfunctions and unburned gasoline is
pumped into the exhaust system. It takes only a few minutes to
reach ceramic melting point temperatures under this condition.
3. One GM converter had high back-pressure caused by small catalyst
particles lodging in the output screen due to attrition of the catalyst.
4. One of the Chrysler cars appears to have been driven on leaded
gasoline since the lead found on the face was more than 10 times
greater than on any of the other monoliths.
-------
Carburetor:
TABLE 1
1973 Ford 400-CID V-8
Operating Parameters
D3MF-EA (Ford)
ASTM manual STP 315F
Sequence V-C - carburetor modification with
V50F main jets and power valve drilled to 0. 078"
Distributor Timing:
6° ETC @ 625 rpm
26° ETC @ 1900 rpm
50-mph Road Load:
1900 ± 25 rpm @ 37# Beam = 70. 3 BHP
A/F
T-T (""" T-\ r)T~n
a \j $ L/U/I.J.J.
CO %
C02 %
02 %
TXTO nnm
15
146. 0
0. 309
14. 60
0. 7
?.87n
16
105. 0
0.180
13. 59
1.9
7.Q17
17
81 0
\j J. \J
0. 089
12. 83
3. 15
1 045
18
0. 003
12. 20
4. 12
-------
TABLE 2
Equilibrium Conversion Data (50 mph Road Load)
Cat.
#
Converters Removed from High- Mileage 1
0 C ° C HC ppm HC ppm % CO %
In Out In Out Re duct. In
.975 Cars
CO %
Out O? %
A/F
Chrysler Monoliths:
511
512
513
Ford
524
525
526
552 540 78.58
565 526 68. 28
563 551 75.81
Monoliths:
553 535 77.80
552 515 80.48
550 520 81.65
26.
52.
23.
35.
66.
46.
19
21
94
10
74
66
66.7
23. 5
68.4
54. 9
17. 1
42. 9
0. 067
0. 081
0. 075
0. 067
0. 064
0. 070
0. 056
0. 064
0. 063
0. 063
0. 064
0. 060
1.
2.
2.
1.
1.
1.
95
08
00
95
95
95
15.
16.
15.
15.
15.
15.
92
06
91
97
90
90
GM Pellets:
537
538
539
562 537 87. 00
558 516 86.35
555 520 90.86
12.
36.
23.
00
95
93
86. 2
57. 2
73. 7
0. 064
0. 056
0. 075
0. 053
0. 053
0. 053
1.
1.
1.
93
98
95
15.
15.
15.
90
95
95
cylinders
spheres
spheres
Vehicle Identification:
#511
#512
#513
#524
#525
#526
#537
#538
#539
Plymouth Duster
Dodge Charger
Plymouth Wagon
Mercury 250-6
Ford 400- CID Custom
Ford LTD
Chevrolet Nova 250-6
Chevrolet Malibu
Buick Century Wagon
RGL:ah
-------
TABLE 3
Element
Aluminum
Barium
Berylium
Boron
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Palladium
Phosphorus
Platinum
Silicon
Strontium
Tin
Titanium
Vanadium
Zinc
Lead by A. A.
HC Reduction
Warm-up Time, sees.
Back Pressure WOT
Elements Found on Inlet Faces of
Chrysler Converters
Values are "Order of Magnitude" Percentages
Converter 511 Converter 512
Inlet 1
>;
0.
0.
0.
0.
1-
1-
> ]
0.
0.
0.
-
1-
0.
> ]
0.
0.
0.
0.
1-
67
62
8.
LO
1-1
1-1
1-1
01-0. 1
10
10
[0
1-1
001-.01
01-0. 1
10
01-0. 1
to
001-. 01
001-. 01
1-1
001-.01
10
0
>
0
0
0
0
1
1
>
0
0
0
1
0
>
0
0
0
0
0
Inlet 2
10
. 1-
. 1-
. 01
. 01
-10
-10
10
. 1-
. 00
. 01
-10
. 01
10
.00
1
1
-1
-0. 1
1
1-. 01
-0. 1
-0. 1
1-. 01
. 001-. 01
I _
. 00
. 1-
1
1-.01
1
Inlet 1
> 1
0.
0.
0.
0.
1-
> 1
>1
0.
0.
0.
0.
1-
0.
> 1
0.
0.
0.
0.
1-
?Q
^ /
24
11
0
01-0. 1
1-1
01-0. 1
01-0. 1
10
0
0
1-1
001-. 01
01-0.1
01-0. 1
10
01-0. 1
0
001-. 01
001-. 01
1-1
001-. 01
10
1 0
1 \J
. 0
>
0
0
0
0
1
1
>
0
0
0
0
0
0
>
0
0
0
0
0
Inlet 2
10
. 01
. 1-
. 01
-0.
1
-1
. 001-.
-10
-10
10
. 1-
1
. 001-.
. 01
. 01
. 1-
. 01
10
-0.
-0.
1
-0.
. 001-.
. 00
. 1-
1-.
1
. 001-.
. 01
41
" A
-0.
1
01
01
1
1
1
01
01
01
1
Converter 513
Inlet 1
> 10
0. 1-1
0. 1-1
0. 01-0. 1
0. 1-1
1-10
1-10
>10
0.1-1
0. 001-. 01
0. 01-0. 1
1-10
0. 01-0. 1
0. 1-1
0. 001-. 01
0. 1-1
2.21
68
50
6. 2
Inlet 2
0. 1-1
0. 1-1
0. 01-0. 1
0. 01-0. 1
1-10
1-10
>10
0. 1-1
0.001-. 01
0. 01-0. 1
0. 1-1
0. 01-0. 1
0.001-.01 0.001-.01
0. 1-1
0.001-. 01
0. 01-0. 1
0. 58
-------
TABLE 4
Elements Found on Inlet Faces of Ford Converters
Values are "Order of Magnitude" Percentages
Element
Aluminum
Barium
Beryiium
Boron
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Palladium
Phosphorus
Platinum
Silicon
Strontium
Tin
Titanium
Vanadium
Zinc
HC Reduction
Warm-up Time, sees.
Back Pressure WOT
Converter 524
Inlet Face
0.01-0.1
0. 01-0. 1
0. 01-0. 1
1-10
1-10
1-10
0.001-.01
0. 01-0. 1
0. 1-1
1-10
0. 01-0. 1
0. 001-. 01
0.1-1
0. 01-0. 1
0. 1-1
55
55
5. 1
Converter 525
Inlet Face
0. 01. 0. 1
1-10
0. 1-1
1-10
1-10
1-10
0.01-0. 1
0. 1-1
0. 1-1
1-10
0. 01-0. 1
0.001-. 01
0. 01-0. 1
1-10
0. 01-0. 1
1-10
17
13. 0
Converter 526
Inlet Face
> 10
0. 01-0. 1
0. 01-0. 1
0. 1-1
0. 01-0. 1
0. 1-1
1-10
1-10
1-10
0.001-.01
0. 001-0. 1
0. 1-1
1-10
0. 01-0. 1
0.01-0. 1
1-10
0. 01-0. 1
0. 1-1
43
4.6
-------
TABLE 5
Elements Found on Aliquot Samples of Catalyst Pellets from CM Converters
Values are "Order of Magnitude" Percentages
Element
Aluminum
Barium
Berylium
Boron
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Palladium
Phosphorus
Platinum
Silicon
Strontium
Tin
Titanium
Vanadium
Zinc
HC Reduction
Warm-up Time, sees.
Back Pressure WOT
Converter 537
Cylinders
0. 01-0. 1
0. 01-0. 1
0. 001-. 01
0. 1-1
0. 1-1
0. 01-0. 1
0. 1-1
0. 001-. 01
0. 1-1
0. 01-0. 1
0. 1-1
0. 01-0. 1
86
<30
5.8
Converter 538
Spheres
0.001-.01
0. 01-0. 1
0. 01-0. 1
0. 01-0. 1
0. 001-.01
0. 1-1
0. 1-1
0. 1-1
0. 1-1
0. 001-.01
0. 1-1
0. 1-1
0. 01-0. 1
0. 01-0. 1
0. 01-0. 1
0.001-.01
0. 1-1
57
150
13. 8
Converter 538
Spheres
0. 001-. 01
0. Oi -0. i
0. 01-0. 1
0. 01-0. 1
0. 001-. 01
0. 1-1
0. 1-1
0.01-0. 1
0. 1-1
0. 01-0. 1
0. 1-1
0. 1-1
0. 01-0. 1
0. 01-0. 1
0.01-0.1
0. 001-.01
0. 1-1
74
75
6.8
-------
Figure 1. Schematic: Ford Engine
and tSylpust system for Conversion
Efficiency Test Work.
Moo c.
-------
Photo 1. Engine Setup
-------
Photo 2. Engine Setup
(Close-up View)
-------
Photo 3. Emission Measuring Consoles
-------
Photo 4. Converter #511 Inlet 1
-------
1*511 OUTLET
'' 7 5 L; 'Ui.ii ijn.1. I '.' r
Photo 5. Converter #511 Outlet 1
-------
IHIV:T
l')75 Plymouth Duster-
6. Converter #511 Inlet 2
-------
Photo 7. Converter #511 Outlet 2
-------
IF
1*512 INLCT 1
1975 Dodge Charger
Photo 8. Converter #512 Inlet 1
-------
4512 OUTLliT 1
1975 Dodge Charger
Photo 9. Converter #512 Outlet 1
-------
1975 Dodge Charger
Photo 10. Converter #512 Inlet 2
(showing melt)
-------
ft 512 OUTUiT 2
1975 Dodge Charger
Photo 11. Converter #512 Outlet 2
-------
#513 ML//:' !
1975 Plymouth V.'ayon
Photo 12. Converter #513 Inlet 1
-------
I :
;'
Photo 13. Converter #513 Outlet 1
-------
Photo 14. Converter #513 Inlet 2
-------
#513 OUTLET 2
1975 Plymouth Wagon
Photo 15. Converter #513 Outlet 2
-------
I
I
I
I
I
I*
I
I
(I
(I
I*
(I
I
I*
[
107 -
Photo 16. Converter #524 Inlet
-------
I
I
Photo 17. Converter #524 Outlet
-------
Photo 18. Converter #525 Inlet
-------
Photo 19. Converter #525 Inlet
(showing melt)
-------
Photo ZO. Converter #525 Outlet
-------
#526 INLET
1975 Ford LTD
Photo 21. Converter #526 Inlet
-------
#526 OUTLET
1975 Ford LTD
Photo 22. Converter #526 Outlet
-------
r ,-ir
__ ,_ _ (-. \;
Photo 23. Converter //538 Inlet Screen
-------
Photo 24. Converter #538
Front of Outlet Screen
-------
Photo 25. Converter #538
Back of Outlet Screen
-------
Photo 26. Converter #538
Back of Outlet Screen (Close-up)
-------
SECTION II
CHARACTERIZATION OF CATALYST SAMPLES
BY INSTRUMENTAL TECHNIQUES
Report by Leonard Niebylski
A. X-ray Diffraction Analyses
1. Core Samples
a. Chrysler Cars
b. Ford Cars
c. GM Cars
2. Surface Deposits
a. Chrysler Cars
b. Ford Cars '
c. GM Cans
B. X-ray Energy Dispersive Spectroscopy - Surface and Core
C. Surface Area Measurements
D. Differential Thermal Analysis
E. X-ray Diffraction Pattern Charts
F. Specific Surface Area Data Tables
G. Differential Thermal Analysis Curves
H. Scanning Electron Micrographs
-------
t X-ray Diffraction Analyses
Both core and. surface deposits were analyzed by X-ray diffraction. A
scanning X-ray diffra.ctometer with filtered copper-X-radiation was used.
The monolithic core with deposits was ground in an automated mortar and
pestle apparatus. The ground material was placed on a microscope slide with
doubled-side":, scotch tape being used to secure the deposit. All materials
were analyzes in duplicate. The extruaate and spherical pelleted catalysts
were similarly processed with several pellets used as the composite sample.
The surface deposits'on both pellets and at the entrance and passages of the
monolith were analyzed. In some instances, particularly when very little
deposit was present, core material became intermixed with the surface deposits.
The X-ray diffraction patterns obtained for each of the catalysts pro-
vided are included with this report. Pattern analyses yielded no surprises
with exception of catalyst 525 which had a melt down. An unknown crystalline
material was characterized for the fused core material.
The reported crystalline composition of the monolith used as a support
material as manufactured, has been confirmee, through bur X-ray analysis of
supports obtained directly from the manufacturer before wash' coating and
.catalytic metal processing. The general composition of Corning Monoliths is
Cordierite, 2Mg02Al2035Si02 dominant phase
Varying trace amounts of other phases include:
Alumina alpha-Al203
Mullite 3Al2032Si02
Spinel MgAl204
A wash coat is added to.the surface of the monolith support. This material
is either gamma or theta alumina or a mixture of the two. This high surface
alumina is present i:a a few mils thickness. It is this layer of the support
that become catalytically activated with platinum and palladium. Normally
our X-ray diffractional analyses -will not pick up this high surface alumina
unless the coating i,s exceptionally thick and free of deposits of combustion.
Pelleted, spherical and extruded catalysts, are normally all pure gamma
or theta, high surface area alumina. The average crystallite size of the
alumina will generally range about 100 to JOO Angstroms. No wash coat is
necessary for this material, therefore the platinum and palladium are added
to the pelletized surface after the pellet is formed to conserve on catalytic
metals used.
The specific core analyses for all the nine catalysts supplied is sum-
marized in the following:
-------
--2
I X-ray Diffraction Analyses Summary of Catalystic Supports
- Core Analysis Onl3r -
-------
Test 526 major component cordierite
20$ " MgAl204
25-30$ <*-Al203
< 10$ Eiullite
C. General Motors Cars: Pelleted support materials are used in these test
catalysts. Test 537 used extruded, cylindrical shaped pellets about 1/8 inch
long - 3/32 inches diameter. Catalytic supports from test 538 and 539
spherical with the spheres ranging from 3/32 to 5/32 inches in diameter.
Test 537 50$ alpha alumina
theta alumina
The presence of alpha alumina suggests the catalyst was subjected to an elevated
temperature in excess of l800°F during a portion of its operation.
Test 538 . 40$ gamma alumina
60% theta alumina
trace of either eta or delta A1203
Test 539 60$ gamma alumina
U0$ theta alumina
trace delta alumina
~ Surface Deposit Analysis -
The core material composition has been subtracted out from the diffrac-
tion pattern if present. The composition data is that of materials deposited
on the catalyst support which is formed by combustion or volatilization of
materials from the engine. The deposits from pelleted catalyst.is that material
which is on the pellet surface. The monolith surface deposit is that which is
deposited at the entrance to the monolith passages.
3. Chrysler Cars:
Test 511-1 and. 511-2 . 70-75$ PbS04
15-20$ Mn304
remainder unknown
Test 512-1 and 512-2 85$ PbS04
15$ PbOPbS04
Test 513-1 and 513-2 15-20$ PbS04
75$ Mixture of unknowns
V> Ford Cars:
In all instances one or more unknown phases are present in the surface
deposits. Catalysts from tests 524 and 526 are approximately the same. Deposits
from car test 525 contains a different set of unknowns with the exception of
possibly one phase being common in all deposits. (See Diffraction Patterns)
-------
c, General Motors Cars:
Unlike the Ford test samples, the surface deposits on General Motor
pelleted catalysts are poorly developed crystallites. Mn304 is present in
concentrations up to 20$ in all catalysts samples. The unknowns present on
catalysts of Ford cars are also present on these supports. (See diffraction
patterns).
g) Surface Analysis by X-ray Energy Dispersive Spectroscopy
To help characterize the unknown compositions of the surface deposits
observed by X-ray diffraction on Ford and General Motors catalysts a surface
analysis was performed using scanning electron microscopy (SEM) and energy
dispersive spectroscopy (EDS). The type of surface deposits formed on catalyst
surfaces is illustrated in the SEM micrographs for catalyst from tests,. 512
(Chrysler monolith) 525 (Ford monolith) and 537 (GM extrudate) and 538 (C-M
deposits on pelleted catalysis will vary from 10 to kO microns. The deposits
within the channels of a monolith will vary from 15 to 60 microns and at the
entrance to the monoliths deposits may be more than 100 microns thick.
Energy dispersive spectroscopy is a technique by which electrons generat-
ing an image in the SSM also generate X-rays characteristic of the element
being irradiated. These X-ray radiations are picked up and a surface analysis
of a 10-20 microns layer thick is obtained. In areas where the deposit may be
thinner than 20 microns some of the supporting catalysts will be detected.
All nine catalysts were analyzed by EDS. The data are presented in the
table on the following page. Only the 9 major elements generating emissions
are detected. These data are quantized relative to weight present on the
surface at the location being irradiated. Elements in greater than 10$ con-
centration will have a significant influence on the bulk crystalline composi-
tion of the deposits.
It should be pointed that Kg, Al and Si are due primarily to support
materials. The presence of Pb and Mn is due to an antiknock present in gaso-
line the vehicle used. The presence of Zn, Ca, P and S are due to oil additive '
constituents. The EDS technique being used does not readily distinguish be-
tween sulfur and lead in concentration less than 3$>- Consequently when sulfur
or lead is detected there will be a question as to which element is present.
Another surface analytical technique is needed to establish the absolute quanti-
tative concentrations of sulfur and lead. When the concentration of Pb is
greater than 3/a secondary lead lines are detected therefore the concentration
of lead present is absolute. Unfortunately it does not yield sulfur data unless
sulfur is present in. excess of 5$-
Based on the surface analysis data it appears that lead contamination
occurred in about half the catalysts provided.
-------
X-ray Energy Dispersive Spectroscopy Analysis of Automotive
Exhaust Catalysts from Chrysler Vehicles
(powdered = entire catalyst used as sample, flat = surface deposit only)
10 =
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-------
X-ray Energy Dispersive Spectroscopy Analysis of Automotive
Exhaust Catalysts from Ford Vehicles
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-------
X-ray Energy Dispersive Spectroscopy Analysis of Automotive
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-------
--5
Major Lead Contamination in Surface Deposits of Exhaust Catalysts
Chrysler Ford. General Motors
Test Pb-Contamination
511
512
513
yes
.yes
slight
Test
524
525
526
Pb-Contamination
yes
questionable
yes
Test
537
.5.38
539
Pb-Contaminat"' on
- possibly
no-
no
some
The unknowns in test 524 and 526 appear to be associated with manganese
and lead. Whereas the unknowns detected in deposits on catalysts from test
537,- 538, and 539 appear to be associated with Mn, Ca and P.
C, Surface Area Measurements
The catalytic activity of a material can be estimated by the specific
surface area measured for that material. Multi-point B.E.T. analyses were
obtained on all nine catalytic samples. An Accusorb Physical Adsorption
Analyzer using nitrogen gas was used to provide the gas adsorption data.
The specific surface area obtained for each sample is summarised in the table
below. All the adsorption data are also provided in the attached computer
print-out sheets.
Specific Surface Area of Test Catalysts
Sample Specific Surface Area
I dent i f i cat ion (mg/g) .
511-1 Plymouth ' 0.68
512 Dodge 6.35
513-1 Plymouth 6.98
524 Ford 5.09
525 Ford 400 3.94
526 Ford LTD 8.08
537 GM 60.9
538 GM: 108.0
539 GM 58.5
-------
--6
Palletized catalysts normally rate 100 to 125 n^g when fresh. The
lower readings of 58 and 60 m2/g suggest some . deactivation of the catalyst.
Monolith support surface area measurements are deceiving since only a very
thin wash coat provides the required high surface area for a catalytically active
material. Therefore,its weight is insignificantcompared to that of the mono-
lith support itself. Consequently, surface area measurement of monoliths
yield values of 5 to 10^ m2/g. Lower reading would suggest possibly some
catalyst deactivation has occurred.
Differential Thermal Analysis
The solid state thermal properties of the.monolith with its deposits
were analyzed by differential thermal analysis (DTA). A DuPont 990 thermal
analysis system was used. It is capable of measuring thermal changes up to 1200°C
in a controlled atmosphere' environment. The thermographs were" obtained on all
nine catalyst samples.'. Approximately 30 milligrams of sample which was
ground and packed into a platinum cell. The atmosphere gas contained 0.8^
oxygen in nitrogen. The oxygen level closely approximates the oxygen level
in exhaust stream when A/F ratio is at stoichiometric and no added air is
injected into the exhaust stream. Both heating and cooling curves were ob-
tained and registered on the same chart. The DTA thermograms are provided
with this report. The thermal sensitivity of the thermal responses obtained
was set at two levels, 0.2 and 1.0 millicalories per inch scale deflection.
Under these sensitivity conditions the thermogram provides a view of the major
ana "rincr thermal reactions that are taking place. The system was heated at
a rate of 10°C per minute. A similar cooling rate was programed. The thermal
data obtained on the nine samples is summarized below:
Chrysler Catalysts: Tests 511. 512, and 515, Cornins's 236 c/in2 supports:
A minor, but'sharp" exotherm, occurs between 170-190°C which cannot be associated
with any known physical change except surface desprption.
A pronounced oxidation reaction reaches an exothermic peak at:
UOO°C for catalyst 511
260°C for catalyst 512
360°C for catalyst 513
In all the samples a-minor exothermic reaction appears to be initiated between
700-750°C. This appears as increased noise in the thermal recording. It
is believed these react:'ons are due to sintering or surface reactions.
A subtle, miner endothermic reaction appears to range from about 620°C
to 850°C. This change, is undoubtedly due to a crystallographic change that
occurs within the cere.
A sharp exothermic phase transition occurs in catalyst 513; a"t 695° C this
is a phase reversal transition since it also occurs endothermically on cooling.
-------
--7
Ford Catalysts
Test samples $2k and 525 represent Corning 200 cells /in2 monoliths.
The monolith fiom test 526, represents an American Lava support which is
considerably less pure than the Corning samples. These were analyzed, by
differential thermal analysis. Some slight high temperature differences
are noted in the DTA curves that would distinguish the Lava support from
the Corning support.
An initial minor but sharp exotherm occurs at 170- 190° C similar to that
observed with the Chrysler supports. Oxidation reactions occur with the exo-
therm reaching a maximum at:
370° C for test 524
340° C for test 525
C for test 526
In the range of 650° -700° an endotherm is initiated and extends to 900° C.
This thermal reaction is believed to be due to a crystallographic phase change.
Minor phase transitions provide a sharp exotherm in the cooling curves
in the range of 970- 10JG0 C . The higher transition temperature represents a
Lava support.
General Motors Catalysts: These pelleted catalysts were analyzed similar, to the
monolith supports. Catalyst pellets from test 537 were extrudates. and pellets
from tests 538 and 539 "vjere spheres. Thermal differences between the two forms
was slight,, only the high temperature phase transitions can distinguish between
the two forms. The spheres show a sharp exotherm on cooling at 1035 °C while the
extrudate produces a, exotherm at 960° C phase transitions. These transitions are
reversible on heating and cooling.
Overall the pelleted catalysts produce an initial strong endotherm in the
range of 35 to 80°C, possibly adsorbed water or gas is being desorbed. A .
minor exotherm is observed in the range of 170 to 190° C similar to that noted
with the monoliths, although it is less pronounced in the case of the pellets.
An oxidation maximum is noted for the different tests sa.-r.ples at:
350° C for test sample 537
290° C for test sample 538
310° C for test sample 539 (
In conclusion^ it would, be necessary to combine high temperature X-ray
diffraction analysis and thermogravometric analysis to gas chromato-
graphic analysis to ascertain the subtle thermal changes that are being ob-
served. In general though the reactions are slight and do :-iot affect the
overall priysical structure of the support when heated to 1200° C. Possibly
higher temperatures may be required to see a catastrophic change in structure.
-------
E. X-RAY DIFFRACTION PATTERNS
-------
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*.':" ~T r~ :
T...... .j_.j _i.
-------
VUMI Ml OI1NMM
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....-.p-..-
_ I . . 4. - _;_ .J-. p. .. .J. ,- (.. .: ...
-------
-------
AVRW03 'Oil S1UVHO Qr>JiaaQ33B 3IMdTOO 1139 S
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-------
jwsnoe -oil siuno sNiouoaaa auumo 1139
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-------
SPECIFIC SURFACE AREA DATA
-------
M I C R 0 M E R I TICS *##########*##«#»#*»*»#
M A T E R I A L S ANALYSIS LABORATORY
MODEL 21COD
DATE RUN 07-17-79
SAMPLE IDENTIFICATION;.._.8URFACE...ANALYSIS &.. RESEARCH 511-1....ELY..
fc^ t\ * » T ^V~.l »"N 1 4."^» » »fc^^~
rimvirui_u vui_*""/> Kl*t / ^~**T*r"W \
. Q-.jQ ML (oTr)
EXTRA VOLUME: 131.270 ML (STP)
_...ST ATI ON .2 FLASK _..NO,...#2 .GUT.GAS _.TEMP 220.._(.C L- .OUTGAS...T.I ME 867, MIN
Wl 21...3364.-G HI 55. I IM i _" N
PO I NT 6 N
0. 4954
150...
150.
155.
4 t
-------
MODEL_21OOD
BLiKF.SCE_AREA_DATA_AND._.C.OMEUTAT.LQN-
DATE RUN 07-18-79
.SAMPLE ... I DENT IF I CAT I ON: _ SURFACE.. ANAL YSI S... & RESEARCH 512 DODGE .TUBE
MANIFOLD VOLUME; 23. 0150 ML (STP) EXTRA VOLUME: 131.270 ML
-------
^y-^-*-^-****-*-^-.-.E1 I_C_B_-0_M._.E.._R_J-_T._1 C S ^**^±^*^Jt******
M ATERIALS ANALYSIS LA B 0 R A TORY
: MODEL_210PD
BATE RUN 07-17-79
i:ci SAMPLE... IDENTIFICATION;...... SURFACE ...ANALYSIS & RESEARCH 513-1. FLY-
MAN I FOLD VOLUME: 28.050 ML (STF)
EXTRA VOLUME: 131. 270 ML (STP)
.. ..
_M p_oun,p..t?_i..c..
.~^1 « *»~ T ">!. i ^~» ^t /\ '"* ^ j» )r*i jj "*«
II-II>.UIN o rt-MoK NO. #o
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(NO.
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PS.
_744..92?6..MM HG
..-.1
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-i. JL UO i
T.-
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//. low
16. 2000 A
.EV_
PI.
_F2
y.
-i.
INFUT PCINT 1 .N
_1MM_HGJ _ C«M_HGJ. __ .U1L , STP) ( P2./PS )_ ____ < ML , STP. ) ...
150. 2200 22. 9340 1. 3397 -ft******** *#»»##«#»*
..... 0.. 05SS75
:i: INPUT POINT 2 N 15p.,...000.0_ 62.._.9.9.00 1. 5689. 0. 0846
_1,.6.3S6_ 0...1224
0. 1502
150. OQOQ 91. 2OOO
INPUT POINT 4
N
155.0000 111.3300 1.7749
0. 099572
'- INPUT... POINT...5 _ N l.p-Q._0_0_QQ 127.. 5300. 1.,3363........_ 0. 1712 1 0....112457
p° I_NP_UT__POINT 6 N 1.64.t_P_Pp.P 1_39_._39_PP. 1 ....3.3.32
. 0... 13.71 P.. 122233
":" SLGr
I NT.ERCEcX_=_
_O...P063_
6. 9765 M /G
STANDARD ERROR OF... LEAST ...SQUARES LINE ..= .0.000123. .. % ERROR = 0.1349
.=_CAT A ...OUT_ OP_._LI NEAR.. REG I ON . OF... I SOTHERMi
NOT USED FOR LEAST SQUARES CALCULATION
-------
r^>^^f^*^'>r->r'H''x'>r-K'*H''H''>r'>r^ t'l 1. _< r\ LJ Fl CL r\ i. i ^ C^ O
MATER I A L S A N A L Y S I S L A B 0 RAT 0 R Y
MODEL 2100D
SURFACE AREA DATA AND COMPUTATION
DATE RUN ; 07-18-79
...S.AMrLE.J.DENTIFJ.^ FORD.
MANIFOLD VOLUME: 23. 050 ML (STF)
EXTRA VOLUME: 131. ,270 ML OUr\OH 1C.. (Mil PVULJCIIM
STATION 2 FLASK NO. #6 OUTGAS TEMP. 20S
-------
M I C R 0 . M E R I T I C S »»»»{(»»»»»*»»»(»»»»»»»»»
MATE R I A L S A N A L Y S I S L A B OR A T 0 R Y
..MQDEL.._.2.1.Q.QD_
DATE RUN 07-17-79
!';; SAnELE.._I.DENIIEICATIQN.;__.SL:REHCE..ANAL.YSIS.....2t...RESEARCH 525.. FORD .400
'MAN I FOLD VOLUME: 28. 050 ML (STP)
AE'SORBATEj NI.TROGEN
EXTRA VOLUME: 131.270 ML (STP)
...STATION .4 FLASK_NQ..Jt4_
__OU.TGA3_TEMR 153 .(.CD. GUTGAS....JIME .867. _..MIN.
j-U 5.5.0..._OOQ.O_MM_.BG._ _.F,S._ 7.4.4....9296 ...MM.. HG..
-1
.. £'.'... V M M V p
_H2 1.7.3...-.36.00 MM_.HQ. ALPHA Q._Q.0.0066_(.M« HG)...
2
TS 77. 1300 (K)
16. 2000 A
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v.o
I__f-ii
EV
P L_. _ P2 _ _ V
(MM HG) (MM HG? LML^JSTFL
...Y. -1...
(ML,STF)
( P2/PS )
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N
150. 2200 17. S9SO 0. 7174 ***»«-»«»» *#*#*><*»«*
Iu i r. i i *- (... » fc »-y f, »(
nr>_i i r.OA.IN (__ .4 i_s
INPUT POINT 3 N
150. 0000 54. 6200 0. 8572 0. 0733 0. 092309
150. 0000 82. 2700 0. 9298
0. 1104
INPUT POINT 4
155. 0000 103. 4700 0. 9816
0
.
_0.._133518l
0. 164332
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INPUT
PU I NT 5
. FO.INT__6
N
N
160.
165.
0000 120.
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0100
2100
1.
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0197
048?
0.
0.
1611
1788
0.
0.
138323
207613
ouurc.
1. 0915 INTERCEPT =
0. 0126
jURFAUE AREA
3. 9425 M /G
STANDARD ERROR OF LEAST SQUARES LINE = 0.000245 'A ERROR = 0. 1557
__^ _OF_ ISOTHERM,
NOT USED FOR LEAST SQU~A~RES CALCULATION"
-------
M I C R J3_M E R...,I__T.._I_.C_. S
MATERIALS ANALYSIS LABORATORY
MODEL 2100D
DATE RUN 07-19-79
SAMPLE IDENTIFICATION: SURFACE...ANALYSIS. &_RESEARCH 526 FORD LTD
MANIFOLD VOLUME. 28. 050 ML ..
2
i i .-^ ^. ^~. rr < c^* f^
wo jz.. o._'i^.i b
..VS. 16.. 278.4.. J1L.
Tf.
&
. 2000
16. 2000 A
EV
PI
:MM KG>
P2
(MM h'G)
V
.
-------
_K_E- R I- T I C S
MATE RIAL S A N A L Y S I S "r L A B 0 R AT 0 R Y
_.tt.QDEL_2.100.D_
SURFACE AREA DATA AND COMPUTATION
DATE RUN 07-18-79
SAMPLE IDENTIFICATION: SURFACE ANALYSIS & RESEARCH #537. MAL #3153
MANIFOLD VOLUME: 28.050 ML (STP)
ADSORBATE: NITROGEN '
STATION 4
EXTRA VOLUME: 131. 270 ML (STP)
tyj_GAS_j:EMP. 1S_S_LC_1 QUTGAS_TIME_._?97i_.MIN
Wl
.22,_S531 __G HI 550. 0000 MM HG PS _'_7_46.' 6702.. MM. HG...
-1
'L 7337 G
H2 141. 9900 MM HG
fHA 0. 000066 (MM HG)
0. 1194 G
TS 77. 2000
16. 2000 A
VS
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PI
(MM HG)
F2
(MM HG)
V
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1
INPUT POINT 1
N
1'50. 2200 23. 13SG 11 2730 ********* **********
; INPUT
PO I NT 2
N
ISO.
0000
57. 9900
12.
/-. « ^-»^>
O*tO-i
0.
0~T~TT
/ / /
0.
006554
: INPUT
INPUT
INPUT..
F'uINT 3
POINT 4
POINT .5
N
N
N
INPUT POINT 6 N
INPUT
F'UINT 7
.N
1 !30.
>; 155.
160.
165.
170!
0000
0000
0000
0000
0000
80. 7200
99. 0000
114. 0300
12.6,_5 910.0.
137. 3200
13.
14.
15.
15.
16.
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5637
1670
6529
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0.
0.
0.
0.
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1326
1527
1695
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0.
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010496
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0.
070.4
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0.
0011
_3 U R F. A CE.._ A R E A 6 0 ._887-4 M._/G.
STANDARD,ERROR..O.r_LEAS.T_SQUARES_.LINE__^___0._000034 _..... % . ERROR . =.. 0. 3123
**^4f^-x-^-4rv"K- - DATA GUT OF LINEAR REGION OF ISOTHERM*
NO.T_USED_FOR_LEAST_.SQU ARES..CALCULATION
-------
y»jrjfX;-H--ir-^'>f-K--x--K--x-'K-^'K--y-K--H-»jc;>r'«-» M I C R O..M E R I T I C S »"»» »»»«» *>* »««
M A T E R I A L S A N A L Y S I S LABORATORY
.MODEL ..... 210QB
DATE RUN 07-18-79
3AEDavT I F I CAT I _QN :._ ..... SURFACE ..... .ANALYSIS ..... & ..... RESEARcsSS . ........ MAL
n, r% -.» r-, r
- I . f~> »-. r h I
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i"" * i » -T* /-. /\ . . -T*I K^ r~» *"» < *"» / i1"* * f^i (IT i~* /* «" T" T M C"
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Vo 17. 7ob'7 ML
r i *
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O.IMT '_' i r UJ.IM 1 1 'is
INPUT FGINT 2 N
T t. t r~* ~r* r~- i"- . T- b i T" . t L i
Aisrij i ru i is 1 o is
INPUT FGINT 4 N
INPUT FUlNT 5 N
INPUT POINT 6 N
INPUT FGINT 7 N
SLUFE 0. 0393
o u K r M L- c. AREA 103.
it.'-. .1 A *-^
n^i x4/.
T;; 77.
Fl
(MM HG)
150. 2200
150. 0000
150. 0000
1!_"5. 0000
160. 0000
165. 0000
170. 0000
iyi^RCEPT
2
0321 M /G
4200 MM HG
2000
F2
(MM HG) (ML
22. 0990 20.
53. 4600 23.
77. 5600 24.
96. S600 26.
112. 3200 27.
125. 9300 23.
136. 3200 23.
= 0.0005
ALPHA
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1 1
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0059
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i s- . . v
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"S . » --S
O.£ / O
2194
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0. 000066 (MM HG)
2
16. 2000 A
'
X Y -1
(P2/FS) (ML/ STF)
**********
0. 0716 0. 003339
0. 1039 0. 004656
0. 1297 0. 005662
0. 151 1 0. 006539
0. 1637 0. 007239
0. 1S32 ^ 0. 007763
STANDARD ERROR _GF_ L^EAST_ _SQ:JARES ..LINE = 0.000021 ". ERROR.- 0. 35S3
w--K--y--^-^-4i--M--K--ir-K- DATA GUT OF LINEAR REGION OF ISOTHERM/
NOT USED FOR .LEAST SQUARES CALCULATION
-------
r\-
MICRO MERITICS
M
TER I A L 3s
N A L Y S IS LAB OR A TORY
r*»l tr-tr « .. r /\ r-. i /\ T-. ** -^ fv /\ ^ lips .»Ns-,t-4r>tt-T*'\-'-v.-%hl
our.r H»--c._j-ir\c.i-i bi-i I H hjNJJ Lurlr U I t-i I J. UIM
.DATE RUN 07-13-79
MA,N' I FOLD VOLUME: . 2S. OCiO ML < STF)
_ADSOREATE: NITROGEN_J ;' / ";- :
EXTRA VOLUME: 131.270 ML (STP)
;, STATION _4_ FLASK_.NQ.._35;l 77. 2000 (K)
16. 2000 A
I NPUT F'O I NT
Ttir- . i I-T- r^ ^". ^ * i T.
i.iNr u I. r u .11 1.1.
- INPUT Pu I NT
INPUT POINT
INPUT F'GINT
EV
1 N
2 N
3 N
4 N
5 N
<: MM
150.
150.
1 55.
160.
165.
Fl
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2300
0000
0000
0000
0000
F2
(MM HG)
26. 5930
55. 4SOO
78. 9600
93. 0100
1 1 3. 3300
v
(ML, STF)
X
(F2/PS)
10. SI 40 K-»- ** * #*£»
12. 3101
13. 2621
14. 0714
14. 5S54
0. 0743
0. 1057
0. 1313
0. 1525
Y -1
(ML, STF)
«H».««M
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0.
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006520
OOS917
01073S
012339
INPUT POINT
INPUT POINT
...SLOPE =;:;;"
6 N
7 N
0. 0733
170.
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INTER
0000
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127. G900
13S. 35GG
0.
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10. Ooo*t
15. 5193
0011
0. 1702
0. 1353
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013597
014655
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_£i '/. ERXQ R= 0. 326:
# = DATA GUT OF: LINEAR REGION OF ISOTHERM,
NL'T USED FOR LEAST SQUARES CALCULATION
-------
DIFFERENTIAL THERMAL ANALYSIS CURVES
-------
PART NO. 990092
RUN NO __ DATE.fch.oll5
OPERATOR
SAMPLE:
ATM O.ft/
FLOW RATE
T-AXIS
SCALE, mv/in 0.8
PROG. RATE. 'C/min_LO_
HEAT_.ri_caoi iso
SHIFT, in_____Q
DTA-DSC
SCALE, 'C/in
(mcal/socJ/in./J^KL::
WEIGHT, mg _3| .00
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST.. Eec_
dY, (mg/minVin
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY. (1O X I. C mils/min )/in .
CO
* *
n:
CO
E
e-o
c:
HI
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m
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ui
a
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BOO
9OO
1OOO
-------
PART NO. 990092
RUN NO
OPERATOR _j VAH
SAMPLE: {.P& £j\2.
FLOW RATE
T-AXIS
SCALE, mv/in __OJ_
PROG. RATE. 'C/min JD
HEAT_^_COOI ISO
SHIFT, in P __ .
DTA-DSC
SCALE. "C/in
(mcal/soc)/in 1
WEIGHT, mg _JS!.>>__
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST.. sac_
dY. (mg/min )/in
TMA
SCALE, mile/in.
MODE
SAMPLE SIZE.
LOAD, g
dY. C1O X ). [ mils/min )/in
a
cu
E
CO
c:
UJ
_l
m
D
UJ
-------
PART NO. 990072
RUN NO._
OPERATOP, .A .KuuA.f_
SAMPLE:
FLOW RATE
T-AXIS
SCALE, mv/in 0-8
PROG. RATE, C/min_\.CL_
HEAT_»_caOI ISO
SHIFT, in 0
DTA-DSC
SCALE. "C/in
[ mcal/sec)/in
WEIGHT, mg 3Z'30_
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST.. sec_
dY. ( mg/rnin )/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE-
LOAD, g
dY. C1OX). Cmils/minJ/in
-------
PART NO. 990092
RUN NO DATE(«laii.|:ia
OPERATOR
AMPLE:
- FO«D
FLOW RATE
T-AXIS
SCALE, mv/in 0.8_
PROG. RATE. "C/min ' O
HEAT_i^COOI _ISO
SHIFT, in 0
DTA-DSC
SCALE. "C/in
( rncol/sec )/in J_l PJL
WEIGHT, mg 5o.?lo
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST.. aec_
dY. (mg/min)/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY, (1O X). (rnils/min )/in
GUU
7OLT
BUO
9OO
1OOO
-------
PART NO. 990092
RUN NO
OPERATOR A
SAMPLE:
._9l....Vf
ATM. 0.3,": 0L (.,
L.OW RATE
T-AXIS
SCALE, mv/in . Q.8
PROG. RATE. 'C/min J.O
HEAT_j/.. COOL ISO
SHIFT, in P ,
DTA-DSC
SCALE. "C/in
C meal/sec) /in _L<^.
WEIGHT, mg ....Tbl. O g>
REFERENCE
TGA
SCALE. mQ/in
SUPPRESSION, mg
WEIGHT, mg
TIME CONST., st-c
dY. ( ms/min )/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY. C1O X). (mils/min )/in
-------
PART NO. 99009J
Kin ____ DATE
Ot-cRATOR
AMPLE:
ATM
FLOW RATE
T-AXIS
SCALE, mv/in _P.-.?
PROG. RATE. *C/min_!P_._
H E AT_^_ CDOI ISO_
SHIFT, in P
DTA-DSC
SCALE. "C/ir
lmc;il/r,nc)/.n.<
WEIGHT, mg ..^.iZ.O
REFERENCE
TGA
SCALE, mg/in .
SUPPRESSION, rng
WEIGHT, mg
TIME CONST.. GOC
cJY, C mn/min )/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY. {1O X ). C mils/min )/in
SOO 6OO 7OO
TEMPERATURE. °C (Pc/Pc-ISS
-------
PART . 9COQ93
CO
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CO
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W
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0
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SAMPLE:
v-
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FLOW RATE
T-AXIS
SCALE, mv/in 0.8
PROG. RATE. °C/min_i.P_..
HEAT.i.COOl ISO
SHIFT, in 0
DTA-DSC
SCALE. 'C/in
(mCc-i!/r,cicVm I
WEIGHT, mg .. .i'i.'Z.
REFERENCE .......
O.S
TGA
SCALE, mg/in
SUPPRESSION, mg
WEIGHT, mg .
TIME CONST., soc
dY. ( rncymin )/tn
TMA
SCALE, mils/in
MODE
SAMPLE SIZE
LOAD, o
dY. 11O X ). (mils/min Vin .
O 1OQ
soo sao Totr
TEMPERATURE.-C (Pc/PC-)3-;Rn)
-------
PART NO. 990092
RUN NO DATE
SCALE, mv/in 0.8
OPERATOR
SAMPLE
SCALE, mils/in
MODE
PROG. RATE, "C/minJ.Q
tmcal/sec)/in l.O.-
WEIGHT, mg ___?A. b !>..
HIEAT_n_COOI ISO
SHIFT, in 0
WEIGHT, mg \
SAMPLE SIZE
LOAD, g
ATM O.B'^..t C"
FLOW RATE
REFERENCE
TIME CONST., s
dY, (1O X ). t mils/min )/in
dY. Cmo/minj/in _...\
-------
PART
IT
RUl
OPERATOR
SAMPLE
FLOW RATE
T-AXIS
SCALE, mv/in _0.8:
PROG. RATE. "C/min !.0_
HEAT_.«'. COOI ISO
SHIFT, in P.
DTA-DSC
SCALE. "C/in
(mcnl/'.-.ocl/in I ^ Q.S
WEIGHT, mg Sl.15_ _...
REFERENCE _.
TGA
SCALE, mg/in
SUPPRESSION. mg_
WEIGHT, mg
TIME CONST.. sec__.
dY. tmQ/min)/in
TMA
SCALE, miln/in.
MODE
SAMPLE SIZE..
LOAD, g
dY. C1OX). tmils/minVin .
oo
4<
c:
03
ru
*«
c-o
Ul
J
m
a
UJ
a
in
01OO
"30O
"SoS ' eoO ' 7oo
TEMPERATURE. *C (Pc/Pc - l3%Rh)
BOO
9OO
1OOO
-------
PART NO. 990092
RUN NO.-
OPERATOR J
SAMPLE:
- S2.C.
T-AXIS
SCALE, mv/in _0._8_
PROG. RATE. °C/min_LQ__
HEAT_n_COOI ___ ISO _
SHIFT, in _ P __
1
DTA-DSC
SCALE. 'C/in
C meal/sec )/inL5.£.'A_
WEIGHT, mg "it.C.Co
REFERENCE
OXIDE
\
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST., soc.
dY, C mQ/rnin )/in ,
TMA
SCALE. milB/iri_
MODE
SAMPLE SIZE.
LOAD, g
dY, (1O X), (mils/min )/in
-------
PART NO. 990092
RUN NO __
OPERATOR A..
AMPLE: tr.4Y,
FLOW RATE
T-AXIS
SCALE, mv/in QJL
PROG. RATE. °C/min_LQ_
HEAT_?LCOOI ISO
SHIFT, in 0
DTA-DSC
SCALE. 'C/in
t
WEIGHT, mg _ Z
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST., sec.
dY, (mo/min )/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY. f 1O X). Cmils/min)/in
100
aoo
3OCI
eoo
soo
1000
-------
PART NO. 9V0092
Rl/ IB DATE
].. MATOR A C
SAMPLE:
ATM
FLOW RATE
T-AXIS
SCALE, mv/in 0.8
PROG. RATE. "C/min...'_?_
HEAT.-__COOI ISO_
SHIFT, in 0.
DTA-DSC
SCALE. "C/in
(mcnl/TT-ficl/in 1
WEIGHT, mg ._£?.,.« ^
REFERENCE
".l_
TGA
SCALE, mg/in
SUPPPL-SSION. mg_
WEIGHT, mg
TIME CONST., coc .
t)Y. ( mfi/min )/in .
TMA
SCALE. rriils/in_
MODE
SAMPLE SIZE..
LOAD, g
dY. (1O X ). {mils/min )/in
TEMPERATURE.'C (Pc/Pc - I
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PART NO. 990092
RUN NO._ __ DATE 0.1 55 (
OPERATOR
SAMPLE:
FLOW RATE
T-AXIS
SCALE, mv/in 0.8
PROG. RATE. "C/minJ.O _
SHIFT, in
DTA-DSC
SCALE. "C/in
( mcal/cec )/in J_^ .0..7.
WEIGHT, mg il .7L.C.
REFERENCE
TGA
SCALE. mQ/in
SUPPRESSION, mg.
VA/EIGHT. mg
TIME CONST.. socl_
dY. ( mQ/min )/in
TMA
SCALE, mils/in.
MODE
SAMPLE SIZE.
LOAD, g
dY, (1O X). (mils/min )/in .
-------
PART NO. 990092
RUN NO DATEC.Uo.Vl3
OPERATOR
SAMPLE:
ATM ..
FLOW RATE
T-AXIS
SCALE, mv/in 0.8_
PROG. RATE. °C/min_LQ_
HE AT_K.COOI ISO_
SHIFT, in 0
DTA-DSC
SCALE. °C/in
(meal/sec )/in _L^Q.Z«
WEIGHT, mg _ il.,1 3,
REFERENCE
TGA
SCALE, mg/in
SUPPRESSION, mg.
WEIGHT, mg
TIME CONST.. sec_
dY. Cm0/rnin)/in
TMA
SCALE. mil3/ih_
MODE
SAMPLE SIZE.
LOAD, g
dY. (1O X). t mils/min )/in
11OO
-------
H, SCANNING ELECTRON MICROGRAPHS
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£ '^^^ ^
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Ik - "*^~^^rj?l,^PSi(l^8'^J * 4J
SURFACE ANALYSIS AND RESEARCH, INC. 17000 WEST EIGHT MILE SOUTHFIELD, MICHIGAN 48075 :, .,(313) 569-2371
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