-------
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*

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                                        •••••••••••I*
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 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
              	Exhaust Catalysts from General Motors	


          (powdered  =  entire pellet used as  sample)
I D: SAMPLE £53?--' POwQERED
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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 insignificant•compared 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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                              M  I  C R  0 M E R  I  TICS  *##########•*##•«•#•»•#•*•»••*••»•#
             M  A T E R  I  A L  S  ANALYSIS   LABORATORY
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                                                                  DATE RUN  07-17-79
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                                   MODEL_21OOD			
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                                                             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  
-------
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                                                                    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)
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                                                                 DATE RUN ; 07-18-79
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-------
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                                                                   DATE RUN   07-17-79
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-------
                               M  I  C R J3_M E R...,I__T.._I_.C_. S
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                                       MODEL 2100D
                                                                   DATE RUN  07-19-79
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                                                             DATE  RUN  07-18-79
 SAMPLE IDENTIFICATION:  SURFACE  ANALYSIS & RESEARCH #537.	MAL	#3153
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                                                                          DATE RUN   07-18-79
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-------
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                                MICRO MERITICS
M
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                                       N  A L Y  S  IS    LAB  OR A  TORY
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INPUT POINT
INPUT F'GINT

EV

1 N
2 N

3 N
4 N
5 N


<: MM
150.
150.

1 55.
160.
165.

Fl
HG)
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
P-
0.
0.
0.
006520
OOS917
01073S
012339

INPUT POINT
INPUT POINT
...SLOPE =;:;;"
6 N
7 N

0. 0733

170.
1 7'5.

INTER

0000
0000

CEPT

127. G900
13S. 35GG

0.

•* er /"• *~* * «
10. Ooo*t
15. 5193

0011

0. 1702
0. 1353



0.
0.
	

013597
014655
	

   .3 U P P A C E  A RE A__=	5_3._J5Q&9__ J1_/G_

                               _£i                              '/. ERXQ R=   0. 326:
              # = DATA GUT OF: LINEAR  REGION  OF ISOTHERM,

                  NL'T USED FOR  LEAST  SQUARES CALCULATION

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DIFFERENTIAL THERMAL ANALYSIS CURVES

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       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
 -J
 m
 D
 ui
 a
 ui
                                                                                                                   BOO
                                                                                                                                     9OO
                                                                                                                                                      1OOO

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       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

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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	

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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	

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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

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       PART    . 9COQ93
CO
*-<
CO
c:
 W
 _i
 ffl
 0
 u
 a
 D
 U)
 <
 IU
no
O
SAMPLE:
                             v-
                              I
       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)

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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

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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	

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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

-------
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

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H,  SCANNING ELECTRON MICROGRAPHS

-------
                                                 £ •'^•^^ ^
                                                 ^.^^'  :
                                        o*- «£?«..» 1 •/<>:-,  •;'^S>^>-^^C^^J
AMAIVCIO rtMPt OCPCAO^I.I
                                                                 101 *»\ CCQ.OQ71

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/oio  AMI™*
                                 nonn WCCT  cirwr Mil F      SOUTHPIELD.  MICHIGAN 48075      (313) 569-2371

-------

SlIRPACF  AMAl vcic  AMP*  OCCCAO^LJ
                                                                           uT  RAM c       er\iiTucict n   n^iruir:AM

-------
                   Ik   - "*^~^^rj?l,^PSi(l^8'^J  * 4J
SURFACE  ANALYSIS AND  RESEARCH, INC.     17000  WEST EIGHT  MILE      SOUTHFIELD, MICHIGAN  48075  :,  .,(313)  569-2371

-------