Fh~ HEWLETT
!.:~ PACKARD
Pyrolysis-GC/MS/IR
Analysis of
Polyethylene
Application Note 228-97
Author
Matthew S. Klee
Hewlett-Packard Co.
Avondale Division
Abstract
Pyrolysis gas chromatogra-
phy was used to demon-
strate the effect of pyrolysis
temperature on distribution
of pyrolysis fragments of
polyethylene. Cryogenic
cooling of the on-column
injector port and oven
(HP 5890 SERIES II) al-
lowed chromatographic
resolution of pyrolysates
down to ethene. Detection
and identification of pyroly-
sates was accomplished
with an MSD and IRD con-
nected in parallel. Pro-
grammable pressure control
allowed fast analysis while
maintaining chromato-
graphic efficiency.
Introduction
Pyrolysis gas chromatography is
a useful tool for characterizing
polymers. Polymers which are
not volatile enough for standard
gas chromatographic analysis can
be thermally cleaved into smaller,
more volatile fragments which
can then be separated and ana-
lyzed. The resulting chromato-
grams yield characteristic finger-
prints relating to the composition
of the polymer, structural infor-
mation s uch as branching and
defects, and information on
additives.
Since many fragments are pro-
duced during the pyrolysis proc-
ess, the ability to provide high
resolution separation of these
frag·ments is very important.
Capillary column chromatography
with low dead-volume connections
and cryogenic cooling of both the
column and injector ensure
maximum resolution of pyroly-
sates. Since the flow rate through
a capillary column decreases with
increasing oven tempPrature
Gas Chromatography
June 1989
(the gas is more viscous. causing
decreased flow with fixed head
pressure), standard pressure-
controlled systems suffer both
losses in efficiency and increases
in analysis time. The HP 5890
SERIES II used in this study had a
programmable pressure controller
which maintained constant flow
rate during the run by automati-
cally increasing the column head
pressure.
In addition, rapid independent
temperature progTamming of the
cool injector, after pyrolysates
have been trapped, ensured sharp
injection profiles of solute bands.
Selective detection of pyrolysate
peaks is very useful for accurate
characterization of the starting
polymer, the mechanisms of its
thermal degradation. and identifi-
cation of additives and residual
solvents. Therefore. the combina-
tion of a capillary gas chromato-
graph with both mass spectral and
infrared detectors can be extremely
effective for polymer pyrolysis
studies.
Experimental Polyethylene was acquired from
Chemical Data Systems, Oxford,
Table 1. Instrumentation and Conditions PA. Pyrolyses were carried out at
700°C and 1000°C using a plati-
Gas Chromatograph: HP 5890 SERIES II
Cold On-Column Injector with Programmable Pressure num coil pyrolysis probe. Sample
and Temperature Control amounts are stated in the caption
Cooling: Cryo Blast, C02 Cryogenic (Oven and Injector) of figure 1 and were less than
Mass Selective Detector: Hewlett-Packard 5970 1 mg.
Mass Range: 19-250 (0 to 8 min)
37-400 (8 min to END) Pyrolyses were carried out in a
EMV: + 0 Vrelative heated interface which is supplied
Transfer Line: 325°C
Data System: Hewlett-Packard 9836C (Rev 3.1.1) for use with HP 5890 GCs (CDS,
Oxford, PA). The standard inter-
Infrared Detector: Hewlett-Packard 5965A
Resolution: 8 em -• (4000 to 700 em -•)
face needle assembly was too large
Transfer A,B: 300°C to fit into the on-column injector
Cell: 300°C and was replaced with a 28-gauge
Data System: Hewlett-Packard 59970C (Rev 1.0) needle via a 1/8-1/16 in. Swagelok
Column: 30m Series 530 JJ., 2.65 JJ.m HP-5 (Part No.19095J-123)
union and graphite!Vespel ferrule.
He Flow: 5 psi@ 0°C, Constant Flow Mode The pyrolyzer interface was used
Oven Program: ooc (1 min) -t275°C (2 min) @ 12°C/min without the standard quartz liner
Injector Program: - 10°C (0.5 min)-t 300°C (1 min) @ 120°C/min and was fed with an auxiliary
Pyrolyzer: Chemical Data Systems (Oxford, PA) Model122
supply of helium carrier gas. This
Interface: 275°C a uxiliary helium was connected to
Probe: Coil an event-controlled solenoid (in
Ramp: Off (ballistic) t he Purge B position) such that it
Interval: 10 sec
could be turned off and on within
Auxiliary He Supply a time program. As long as the
Pressure: 10-12 psi auxiliary pressure supplied to the
OFF Time: 0.5 min
interface exceeds that of the
programmable pressure controller
(PPC), it overrides the PPC and
supplies all of chromatographic
system's carrier gas flow through
the interface. As soon as the sole-
noid turns off the g-as flow to the
interface, th e PPC resumes con-
trol of the column head pressure
and no more helium flows through
the pyrolysis interface.

The inlet of the analytical column

was connected to the on-column
injector and the outlet to one side
of a 1/16-in. zero dead-volume
Swagelok union. To the other end
of t he union , two additional
capillary columns were connected
via a two-holed gTaphiLe!Vespel
ferrule: a sh ort piece of 0.32 mm
HP-5 coated capillary column was
used for connection to the IRD,
and a 2 m x 0.10 mm id blank col-
umn was used for connection to
the MSD.
2
Results and Discussion
1.4E+7 i (A)
The pyrolysis of polyethylene
l . 2E+71
yields three major homologous
series of linear hydrocarbons:
alkanes, alkenes, and dienes (1). ::::::! 1000 c
The ratio of the three compound 6.0E+6

types is dependent on the ~.0E+6 i

pyrolysis temperature, tempera- 2.0E+6

1
•
0
ture ramp rate, and final hold ..c
time. "c
~
.lJ
a:
!. 4E:+7 j
(B)
Figure 1 compares the total ion } . 2E:+7 1

chromatograms (mass spectral) l. 0E+7~

for 1000°C and 700°C pyrolyses 8.0E+6 1
700 c

I~ J
of polyethylene. Figure 2 is the
total reconstructed chromato-
gram (infrared), acquired simul-
taneously with the mass spectral
::::1~/'-~,
2.0E+6 l '+-1'1
i
ij~,,~~~J~,.-4- -t.A-,J.!l.~-.1!.,.-., !...4-.JlWJl~~C22
.l\....!l-l

information. Cryogenic cooling 2 4 6 8. 10

T1me
12 11
Cmtn. )
16 19 20 22 24 26

of the injector and column al-

lowed chromatographic separa-
tion of pyrolysis fragments down
to ethene, as was verified by both
mass spectral and infrared
library searches.
Figure 1. Total ion chromatograms (mass spectral) for the pyrolysis of
0.35 mg of polyethylene at 1000 °C (A), and 0.45 mg at 700°C (B).
Numbers above the clusters indicate the length of the carbon
chain of the hydrocarbons in the cluster.

Chromatographic efficiency was

maintained through both detec-
tors. Peaks are symmetrical and ~ 2500
peak widths correlate well be-
tween detectors. This is in part 10l2'2 c [ 2000

due to the constant flow opera- ::- 1500

r
tion of the programmable pres- l_l-1-LJLJ_L~~~-;: 1 000
sure controller. The column
head pressure was automatically ~500
IJ

increased during the run from "c0 La

the starting pressure of 5 psi at Q_

0 °C, to about 7.8 psi at the "" ::25 00

ending temperature of 275 °C.
Q:
•r 2000
7 .lO C'
.
: 1 500
c2.'
t 1000
Iv-'L~~00
10 15 25
Tlme <m 1 n . )

Figure 2. Total reconstructed clu·omatograms (infrared) cht·omatograms

acquired simultaneously with the mass spectral data of f igure 1.
 FJ/'ff4 HEWLETT
~~PACKARD

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Copyrig ht (c) 1989

Hewle tt -Pacl<at·d Compa ny
P t·inte d in LS A 6 /89
43-5952-02 11
Each cluster of peaks corre-
sponds to a one-carbon incre- 1. dlene
ment over the preceding cluster. 2. alkene
With the 5% phenyl-methyl 3. alkane
silicone <HP-5) column used in
G:I!IE+Gl
(A) 2
these experiments, the order of
elution within each cluster was S.I!IE+Gi

diene, alkene, and then alkane, 4.1!1E+6 1

1000 c
with each containing the same 3.0E+6 3
number of carbons. '
2.€1€:+6

The most probable thermal I .I!IE+G

fragment which is produced from •0
c 0.0E:+0
the pyrolysis of polyethylene is a ,c
~

6.1!1E+6
linear alkene with a terminal :1
.<>
a: C,o (B) c,,
double bond. This is born out by S.l!lE+6 c,2
c,3
the size of the center peak in 4. 0E+6

each cluster of the chromato- 3. 0E+6

700 c
grams in figures 1 and 2 and by
2 . 0E+6
both mass and infrared spectra.
The next most probable fragment
~ !~
1.0E+6

type is either the saturated

alkane or a terminal diene,
0.0E+0 /IJ
13 .1!1
A
1 4 .0
A
IS .1!1 16. 0 I 7 ,1!1
Ttme Cm tn.)
depending on the pyrolysis
conditions. Figure 3 is an ex- Figure 3. Expanded total ion chromatograms for t he 1000°C (A) and
panded view of the total ion 700°C (B) pyrolysis, showing the change in relative heights of
chromatograms for 700°C and the first and third peaks in each cluster as a function of
1000°C pyrolyses, and shows pyrolysis temperature.
that the diene peaks are favored
(higher) over the corresponding
alkane peaks after 1000°C
pyrolysis. For the 700°C
pyrolysis, the alkane fragments
are favored (higher peaks) over
the corresponding diene peaks.

4
The length of the hydrocarbon
chain is also dependent on
pyrolysis temperature. The last (C)
significant cluster of peaks in the
1000 oc pyrolysis is C 18, whereas
in the 700°C pyrolysis, the
maximum chain length is at least
C22 (thG analysis was stopped
before elution of all pyrolysates).
The distribution of the pyrolysis
ae I (B)
&9
fragments for the 700°C t:NE ~

pyrolysis is also shifted to longer

chain length, as is evidenced by ;: }; \ ~ ;i ~ a_t
e~------~~------.-~~~~~
the flatter pyrolysis fingerprint. 10Qiil
101!10
WAVENUMBER
201i11!1
l t~- 1 l

These results are expected, since

higher thermal energy breaks IS
more molecular bonds, leading to 10
DIENE (A)
smaller fragments and more
doubly unsaturated hydrocar-
bons. 30Q0 2000
WAVENUMBER ( «•" 1 l

Figure 4 shows infrared spectra

Figure 4. Infrared spectra corresponding to the first (A), second (B), and
for the three peaks in the chro- third (C) peaks in the chromatographic cluster around 12.2 min
matographic cluster around of the 1000°C pyrolysis.
12.2 min. The relative heights of
the major absorption bands due
to the terminal alkene woups
(3084 em -1 and 914 em · 1) can be 1612!12!0
seen to increase in significance 1412!00 2867 cm-1
going from alkane to alkene to 1212!00
10000
diene.
8000
6000
Figure 5 compares selected- 4000
wavelength chromatogTams 200 0
of the -C-H absorption at e~~~~--~~~~~----~~~~~~~~--~~
:0. 0 12.0 J4.e
2867 em · 1 to the =C-H absorp- Time Cm1 n . )

tion at 3084 em - 1 for the 1000°C

pyrolysis. At 3084 em · 1, the
height of the first peak relative
to the second peak in each
Ql
{/)
c
0
::::l 3084 em-!

::::l
cluster is higher than in the a.
{/J

2867 cm·1 chromatogTam since n:" I

the ratio of double bond to single 0~ AJl .A .A
bonds is twice as large. 12.0 14.0

Figure 5. Selected-ion chromatograms from 8 to 15 min in the 1000 °C

pyrogram, comparing the relative h e ights of infra1·ed a bsor·
bances at 2867 em · ' (-C-H) and 3084 em · ' ( = C· H).