Thermal degradation of polyethylene and

polytetrafluoroethylene during vacuum evaporation

received 29 February 1968; accepted I May 1968
P P Luff and M White, Department of Applied Physics, Brighton College of Technology, Brighton, Sussex

The thermal breakdown of polyethylene and PTFE has been studied by means of an MS 10 Mass
Spectrometer. Spectrometer traces are presented which show that polyethylene degrades to homologous
series of hydrocarbons including the paraffins, olefins and higher order acetylenes. The polyethylene was
maintained at 400°C during degradation at a total indicated pressure of 10-5 torr. The PTFE samples were
evaporated at 500°C at a total indicated pressure of 1.5× 10-s torr and degraded to give mainly
CF, CF2, C2F3, OCFz and OCzFs compounds. No homologous series of fluorocarbons were observed.

1. Introduction stainless steel source constructed as shown in Figure 1. Since

Thin insulating films have been obtained by the vacuum
evaporation of polyethylenez, and PTFE =, and have been shown
to possess electrical properties not unlike the bulk material. In
an attempt to relate the mechanisms responsible for electrical
conduction in thin polymer films with structure and composition,
and to determine which type of polymer is most suitable for the
production of electrically stable films, a knowledge of the
evaporation, breakdown, and possible repolymerization pro-
cesses is essential. The thermal breakdown of PTFE and other
fluorocarbons at high temperatures and pressures and in various
gas atmospheres has been well reported 3-6. It is known that a
Nitrogen atmosphere suppresses the formation of the toxic
compounds OCF 2 and OC2F5, whilst atmospheres of air and
oxygen allowed the compounds to form. The present paper
describes the thermal breakdown of polyethylene and PTFE
under normal vacuum evaporation conditions.
2. Experimental details
Samples of polyethylene and PTFE were evaporated from a
molten polyethylene boils vigorously during evaporation the
source had a lid in the form of a matrix of holes each 0.014 inch
in diameter to prevent the polyethylene from overflowing. A
thermocouple was inserted into the side of the source to monitor
the temperature during evaporation.
The polyethylene used was ICI type WSG 22 medium density
Alkathene in pellet form. This is a straight chain polymer,
CH 3 (CH~) n CH 3 with a number average molecular weight of
21,000, it has no additives. The PTFE used was that prepared
to British Standard specification BS 3784, 1964, which has a basic
structure of the type --(CF~)n--. The vacuum system was a
nitrogen trapped 19 inch coating unit which had an MS l0 mass
spectrometer fitted to the top of the bell jar as shown in Figure
2. Craig and Harden 7 have reported the use of the MS l0 in
-- ELECTROMETER
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Figure 2. Vacuum SOURCE
Figure l. Polymer evaporation boat. evaporation unit.
Vacuum/volume 18/number 8. Pergamon Press LtdlPrinted in Great Britain 437
P P Luffand M White: Thermal degradation of polyethylene and polytetrafluoroethylene during vacuum evaporation
residual gas analysis in a vacuum system, and our operating
technique was similar to that described. The ion source para-
meters were set with the electron-accelerating voltage + 70 volts
wrt cage, a trap current of 50 t*A and an ion-repeller voltage of
+ 1 volt wrt cage.
In order to obtain the background spectrum the source was
outgassed at 600°C for one hour prior to the evaporations. The
mass spectrum obtained during outgassing is shown in Figure
3. The height of the peak due to oxygen at mass 32 is larger
than would normally be expected, but was reproducible over
many mass spectra. The reason for the abnormal peak height
RELAT IVE
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il
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Figure 3. Mass spectrum of background when empty source heated to 600°C. (Broken lines are × 25 on intensity scale).
is unknown. The total pressure in the system during outgassing
as measured by the ion gauge was steady at 3.2 × 10 e torr. The
sum of the partial pressures of nitrogen and oxygen computed
from peak height and manufacturers sensitivity data was
3.13 × 10 -6 torr.
For the evaporation of polyethylene 0.1 g of material was
placed in the source and the system evacuated to a pressure of
2 × 10 -e torr. The shuttered source was then heated slowly to
400°C during which time the total pressure in the system rose
to 1 × 10 ~ torr and stayed at this value during the evaporation
period of 30 minutes. This corresponds to a deposition rate of
60 /~ per minute. Degradation was first observed at a tem-
perature of 300°C.
For the PTFE samples the evaporation temperature was
500°C and the total pressure 1.5 × 10 - ' tort. Degradation was
first osberved at a temperature of 350°C.
The polyethylene evaporated completely leaving no residue
in the source. The PTFE on the other hand left a black deposit
in the source indicating carbon as a degradation product.
The mass spectrometer scanned the mass values from m/e - 12
to m/e =200 in two ranges with a total scan time of 25 minutes,
438
and its output recorded on an instrument with sensitivity
10 mV, FSD.
3. Results
The mass values of the peaks were indexed as they occurred.
The spectrum covering the mass range 12 to 200 for polyethylene
is shown in Figure 4, and that for PTFE in Figure 5.
The ordinates are plotted on a logarithmic scale.
(a) Polyethylene The largest peaks in the polyethylene spectrum
occur at the mass ranges 42 to 43, 53 to 58, 67 to 71, 81 to 94,
I
I
i
II
I, I
MASS NO.
and 96 to 100, with the largest single peak at m/e =43 which
corresponds to the C3H7+ ion. The mass range 110 to 142
includes groups of resolvable peaks which are of very low
intensity. At masses higher than 142 several unresolved broad
peaks were obtained with maxima at mass numbers 156, 170, 184,
and 198. A full list of peaks obtained for the three spectrograms
is shown in the table. The small peaks at mass values 92, 94, 122
and 137 are of unknown origin, although it is possible to identify
them with fragmentation products as indicated.
(b) P T F E The PTFE spectrum gives large peaks at mass numbers
31, 50, 81, and 100 which correspond to the compounds CF,
CF v C~F3, and C~F, respectively. Very much smaller peaks
occurred at mass numbers of 12, 24, 66, 68, 131, 135, and 150.
The largest single peak occurred at mass 31 corresponding to
CF. The mass peak at m / e = 1 2 confirms the presence of free
carbon.
4. Discussion
It is obvious from the mass spectra that the degradation of the
two polymers is very different. The polyethylene molecules
P P Luffand M White: Thermal degradation of polyethylene and polytetrafluoroethylene during vacuum evaporation

RELAT I VE
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UNRESOLVED MASS GROUPS

WITH PEAKS AT MASS NOS.
SHOWN
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40 60 80 IOO 120 140 156 170 184 198
Figure 4. Mass spectrum of polyethylene at a source temperature 400°C. Unresolved mass groups with peaks at mass numbers shown:
(Broken lines are × 25 on intensity scale).

RELAT I V E
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I0.0

IO
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I 50 6'0 70 80 9'0 I00 lib
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120 130
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140 150
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Figure 5. Mass spectrum of PTFE at a source temperature 500°C.

which are straight chain hydrocarbons may be expected to groups of peaks differing on the mass scale by 14. It is probable
break down into homologous series which would include the that some of the ionized breakdown products undergo further
paraffins, CnH2n+2, the olefins, CnH=n, and the higher order fragmentation in the mass spectrometer yielding neutral
acetylenes, CnH=,_=. This in fact occurs, and is characterized by products. This has the effect of modifying the true composition

439
P P Luffand M White: Thermal degradation of polyethylene and polytetrafluoroethylene during vacuum evaporation

Table 1. Full List of peaks recorded

(600°C) (600°C)
m/e Background (400°C) (500°C) m/e Background (400°C) (500°C) m/e (400°C) (400°C)
Spectrum Polyethylene PTFE Spectrum Polyethylene PTFE Polyethylene PTFE
2 Ha H2 54 C4H 8 110 CsH~4
12 C55 C4H 7 C4H 7 111 CsH15
13 CH 56 Call 8 C4H 8 112 C8H16
14 N N N 57 C4H 2 C4H 2 113 CaRl7
15 CH 3 CHa 58 C4Hlo 114 CsH18
16 O O O 62 C2H4(OH)2 ? 122 C2H14
17 OH OH OH 64 SO2 SOs? 123 C2H15
18 H20 HzO H20 65 CsH 5 124 C2Ht6
20 A ++ 66 C5H2 OCF 2 125 C2Hl7
28 "~,Nz, CO, CO "\N2, CO2, CO"t N,, CO,, CO 67 C5H7 CnH, 126 C9H18
29 .f .f f 68 C~H8 C5H8 (OC2F5)++ 127 C2H12
31 CF 69 C5H2 CsHa CFa 128 C9H2o
32 O~ O~ 03 70 CsHlo C5Hlo 131 CaF 4
36 "] 71 C5H1~ C5Hll 135 OC2F~
37 / several 79 C2H7 137 CaoH17
38 | small peaks 80 C6H s 138 C10Hxs
39 [ d u e to 81 C8H9 C2F3 139 Cx0H19
40 A [-cracking A 82 "]Kr C6Hxo 140 CloH~o
41 "] Calls ] p a t t e r n of 83 }-cracking Call11 141 C10H21
42 [cracking /C~H. 84 ] pattern Cell12 142 CloH22
43 ~-pattern ] 92 CTHs 143
44 |CO~ C3H s 94 CTHlo 150 CaF6
45 ] "~ Call s 96 CTHaz 156 CllHz4
46 COs J cracking pattern 97 CTHla 170 Ca2H2s
50 CIH 2 CFz 98 C7H14 184 CxaH2s
51 C4H a 99 C7H15 198 CI4Hao
53 C4H 5 100 C7H1~ C~F4

a n d a b u n d a n c e of h y d r o c a r b o n s arriving at the ion source. A n ethylene. N o h o m o l o g o u s series of f l u o r o c a r b o n s are observed.

example is the case o f p r o p a n e which, o n collision with a n
electron, undergoes the r e a c t i o n
e-+C3H 8 -~CzH~+ + 2 e -
followed by
(C3Hs + -+C2H7++H )
the h y d r o g e n going unrecorded.
T h e actual t h e r m a l b o n d - b r e a k i n g m e c h a n i s m we o b s e r v e d
is c o m p a t i b l e with the Rice-Kossiakoff theory of c r a c k i n g in
the absence of a catalyst ~. T h a t is, a molecule loses a h y d r o g e n
a t o m by collision with a n o t h e r free h y d r o g e n a t o m or a small
free radical a n d itself becomes a radical which t h e n b r e a k s away:
HH
If : polyethylene will b r e a k d o w n u n d e r t h e r m a l e v a p o r a t i o n
CHr(CH2)m.CH 3 + CH3.C.C - - - _ CH2.(CH2),.CH 3
II : likely value at three units.
H A f l u o r o c a r b o n like P T F E o n the o t h e r h a n d a p p e a r s to yield
+ C H 3.H C = C H 2 + radical
T h e b r e a k a l m o s t always occurs at the t h i r d c a r b o n - c a r b o n
b o n d . It will be n o t e d t h a t there is a n absence f r o m the mass
s p e c t r u m of the lower order h y d r o c a r b o n s , C2H~, CH4, CH~,
a n d C2H ~. This is likely to be due t o the lack o f sufficient
t h e r m a l energy at the source to b r e a k the c a r b o n b o n d s into
s h o r t e r lengths. T h e v a r i a t i o n of a b u n d a n c e with mass, parti-
cularly o f the higher o r d e r h y d r o c a r b o n s is a l m o s t certainly
influenced by the large distance between the e v a p o r a t i o n source
a n d the ion source, which in o u r case was 50 cm.
T h e p e a k at mass 50 c o r r e s p o n d s to the c o m p o u n d CF~, its
presence in figure 4 together with the peak at mass 51 is unlikely
to be as the result o f polyethylene f r a g m e n t a t i o n . T h e only
sources o f f l u o r o c a r b o n s in the system d u r i n g the experiments
o n polyethylene were P T F E insulators o n the H T cleaning
electrodes. It is possible t h a t some f l u o r o c a r b o n was liberated
d u r i n g the preliminary discharge cleaning processes.
T h e b r e a k d o w n of P T F E is very different f r o m t h a t o f poly-
T h e largest molecule detected was C3F6, a n d this in very small
quantities. N o n e of the f l u o r o c a r b o n s CF4, C~F~, or CaF s were
detected a n d n o free fluorine was observed. This is because the
reactions likely to p r o d u c e fluorine either give neutral f r a g m e n t s
or negative ions. F o r example.
e - ~-CF 2 -+CF++F +2e
CF 2 +CF ++ F "
It is o f interest to note t h a t n o H F was detected, in a g r e e m e n t
w i t h results r e p o r t e d elswhere 4.
5. Summary
T h e results show that a straight c h a i n h y d r o c a r b o n like
c o n d i t i o n s to give a n h o m o l o g o u s series of h y d r o c a r b o n s whose
c a r b o n chain length varies over a wide range, but with a most
a m a x i m u m c a r b o n chain length o f three units, a n d to degrade
to free carbon. In considering therefore the use of polymer
materials in the f o r m a t i o n o f thin films p r o d u c e d by n o r m a l
e v a p o r a t i n g procedures polyethylene shows far m o r e promise
than PTFE.
Acknowledgements
T h e a u t h o r s are indebted to D r L H o l l a n d a n d M r J S Olejniczak
for their advice a n d e n c o u r a g e m e n t d u r i n g this work.
References
1 M White, Vacuum, 15, 1965, 449.
2 j A Lane, Brighton College of Technology, Project Report, 1967.
a E Mathais and G Miller, J Phys Chem, 71 1967, 2671.
4 R E Kupel et al, Anal Chem. 36, 1964, 386.
B Greensfelder, H Voge and G Good, Indust and Eng Chem, 41, 1949,
2573.
6 H Voge and G Good, J Am Chem Sac, 71, 1949, 593.
7 R D Craig and E H Harden, Vacuum, 16, 1965, 67.

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