Polymer Degradation and Stability 32 (1991) 131 153

Aspects of Poly(ethylene terephthalate) Degradation for

Archival Life and Environmental Degradation

M. Edge, M. Hayes, M. Mohammadian,

N. S. Allen, T. S. Jewitt
Centre for Archival Polymeric Materials, Department of Chemistry,
Manchester Polytechnic, Chester Street, Manchester MI 5GD, UK

K. Brems
Agfa Gevaert N.V., Motion Picture Division,
27 Septestraat, Mortsel, Belgium

&

K. Jones
ICI (Chemicals and Polymers Group), Wilton,
Middlesborough, Teeside TS6 8JE, u K

(Received 19 April 1990; accepted 3 May 1990)

ABSTRACT

The degradation of poly(ethylene terephthalate) (PET) (as substrate for

audio-visual materials, amorphous sheet and bottles ) has been studied by both
accelerated thermal and photo-ageing methods. The degradation has been
considered from the opposing viewpoints of environmental acceleration of
degradation and prolongment of archival lifetime. In the former case, samples
of both polyester sheet and bottles have been aged in contact with dr), and wet
soils in dark and light conditions at different temperatures to emulate
environmental breakdown. In the latter case, non-processed 35mm
cinematographic film has been aged at various relative humidities and
temperatures in contact with film containers (metal can) to emulate archival
storage conditions. Results of both accelerated ageing studies indicate that
breakdown of PET motion picture.film is negligible at 60°C and relatively
unaffected by variations in humidity of the surrounding environment, over the
131
Polymer Degradation and Stability 0141-3910/91/$03"50 @ 1991 Elsevier Science Publishers
Ltd, England. Printed in Great Britain
132 M. Edge et al.

time period studied (300 days), due to its high crystallinity (55%). A t 70 and
80°C the motion picture film exhibits signs of crosslinking rather than
degradation due to the high crystallinity and emulsion inhibiting the diffusion
of oxygen into the polymer. The presence of iron from the container has an
accelerating effect on the degradation rate of motion picture film material but
only at temperatures above 90°C. In contrast, normal amorphous polyester
sheet and orientated bottles degrade due to their much lower crystallinity (1
and30%, respectively) and at higher temperatures (70-90°C) breakdown, as
characterized by viscosity and chain seission measurements, is indicative of
significant polymer deterioration. Breakdown is enhanced by increasing
temperature, increasing relative humidity and UV irradiation. The polyester
bottles are more stable than sheet due to a greater degree of orientation in the
former case and hence higher degree of crystallinity. Both soil (in the case of
amorphous P E T sheet and bottles) and metal storage can (in the case of
cinematograph film) have a significant effect on stability. At temperatures
above the glass transition, i.e. 80°C, differences in rates of degradation up to
45% relative humidity are not significant. Videotapes of various archival
histories have also been studied using high resolution light microscopy. White
crystalline deposits and surface conglomerates are observed with increasing
age and these appear to be consistent with artificial ageing experiments.

INTRODUCTION

Poly(ethylene terephthalate) (PET) is a thermoplastic material widely used in

the form of fibres and films. The stability of film, sheet and moulded PET is
of considerable interest with respect to environmental pollution. On the
other hand, where PET is used as support for photographic and magnetic
media, longevity is of prime importance.
The degradation of PET has recently been reviewed by Zimmerman I and
is shown to be characterised by its complexity. Although the thermal
stability of this polymer is high, its sensitivity to impurities and the
microenvironment places constraints on its longevity. Factors such as
relative humidity and the presence of trace metal ions may play a significant
role in the rate of degradation. The latter may be particularly important
since metal derivatives are used as either transesterification or poly-
condensation catalysts during the manufacture of PET. Furthermore,
during the manufacture and processing of PET into film or moulded
products the polymer is subjected to temperatures in the range 200-300°C
which are sufficient to instigate thermal breakdown.
The initial stage of thermal degradation is a random scission of the in-
chain ester linkage resulting in the formation of vinyl ester and carboxyl
end-groups. Transesterification of the vinyl ester then occurs to give vinyl
 Aspects of PET degradation for archival l(['e 133

alcohol which is transformed immediately to acetaldehyde. The polyester

chain is thus regenerated and an average degree of polymerisation
maintained. The net result of such a reaction is the replacement of hydroxyl
end-groups by carboxylic acid end groups producing, in the process, an
equivalent amount of acetaldehyde (see Scheme 1). Hydrogen atom
abstraction may also occur to some extent by impurities in the polymer

Poly(ethyleneterephthalate)

-.-..-OC~C--OC H 2CH z - - O C ~ C O ~
O O O O
In ChainDegradation
~Heat ~H20

"wO'Ci - ' ~ ) ) " C " O " C H 2 C H 2 " e t c I , ~CHzOH + H O ~ ~ ) ~

0 0 __ 0
Random scission AH~Uv Desterification

H'tatt°2tionby
l lmpurt es ~~O OCH=
:C
:H2 O

HOCH2CH2 OC--
II
----,-OC~CO--CHCH 2~ O
ii L ~ / I I "
O O

Oxidation
~~ -COCH2CH2OC~~"
II Lt L ~ /
O + O
CH3CHO
O2
L
O2H
Polymer ~ I
-~)C~O--CHCH 2. ~ -~OC CO--CHCH2--
II k~/ II H-a*om
Abstraction II ~ II
O O 0 0
Hydroperoxide
ChainscissionI
O2H
I
.~.OC~--O..CH2CH2--
ii ~ It
O O
Scheme 1. Degradation mechanismsof polyester.
134 M. Edge et al.

generating macroradical sites. These will react with oxygen producing

peroxy radicals and subsequently hydroperoxides which are themselves
thermally and photochemically unstable and will induce further breakdown
of the polymer.
The presence of moisture and acid/alkaline impurities will affect
hydrolysis. Hydrolysis of PET is a little understood process; albeit an
essentially hydrophobic polymer sensitive to moisture and hence overall
hydrophilicity, it is thought to be determined by the nature of its chain ends. 2
In this respect an increase in the carboxyl end-group concentration increases
the rate of hydrolysis of the polymer.
Photodegradation of PET occurs on exposure to near ultraviolet light
resulting in both chain scission by analogues of Norrish type I and II
processes shown in the reaction scheme or a photo-Fries type reaction. 3
Crosslinking also takes place, polymer films becoming brittle, discoloured
and developing crazed surfaces. 4-6 Infrared and gas-chromatographic
analysis studies have shown both hydroxy- and carboxylic end-groups along
with carbon monoxide and carbon dioxide to be the main products of
photodegradation. 7 Attenuated total reflectance spectroscopy has indicated
carboxyl end-group formation to be surface concentrated. 8 Hydroxyl
groups have also been found to arise as a consequence of substitution
reactions in the aromatic ring, resulting in the formation of mono- and
dihydroxyterephthalate units. The latter have been identified by fluores-
cence spectroscopy. 9
Although some aspects of the stability of PET have already been
considered in the literature, its end use will be the most significant feature
with regard to subsequent longevity. Such considerations are necessary not
only for a reliable assessment of the performance of this polymer but for a
realistic interpretation of the mechanistic processes involved. Degradation
pathways occurring by possibly different and complementary mechanisms
may serve to exacerbate the underlying situation. This study therefore
considers the inter-relationship between such interactive processes as
relative humidity, pH, temperature, light and microenvironment.

EXPERIMENTAL

Materials and suppliers

Samples of amorphous PET sheet (Melinar, 200 microns thick) and bottles
were supplied by ICI, Chemicals and Polymers, Wilton. Samples of non-
processed 35mm cinematograph film were provided by Agfa-Gevaert,
 Aspects ~?[PET degradation Jbr archival l([e 135

Mortsel, Belgium. The cinematograph film is composed of a PET substrate

(120 microns thick), cross-linked polyurethane/epoxy acrylate adhesive
layers and a non-photographic-processed emulsion. Samples of 1 in home
videotapes were supplied by Agfa-Gevaert N.V., Belgium, and 2in
commercial television videotapes of various archival histories were supplied
by the National Film Archives, Berkhamstead, UK.

Accelerated ageing of PET film and bottles

Samples of polyester sheet and bottles were oven aged in dry, dry soil, wet
soil, 45 and 100% relative humidity (RH) conditions at 60, 70, 80 and 90°C.
Samples of polymer were also irradiated in the absence and presence of soil
in quartz tubes using a Microscal Light exposure unit (Microscal Ltd,
London) utilising a 500 W high pressure Hg/tungsten fluorescent lamp (50°C
and ambient humidity).

Accelerated ageing of PET substrate cinematograph film

Samples of non-processed cinematograph film were oven-aged in dry, 45

and 100% RH conditions at temperatures of 60, 70, 80 and 90'~C.

Viscometry

In the case of PET sheet and bottles, 0"1 g of polymer was dissolved in 10 cm ~
60:40 w/v phenol/tetrachloroethane and a flow time was obtained using a
U-tube viscometer at 25°C.
For cinematograph film the emulsion was first removed by dipping in
dilute sodium hypochlorite solution and washing thoroughly. Backing
layers were then removed by placing the film in sodium carbonate solution
(10 g/litre). The PET substrate (0" 1 g) was then dissolved in 10 cm 3 o-chloro-
phenol and a flow time obtained using a U-tube viscometer at 25°C.
Values of intrinsic viscosity (IV) were obtained from standard calibration
tables supplied by the Analytical Department of ICI C & P Group,
Middlesborough, using corrected relative viscosity values for each solvent
system (flow rate of sample solution (ts)/flow rate of solvent (t o) x correction
factor). The correction factors were determined by comparing the ratio of
the measured I V values obtained for standard samples of polyester with
those given in the standard table. Number average molecular weight values
were obtained from the following modified relationship: 1°'tl
I V = 1"7 x 10 -4 x M n °'83
136 M. Edge et al.

Chain scissions were then obtained using the standard relationship:

CS - Mn° 1
Mnt
Microscopic examination

The surface analysis of videotapes was carried out using a Vanos-T high
resolution light microscope, Model AH-2, available from Olympus Ltd,
London, UK. Surface magnification was 300 × and photographs were
obtained using a standard high speed Polaroid Camera.

R E S U L T S A N D DISCUSSION

Polyester film

The amorphous polyester sheet studied in this programme had a thickness

of 200 microns and a crystalline content of only 1% obtained using an
80
O
/°
[]
>.
I-

9
>
o
B

I1:
i-
z 40 0
~ r4 •
u.l I
~ O WET SOIL
I,U
o
o • 4s% RH
~e 20 (
j [] 100% RH

• DRY SOIL

L.m e i
0 100 200 300
AGEING TIME ( D A Y S )

Fig. 1. Percentage decrease in intrinsic viscosity versus ageing time in days for amorphous
polyester sheet material (ICI) at 90°C under (O) wet soil, (V1) 100% RH, (O) 45% R H and
(m) dry soil conditions.
 Aspects of PET degradation L~r archival 1(/~' 137

appropriate density column. Samples were degraded under wet soil, dry soil,
100 and 45% RH conditions at 90 and 80°C. At 70°C, dry soil conditions
showed negligible degradation and is excluded and at 60°C degradation was
evident only under wet and 100% RH conditions. Thus, in terms of the
degradation mechanism of polyester breakdown, hydrolysis appears to be
the dominant reaction. Changes in intrinsic viscosity for polyester film at
90°C are shown in Fig. 1 for all the conditions studied. From the plots
obtained it is interesting to note that the most severe degradation condition
is that under wet soil followed by 100% RH, 45% RH and then dry soil. From
the plots of percentage decrease in intrinsic viscosity plots of chain scission
versus degradation time were obtained. These graphs for the conditions at
60, 70, 80 and 90°C are shown in Figs 2 to 5, respectively, and give a more
quantitative indication of the differences in rates of degradation under the
various conditions. Apart from wet soil at 60°C the plots of chain scission
versus ageing time are virtually linear. From these results, two interesting
features may be noted. The first is the observation that at 80 and 90°C,
0.8

O W k ~ l" S O I L

0.6 • lOO%RH

(n
z

~ 0.4
_z
.p

• O

00
• ~" • | i
' 1

0 100 200 300 400

AGEING TIME (DAYS)

Fig. 2. Increase in chain scission versus ageing time in days for amorphous polyester sheet
material (1CI) at 60cC under (©) wet soil, (O) 100% RH conditions.
138 M. Edge et al.

o.o. \1" .0 ~'_~"

o ~ ~ ~
SNOISSIOS NIVHO ~ o ._~
~

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o ~ C: O

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< .~ ~.
c~

I I I I
¢o lID ~r N
d d c5 o e-

• 0
SNOISSIOS NIVHO
 Aspects o,f PET degradation ./~r archival li[k" 139

o
.~s8

e..,

•.s ; - . B

>-
0
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X\ \t ° <(
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SNOISSIOS NIVHO
•- ~ z g
r~ r,-.O

o
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z_
I-,-
._~ ~ "
Z
o ,7,
• o
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SNOISSIOS NIVHO
•-~ E g
140 M. Edge et al.

° " °
, .-~ 0 0

.~ ~ 0

P =.-~N

e~ __ o

SNOISSIOS NIVHO o~• ~;~,

..=o

*-, 0

[]o~\
[]
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.-~ ~ . ~
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SNOISSIOS NIVHO
 Aspects o/ PET degradation./br archival l![e 141

degradation rates under the wet soil condition are greater than those at
100% RH whereas at lower temperatures the effect is reversed. This may be
associated with the fact that at temperatures above 80°C the glass transition
temperature of the polymer is exceeded and metal ions from the soil are able
to migrate more readily into the polymer and accentuate the degradation
rate. The second interesting feature is the observation that differences in the
rate of degradation are less significant at 90°C than that at 80°C between dry
conditions and 45% RH. Thus, at higher temperatures the effect of thermal
degradation appears to be more prominent whereas at lower temperatures
hydrolytic degradation dominates.

Polyester bottles

The rates of degradation of polyester bottles measured by chain scission at

90, 80, 70 and 60°C are shown in Figs 6 to 9, respectively. In this case, at 90°C,
the rate of degradation in wet soil is more significant than that at 100% RH,
and at 80°C the differences are minor. At 70°C the rates are reversed,
whereas at 60°C differences in degradation rates are difficult to predict due to
0.6

0 WET SOIL
[]
0.5
• ~ % RH

r'l 100% RH
U) 0.4
Z
9
0
O

o/
0.3
Z
=
0

0.2

0.1

0.01
100 200 300

AGEING TIME (DAYS)

Fig. 9. Increase in chain scission versus ageing time in days for polyester bottle material
(ICI) at 60°C under (C)) wet soil, (O) 45% and (U]) 100% RH conditions.
142 M. Edge et al.

the low rates of degradation and scattering of the points. However, the
differences in rates of degradation under dry conditions and at 45% RH are
similar to those observed for the polyester film material. Thus, at 90°C
differences in the rates of degradation are minimal whereas at 80 and 70°C
the differences become more marked. One interesting feature of the results
for the bottles is the marked difference in the rates of degradation between
0% RH and dry soil at 90°C. At 80°C this difference is not evident and
supports the hypothesis of metal ion migration into the polymer at higher
temperatures.

Motion picture film (non-processed)

The degradation rates of non-processed polyester motion picture film

material with an emulsion layer at 90, 80, 70 and 60°C at 100% RH are
shown in Figs 10 to 13, respectively. These plots illustrate the changes in
chain scission rates and show a number of interesting features. Inter-
comparative studies in other conditions are still being carried out and will be
published later in a paper dealing specifically with aspects of motion picture
0.5

O IRON (90C)

0.4
• GLASS (90C)

u)
z
_0 0.3
o~

z
"1" 0.2
o

0.1
o

0.01
0 10 20 30 40 50

AGEING TIME (DAYS)

Fig. 10. Increase in chain scission versus ageing time in days for polyester motion picture
film material (Agfa-Gevaert N.V.) at 90°C and 100% RH in the presence of(Q) glass and (O)
iron.
 0.2

0.1

03
Z
,o

ro O
¢n 0.0~
Zm
<
-v
¢J

-0.1 0 IRON (80C)

• GLASS (80C)

i i i I
-0.2
20 40 60 8O 100
AGEING TIME (DAYS)
Fig. 11. Increase in chain scission versus ageing time in days for polyester motion picture
film material (Agfa-Gevaert N.V.) at 80c'C and 100% RH in the presence of(O) glass and (©)
iron.

0.2

0.1

.o/Y
z o
0 O.OI
¢n

z
< -0.1 • 0
c) 0

O IRON (70C)

-0.2
• G L A S S (70C)

-0.3
0 100 200

AGEING TIME (DAYS)

Fig. 12. Increase in chain scission versus ageing time in days for polyester motion picture
film material (Agfa-Gevaert N.V.) at 70°C and 100% RH in the presence o f ( O ) glass and (©)
iron.
144 M. Edge e t al.

0°1 - i - i - , • , • ,

l / ~ IRON (60C)

Z
9
0

-i-
O
-0.1

i , i . i . i
-0.2 " ' "
0 20 40 60 80 100 120

AGEING TIME (DAYS)

Fig. 13. Increasein chain scission versus ageing time in days for polyestermotion picture
filmmaterial(Agfa-GevaertN.V.)at 60°C and 100% RH in the presenceof(Q) glass and (©)
iron.
film material. In this study films were aged as small reels in pyrex dishes with
and without an iron base cut from the metal container used to store the film.
At 90°C it is seen that the degradation rate of the polyester motion picture
film is greater in the presence of the iron base whereas at lower temperatures
the effect is reversed but only to a minor extent. The one interesting feature of
these results, however, is that at temperatures lower than 90°C there is an
initial crosslinking of the polyester, the extent of which increases as the
degradation temperature is decreased. This effect would appear to be
associated with the emulsion layer on the film which would impair the
diffusion of oxygen into the polymer base at temperatures below the glass
transition temperature of the polymer. The lower the temperature the
greater the degree ofcrosslinking. The iron also appears to be catalysing the
crosslinking to a minor extent.

Irradiation effects

The effect of irradiation on the amorphous polyester sheet and bottle

materials, as determined by the rate of change in chain scission, is shown in
Fig. 14. Unlike thermal degradation the rate is autocatalytic in both cases
except that the bottle material displays an initial induction period before the
 Aspects o[ PET degradation ./or archival li/b 145

0 sheet

• bottle

[ ] b o t t l e in s o i l
[]

[]

[]
[]

[]

[] 0

[] Q

i i i
0 100 200 300 400

IRRADIATION TIME (DAYS]

Fig. 14. Increase in chain scissions versus irradiation time in days in a Microscal Unit for
(C)) amorphous polyester sheet and bottle materials in the (Q) absence and ([5]) presence of
soil.

onset of severe chain scission. This induction period may be associated with
the higher crystallinity of the bottle material compared with that of
amorphous sheet. One interesting feature of these results is that in contact
with soil the polyester bottle degrades at a faster rate. Again contact of the
polyester with metal ions on the surface may be important.

Intercomparison of data and Arrhenius predictions

Comparison of the above data shows a number of similar trends. However,

it is noticeable that the motion picture film material degrades in a totally
different manner due both to the higher degree of crystallinity (55%) and to
the emulsion layer. Furthermore, the motion picture film is significantly
more stable than normal amorphous polyester film material and this is
confirmed by the results shown in Fig. 15 for chain scission rates at 90°C.
This is associated with the much higher crystallinity of the former polyester
which was determined to be 55%. The normal Melinar polyester film has a
crystallinity content of about 1%.
146 M. Edge et al.

4 i i

90oc
o ,0o~.. ~.o..o.,~.u...~

z 2
o
(/)

U)

a: 1

~...o .O "°t

i i I i i
"10 210 40 610 80 100 20

AGEING TIME (DAYS)

Fig. 15. Increasein chain scissionsversusageingtimein daysat 90°C and 100% RH for (O)
amorphous polyester sheet (ICI) and (O) polyestermotion picture film.

Predicting the stability of polymer materials at ambient temperatures is

theoretically possible through modification of the Arrhenius expression
assuming, of course, that the rates of degradation follow first-order
kinetics. 12,13 This is invariably not the case and such predictions therefore
serve only as an approximation. Our results are no exception and even with
the aid of computer predictions and data extrapolation are in error by
+ 10 years. In this work the logarithm of the times for amorphous polyester
sheet and bottle materials to achieve a 50% loss in intrinsic viscosity are
plotted against the reciprocal temperature in K and the data extrapolated to
20°C (293 K) ~1 (Figs 16 and 17). The right hand side of the x-axis is set at
20°C. For these materials this is a suitable point in time when the polyester is
assumed to be environmentally degraded, i.e. all physical characteristics are
lost and the material crumbles to a powder. On the basis of these results
therefore, polyester film has an average life expectancy at 45% RH, wet soil
and 100% RH of 32, 30 and 25 years, respectively (Fig. 16). For polyester
bottles, on the other hand, the life expectancies are longer, with predictions
of 48, 35 and 27 years for the same conditions (Fig. 17). In the case of motion
 Aspects o1 P E T degradation/~r archival l(lz~ 147

100000

O 100% RH 25 YRS

• 45%RH 32 YRS y
10000
A
>
[ ] WET
////
Z
B

0
.J

o 1000

o- /

|
10
0 . 0 l 125 0.0030

1/T (K)
Fig. 16. Arrhenius plot of the logarithm of time to 50% loss in intrinsic viscosity (days)
versus the reciprocal temperature in K i for amorphous polyester sheet (ICI) material at (0)
45 and (©) 100% RH and (D) wet soil conditions.
picture film material degradability must be a minimum in order to preserve
the photographic image for archival purposes and a 20% loss in intrinsic or
relative viscosity would result in an irrevocable loss in the physical
characteristics of the film material. Figure 18 shows such a plot of the
logarithm o f the time for the film to achieve a 20% loss in relative viscosity
versus the reciprocal of the temperature. In this case it is determined that the
polyester has an archival life of 91 and 87 years in glass and iron containers,
respectively, at 100% RH. Predictions at relative humidities lower than 45%
are expected to exceed 1000years 13 and will be reported on later.

Microscopic examination of videotapes

Samples o f 2 in commercial videotapes of various archival histories were

supplied by the National Film Archives (NFA), Berkhamstead, U K , and
148 M. Edge et al.

100000

0 100 % RH 27 YRS

O 45% RH 48 YRS

A
> 10000
[] WETSOIL 35 YRS
_z
u)
0
,,J

o
1000
0
I--
(/)
>,,

0
0
,-I
100 :/

10 J
0.0025 0.0030

I/T K -{

Fig. 17. Arrhenius plot of the logarithm of time to 50% loss in intrinsic viscosity (days)
versus the reciprocal temperature in K- ~for polyester bottle (ICI) material at (O) 45 and (O)
100% RH and ([~) wet soil conditions.

examined under the high resolution light microscope at 255 × magnifica-

tion. Polaroid photographs were taken and compared with those taken for
new 1 in videotape as well as videotape which had been aged at 90°C for
63 days in contact with iron. The results are shown in photographs 19 to 23.
Figure 19 is that of the surface of new home 1 in Agfa-Gevaert videotape and
shows no obvious signs of any degradation or surface deposits. Figure 20 is
Scotch 2 in videotape manufactured in 1986 and is beginning to show some
signs o f surface deterioration. On the other hand, Fig. 21 is 2 in commercial
videotape which was manufactured in 1976 and clearly shows severe white
deposits on the surface which m a y be due to the lubricant. Of particular
interest however, is the Scotch 2 in videotape manufactured in 1968 which
shows very severe signs of degradation with globular conglomerates on the
surface (Fig. 22).
In this connection we also examined the surface of a 1 in Agfa-Gevaert
videotape which had been aged under accelerated conditions at 90°C for
63 days and from Fig. 23 it m a y be seen that the type of degradation is
similar to that for the Scotch videotape manufactured in 1968. Thus, in
 100000 i

O IRON (100% RH) 87 YRS

A • GLASS (100% RH) 91YRS

>
n- 10000
Z

O~
(/1
o
.J

o
~4
o
h-
1000
>-
<
O
~O

O
.J
100 / O

10 I z
u.u025 0.0030
I/T K -~

Fig. 18. Arrhenius plot of the logarithm of time to 20% loss in relative viscosity (days) versus
the reciprocal temperature in K ~ for polyester motion picture film material (Agfa-Gevaerl
N.V., Belgium) at 100% in (Q) glass containers and in the presence of (©) iron.

Fig. 19. Surface analysis (255 x ) of new(1990) 1 in videotape (Agfa-Gevaert N.V., Belgium).
150 M. Edge et al.

Fig. 20. Surface analysis (255 × ) of 2 in commercial videotape (Scotch) from the National
Film Archive, Berkhamstead, made in 1986.

Fig. 21. Surface analysis (255 x) of 2in commercial videotape (Scotch 3M) from the
National Film Archive, Berkhamstead, made in 1976.
 Aspects 0[" PET degradation Jbr archival l(]e 151

Fig. 22. Surface analysis (255 x ) of 2 in commercial videotape (Scotch) from the National
Film Archive, Berkhamstead, made in 1968.

Fig. 23. Surface analysis of ! in home videotape (Agfa-Gevaert N.V., Belgium) aged at 90'C
for 63 days at 100% RH.
152 M. Edge et al.

terms of surface analysis of videotape coatings, natural and artificial ageing

conditions result in similar degradation reactions. The degradation
phenomena observed in the case of the videotapes studied here were
c o m m o n to all manufacturers' materials.

CONCLUSIONS

F r o m the results to date the degradation rate of polyethylene terephthalate

is found to be dependent upon the nature of the material. Thus, motion
picture film is more stable than bottles which are more stable than
amorphous sheet. This effect is associated with differences in the degree of
orientation and hence in the crystallinity of the polymers. Degradation rates
of polyester increase with increasing temperature especially above the glass
transition temperature. The degradation rate increases significantly with
increasing humidity due to an increase in the rate of hydrolysis. At
temperatures above 80°C differences in the rates of degradation up to
45% RH are not significant. Thus, at lower temperatures hydrolysis is the
dominant process. At temperatures below the glass transition polyester
motion picture film material exhibits some initial crosslinking. Here the
emulsion layer is inhibiting the diffusion of oxygen into the polymer. The
presence of iron from the container has an accelerating effect on the rate of
degradation of polyester motion picture film but only at temperatures above
the glass transition (80°C).

A C K N O W L E D G E M ENTS

The authors thank Agfa-Gevaert N.V., Belgium, and ICI C & P Group Ltd,
UK, for materials, advice and financial support in carrying out this
programme of work.

REFERENCES

1. Zimmerman, H. In Developments in Polymer Degradation--5, edited by N.

Grassie. Elsevier Applied Science, London, 1984.
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