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COATINGS
ELSEVIER Progress in Organic Coatings 27 (1996) 95- 106

Analysis of test methods for UV durability predictions of

polymer coatings
B.W. Johnson, R. McIntyre
Courtaulds Coatings Ltd., Stoneygate Lane, Felling, Gateshead, Tyne Br Wear, NE10 OJY, UK

Received 17 October 1994; accepted 22 March 1995

Abstract

The purpose of this paper is to review procedures which are used for the evaluation of the durability of polymer coatings. In
particular, methods of environmental acceleration and techniques of assessment of coating degradation have been examined, with
an emphasis upon those which may produce reliable fast answer durability predictions. The advantages and disadvantages of the
various exposure regimes currently used (such as Florida exposure, EMMAQUA or artificial light sources) have been discussed
in terms of correlation with actual durability data and of degree of acceleration. A general rule of thumb is that the correlation
of accelerated methods with natural exposure is inversely proportional to the degree of acceleration used. The common physical
methods used to assess the extent of coating durability have been presented, with the general drawbacks to these techniques being
highlighted. Finally, the benefits and drawbacks of a number of chemical techniques (in particular electron spin resonance (ESR),
Fourier transform infrared spectroscopy (FTIR), hydroperoxide determination and chemiluminescence), which in principal could
provide durability information in a fraction of the time of the physical techniques mentioned earlier, have been discussed. Of
these, both ESR and FTIR spectroscopy show particular potential because of the short exposure times necessary to obtain
significant results under UVA exposure.

Keywords: Durability; Polymer coating; Coating degradation; Accelerated exposure tests

1. Introduction etc. As the primary function of a protective coatings

The exterior durability of any organic coating can be
defined as its resistance to undesirable changes caused
by the natural environment to which it is exposed
during its service life. The main constituents of the
environment which cause the weathering, or degrada-
tion of, polymer films are sunlight (in particular UV
radiation), temperature, oxygen, water and pollutants.
When these factors are combined with other environ-
mental variables, such as wind and seasonal periodicity,
the magnitude of the problem of producing weather
resistant coatings becomes very apparent. Of the above
factors, it is usually found that sunlight (that is
photodegradation caused by W-Vis radiation) is the
most damaging, although the synergistic contribution
from the others plays a significant part [l-5]. The
degradation of a polymer coating as a result of weath-
ering can manifest itself in many ways, for example by
loss of gloss, discolouration, chalking, embrittlement
(paint) is to protect the substrate and, usually, to fulfil
a decorative role, its resistance to outdoor weathering is
of paramount importance.
The rate at which polymer degradation occurs will
vary widely, depending upon temperature, exposure
site, time of year, substrate, polymer material etc., all of
which makes the evaluation of coating durability
difficult. The ideal evaluation of a protective or decora-
tive coating would be to expose it in its intended service
environment. However, in an industry which is striving
to produce coatings of longer and longer lifetimes, this
type of evaluation would take an unacceptably long
time. Therefore, it is necessary to reduce the time
needed to predict coating life.
The current method of assessing coating durability is
to monitor the gloss loss, colour retention and chalking
during natural exposure in areas of high sunlight inten-
sity (for example in Florida or Arizona), a procedure
which, for more durable systems, can take upwards of

0300-9440/96/%15.000 1996 Elsevier Science S.A. All rights reserved

SSDI 0300-9440(94)00525-6
96 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106
five years to obtain satisfactory results. This length of
time is significantly reduced to 12-18 months by the
employment of a series of mirrors to intensify the
sunlight falling upon the sample, processes known as
EMMA and EMMAQUA [6]. Although the results
obtained from EMMA and Florida exposure generally
give rise to reliable predictions of polymer durability,
the techniques themselves are both time consuming and
expensive.
It is clear that, if successful, the development of a
reliable fast answer test which could determine polymer
durability in significantly shorter times would reduce,
or even obviate, the necessity to send panels to Florida/
Arizona for natural weathering thus saving both time
and money. Furthermore, such a fast answer methodol-
ogy would accelerate the coating development process
and facilitate the rapid transfer of new coating tech-
nologies to the market place. The two general ways to
accelerate durability testing are either:
(a) Use higher intensity and/or shorter wavelength
radiation, such as QUV, xenon arc or carbon arc. The
advantage of these techniques is that gloss loss and
colour retention characteristics can be acquired in times
of l-2 months. However, for such accelerated exposure
media to provide data which can be extrapolated to
long times and which will correlate with natural expo-
sure results, there must be no change in either the
relative rates of degradation processes occurring or the
type of degradation chemistry. Unfortunately it is often
the case that ‘unnatural chemistry’ occurs due to higher
energy radiation [7,8], which is consequently reflected
by a poor correlation between accelerated and natural
exposure data.
(b) Use more sensitive techniques to evaluate the
degradation process. The standard methods of assess-
ment are gloss loss, chalking etc., which are essentially
measurements of the physical manifestation of degrada-
tion. Whilst it is recognised that it is possible for a
coating to fail due solely to physical effects, in general,
before the physical properties change the chemical
properties (especially at the coating surface) will
change. Hence, the use of techniques which can detect
and quantify chemical changes ought to provide
durability information in a fraction of the time.
In order that a fast answer test be implemented
within the coatings industry, a certain number of crite-
ria must be satisfied.
By definition the test method must be significantly
faster than EMMAQUA and Florida exposure.
The technique must not be labour intensive. Florida
exposure involves the measurement of gloss, colour and
chalking, all of which are very quick and easy, meaning
that a high number of samples may be examined in a
short time period. Any new method should aim to have
a similar measurement time in order that sample
turnover remains high.
No more than a low level of expertise should be
required. If a new method necessitates skilled personnel
with a high level of training, then its introduction to,
and acceptance by, the coatings industry will be more
difficult to achieve.
A good correlation with natural/Florida exposure
should be apparent, otherwise any time savings will be
offset by uncertainty and lack of confidence in the
results (in the same way as with QUVB exposure).
The running costs should be low (cheap). However,
if the technique satisfies the above criteria, the expense
may not be too critical.
A sensitive technique is required as differences which
manifest themselves over long time periods are being
sought in much shorter times.
Reproducibility of results is important, however re-
producibility compared with a known standard would
be sufficient.
It is the aim of this paper to consider the current,
and possibly future, techniques of assessing the extent
of polymer degradation, with an emphasis upon those
which operate upon much accelerated timescales. The
test methods discussed will be illustrated by a series of
examples involving a range of polymers and polymer
blends.
2. Exposure media
2.1. Natural exposure
There are a number of exposure sites around the
world, each with a different climate, which can be used
for the purpose of predicting the exterior durability of
coatings. The site chosen should be the one which is
most representative of the general environment of inter-
est, however, it is more usual to choose sites of extreme
climates and compare the resulting degradation with
the degradation which occurs under the service environ-
ment. In this way ‘natural’ exposure is achieved, even
though the UV, temperature and humidity levels may
be vastly different from those met in service. The expo-
sure sites are as follows:
(a) Miami, Florida. This region of Southern Florida
has been the benchmark for environmental testing for a
number of years. High levels of UV radiation, humidity
and temperature provide a sub-tropical environment
which is itself an acceleration of European climates (an
acceleration of approximately four times [9]). The key
element of Florida exposure is that, although it may be
an ‘artificial’ test (because it cannot replicate all the
variables found in different climates around the world),
it does use natural sunlight in a defined environment
that provides reproducible results. Florida exposure is
an industrially accepted standard and is widely specified
for outdoor exposure testing.
 B. W. Johnson, R. McIntyre
(b) Wittmann, Arizona. With an annual rainfall of
200 mm and an average high temperature of 26 “C this
site provides a hot dry climate for durability testing.
Arizona exposure is the second most accepted site for
environmental testing.
(c) Hook of Holland. This site provides the combined
conditions of an industrial and a marine environment.
It is generally used for the evaluation of coil coatings
and is specified in the European Coil Coaters Associa-
tion T19 test method.
There are also a number of other exposure sites
around the world, including Australia, Israel, France
and Saudi Arabia, each with its own particular climatic
characteristics.
It is important, during natural exposure evaluations,
to monitor the exposure conditions (for example, rain-
fall patterns, pH of rain, radiation exposure (either
spectral density with time or at a given wavelength, e.g.
340 nm, with time), pollutant concentrations and time
of initial exposure. The latter is particularly important
because the exposure sites themselves are subject to
seasonal changes and the results are likely to be depen-
dent upon the time of year of initial exposure.
2.2. EMMA /EMMAQ UA
The weathering of materials can be further acceler-
ated by a more efficient use of outdoor exposure. An
example of this is the widespread use of EMMA (Equa-
torial Mounts with Mirrors for Acceleration) and
EMMAQUA (EMMA with a water spray cycle). These
machines have ten highly polished moveable aluminium
mirrors which enhance the rays of sun focused upon a
test sample. Although the total amount of radiation
reaching the surface with EMMA and EMMAQUA is
around nine times that of ‘natural’ exposure, the deteri-
oration rate is found, on average, only to be in the
region of 5-6 times faster. This is a consequence of the
fact that the aluminium mirrors reflect the more dam-
aging UV components of sunlight less efficiently than
the visible and infrared components. As a result of the
high radiation intensity focused upon a sample, temper-
atures of up to 150 “C at the sample surface may
develop, hence the application of air cooling is neces-
sary. A drawback of these techniques is that a continu-
ous clear sky is required for their most efficient use,
hence, Arizona, with over 4000 hours sunshine per
annum, is an ideal test site.
The correlation of results with natural exposure is
often relatively good [lo, 1l] but difficulties can arise
due to the fact that polymer coatings have different
levels of a number of constituents, the degradation of
each likely to be accelerated by different degrees. For
example, a correlation of gloss results has previously
been observed for a series of paint films, yet colour
retention for the same samples exhibited a poor correla-
1Progress in Organic Coatings 27 (1996) 95-106 91
tion [12]. It is important to note that the temperature of
EMMAQUA samples may vary over a wider range
than the temperature of Florida samples which is
highly likely to contribute somewhat to any lack of
correlation.
The major assumption of EMMAQUA is that gloss
loss (extent of degradation) is directly proportional to
the total cumulative exposure medium energy. Thus,
EMMAQUA results are usually represented as gloss
loss versus total energy of exposure, the total energy
normally being converted to equivalent Florida years (1
Florida year = 308 MJ rns2 radiation [13]). It has been
clearly demonstrated [14] that this assumption is not
strictly true and that the gloss loss is in fact propor-
tional to both the total energy and the energy flux. In
other words, a seasonal variation occurs in which sam-
ples exposed will exhibit quite different gloss loss char-
acteristics depending upon the time of year of initial
exposure.
2.3. Art$cial exposure methods
The main reason for using artificial weathering
methods is to accelerate degradation, under controlled
conditions, in order that the durability characteristics of
a particular polymer can be assessed in an acceptably
fast time. There are many disadvantages in the use of
artificial acceleration regimes for durability evaluation.
For example, an accelerated test is only viable if all
degradation processes in a sample are accelerated to the
same extent, a condition which, unfortunately, is rarely
achieved [7,15]. Also, if the wavelength of the light
source is of higher energy than solar radiation (e.g.
QUV-b) then photochemistries which would not occur
under natural exposure may result [8]. There are a large
number of commercial artificial acceleration procedures
available, generally based on the same two or three
light sources, as follows:
2.3.1. Carbon arc sources
The enclosed carbon arc lamp was the original artifi-
cial weathering source, being first employed in 1918 to
evaluate textiles. Its spectral output has little compari-
son with natural sunlight, the main radiation taking the
form of three high intensity peaks between 350-
450 nm. Furthermore, it has a significant amount of
radiation below 295 nm (the approximate solar cut off)
although this can be removed by the use of suitable
filters. Test procedures specifying the use of enclosed
carbon arc are becoming fewer in number, but it is still
used for some US (AATCC) and Japanese (JIS)
standards.
The sunshine carbon arc is also being progressively
phased out of international test specifications but is still
widely used in industry for company specifications. Its
output is closer to that of sunlight, but it still has
98 B. W. Johnson, R. McIntyre 1 Progress in Organic Coatings 27 (1996) 95-106
significant differences, in particular being more intense
in the 350-450 nm region and less intense below
350 nm. Despite this, the sunshine carbon arc is still
commonly used to reproduce the effect of daylight
exposure on textiles. Control of temperature, humidity
and water spray is possible with these systems.
2.3.2. Xenon arc sources
This light source provides a much better simulation
of sunlight than carbon arc sources, which explains its
growing use in the testing of a wide range of materials.
Xe arc contains UV radiation of wavelengths shorter
than the cut off level of solar radiation, however this is
removed by use of a filter system. Other problems with
Xe arc are that a high intensity of infrared radiation is
emitted which must be removed in order to prevent
overheating of the samples and that both the Xe burn-
ers and filters deteriorate with use; thus their perfor-
mance must be regularly checked [16]. Apart from its
close simulation of the solar spectrum, other advan-
tages of Xe arc include automatic control of light
intensity, temperature, light/dark periods and humidity
giving rise to a consistent and reproducible testing
method. Furthermore, the incorporation of atmo-
spheric pollutants into the system make these instru-
ments very useful in relating the behaviour of materials
to the aggressive factors of the outdoor environment.
2.3.3. Fluorescent tube lamps
These sources are much cheaper to run than Xe arc
and have the advantage that they do not produce any
unwanted heat. Tubes are available with different spec-
tral outputs, the most common being UVB and UVA
bulbs. The UVB spectrum has a peak intensity at
around 313 nm, with a high intensity at wavelengths
below the solar cut off (i.e. 270-290 nm). Consequently
they provide strong acceleration, but are also likely to
induce unwanted or unnatural chemical reactions [4].
UVA bulbs provide a much closer reproduction of the
solar spectrum up to around 350 nm and can therefore
produce a much closer correlation with natural expo-
sure. As only a negligible heating effect is produced
with these lamps, a separate heating source is necessary
which imparts reasonable temperature control to the
user. Again, with these systems, temperature, humidity
and light/dark cycles can be controlled.
The correlation of results between artificially and
naturally weathered samples is often quite poor [6,17-
191, The main reason for this is the non-agreement
between the solar spectrum and that of the artificial
light source. Differences in the visible region can lead to
poor correlation with coloured materials, although it is
generally differences in the UV region which are most
likely to cause deviation. It can be taken as a general
rule of thumb that the correlation of accelerated meth-
ods with natural exposure is inversely proportional to
the degree of acceleration used.
3. Physical measurement techniques
The standard methods of assessment of the perfor-
mance of polymers exposed in Florida are gloss loss,
chalking, colour retention, cracking and crazing, and
dirt retention. Dirt retention is not strictly a measure of
the extent of degradation, but obviously can be very
important, as for architectural/decorative coatings. The
remainder, along with several others, measure physical
changes due to weathering and will be briefly discussed
below.
3.1. Gloss loss and chalking
As a pigmented film degrades, the surface gradually
roughens due to the body of the binder being lost,
which is seen as a loss of gloss. This disappearance of
the binder eventually leaves behind the more stable
pigment particles, which remain upon the surface of the
film in the form of non-bound powdery particles, a
process termed chalking. Chalking and gloss measure-
ments generally go hand in hand, with gloss loss be-
coming evident before chalking (chalking will not
usually be seen until a significant loss of gloss has
occurred). Gloss is assessed by monitoring the reflection
from the surface of a visible beam of light in relation to
a standard back glass surface, e.g. Fig. 1. Chalking is
measured either by performing a ‘tape pull’ or simply
by visual assessment.
It is common for many coating specifications to
indicate the minimum time to which the coating will
maintain a gloss level of greater than 50% of its original
value. The advantages of gloss and chalking measure-
ments are that they are very fast and easy to perform
and are accepted as being an accurate indication of the
overall durability of a polymer film. Moreover, whether
the polymer is degrading mainly via photodegradation
100
80
20
0
0 200 400 600 ml lotHI
QW Time I Houn
Fig. 1. Gloss retention vs. QUV exposure time for a series of
poly(ester)/acrylic blends. - 0-, 100% acrylic; -A-, 80:20;
-m-, 60:40; -0-, 40~60; -A-, 20:80; -!I--, 100% PE.
 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106
0.1 1 I
0 so0 1ooo 1500
QUV Time / Hours
Fig. 2. Change in M, with QUVB exposure time for a crosslinked
poly(ester) coating.
or mainly via mechanical stressing, gloss loss will still
detect the changes. The disadvantages are that they are
a measurement of the physical manifestation of degra-
dation and, in most cases, will not detect the changes
due to photodegradation as quickly as the more sensi-
tive chemical techniques discussed later.
3.2. Colour retention
For a pigmented coating system there are three
possible effects upon the colour; either the colour fades,
it darkens or there is an overall yellowing due to
oxidation products. This is usually assessed visually and
any change from the initial state graded. Colour reten-
tion in paint coatings is obviously very important,
hence, it is necessary to record such data. The value of
this information would be highlighted in a situation
whereby the polymer itself was stable to UV and the
pigment unstable. Changes due to polymer degradation
would not be seen by the conventional gloss and chalk-
ing measurements, yet fading/darkening could still
occur.
3.3. Cracking and crazing
The cracking and crazing of most solvent-based clear
polymer systems has been well known for many years
[5,20]. Exposure of a clearcoat to UV radiation results
in a gradual transformation of the longer, more flexible,
molecules into shorter, more brittle, ones meaning that
the film in general hardens and cracks begin to appear,
which can eventually penetrate the whole film. It is
possible for an abrupt failure due to cracking to occur
before any appreciable changes in coating gloss become
apparent, hence this is an important parameter to
monitor.
3.4. Contact angle
The surface tension of most polymer coatings would
be expected to increase in proportion to the extent of
degradation which has occurred at the surface, due to
an increase in polar groups (i.e. oxidized species) and to
suface roughening. This can be estimated by recording
99
the contact angle that a drop of deionized water makes
with the polymer film. For lower surface tension mate-
rials (undegraded), the contact angle made by water is
high whereas for higher surface tension materials (de-
graded) a lower angle results. This method has been
used to demonstrate that pigmenting a poly(urethane)
top coat results in reduced durability when exposed to
QUVB radiation [21]. Similar work has been performed
upon a range of Courtaulds poly(ester)/acrylic blends
with similar results [22]. However, this method did not
distinguish between the performance of the different
blends any faster than did standard gloss loss measure-
ments.
Although contact angles can give a general idea as to
whether a polymer film is degrading, they do not give
any comparative durability information in timescales
significantly less than do standard gloss measurements.
Therefore, it is unlikely that contact angle measure-
ments can be used in a fast answer role; however useful
support data can be obtained from this quick and easy
technique.
3.5. Weight loss and film thickness
As described before, there is a gradual erosion of a
paint film surface with time due to weathering. Thus,
the degradation of a coating can be monitored with
time by measuring its dry film thickness (DFT) or its
actual weight loss. Most polymers show an average loss
in DFT of between 5 and 25 um/year [20,23-251, except
for a few more stable polymers such as poly(methacry-
lates) and poly(vinylfluorides). The loss in DFT has
been used [20] to help demonstrate the influence of
molecular weight upon durability. For co-polymers
with the same chemical composition but an order of
magnitude difference in molecular weight (100 000 com-
pared to over 1 000 000) the higher molecular weight
systems possessed outdoor durabilities of over twice
their lower molecular weight counterparts.
3.6. SEA4 and optical microscopy
Scanning electron microscopy can be used to take a
snapshot of surface morphology, at magnifications of
up to 100 000 and resolutions of around 8 nm, at any
time during a weathering test. If suitable times are
chosen then this may provide support evidence for
other more sensitive durability tests, as well as giving
an excellent visualisation of the physical results of
degradation. For example, previous work [26] has used
SEM to demonstrate that there is little change in the
surface appearance of an alkyd, a poly(urethane) or an
acrylic latex top coat during the early stages of degra-
dation, even though more sensitive techniques, such as
X-ray photoelectron spectroscopy (XPS), were able to
pick out changes in chemical composition. In the same
100 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106

work, after longer exposure times, the magnitude of the been applied in order to assess the extent of weathering
chemical changes quantified by XPS had increased and [5,21,26,28-301. These measurements generally do show
it was possible to observe surface changes using SEM. a rough correlation with exposure time but are difficult
Work performed in our laboratories [22] has used SEM to reproduce and do not have the sensitivity to give
to monitor the surface of clear poly(ester) films with more than a qualitative indication of durability.
QUVB exposure time. This work demonstrated the
gradual growth of spots of degradation product, which
eventually developed into cracks penetrating into the 4. Chemical measurement techniques
coating. However, the actual quantification of this
degradation using SEM was very difficult, as has been The mechanism of polymer photodegradation is
shown before [22,27]. widely proposed [5,31,32] to follow a general scheme
Apart from the capital expense and the necessity for which involves the production, and further reaction, of
a skilled operator, the main disadvantage of SEM is free radicals formed as a result of exposure to UV
that it is a destructive technique, hence the surface of radiation:
one particular piece of polymer cannot be monitored
Initiation: R+hv-2R’
with time. All of these problems can be overcome with
the use of optical microscopy, the penalty being a Propagation: R’ + O2 - ROO’
reduction in the degree of magnification possible.
ROO’ + RH - ROOH + R’
3.7. Dynamic mechanical analysis Chain Branching: ROOH- RO’ + HO’
2ROOH - ROO’ + RO’ + H,O
Dynamic mechanical analysis (DMA) has been used
[21] to investigate the effect of QUVB exposure upon RO’+RH-ROH+R’
the storage modulus and the Tg of clear and pigmented
HO’+RH-R’+H,O
poly(urethane) coatings. Large differences in both the
Tg and the storage modulus with weathering time Termination: 2 radicals - products
were observed in these systems over periods of up to
From this general model, several chemical tech-
6000 hours exposure. DMA experiments have been
niques which would monitor such reactions become
performed in this laboratory upon a series of poly-
immediately obvious and will be discussed in the fol-
(urethane)-acrylic systems with similar results [22],
lowing sections. Surface analysis techniques, such as
however, great care had to be taken when interpreting
FTIR-ATR and XPS, would appear particularly suit-
results to consider the contribution residual solvent loss
able as the UV light intensity is highest at the polymer
made to the increase in Tg (as compared to further
surface and oxygen is not diffusion limited. There are
curing of the system).
also a number of other chemical methods which may
In the same work, DMA was used to show that very
fulfil the role of a fast answer test and these will also be
little change in the value of the Tg of a range of
considered.
crosslinked poly(ester) coatings after 1200 hours QUVB
exposure occurred [22], whereas a significant reduction
4.1. Electron spin resonance spectroscopy
in the rubbery modulus and a decrease in the height of
the tan 6 peak associated with the glass transition were
Probably the most obvious technique which suggests
observed. Analysis of these results indicated that the
itself to monitor photodegradation is electron spin reso-
degradation of the poly(ester) coating was predomi-
nance (ESR) spectroscopy. The above mechanism
nantly by chain scission as opposed to oxidative
crosslinking (Fig. 2). Although DMA tests the proper- x
ties of the whole of a polymer film, it is still a fairly
sensitive technique towards extent of degradation. It
would not form the basis of any fast answer technique,
but can lead to information as to the physical changes
upon weathering.

3.8. Other physical methods a “““““““““““““’

0 1 2 3 4 5

There are a number of standard physical and me- Nitroxide Concentration

chanical tests such as impact, tensile strength, elonga- Fig. 3. The relative photoinitiation rate (PIR) of three different
tion at break, solvent swelling, water vapour coating systems after several hours exposure to UVA irradiation.
transmission and laser stylus profilometry which have - * -, epoxy; - 0 -, poly(ester); - A - , lumiflon.
 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106 101

shows that free radicals are involved in both the initia-

tion and the propagation steps of degradation. The
advantages of using ESR are that it is chemically
specific, sensitive and quantitative, thus would lend
itself well to the early quantification of photodegrada-
tion reactions.
There are two approaches to using ESR. The first
[33-361 involves the measurement of free radicals pro- * 0

0 ...,,,...,,,..........*”
duced by in situ UV irradiation. However, as free 0 200 400 600 806 1000 1200
radicals are generally highly reactive and very short Expomm (QUV houn)
lived at room temperature, it is usually necessary to
Fig. 4. Changes in gloss retention for the above coatings when
perform the experiments at 77 K. In doing so, there is a epoxy;
exposed to QUVB irradiation. -A-, lumiflon; - 3 -,
level of uncertainty introduced as there is no guarantee --o-, poly(ester).
that the free radicals produced and observed at such
low temperatures will be the same as those which occur the diffusion of gaseous nitroxide (with the aid of a
at ambient temperatures. Previous work, using low transfer agent) into the polymer. The determination of
temperature ESR [35], has successfully ranked twenty the PIR of acrylic-melamines and poly(ester)-
different clear 2-pack poly(urethane) coatings, correlat- urethanes after ‘near ambient’ exposure, i.e. UVA type
ing the rate of radical formation with the time to failure light, has shown that the acrylic-melamine system
(cracking in this case) under different accelerated reaches a steady state after around 10 h exposure which
weathering regimes. The effect of the addition of differ- is sustained for times of over 1000 h, whereas the
ent stabilizers and different curing chemistries was suc- poly(ester)-urethanes display a gradual increase in PIR
cessfully evaluated. Other work [36] has used low over the first 50-100 h before the photooxidation turns
temperature ESR to highlight the effect of different autocatalytic and the PIRs increase rapidly [41]. The
crosslinker levels in epoxy-melamine coil coatings, sug- lack of auto-catalytic peroxide decomposition in the
gesting that higher melamine levels lead to lower melamine-acrylics was attributed to the decomposition
durability. This method has been used on a series of of hydroperoxides by the melamine crosslinker before
Courtaulds poly(ester) systems comprising co-polymers they could reach a high enough concentration to go
of poly(esters) of different natures [37] to demonstrate auto-catalytic. A correlation between the PIRs of a
successfully a correlation between outdoor durability series of aircraft urethane systems and their Florida
and acyl radical concentration (formed in the primary exposure performance has been achieved [21], highlight-
photolysis step). In all of the above work, the exposure ing the great potential of the ESR technique for com-
time necessary to generate results was no more than ten parative fast answer data.
hours. Similar work has been performed [43] using a phe-
The second method, pioneered by Gerlock and co- noxyl radical instead of the nitroxide radical. This work
workers [38-421, involves the infusion of a persistent evaluated the effects of the addition of various UV
nitroxide into a coating which scavenges the free radical stabilisers to an acrylic clearcoat and also correlated the
intermediates formed during photolysis. In the early ESR results with time to failure under QUVB exposure.
work, stable nitroxide radical was homogeneously Work performed in this laboratory has used ESR to
added, during preparation, to the polymer film in differ- compare systems of known relative durabilities, namely
ent concentrations (in order to eliminate the effect of lumiflon, a poly(ester) and an epoxy. Fig. 3 displays
side reactions) and its ESR intensity monitored with the PIRs of each of the systems when irradiated
time. From such experiments the initial photoinitiation with UVA radiation for periods of up to 10 h,
rate (PIR) of the coating can be determined, which has
been shown to be related to its overall durability. For
example, the PIRs of a series of acrylic-melamines [38]
and acrylic-urethanes [39] have been determined in
timescales of around 1 h and found to correlate very
well with gloss loss measurements determined after over
several hundred hours QUVB exposure. This work was
extended to examine post-weathering nitroxide infu-
sion, rather than pre-weathering, with similar results 0 loo 200

being obtained [40]. WV Tie I Hours

In order to examine post-weathering films, the ni- Fig. 5. FTIR-ATR assessment of the degradation of poly(ester)/
troxide could not be added in the preparation stage, acrylic blends exposed to QUVA. -0--, PE 100%; -A-, PE
hence a second method was developed which involved 75%; - 0 -, PE 50%; ~ 0 -, PE 25%.
102 B. W. Johnson, R. McIntyre / Progress
whilst Fig. 4 gives the data obtained from gloss read-
ings over a considerably longer period of exposure to
QUVB.
It should, of course, be mentioned that these three
coatings are vastly different in their UV durability and,
therefore, achieving a good correlation could be consid-
ered to be an easy test of the ESR method.
For this approach to be a valuable fast answer
method it really ought to be capable of discriminating
between coatings with only lo-20% difference in their
actual external exposure performance, for different
polymer chemistries and also for materials consisting of
blends of different chemistries. To this end, further
work was performed which was successful in ranking
the relative durabilities of a range of poly(ester),
poly(ester)/acrylic and acrylic systems using both the
phenoxyl radical [44] and the nitroxide radical [45,46]
techniques.
As a fast answer method for the prediction of coat-
ing durability ESR has great potential, chiefly because a
coating can be fully tested in a mater of hours. The
nitroxide infusion method is at a disadvantage to the
low temperature irradiation method in terms of time as
it requires a number of experiments at different nitrox-
ide concentrations in order to eliminate the effect of
side reactions. However, the nitroxide method is per-
formed at room temperatures, removing any uncertain-
ties regarding the validity of measuring degradation
processes at lower temperatures. The main disadvan-
tages of using ESR are that it is a labour intensive
operation requiring highly skilled personnel, the capital
expenditure is relatively high and it requires a great
deal of effort in optimization before any meaningful
measurements can be made.
4.2. Fourier transform infrared spectroscopy
Fourier transform infrared spectroscopy is both a
chemically specific and a very sensitive technique which
renders it potentially a very powerful tool in the areas
of fast answer methodology and photodegradation
product identification. Early work to assess the rate of
degradation [ 1,31,47,48] using FTIR was generally per-
formed upon non-carbonyl containing polymers, such
as linear low density poly(ethylene) or poly(propylene)
to monitor quantitatively the growth of carbonyl inten-
sity formed as a result of photooxidation. In order to
gain information upon the products of photodegrada-
tion, derivatization reactions have been performed [49-
51] whereby the products will further react with a
chosen reactive gas (such as NO or SF,) to give prod-
ucts which can be very clearly identified.
Much of the previous work [5 1- 551 has been centred
upon transmission FTIR through thin polymer films
(Z 5 pm). It has been shown, for example [52], that
melamine-acrylic coatings exhibit a quantitative reduc-
in Organic Coatings 27 (1996) 95-106
0 so 100 150 mo
QLwnme/Hour
Fig. 6. FTIR-ATR assessment of the degradation of polyester/acrylic
blends exposed to QUVB. - 0--, PE 100%; -A-, PE 75%;
- ? -,? PE 50%; - ?? -, PE 25%.
tion in the C-H vibration with exposure time, a result
which was reproducible. For the same coating systems,
the effect of adding either UV absorbers or hindered
amine light stabilizer (HALS) upon the FTIR charac-
teristics has been clearly demonstrated, with the HALS-
containing systems showing the least changes during
3000 h UVB exposure [54]. Work performed upon
poly(urethane)-acrylic topcoats has used transmission
FTIR to illustrate the effect of crosslinker type upon
the rate and type of degradation [53].
As weathering is a surface phenomenon, FTIR-ATR
(which samples the top 2-3 urn) would suggest itself
very strongly as a method of following quantitatively
the chemical changes which occur during degradation.
A significant amount of work has appeared in the
literature using this technique with some success
[7,19,28,47,49,52,56,57]. An example of its use, not only
in monitoring degradation but also following the chem-
ical changes, has been provided for acrylic-urethane
coatings [19]. It was shown that, although the samples
degraded during both carbon arc and Florida exposure,
the chemistry of degradation was different, meaning
that the carbon arc could not be used as a valid
accelerated exposure medium for the coatings in ques-
tion. Other work [7,49] carried out upon poly(styrene)
films indicated that the products of photooxidation
resulting from exposure to either 253.7 mn or > 300 nm
radiation were the same but that their distribution was
different, that is the acceleration factors for the various
processes, resulting from irradiation at shorter wave-
lengths, were not the same.
The FTIR-ATR technique has been used upon a
series of Courtaulds poly(ester)/acrylic blends [22] ex-
posed to either UVA or UVB radiation. The results
obtained highlighted that, although a faster rate of
degradation occured under UVB exposure, the tech-
nique could predict reproducibly their relative durabili-
ties in the order expected from known durability data
after less than 300 h irradiation (Figs. 5 and 6).
Similar work [22] was performed upon a poly(ur-
ethane)-acrylic system to demonstrate the effect of
adding a hindered amine light stabilizer (HALS) to the
coating. In the case of the non-HALS containing
 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106
0.4 c
0300600900 1200
QUV TIME I HOURS
Fig. 7. The relative degradation (arb. units) of a HALS and a
non-HALS containing poly(urethane)-acrylic coating exposed to
QUVB radiation. 0, HALS Sample 1; A, HALS Sample 2; I,
HALS Sample 3; x , No HALS; 0, No HALS; 0, No HALS.
coating the onset of degradation was immediate and
continued at a constant rate for up to 1000 h UVB
exposure, whereas, for the HALS containing film, there
was essentially no change in the infrared characteristics
for around 500 h, after which the coating degraded at
approximately the same rate as the former coating (Fig.
7). It appears likely that the ‘incubation time’ of 500 h
observed for the latter coating could be representative
of the effective lifetime of the HALS.
Photoacoustic (PAS) FTIR has also been used to
study photodegradation [8,21,58]. PAS has the advan-
tages that the sample does not have to be removed from
the substrate and that not only is it a surface technique
but it can sample to different depths into the surface.
The disadvantages of PAS are that the signal-to-noise
ratio is often high making the acquisition of high
quality spectra difficult, saturation of the stronger
bands can occur at penetration depths of only a few
microns and considerable spectral distortion is also
often apparent.
For fast answer durability assessments, FTIR-ATR
appears to be very useful as it examines the polymer
surface which is the region of greatest interest. Other
advantages are that FTIR spectrometers are relatively
inexpensive and easy to use, computer manipulation
allows accurate determination of the chemical differ-
ences due to weathering, the average time required per
LOOEM
= T Ezl
l.MIE-07 1
0 10 20 30
QIJV Time I Days
Fig. 8. Hydroperoxide levels for an epoxy and a poly(ester) coating
exposed to QUVB radiation. 0, epoxy; 0, PE.
103
sample is 5- 10 min, the reproducibility of results is
good and pigmented materials can be examined. Draw-
backs to the technique are that it could reveal specific
chemical information about the coating being tested
and a series of measurements are necessary per coating
system.
4.3. Iodometric titration
1
lsoo The presence of hydroperoxides (ROOH) as stable
intermediates in the photodegradation of polymers can
be exploited by utilizing standard analytical methods
[59-611 to measure thier concentration with time. The
most common method of assessing the ROOH concen-
tration is via iodometry, in which the iodide (I-) ion
reduces the ROOH to water and alcohol and is itself
oxidized to iodine (IT):
ROOH + 31-(xs) - ROH + H,O + I, (1)
As the reaction is one to one, a quantitative determina-
tion of the free iodine produced will lead to the original
ROOH concentration. The I; concentration can be
determined via its UV absorbance, via potentiometry
(the electrochemical potential set up at a platinum
electrode is proportional to iodine concentration) or via
back titration with a suitable reducing agent such as
thiosulphate.
Much work has been performed in this area in an
attempt to use iodometric titration as a cheap and easy
fast answer technique [42,50,57,62-641. For example,
the ROOH concentration detected in melamine-acrylic
coatings has been shown to increase by over two orders
of magnitude after 500 h exposure to UVB before
falling to a sustained lower level [62]. The durability of
these coatings was claimed to be strongly dependent
upon the magnitude of this sustained hydroperoxide
concentration. Further, the ROOH concentration in
these coatings was found to be proportional to the
photoinitiation rate detected by ESR spectroscopy [42],
a correlation which led to investigations as to how
quickly changes in the ROOH concentrations with ex-
posure time could be detected. The result of this work
[64] indicated that the ROOH levels in acrylic-
melamines and acrylic-urethanes increased after only
l-2 d ambient exposure. Two very important points
were highlighted as a result of this, and other [63],
investigations. First, the profile of ROOH with time
was different between the two coating chemistries used,
with no sustained level after the initial increase being
reached with the acrylic-urethanes. Instead, in these
systems the hydroperoxide concentration eventually
reached a critical level and autoxidation occurred,
I which then caused a very rapid increase in ROOH with
40
time. Second, the consideration of any additives to a
coating is important as, for example, nitroxide itself can
oxidise iodide to iodine and can clearly affect any
results [63].
104 B. W. Johnson, R. McIntyre / Progress in Organic Coatings 27 (1996) 95-106
Such success prompted Courtaulds Coatings to ex-
plore the value of the technique when applied to its
own proprietary coatings [22,45,65]. Initial work [22]
was performed upon an epoxy (based on Epikote 1004)
doped with known amounts of t-butylhydroperoxide
(t-BOOH) under a nitrogen atmosphere. Analysis of
the films via potentiometry resulted in the expected
Nernstian response of 30 mV difference between sam-
ples, with over 70% of the t-BOOH added to the
coatings being detected in all cases. Later work (Fig. 8)
proceeded to demonstrate that this technique could
distinguish quite clearly between a more durable
polyester and a less durable epoxy coating exposed to
QUVB radiation for up to 40 d.
However, this iodometric technique could not clearly
separate two poly(ester) systems of different known
durabilities when exposed to UVA [45,65] or UVB [22]
irradiation, even though, in both cases an increase with
time was observed.
The benefits of using hydroperoxide titration as a
fast answer durability predictor are that it is simple,
inexpensive, no highly trained operators are necessary,
pigmented systems can be analyzed and specific chemi-
cal information relating to the materials tested will not
be revealed. However, there are many drawbacks to
this technique such as it is destructive, the extent of
penetration of the iodide into the polymer matrix is not
known and will probably vary between polymer types,
any reducible species (e.g. 0,) present in the coating
could oxidize the iodide, reproducibility is difficult and
the ROOH concentration is assumed constant through-
out the polymer (which is not true, hence the thickness
of the material tested is of importance).
4.4. Chemiluminescence
The occurrence of very weak chemiluminescence
(CL) upon oxidation of organic compounds has been
known for many years and is a feature for most com-
mon organic polymers [66-711. The source of the lu-
minescence is generally agreed to be an excited carbonyl
species, but the origin of this carbonyl is under dispute
[67-691. However, whatever the mechanism of lumines-
cence, it is directly proportional to the concentration of
peroxide groups in the polymer. Therefore, CL can be
used as a measure of hydroperoxide content and,
hence, as an indication of the rate and extent of
photodegradation.
Attempts to use CL to predict the relative degrada-
tion rates of a series of Courtaulds poly(ester) coatings
have been made [72]. After 203 h QUVB irradiation it
was possible to distinguish between a less durable sys-
tem and two more durable systems, however the latter
two systems could not be separated as the exposure
time was not long enough. Later work [73-751 upon
similar systems could not separate these latter two
systems even after over 1500 h UVB exposure.
Investigations upon three general systems of widely
different and known durabilities [76] concluded that,
after 532 h QUVB exposure, their relative durabil-
ity order was Lumiflon > poly(urethane)-acrylic > an
Epikote 1001 based epoxy coating.
CL is not particularly suitable for fast answer
durability predictions, chiefly because of the long expo-
sure times necessary (upwards of 1500 h QUVB for the
more durable systems). When UVA exposure is used
instead of UVB, there is very little change in the CL
characteristics for a low durability poly(ester) system
even after more than 3000 h exposure [75]. Other draw-
backs include the non-ability of the method to examine
pigmented systems and the fact that CL is destructive,
hence a large number of samples are necessary.
4.5. X-ray photoelectron spectroscopy (XPS)
As XPS is a powerful surface technique it may be
expected to provide useful data regarding chemical
changes caused by weathering and has been suggested
as having great potential in this area [27]. In reality,
XPS has not been used with any great success because
of its very small sampling depth, roughly 5 nm into the
surface. Due to the small surface layer examined it is
difficult to be sure that the results obtained are repre-
sentative of the polymer in question as, for example,
the presence of impurities at the surface could act as
chromophores and induce changes. Furthermore, if the
products of degradation at the surface are friable and
drop off the polymer then XPS will be extremely sensi-
tive to this, resulting in problems in making repro-
ducible quantitative measurements.
Despite these drawbacks, XPS has been used to
demonstrate that the changes in the oxygen/carbon
(O/C) ratio at a poly(urethane) surface are similar after
3000 h QUVB and 18 months Florida exposure [21].
The technique has also been used to correlate the
changes in the O/C ratio of a poly(urethane), an alkyd
and an acrylic latex during exterior exposure with the
changes during a corrosion weathering cycle [26].
Within Courtaulds Coatings XPS has been used to
detect an increase in the O/C ratio for a poly(ur-
ethane)-acrylic, a poly(ester)/acrylic blend and an
alkyd [22]. These changes, in most cases, were small
and of a cyclic nature, suggesting the formation and
loss of surface oxidation products with time.
As a fast answer technique XPS is not particularly
suitable. The changes that are detected are difficult to
reproduce and are often not significant enough to lead
to any overall durability prediction. Moreover, the
equipment is expensive, the turnover rate of samples
can be low (up to 3 h per sample) and specialized
personnel are required.
 B. W. Johnson, R. McIntyre / Progre Orgunic Coatings 27 (1995) 95- 106 105

Table 1 Of the other techniques considered, the two which

Advantages and disadvantages of ESR and FTIR-ATR methods for
appear most likely to form the basis of a fast answer
providing a fast answer method to quantitatively predict coating
lifetimes method to predict quantitatively coating lifetimes are
ESR and FTIR-ATR spectroscopy, chiefly because of
Requirements Ideal ESR FTIR-ATR their significant time advantages over EMMAQUA and
Florida exposure. In both cases, further work would be
Timescales d Fast <24h <300 h
necessary in order to establish their correlation with
One point measurement Yes No No
Measurement time Fast Ih 30 min
Florida and EMMAQUA. Table 1 summarizes the pros
Sensitive Yes Yes Yes and cons of the two techniques.
Reproducible Yes vs. standard vs. standard
Capital Low > &20 000 > f20 000
Running costs Low Low Low
Skilled operator No Yes Easy training References

a Depend upon the exposure medium and the material being tested.
The figures quoted here are for a 1 -5 year (Florida durability)
poly(ester) under UVA exposure.
4.6. Oxygen absorption
As can be seen from the general mechanism of
polymer photodegradation, the consumption of oxygen
is an integral part of the process. The direct measure-
ment of this should be proportional to the extent of
degradation and, if sensitive enough, could form the
basis of a fast answer test. The technique has been used
previously to evaluate the durability of an alkyd system
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