Quantitative Investigation of the

Photodegradation of Polyethylene
ARTICLE

Terephthalate Film by Friction Force

Microscopy, Contact-Angle Goniometry,
and X-ray Photoelectron Spectroscopy
Claire R. Hurley and Graham J. Leggett*
Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF, United Kingdom
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT Studies of the UV-induced photodegradation of poly(ethylene terephthalate) (PET) have been carried out using contact-
angle goniometry, X-ray photoelectron spectroscopy (XPS), and friction force microscopy (FFM). The advancing contact angle of water,
θ, decreased following exposure of free-standing PET films to UV light. Measurements of surface friction by FFM showed that the
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coefficient of friction µ increased as the degradation proceeded, reaching a limiting value after ca 200 min, in agreement with the
contact angle data. Using a modified form of the Cassie equation, a quantitative analysis of the extent of modification could be carried
out. There was a very close correlation between the coefficient of friction determined by FFM and the value of cos θ. XPS provided
more detailed information on surface bonding that also correlated closely with the FFM data. Although FFM provides quantitative
data on surface modification with nanometer-scale spatial resolution, it does not provide detailed structural information such as is
provided by XPS. The oxygen content at the surface was found to increase as photo-generated radicals within the PET reacted with
atmospheric oxygen. Increases in both ester and carbonyl contributions within XPS data accompanied this increase. It was concluded
that the photodegradation process follows mainly Norrish type I reaction pathways, following previous work by Fechine et al and
Grosstête et al.

KEYWORDS: polymer surface • friction force microscopy • X-ray photoelectron spectroscopy • poly(ethylene terephthalate) •
photodegradation • contact angle goniometry

INTRODUCTION high spatial resolution. For example, FFM has been used to

T he quantitative investigation of surface structure and quantify rates of photopatterning processes at a resolution
chemical composition at the nanometer scale re- of a few tens of nanometers (23). Such data are not acces-
mains a significant challenge in surface analysis. sible by any other analytical technique. In previous studies
Although substantial advances have been made in recent of surface composition by FFM, attention has largely focused
years in the analysis of surfaces by secondary ion mass on the analysis of well-defined monolayer systems. The goal
spectrometry (SIMS) at high resolution, characterization at of the present work is to extend such methodologies to
a resolution of tens of nanometers remains difficult, and polymer systems, because polymer surfaces constitute an
other conventional surface analysis techniques yield data important class of materials and because they remain dif-
with substantially lower resolution. Friction force micros- ficult to characterize at high spatial resolution by conven-
copy (FFM) has emerged as a powerful tool for the investiga- tional tools. In particular, the photodegradation of poly(eth-
tion of nanometer scale tribological phenomena (1-6), and ylene terephthalate) (PET) has been investigated by FFM,
its capacity for qualitative investigation of surfaces is well- and the data compared with those obtained by analysis of
established. There has been a great deal of interest in using measurements made by contact angle and X-ray photoelec-
FFM to study molecular tribological phenomena, and it has tron spectroscopy (XPS).
been used to study a wide range of molecular interfaces, Photochemical processes are a major cause of degrada-
including self-assembled monolayers of alkylsiloxanes (7-10),
tion in polymeric materials (24 –26), and thus present an
alkanethiols (11-17), alkoxy compounds (18), alkylphos-
important class of problem on which to test the utility of
phonic acids (19, 20), and polymers (21, 22). Importantly,
quantitative data obtained from FFM measurements. Pho-
however, it is becoming clear that through comparatively
tooxidation under controlled conditions is a useful means
simple analyses of FFM data, it is possible to obtain informa-
of simulating the aging process (26) and for exploring the
tion of surface chemical composition that is quantitative, at
impact of processing steps during manufacturing, such as
drawing (27, 28) and the incorporation of additives ( 29, 30).
* Corresponding author. E-mail: [email protected].
Received for review April 9, 2009 and accepted July 14, 2009 Photodegradation also causes polymer breakdown and may
DOI: 10.1021/am900250q contribute to waste reduction (31, 32). Surface modification
© 2009 American Chemical Society by photodegradation (33, 34) is used to aid the attachment

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Published on Web 07/28/2009
Scheme 1. Norrish Type I and II Reactions of PET

ARTICLE
of enzymes and antibodies to surfaces in bioassays. To oxygen but via a cyclic intermediate (40). In contrast,
understand such phenomena, it is valuable to have the Fechine et al. have reported a depth-dependence in the
ability to make quantitative measurements of surface struc- photo-degradation process (29) and have proposed an al-
ture and composition with high spatial resolution. ternative mechanism (Scheme 2) based on Norrish Type I
There has been a substantial amount of work on the reactions that proceed via a radical species to produce mono
photodegradation of PET, although the mechanisms are not or hydroxy terephthalates, carboxyl end groupsm and alde-
fully understood (35). A wide range of wavelengths have hydes. This mechanism proceeds via the main radical
been investigated, from the deep UV (36-38) to the near discussed by Grossetête et al., who indicated the possibility
UV (24-26, 29-31, 39). The main degradation process of further reaction from the aldehyde to another carboxylic
during photo-oxidation of PET is known to be chain scission acid (38).
leading to a decrease in molecular weight of the polymer and In the present study, the photodegradation processes in
the generation of carboxyl end groups, particularly at the a free-standing film of polyethylene terephthalate (Melinex
surface. The activated ketones can fragment via two path- OD) have been investigated following exposure to light with
ways: the Norrish Type I and II mechanisms (40) (Scheme a wavelength of 254 nm. Evidence has been provided that
1). The Norrish Type I reaction involves the formation of FFM may be used to derive quantitative information on the
radicals around the ester linkage and termination of the effects of photodegradation on polymer structure and com-
polymer chains. The Norrish Type II reaction occurs via position. On the basis of XPS data, a mechanism for PET
intramolecular abstraction of a γ-hydrogen through a cyclic photodegradation is proposed that is very similar to that of
intermediate and results in the termination of polymer Fechine et al.
chains ending in carboxylic acids and alkenes (39). In
addition the evolution of volatile products such as carbon EXPERIMENTAL SECTION
Melinex OD Film (thickness 125 µm) was obtained from
monoxide and carbon dioxide is observed. Day and Wiles DuPont Teijin Films. Prior to exposure, 1 cm2 samples were
have proposed a Norrish Type II pathway arguing that the sonicated for 5 min in diethyl ether and dried under a stream
carboxyl end groups are not generated by reaction with of nitrogen to remove any particulates.

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 Scheme 2. Proposed Mechanism for the Photo-oxidation of PET; This Mechanism Proceeds via Norrish Type I
Reactions
ARTICLE

Photo-oxidation was carried out using a UV lamp (model immediately after exposure in order to remove low-molecular-
R-52G) emitting at 254 nm with a power of ∼1 mW cm-2 weight material at the surface.
measured using a power meter. The lamp was switched on and FFM measurements were performed on a Digital Instruments
left to equilibrate for 10 min prior to sample treatment. PET Nanoscope IIIa Multimode Atomic Force Microscope operating
films were treated at a constant distance of 3 cm. The length of in contact mode. The tips were silicon nitride Nanoprobes
the exposure, performed under ambient conditions, ranged (Digital Instruments, Cambridge, UK) with nominal force con-
from 0 to 6 h to allow complete irradiation of the sample stants of 0.06 N m-1. To acquire quantitative data on the surface
surface. Samples were analyzed within 40 min of UV treatment using FFM it was necessary to calibrate the Nanoscope. This
with the exception of samples submitted for XPS analysis, which calibration of normal forces involved two steps. First, the
were stored in low light conditions overnight. photodetector sensitivity was calibrated by measuring a force
Sessile drop water contact angles were measured using a curve for the cantilever in contact with a stiff sample (mica).
Rame-Hart 100-00 goniometer. A 2µL droplet was released Relative to the cantilever, the stiffness of mica is sufficiently
from a syringe suspended above the sample stage. The sample large that it may be assumed that all deflection during the force
was raised until it contacted the droplet whereupon the stage measurement will be in the lever. Under these circumstances,
was retracted slowly until the drop broke free of the meniscus the photodetector sensitivity is the gradient of a plot of photo-
formed with the syringe. The droplet was then allowed to detector signal versus displacement while measuring repulsive
stabilize for 1 min before the advancing contact angle was forces. The spring constants of the levers were determined from
measured. A minimum of four contact angles was obtained on their thermal spectra using a routine implemented within the
different samples for each exposure time. These experiments microscope software (Digital Instruments PicoForce software)
were repeated with surfaces immersed in ethanol for 30 min and based on the method of Hutter and Bechhoefer (41). This

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approximates the cantilever as a harmonic oscillator, the motion
of which is driven by thermal noise. Applying the equipartition
theorem, Hutter and Bechhoefer derived a relationship between

ARTICLE
the spring constant and the power spectrum of the cantilever
response. Experimentally, the laser spot was focused on the
apex of the cantilever, and the thermal fluctuations of the
cantilever were measured and used to derive the power spec-
trum. Prior to any measurements the applied load was mini-
mized recording the set point value of zero load. This was done
by retracting the tip, allowing it to lose contact with the surface
and extending it until it snapped back into contact. Quoted loads
are the products of the spring constants; photodetector sensi-
tivities and deflection set points.
To minimize uncertainty due to the many parameters influ-
encing the tip-sample interaction, we used the same probe
throughout whole experiments. Trace-retrace subtraction of
data from friction loops enabled elimination of topographical
effects from the data, giving a resultant signal equivalent to
twice the frictional force (1, 2). Experiments were performed
under ethanol using a liquid cell fitted with a silicone O-ring to
enable the use of Amontons’ law to model these data (21). The FIGURE 1. Reduction in the contact angle as PET is exposed to 254
AFM was first setup to image the surface; simultaneous com- nm UV light over 7 h.
parison of friction images with topographical imaging ensured
the tip was still in contact. Friction loops were acquired from This increase in overall surface oxygen results in increasing
an initial set point of ∼2.5 V, and the load was then reduced dipole-dipole interactions and hydrogen bonding with the
incrementally in steps of 0.2 V until the tip pulled free of the water droplet, and hence the surface becomes more hydro-
surface. Areas of 5 µm2 were scanned with 256 scan lines at a philic (36, 43).
frequency of 1 Hz to minimize sample damage. Measurements
were taken at three positions on three sample surfaces for each Initially, the rate of decrease in the contact angle was
exposure time, and from these an average friction coefficient high, but it declined, and the rate of change began to
was obtained. approach zero after 100 min, when the contact angle was
XPS measurements were taken on a Kratos Axis Ultra X-ray 47°. However, as the exposure was increased still further,
photoelectron spectrometer. Samples were prepared 12 h in the contact angle again began to fall and eventually reached
advance and stored in low light conditions overnight. Im-
mediately prior to XPS analysis samples were maintained under a minimum of 14 ( 2°, following exposure for 7 h. A
a vacuum of 1 × 10-8 mbar for approximately 2 h. A minimum sigmoidal curve was fitted to the data, suggesting a two-step
of three XPS spectra was obtained on different sample runs for process.
each exposure time. Analysis was carried out using CasaXPS Previous studies have reported that the contact angle of
software (Casa, http://www.casaxps.com, UK). Survey and nar- PET falls from ca. 75° to ca. 40° following UV exposure.
row scan spectra of C1s and O1s peaks were obtained. Peaks
were fitted using combinations of Gaussian (30%) and Lorent- Arefi-Khonsari et al. studied PET surfaces after both laser and
zian (70%) curves against a linear background. The FWHM of plasma treatments. After plasma treatment for 5 s, the
all components was constrained to be equal to that of the contact angle had stabilized and was reduced from 77 ( 3°
aliphatic carbon, but all other parameters were left free to vary to 38°, whereas after laser treatment, the wettability was
during fitting, optimizing parameters taken from a PET table enhanced to different degrees depending on the laser flu-
of standard spectra (42). These experiments were repeated with
surfaces immersed in ethanol for 30 min immediately proceed- ence, a lower fluence resulting in a higher surface wettability
ing exposure in order to remove low-molecular-weight material (37). The lowest contact angle achieved in this case was also
at the surfaces. 38°. Similar results have been obtained by other authors
To test for hydroxyl group incorporation into UV-modified (36). These findings were consistent with the behavior
PET samples (see Scheme 2), they were attached to glass slides observed here over the first 100 min. However, here a
using an adhesive carbon tab. The slides were then mounted
at a 45° angle in an enclosed sample tube containing 100 µL of further reduction was also observed in the contact angle after
trifluoro acetic anhydride (TFAA). Samples were left in a satu- long exposures.
rated, ambient TFAA environment for 1.5 h. The films were To test whether this could be connected with the forma-
then washed with ethanol and dried in a low stream of nitrogen tion of low-molecular-weight material at the sample surface,
gas to remove any excess reagent. the experiments were repeated and each sample was im-
mersed in ethanol for 30 min prior to contact-angle mea-
RESULTS AND DISCUSSION surement to remove any surface debris. Following rinsing
Contact-Angle Measurement. The effect of UV in this fashion, the behavior was significantly altered: the
exposure was first monitored by contact angle goniometry second period of declining contact angle was absent and the
(Figure 1). The contact angle was initially 76 ( 2°, in contact angle did not change significantly after ca. 200 min.
agreement with previously published values, and decreased These data suggest that the second period of falling contact
following UV exposure. This behavior was consistent with angles measured for the unwashed samples is due to the
the expected increase in surface oxygen content brought formation at the surface of low-molecular-weight hydrophilic
about by irradiation of the surface, which photosensitizes material that is removed by washing in ethanol. Grossetête
the polymer and causes it to react with atmospheric oxygen. reported the removal of photo-oxidized material from the

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ARTICLE

FIGURE 3. Observed increase in normalized friction coefficients as

PET is exposed to 254 nm UV light over 360 min.

FIGURE 2. Friction-load plots after a 360 min UV exposure at 254

nm.

PET surface following 24 h immersion in methanol. Analysis

of the wash showed evidence of molecular terephthalic acid,
and that some of the low-molecular-weight material was the
substituted terephthalate (38).
Friction Force Microscopy. FFM was performed on
PET exposed to 254 nm UV light for 0, 40, 80, 135, 200,
260, and 360 min. These measurements were performed
under ethanol because previous studies have shown that in
this medium, FFM data may be analyzed using Amontons’
law (ie. a linear relationship is typically observed between
the friction force and the applied load) (21). Because of this,
the experiment is also equivalent to the contact angle
experiment conducted following washing of the sample.
Typical friction-load plots obtained on PET at a selection
of representative exposure times are shown in Figure 2. In FIGURE 4. Relationship between the coefficient of friction (µ) and
the cosine of the advancing water contact angle (cos θ).
all cases, the photodetector response (which is proportional
to the friction force) increased linearly as the load was
forces acting at the tip-sample contact would increase
increased, in accordance with the predictions of Amontons’
(16, 43, 44). As a consequence, more work must be done
law. Straight lines could be fitted to the data by linear
regression with a regression coefficient of at least 0.998 in shearing intermolecular interactions as the tip slides across
all cases. Within experimental error, the lines were found the surface, leading to a higher rate of energy dissipation
to pass through the origin (data for 0, 40, and 80 min and hence a stronger frictional interaction. The data in Figure
exposure have been shifted vertically to aid clarity). A 3 reflect this, with the increase in the normalized value of
gradual increase was observed in the magnitude of the the coefficient of friction being clearly correlated with the
gradient as the exposure time increased. Friction coef- increase in wettability shown in Figure 1.
ficients, µ, were determined from the gradients of the The extent of agreement between data obtained on the
friction-load plots, and normalized to the largest value macroscopic and nanometer scales is demonstrated explic-
measured. These are shown as a function of the UV exposure itly in Figure 4, which shows the variation in the friction
time in Figure 3. The normalized coefficient of friction coefficient with cos θ. A linear relationship was observed,
increased from 0.47 ( 0.02 to 1.00 ( 0.03 over 360 min. suggesting that the data were correlated. Cos θ is ap-
The friction coefficient reached a limiting value after ca. 200 proximately proportional to the interfacial free energy, and
min, in agreement with the contact angle measurements for determines the work of adhesion at the tip-polymer contact.
the washed PET. The data in Figure 3 were fitted with an A linear relationship was previously reported between cos
exponential function. θ and µ in studies of mixed self-assembled monolayers
In the present case, a silicon nitride probe was used, the (16, 45, 46); the present work supports these findings and
outer surface of which consisted of silicon dioxide, a polar shows that similar correlations exist for treated photo-
material. As the surface became more hydrophilic, it would degraded PET surfaces. As the photo-degradation continues
be expected that the strength of the non-covalent attractive the surface is seen to become more hydrophilic and there-

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 ARTICLE
FIGURE 5. Decrease in the surface composition of carbon over the
exposure to 254 nm UV light.
fore loses some of its ability to dissipate energy; this change
occurs in a quantifiable manner.
The data in Figure 1 suggest that low-molecular-weight
material may be created during the UV degradation of PET.
In previous AFM studies of the plasma treatment of PET (43),
it was reported that substantial changes in surface morphol-
ogy occurred, that were attributed to preferential etching of
the amorphous fraction of the polymer yielded. In the
present study; however, AFM topographical images exhib-
ited only small changes to surface morphology resulting
from UV exposure, suggesting that the rate of removal of FIGURE 6. C1s spectra for PET exposed to UV light for 0 min (top),
material was slow and indicating that changes in surface 150 min (center), and 300 min (bottom).
friction were attributable to modification of surface chemical
structure rather than, for example, a change in the amor- sition through the first 10 nm of the samples. Their data
phous/crystalline ratio. suggest that it is possible that although surface modification
X-ray Photoelectron Spectroscopy. XPS analysis occurs through a substantial depth of material, washing only
was used to determine the change in surface composition removes the top-most layers of material, leading to a very
following exposure to UV light. A series of survey scans were small change in the spectra after washing.
taken over the range of exposure times (not shown). The High-resolution C1s and O1s spectra were also acquired.
samples exhibited only peaks due to oxygen and carbon. The C1s spectrum of the virgin polymer exhibited three
The surface composition was determined, and the results principal bonding environments (Figure 6a). A strong peak
are shown, as at % carbon, in Figure 5. The carbon content at 284.7 eV resulted from the aromatic carbon and was used
was found to decrease from 71.8 ( 0.7% to 62.2 ( 0.9% as a reference. Components were additionally observed that
over 6 h. The decrease was attributed to reaction between were attributed to an ether (a peak at 286.5 eV) and an ester
atmospheric oxygen and the radical species formed within (at ca. 288 eV). The ester, ether, and aromatic carbon were
the PET by UV exposure. Additionally, it is likely there was present in a 1:1:3 ratio. In addition a small shake-up satellite
a loss of volatile species such as CO and CO2. There was a was observed at 291.5 eV. The O1s spectrum exhibited two
corresponding increase in the percentage composition of principal components, corresponding to the ether and car-
oxygen in agreement with the work of Kikuchi et al. The bonyl oxygen atoms (single and doubly bonded, respec-
compositions of the washed and unwashed samples were tively), with the ether component appearing at slightly higher
found to be indistinguishable (including washed and un- binding energy than the carbonyl one.
washed unirradiated samples). This is likely due to the Following UV exposure, the oxygen peaks broadened and
desorption of low-molecular -weight material and volatile they became difficult to resolve. The C1s spectra were more
gases produced during the photo-oxidation following trans- informative, although even here the changes were rather
fer of the unwashed samples to the vacuum system for subtle. Figure 6 shows spectra acquired after exposures of
analysis. However, an alternative explanation that cannot 150, and 300 min. The most significant change in the
be discounted is suggested by the work of Lubarsky et al. spectrum was the appearance of a new peak, corresponding
(47) and Strobyl et al. (48), who depth-profiled the composi- to a carbonyl carbon atom, at a chemical shift of 287 eV. A
tion of UV-treated PET film and found no change in compo- substantial increase was observed in the size of the carbonyl

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FIGURE 8. Variation in the extent of reaction, , as determined

from contact angle (white squares), FFM (gray squares), and XPS
carbonyl peak intensities (black squares), as a function of UV
exposure time.

However, a simple measure of the extent of reaction may

be derived from the contact angle and FFM measurements.
If the final value of the cosine of the water contact angle is
cos θf, the initial value is cos θi, and the value at time t is
cosθt, then we can write, using Cassie’s equation

cos θt ) cos θf + (1 - )cos θi

where  is the extent of completion of the reaction and 0 e

 e 1. Hence

cos θt - cos θi
)
cos θf - cos θi

If the FFM data are treated in the same way, an approach

that is justified by the correlation between cosθ and µ shown
in Figure 4, then the following equivalent expression may
FIGURE 7. Surface composition kinetics showing the change in
contributions to the C1s peak from the (a) aromatic carbon, (b)
be derived
carbonyl, and (c) ester components.
µt - µi
component during the initial 50 min of exposure. This )
µf - µi
correlated with the contact angle data, which exhibited an
initial high rate of change but then changed more slowly
after 50 min. where µt is the friction coefficient at time t and µi and µf are
The appearance of the new component was accompanied the initial and final values of µ, respectively. The XPS data
by a reduction in the amount of aromatic carbon from 54.6 can also be analyzed in an analogous fashion, using the ratio
( 0.68 to 41.0 ( 0.15 %. The fall in the fraction of aromatic of the area of each component (e.g., carbonyl or ester
carbon (see Figure 7a) was found to be closely correlated carbon) to the total C1s signal in place of µ or cos θ. When
with the fall in the total percentage of surface carbon (Figure the data were analyzed in this way, a good correlation was
5). The ether contribution exhibited a negligible change from found between values of  calculated from the contact angle
20.5 % of the total carbon contribution at the surface. In and FFM measurements, as expected based on the data in
contrast, the carbonyl component increased to reach a Figure 4. A good correlation was also observed between
limiting area of ca. 8% of the total carbon signal after 6 h these sets of data and the values of  calculated using the
exposure (Figure 7b). The area of the ester component was variation in the intensity of the carbonyl component (Figure
observed to increase, to nearly 25 % of the total carbon 8). Overall, the agreement between the three approaches is
signal (Figure 7c). excellent, emphasizing the value of FFM as a simple route
Comparison of Data from Contact Angle Mea- to quantitative data on surface composition with high resolu-
surement, FFM, and XPS. A detailed kinetic analysis tion. In previous studies of the plasma treatment of PET, an
proved complex because of the diversity of reaction path- increase in the surface energy following treatment was found
ways involved and because several different functional to be correlated the appearance of a carbonyl component
groups are modified during the photo-oxidation reaction. in the C1s spectrum (49). The carbonyl groups are thought

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Scheme 3. Proposed Mechanism for the Photo-oxidation of PET

ARTICLE
Table 1. Comparison of Observed Results with Those Predicted from the Mechanism Predicted in Reaction
Scheme 3
0 t observation inference

C-C-C 6n (6 - x)n decrease ring hydroxylation occurs

C-C-O 2n (2+ x - y)n constant rates of chain scission and ring hydroxylation are equal
O-CdO 2n (2 + z)n increase chain scission to form aldehydes is followed by further oxidation
C-CdO 0n (y - z)n rate dependent chain scission occurs, leading to aldehyde formation

to exhibit basic character and contribute to the raising of the to ether and phenolic oxygens) and consequently there
surface free energy by increasing the acid-base component would be a decrease in aromatic carbons as one or two of
of the surface free energy. these bind to the hydroxy groups to form the hydroxy
The most significant criticism of the FFM data is that they substituted terephthalate, unless the rate of chain scission
lack the structural specificity of the XPS measurements. FFM exceeds the rate of formation of phenolic groups. The
data-at least in the present case where no effort was made, appearance of a carbonyl species in the C1s spectrum is
for example, to functionalize the probe-do not enable one expected due to the formation of the aldehyde. Finally, the
to differentiate between, for example, contributions to the contribution from the ester component should remain con-
surface free energy from carboxylate and carbonyl groups. stant. With the exception of an observed increase in the ester
In many ways, the data are analogous to contact angle component, which can be explained by the further reaction
data-the chemical structural content is limited and the of the aldehyde proposed by Grossetête et al (38), our XPS
signal is largely determined by the surface free energy. data are consistent with these findings.
Against this, the greater spatial resolution of FFM may be Vapor-phase chemical derivatization with TFAA can de-
important in other circumstances, and the evidence pre- rivatize hydroxyl groups selectively in the presence of car-
sented here that it may yield quantitative data for complex boxylic acids and carbonyl groups to a high degree (50).
polymer systems that correlate with macroscopic measure- Fluorine peaks were observed in the survey spectrum of the
ments is significant for polymer surface analysis at the fully exposed and derivatized PET, but with a very weak
nanometer scale. intensity (∼0.7 %). Contact-angle data were also obtained
Mechanism of Photodegradation of PET. If the after exposure to UV and TFAA. No significant change was
mechanism of Fechine et al. is correct (29), the number of observed from that of the exposed polymer. These data do
carbon atoms singly bonded to oxygen will tend to increase not confirm the presence of the hydroxy-substituted tereph-
(XPS would not discriminate between carbon atoms bonded thalate. However, the absence of positive confirmation does

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 not necessarily exclude the possibility of formation of a the aldehyde peak approaches a steady state suggests that
hydroxy-substituted ring product. First, it is thought to be a an equilibrium is ultimately reached in which the rate of
major product of the photo-oxidation because of the dra- chain scission is approximately equal to the rate of aldehyde
ARTICLE

matic decrease in aromatic carbon. Second, the possibility oxidation. These data thus support the validity of Scheme
that this derivatization would not proceed in the case of a 3, and suggest that ring hydroxylation and main chain
hydroxy substituted aromatic compound must be consid- scission occur with approximately equal probability.
ered because hydroxyl groups attached to aromatic rings are
less strongly nucleophilic than aliphatic alcohols (on which
CONCLUSIONS
the surface derivatization literature has largely focused). The kinetics of the photodegradation of PET at the surface
Grossetête cited the observation of an adsorption band with was observed on both the micro- and macroscale by contact
a maximum at 340 nm, corresponding to the fluorescent angle goniometry and FFM respectively. The hydrophilicity
monohydroxy terephthalate, as evidence for its formation of the surface was seen to increase as atmospheric oxygen
(an adsorption band for the dihydroxy substituted tereph- reacted with the photosensitized polymer until it reached a
thalate was noticeably absent) (38). This degradation product limiting value after ∼200 min. XPS data were then used to
was also observed in the work of Fechine et al. and Lee et elucidate the mechanism of the degradation. The photodeg-
al. who used UV absorbers to prevent its formation during radation process was shown to proceed through radicals
photodegradation (29, 30). From these data it may be formed via Norrish type I reactions, leading to a carboxylic
concluded that the main mechanism is likely to be that acid and an aldehyde, in agreement with earlier work by
proposed by Fechine leading to the monohydroxy substi- Fechine et al. (29) and Grosstête et al. (38). There was
tuted terephthalate, aldehyde, and carboxylic acid. To ex- excellent quantitative agreement between the three tech-
plain the significant increase in the ester component, it is niques when used to determine the extent of the reaction.
necessary to look at the work of Grossetête who reported The limited molecular specificity of FFM meant that for this
the further oxidation of the aldehyde to form an additional system, XPS yielded mechanistic insights with greater preci-
carboxylic acid terminus. sion. However, evidence was provided of the capacity of
Scheme 3 illustrates the proposed mechanism for the FFM to yield quantitative data on modified surfaces that
photodegradation of PET. A simple mathematical analysis correlate closely with those obtained from macroscopic
can be used to predict increases and decreases in the surface analysis methods.
contributions to the C1s peak. Suppose that the amount of
polymer at the start of the experiment is n. The amounts of Acknowledgment. C.R.H. thanks the Engineering and
Physical Sciences Research Council for a Research Student-
carbon atoms in the different bonding environments at time
ship. The authors thank Tracie J. Whittle for assistance with
t ) 0 will be as shown in Table 1. Suppose that a fraction x
the XPS measurements.
of the aromatic carbons undergoes ring hydroxylation. The
amount of aromatic ring carbon atoms (with corresponding REFERENCES AND NOTES
peak at 285 eV in the C1s spectrum) will decrease to (6 - (1) Grafstrom, S.; Neitzert, M.; Hagen, T.; Ackerman, J.; Neumann,
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