a p p l i c at i o n N o t e

FT-IR Spectroscopy

Authors:
Enrique Lozano Diz
Richard Spragg
PerkinElmer, Inc.
Seer Green, UK

Analysis of UV-
Introduction
Curable Resins There are on the market an increasing number of

by FT-IR special adhesives, coatings and sealants that allow

curing in just few seconds upon exposure of the
resin to the appropriate radiation. Those adhesives
are gaining great interest in specialized applications (medical, glass and lighting
repairs, rapid prototyping, etc.) because they allow accurate and immediate
bonding and avoid some of the more problematic aspects like toxicity, polluting
and organic solvent formulations of conventional adhesives.

Typically these resins cure by using UV and, more recently, visible radiation to
initiate a photochemical reaction that proceeds to the curing of the resin. Many
parameters may affect the speed and depth of the curing, including the intensity
of the illumination, the spectral range used during the curing (single wavelength
or range of wavelengths), thickness of the curing area, distance to the light
source, transparency of the substrate the light must pass through, and many
other environmental parameters, such as nature of the material to bond and
presence of external oxidizing materials, that affect the time of hardening the
adhesive.

It is important to have a good understanding not just of the speed of cure but
also of the mechanism of the curing process. One way to investigate and quantify
the curing process is to measure spectroscopic changes of the functional groups
involved in curing. The formation and destruction of functional groups is easily
followed by rapid scan FT-IR. Determining relative peak areas can help to under-
stand the kinetics process and identifying the presence of reaction intermediates
can help to understand how changing conditions affect the curing process.
 Many photo-curable adhesives, coatings and sealants are reach a peak during the most rapid phase of the reaction
based on acrylates. The curing process involves a photo- Figure 5. Thus the second PC can provide information about
initiator that forms free radicals when exposed to UV the intermediate stage of the reaction that is not available
radiation. The radicals react with acrylate monomers, from DSC measurements.
opening the double bonds to form further radicals. These
react with further acrylate molecules, building up chains Experimental
with cross-linking to provide a network that gives mechanical
Spectra were measured with a Frontier™ FT-IR spectrometer, a
strength to the cured product. The kinetics of the curing
research grade instrument with fast scanning, collecting up
process depends on the generation of the reaction inter-
to 16 scans/second which is more than sufficient to follow
mediates, so their detection, characterization and quantification
reactions with half-lives of a few seconds. Data collection
are fundamental to understanding the properties of a resin.
was controlled using PerkinElmer® TimeBase™ software. The
same software can generate profiles of specific band intensities
Monitoring the reaction or intensity ratios as a function of time. Data were also
Numerous techniques have been used to study the curing analyzed with Principal Components Analysis (PCA) using
process. Differential scanning calorimetry (DSC) measures the Quant+ program.
the heat produced by the reaction and so can determine the
degree of cure as the reaction proceeds. Dynamic mechanical The most convenient approach to making these measure-
analysis (DMA) measures the modulus of the resin so that ments is to use a diamond ATR accessory. The liquid resin is
the properties of the cured material can be related to the placed on the diamond crystal and illuminated from above.
degree of cure. FT-IR spectroscopy provides more chemical We used a UATR accessory with a single-bounce diamond
information than DSC because many absorption bands are crystal (Figure 1). The UV source was an Omnicure® S2000
measured. For example in an acrylic resin the curing process and fiber-optic light guide with variable output, providing
involves the disappearance of C=CH2 groups in the monomer. radiation from 320 to 500 nm.
The progress of this can be followed by measuring the
The resin was Loctite® 3494, a clear light cure adhesive used
intensity of absorption bands that are specifically associated
for bonding glass and plastics.1 It contains a mixture of acry-
with these groups, such as the C=CH2 twisting at 812 cm-1
late and methacrylate monomers with a benzoyl phosphine
or the =CH2 deformation near 1400 cm-1. No bands are
oxide initiator. We verified that curing was extremely slow
completely free from overlap which hinders kinetic analysis
under the background laboratory illumination.
but qualitative measurements are straightforward. Figure
4 shows the decay in absorbance of the 812 cm-1 band A drop of resin was placed on the crystal and the UV
for two different UV intensities. However disruption of the illumination was switched on a few seconds after starting
double bond is only the first step in the reaction as radicals data collection. Spectra were recorded with 16 scans/
produced by photoinitiation react with acrylate groups and second. Two illumination levels were used, 10 and 50%
cross-linking proceeds. of the maximum, corresponding to outputs of 75 and
430 mW at 365 nm.
An overview of the reaction is obtained by applying principal
components analysis (PCA) to the data. For a simple reaction
there should be a single
principal component
representing the difference in
spectra between the starting
material and the product.
For the resin studied here
we consistently find two
principal components. The
first PC accounts for about
99% of the variance while
the second PC accounts
for the remaining variance
except noise. The scores for
the first PC correspond to
the overall reaction, chang-
ing monotonically, but the Figure 1. Frontier spectrometer with Figure 2. Typical TimeBase screen with intensity profiles from resin curing.
ATR accessory.
scores for the second PC

2
Results
Spectra of the initial and fully cured resins are seen in Figure 3.
Typical intensity profiles derived from the =CH2 twisting
vibration at 812 cm-1 are shown in Figure 4. The profiles
are taken from 800 scans obtained in 50 seconds. The
reaction is much faster with the higher illumination level,
being nearly complete after 10 seconds.

The results from PCA for the two illumination levels are seen
in Figure 5. Clearly they show the same pattern, the scores
on PC2 peaking in both cases at the time that scores on PC1
are changing most rapidly.

Discussion
These data clearly show the suitability of the Frontier
Figure 4. Intensity profiles of the =CH2 twisting band at 812 cm-1 for different
spectrometer with TimeBase software for studying the UV illumination levels.
curing process. PCA demonstrates that the data contain
more information than can be obtained from UV-DSC
measurements as an intermediate process is revealed.
The complexity of this commercial formulation makes inter-
pretation difficult but investigation of simpler systems would
be feasible.

Using ATR is very convenient and allows UV illumination

without an intervening window. One limitation is that curing
is being measured only for the layer in contact with the
crystal. In this case the amount of the resin as uncontrolled
but curing at different depths can be studied by varying the
thickness of the resin layer.

Reference
1. Henkel Ltd., Hemel Hempstead, England.

Figure 5. Principal component scores for resin curing at different illumination

levels.

Figure 3. ATR spectra of Loctite® 3494 resin before and after curing.

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