Raman Spectroscopy for Reaction

Advancement Monitoring
Application Note

Epoxy is a general term referring to epoxy resins, both the

KEYWORDS individual components and the cured results. Epoxy resins
• • Epoxide groups are a family of reactive polymer precursors and polymers
• Reaction completion that include epoxide groups. These resins are used in an
• QE Pro-Raman+ spectrometer extensive array of consumer and engineering applications
because of their durability, strong adhesion, chemical
TECHNIQUES resistance, and other specialized properties.
• Raman spectroscopy
Epoxy resins are used in the manufacture substrates including concrete and wood.
of adhesives, plastics, paints, coatings, Epoxies can stick to metal, glass, stone,
APPLICATIONS primers and sealers, flooring and other wood and some plastics, and are more
products and materials that are used in heat- and chemical-resistant than
building and construction applications. most glues.
• Reaction monitoring Most materials known as “structural”
• Kinetics analysis or “engineering” adhesives are epoxies. However, all these properties are
These high-performance adhesives are contingent on proper proportions and
• Materials analysis mixing. In this application note, we use
used to make laminated woods for decks,
walls, roofing and for other products a readily available two-part epoxy as a
that require strong bonds to a variety of model system for monitoring the kinetics
and reaction completion of industrial
processes, generally, and adhesive
US +1 727-733-2447 curing, specifically.
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Experimental Setup
The two-part epoxy used in this demonstration, Devcon® 15
Minute Epoxy, is composed of bisphenol A diglycidyl ether
resin and a polymercaptan/polyamine mixture (2,4,6-tri-
(dimethylaminomethyl)-phenol and mercaptan amine blend).
Mercaptan is an organo-sulfur compound that donates a thiol
group to the curing process. Thiols react readily with the epoxide
group and are typically used where heat cures are not pos- sible,
or a fast cure is needed.

To monitor the curing process, we used an Ocean Optics QE

Pro-Raman+ with a 300 mW, 785 nm laser (LASER-785-LAB-
ADJ-FC) and a Raman probe (RIP-RPB-785-FC-SMA) suspended
at a fixed distance over the curing epoxy. Ambient light was
excluded from the laser-sample interaction region with a black Figure 1. Devcon® 15 Minute Epoxy (1:1 resin to hardener), as a
cloth. Raman signals were acquired with 3 s acquisition time function of cure times (minutes).
and 10x averaging. Signals were acquired on the epoxy samples
immediately upon mixing and then in 2-3 minute intervals after
that. In some cases, signals were acquired the following day, The change of the 1254 cm-1 feature with time can be interpreted
but in no instance did these signals vary appreciably from those as the consumption of the free epoxide groups during the
collected at 40-45 minutes after mixing. vitrification of the epoxy. The reduction of the intensity of the
Raman feature at 2575 cm-1 shows the consumption of the
Measurements thiol in the hardener as the material reacts. The rate of the initial
Two samples of different proportions of resin and hardener were loss of the S-H feature appears to be a function of the initial
mixed, at the recommended ratio of 1:1 and at a 2:1 hardener-to- concentration of the hardener.
resin mixture. Following the mixing of the two components, the
The S-H stretch, related to the presence of thiol, is readily
curing process was monitored with Raman spectroscopy. The
observed at 2575 cm-1. In the case of the measurement of 1:1
analytical focus was principally on the epoxide and thiol features,
hardener-to-resin, the S-H feature is still present when the curing
which diminish upon curing.
process stops. Note that this sample was still slightly sticky to
Raman bands corresponding to epoxide vibrational frequencies the touch the next day, far after the 15 minute cure time assured
have been reported previously [1], with 1254 cm-1 assigned to be on the package. This result could be due to either the incorrect
the breathing mode of the epoxide ring (Figure 1). The intensity proportions of the two substances or perhaps inadequate mixing
of this peak is linearly dependent on the concentration of epoxide of the two.
groups in the resin mixture [1 and references therein]. The peak
In the 2:1 hardener-to-resin sample, the initial peak of the thiol
at 921 cm-1 is likely the epoxide ring deformation and is much
feature is slightly higher than in the 1:1 case (Figure 2). This was
weaker. The Raman peaks at 1114 cm-1, 1186 cm-1 and 1610
not evaluated for quantitative behavior, but the ratios of peak
cm-1 have been assigned to resin backbone vibrations and do not
heights seem reasonable given that in the 2:1 case, the hardener
change in intensity during the curing reaction.
accounts for 67% of the total material present (two-thirds) and
in the 1:1 case, only 50% (one-half). In this second case, there
is not enough resin to react stoichiometrically with the available
resin, and there is an appreciable amount of thiol remaining in the
product epoxy. It is not surprising that the epoxy did not cure well
in this case, either.
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 Additionally, the data markers show that onset of the reaction is
slightly accelerated when excess hardener is present. Fitting the data
in the region where S-H reactivity is the fastest (excluding the first
three points in the 1:1 case) to a simple exponential with an offset
(eq. 1), it is apparent that the kinetics of the bulk of the reaction are
the same in both mixtures with τ (1/e half-life) of 4.5 minutes. Finally,
it is also clear from the tail of both sets of data (markers) that more
unreacted S-H remains in the case where more hardener has been
added, which is reasonable because the hardener is the source of
the thiol.

Figure 2. Devcon® 15 Minute Epoxy (1:2 resin to hardener), as a Summary

function of cure times (minutes).
This brief application note details the use of Raman spectroscopy
to elucidate details of the epoxy curing process in real time. This
utility can be easily extended to other types of reactive processes,
The S-H feature (analyzed using peak area from 2487-2639 cm-1) even those that are faster than this relatively slow epoxy vitrification.
in the case of the 2:1 mix comprises about 1.36x more integrated Ocean Optics supports a line of Raman spectrometers and lasers
area than that associated with the 1:1 mix. This agrees with the that are ideal to perform this type of analysis, and the applications
fact that in the 1:1 mix, there is 50% hardener. In the 2:1, there is expertise to help you solve similar problems.
67% hardener (a 1.34x increase).

The 2:1 mixture has an appreciable amount of S-H remaining; 1:1

References
has less S-H remaining at the end of the cure. 1. Křesálek, V. and H. Vašková, “Raman spectroscopy of epoxy
resin crosslinking,” Recent Researches in Automatic Control,
Kinetics Analysis Conference Paper, May 2011.

A kinetic analysis of the S-H loss is readily performed on the data

produced with the Ocean Optics Raman system.

Behavior as a function of time of the S-H feature is shown in

Figure 3. A visual comparison of the two data traces (markers)
shows that first, there is more S-H at the beginning of the process
in the case of the 2:1 hardener-to-resin mix than in the 1:1 case.

Figure 3. Integrated areas under the S-H feature in both the

described cases; also, the exponential fits to the data.
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