SPE 106160
Kinetic Parameters for Dilute Epoxy Resins Measured by Nuclear Magnetic
Resonance Spectroscopy
Richard D. Rickman, SPE, J. Michael Wilson, SPE, and Jim D. Weaver, SPE, Halliburton
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 28 February–2 March 2007.
This paper was selected for presentation by an SPE Program Committee following review of
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presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
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Abstract
Thermosetting resins are employed in a wide variety of
oilfield applications. The development of dilute resin
formulations offers several advantages over conventional resin
systems and new resin applications are making increasing use
of dilute formulations. Knowledge of the thermodynamic
properties of the resin system is essential to ensure that they
perform as expected. We report here on the use of nuclear
magnetic resonance, NMR, to measure activation energies,
enthalpies, entropies, and frequency factors for the curing of a
diglycidylether bisphenol A epoxy resin with a modified
cycloaliphatic amine hardener. Results calculated with this
technique are presented here and are in good agreement with
values calculated using more conventional techniques.
Introduction
Epoxy resins are an important subset of thermosetting
polymers because of to their relatively low cost, good
performance characteristics, and application versatility. They
are used in technical applications that range from structural
adhesives, to coatings and composite matrices. Applications
for curable resins in downhole operations are also numerous
with their use dating back to the early 1960s.1 Four of these
applications are discussed below.
Near-Wellbore Consolidation
An alternative to conventional sand control completions using
gravelpacks and screens is chemical consolidation. In this
approach, a curable resin is injected into the region
surrounding the near-wellbore, followed by an afterflush to
displace excess resin from the pore spaces.2 As the resin cures,
the formation is transformed into a hardened, permeable mass.
An alternative to this approach is to inject the resin into the
formation without the subsequent afterflush.3 Permeability in
the near-wellbore area is dramatically reduced so the zone
must be fractured to provide conductivity to the productive
zone.
Proppant Flowback Control
Proppant flowback from fracture-stimulated wells can cause
problems with both surface and subsurface equipment.
One solution that can reduce or eliminate proppant
flowback is to coat the proppant with a curable liquid resin.4
The coated proppant is transported to the fracture during
stimulation operations. As the resin cures, the proppant is
consolidated. This helps prevent the production of the coated
proppant with the produced fluids. This approach is used on
new completions. Curable resins can also be used as a
proppant flowback remediation treatment on previously
fracture-stimulated wells.
In this approach, a dilute form of the curable liquid resin is
injected into the fracture, followed by an afterflush to re-
establish the fracture conductivity.5 The thin coating of resin
on the proppant cures and locks the proppant into a hardened,
permeable proppant pack.
Diagenetic Degradation of Proppant Pack/Fracture
Face
An issue that has recently been brought to the attention of the
oil field community is the diagenetic degradation of the
proppant pack and/or the fracture face.6 In short, the
introduction of materials foreign to the reservoir, i.e. proppant
and frac fluids, can disturb the geo-chemical equilibrium that
exists in the reservoir. This can result in the rapid production
of new minerals that can appear as overgrowth on the
proppant itself or as porosity-filling materials. As a result of
this process, fracture width can be reduced and porosity lost;
both conditions will result in conductivity loss. It has been
shown that by coating the proppant and fracture face with a
thin resin coating this degradation mechanism can be reduced.
Formation Fines Stabilization
Yet another application for liquid curable resins is to stabilize
formation fines. In this case a very dilute formulation of the
resin is injected into the formation.7 As the resin cures, a thin
coating is deposited onto the formation materials, essentially
locking the fines into place and thus preventing their
migration. A key benefit to using a low resin concentration
formulation in this application is that no afterflush is required.
Key to obtaining desired performance of the liquid resin
systems downhole is achieving proper cure after placement.
2 SPE 106160
Therefore knowledge of certain thermodynamic properties of
the resin is requisite. If the resin cures too rapidly, several
problems can arise: (1) the resin can cure in the tubulars
resulting in their plugging; (2) the resin may cure in the
formation before having a chance to coat, thus plugging the
pore throats; or (3) the resin may cure on the proppant before
fracture closure and grain-to-grain contact has been initiated;
in this case, the proppant pack will not consolidate and
proppant flowback control is not assured. There are several
methods routinely used to measure the thermodynamic
properties of resin systems.
Measurement of Thermodynamic Parameters
Numerous analytical techniques are available to measure
thermodynamic parameters associated with the curing of resin
systems. The most widely used is differential scanning
calorimetry (DSC). DSC is a technique wherein the amount of
heat required to increase the temperature of the sample and a
reference is recorded as a function of temperature. When the
sample undergoes a change in its physical state, i.e. curing, the
amount of heat required to maintain the temperature changes
depending on whether the process is endo- or exothermic. This
difference can be plotted against temperature and
mathematical treatment of this curve can reveal information
such as the enthalpy of reaction, ΔHrxn, the activation energy,
Ea, and the pre-exponential or frequency factor, ln (A), for the
reaction.
In addition to DSC, other techniques include dynamic
mechanical analysis (DMA), differential thermal analysis,
DTA, and to a much lesser extent nuclear magnetic resonance
(NMR). 8, 9
Many of the previous studies of resin curing by NMR
were geared to elucidating structural information about
intermediate and final reaction products. It is believed that this
is the first application of this technique to measure
thermodynamic parameters for the resin system curing process
for oilfield applications.
Resin systems where the bulk of the formulation consists
of non-reactive diluents (up to 98% v/v) pose a special
problem for conventional DSC. The endotherm from the
evaporation of the diluent very often masks the exotherm from
the curing resin. Pressure cells can compensate for this;
however, in a sample that weighs 10 mg, only 2-3% may be
curable resin.
With these limitations in mind, we illustrate how NMR can
be used to measure certain thermodynamic parameters
associated with the curing of a highly diluted epoxy-amine
resin system.
Experimental
Materials
The epoxy/hardener system used here is a diglycidylether
bisphenol A (DGEPA) -type resin along with a modified
cycloaliphatic amine hardener. Additives include viscosity
modifiers, coupling agents, and surfactants to aid in wetting
the substrate. This system is designed to be used in wells with
bottomhole temperatures below approximately 105oC.
A suite of resin concentrations were investigated ranging
from 2.5% to 25%. The resin was diluted in a non-reactive
solvent, i.e. the diluent was not consumed during the curing
process. The (resin-hardener)/diluent samples were prepared
from a single stock solution and placed in NMR tubes. The
tubes were sealed under vacuum and stored in a Dewar filled
with liquid nitrogen to retard the curing process until they
were ready for analysis.
NMR
The natural abundance 13C DEPT 135 (distortionless enhanced
by polarization transfer) experiment10 was chosen to determine
the kinetics for resin polymerization after some initial
exploratory investigations. This experiment was chosen for
several reasons. In the 13C DEPT 135 experiment, only the
carbon atoms with attached hydrogens appear in the spectra.
Carbon atoms with no attached hydrogens disappear and, more
importantly, resonances from carbons with either CH or CH3
appear to be “up,” while all CH2 resonances are 180 degrees
out of phase or “down.” This greatly simplified spectral
interpretation and integration of the spectra. At each
temperature investigated, the probe tune and match was
performed on a sample of the resin and solvents but no
hardener. Field homogeneity adjustments (shimming) were
also made on this sample at the test temperature. Once the
resin solutions were placed in the probe and brought to the
desired test temperature, a quick re-shimming operation was
performed and an automated acquire program was started to
record the spectra with time. The time between each
acquisition period (wait time) was adjusted depending upon
the particular resin solution and temperature. As the
experiments were conducted at the higher temperatures, hence
faster rates, the wait time between data acquisition was
shortened.
Because this is a natural abundance 13C experiment,
multiple scans were required for each data point collected.
Typically, a total of 168 scans was adequate to acquire data
with good signal to noise ratio and suitable for integration.
The acquisition of each data point required 20 minutes to
complete; the wait time between acquisitions varied from 20
minutes to zero (for the higher temperatures).
At the onset, line broadening was expected, in the carbon
resonances of molecules that had already reacted, because of
the expected shortening of the longitudinal relaxation time
(T1) and introduction of small variances of chemical shift. In
fact, the expectation was to see the unreacted monomer signals
perched on top of broad polymer humps. This was not
observed in any of the spectra.
Integration of the aromatic carbon resonance signals was
performed using Bruker BioSpin TopSpin® software and,
comparing this against the internal standard, enabled the
polymerization kinetics to be determined by measuring the
disappearance of the aromatic “monomer” carbons with time.
Results and Discussion
Fig. 1 shows a 13C DEPT 135 NMR spectrum of the
epoxy/amine system. As the resin system cures, the NMR
signal from the aromatic carbon decreases, as seen in Fig. 2.
The cured resin deposits, as a thin film coating, on the wall of
the NMR tube. The NMR signal decreases until all of the
epoxy is consumed (the amine hardener is in excess). To
follow the curing process we calculate the ratio of the peak
areas of signals arising from the resin, IRes, to that of an
SPE 106160
internal standard, IIPA. This value is then plotted against time.
The cure rate constant for the reaction, k, is then:
I Re s
d
I IPA
k =− …………………………...…………….(1)
dt
with k having units of s-1. Figs. 3–5 are plots generated in this
manner for three different temperatures. In this case, the 2.5%
resin solution was used.
The rate constant is assumed to have an Arrhenius
dependence on temperature thus the following equation holds:
k = Ae( − Ea / RT ) ………………………………………(2)
where A is the pre-exponential or frequency factor, Ea is the
activation energy, R is the universal gas constant, and T is the
temperature in Kelvin. By plotting ln (k) against the reciprocal
of the temperature (for at least three different temperatures) an
Arrhenius plot is generated. Fig. 6 is such a plot for the 2.5%
curable resin system.
Linear regression gives the slope, Ea/R, and the intercept,
ln (A). Table 1 summarizes this information for all four
curable resin formulations tested. These values are in good
agreement with previously published values for the
epoxy/amine reaction. 11–13
Recall that Ea is the minimum kinetic energy two colliding
molecules must have in order to react. The activation enthalpy,
ΔHa, is the difference between the transition state of the
reactants and their ground state. In general, ΔH a ≈ Ea .
The entropy of activation, ΔSa, and ΔHa can be calculated
using the Eyring equation which has the following form:
k ΔH a 1 k ΔS
ln( ) = − * + ln( b ) + a …………….(3)
T R T h R
where kb is Boltzmann’s constant and h is Plank’s constant.
An Eyring plot for the 2.5% curable resin system is given in
Fig. 7. By plotting ln (k/T) versus 1/T a linear regression
yields a slope equal to -ΔH/R and an intercept equal to (23.76
+ ΔS/R). Table 2 gives the entropy and enthalpy of activation
for the curing of the epoxy/amine resin system at various
epoxy concentrations. Using the following equation:
ΔGa = ΔH a − T ΔS a ……………………………..….(4)
the temperature-dependent free energy of activation ΔGa, can
be calculated for a range of temperatures. For all four cases
studied here, the contribution from T ΔS a is relatively minor,
so ΔGa ≈ ΔH a .
An interesting observation is made when plotting Ea as a
function of the resin concentration in the dilute system (Fig.
8). For dilute systems (5% or less resin), a decrease in the
activation energy is noted. Two mechanisms are generally
accepted for the epoxy/amine curing reaction, one is
noncatalytic and the other is catalytic.11,13 A possible
explanation is that in systems where the majority of the
formulation is a nonreactive diluent, the contribution from
noncatalytic processes is relatively minor. Activation energies
3
for the autocatalytic reaction have been reported that are 10 to
25% lower than the noncatalytic reaction activation energy,
for this case the ratio of activation energies for the 2.5% resin
system to 25% resin system is 0.81, which is in agreement
with the previously published values.11,14,15 The value for ln
(A), Fig. 9, also decreases with decreasing concentration; this
is to be expected as the probability for two reactant molecules
to collide decreases as their concentration diminishes.
Conclusions
We report here thermodynamic values calculated using NMR
for the curing of DGEBA with a cycloaliphatic amine
hardener. Rate constants, activation energies, frequency
factors, and activation entropies and enthalpies were
calculated for this reaction in formulations containing 2.5% to
25% resin. The values for the higher concentrations compare
favorably with previously published data.
For very dilute solutions, lower activation energies were
measured. One possible explanation is that in dilute resin
systems the autocatalytic cure mechanism dominates.
Acknowledgements
The authors would like to thank the management of
Halliburton for its support of these studies and permission to
publish this paper.
References
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4 SPE 106160

and their Effects on Final Resin Properties”, Brit. Poly. J. 22,
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Table 1—Measured Activation Energy

and Pre-Exponential Factors
Resin System Ea ln (A)
(% DEGBA Resin) (kJ/mol) (rate/[min-1])
25 69 23
6.25 67 23
5 65 20
2.5 55 15

Table 2—Calculated Enthalpies and Entropies

Resin System ΔHa ΔSa
(% DEGBA Resin) (kJ/mol) (J/(mol∗K))
25 66 -61.3
6.25 63 -62
5 62 -88
2.5 52 -133

O
DGEBA CH3 O OH
H 2C CH O
H
C C
H
C O CH CH 2
IPA
C C C C C C CH
H2 H2
CH3 CH3 CH
CH3
HC CH HC CH
C
H
C
H
IIPA

IRes
Relative Intensity

Concentration, ppm

Fig. 1—13C DEPT135 spectrum of the epoxy/hardener system with IPA.

SPE 106160 5

Fig. 2— 13C DEPT135 spectra of the epoxy/hardener system at different time during the experiment.

Fig. 3— Ratio of the peak areas of DGEBA and internal standard as a function of time, at 30°C and 2.5% resin.
6 SPE 106160

Fig. 4—Ratio of the peak areas of DGEBA and internal Fig. 5—Ratio of the peak areas of DGEBA and internal standard as
standard as a function of time, at 40°C and 2.5% resin. a function of time, at 60°C and 2.5% resin.

Fig. 6—Arrhenius plot (ln(k) vs. 1/T) for the 2.5% resin Fig. 7—Eyring plot (ln(k/T) vs. 1/T) for the 2.5% resin formulation.
formulation.

Fig. 8—Ea as a function of resin concentration. Fig. 9—ln(A) as a function of resin concentration.