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Cure kinetics of several epoxy–amine systems at ambient and high

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Article in Journal of Coatings Technology and Research · March 2014

DOI: 10.1007/s11998-013-9565-4

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J. Coat. Technol. Res., 11 (2) 143–157, 2014
DOI 10.1007/s11998-013-9565-4

Cure kinetics of several epoxy–amine systems at ambient

and high temperatures
Monoj Pramanik, Eric W. Fowler, James W. Rawlins

 American Coatings Association 2014

Abstract Epoxy-crosslinker curing reactions and the system compared to control supported the catalytic
extent of the reactions are critical parameters that effect of CSR particles on the epoxy-amine reaction of
influence the performance of each epoxy system. The epoxy prepolymer and amine blends.
curing of an epoxy prepolymer with an amine func-
tional group may be accompanied by side reactions Keywords Epoxide, Hardener, Crosslinker,
such as etherification. Commercial epoxy prepolymers Core–shell rubber particles, Near IR
were cured with different commercial amines at
ambient as well as at elevated temperatures. Singu-
larly, only epoxy–amine reactions were observed with Introduction
diglycidyl ether of bisphenol-A (DGEBA)-based epox-
ides in our research even upon post-curing at 200C. Epoxy prepolymers are widely used in coatings, adhe-
Etherification side reaction was found to occur at a sives and composites because of their ease of process-
cure temperature of 200C in epoxides possessing a ing, excellent thermal stability, and range of
tertiary amine moiety. A combined goal of our mechanical properties.1–5 Epoxy–amine thermosetting
research was to understand the effect of tougheners glassy polymers are inherently brittle due to their
on the cure of epoxy–amine blend. To discern the highly crosslinked network structure.6–9 In spite of
effect of tougheners on the cure, core–shell rubber having higher mechanical strength, resistance to defor-
(CSR) particles were incorporated into the epoxy– mation, and transition temperature, inherent brittle-
amine blend. It was observed that CSR particles did ness limits epoxy thermosetting glasses to be used in
not restrict the system from proceeding to complete the fields where certain toughness is required. Degree
reaction of epoxy moieties. Besides, CSR particles of crosslinking, network connectivity, chain packing,
were found to accelerate the epoxy-amine reaction at a and molecular backbone of monomers are dominant
lower level of epoxy conversion. The lower activation parameters that drive material properties of epoxy
energy of epoxy–amine reaction of CSR incorporated thermoset glasses. The extent of cure dictates the
degree of crosslinking, network connectivity and sub-
This paper was presented at the 40th Annual International sequently, the epoxy–amine thermoset properties. It is
Waterborne, High-Solids, and Powder Coatings Symposium, therefore important to accurately quantify the degree
held February 4-8, 2013 in New Orleans, LA. of conversion and connectivity during practical cure
conditions.
Electronic supplementary material The online version of this
article (doi:10.1007/s11998-013-9565-4) contains supplementary
Tougheners incorporated to enhance toughness of
material, which is available to authorized users. epoxy thermosets may affect cure of epoxy prepoly-
mer.10–18 Tougheners are either preformed particles
M. Pramanik (&), E. W. Fowler, J. W. Rawlins that remain insoluble throughout the entire period of
School of Polymers and High Performance Materials, cure or soluble polymers that phase separate only after
The University of Southern Mississippi, 118 College a certain extent of cure of epoxy–amine blend. Epoxy–
Drive #5217, Hattiesburg, MS 39406-0001, USA amine crosslinker cure commonly involves four reac-
e-mail: [email protected] tions: epoxy–primary amine, epoxy–secondary amine,
E. W. Fowler epoxy–hydroxyl etherification, and epoxy–epoxy hom-
e-mail: [email protected] opolymerization that are governed by their energy

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J. Coat. Technol. Res., 11 (2) 143–157, 2014

barriers of 55–60,  71,  104, and  170 kJ/mol, Paraloid EXL 2691A, a commercial core–shell mate-
respectively.19,20 Energy barriers for these reactions rial (comprised of a styrene–butadiene core with a
may vary depending on the physical state and chemical poly(methyl methacrylate) shell) was donated by
structures of monomers. Rohm & Haas (Dow Chemical). 2-Methylpentanedi-
The extent of reaction between an epoxy prepolymer amine (MPMD) and polyetheramine are aliphatic
and curing agent is usually determined from the cure amines in liquid form, while 4,4¢-DDM and 3,3¢-DDS
kinetics acquired via differential scanning calorimetry are aromatic amines in solid form. All chemicals were
(DSC) and infrared (IR) spectroscopy.21–26 DSC cure used as received unless mentioned otherwise. Basic
kinetics provide only the overall extent of reaction chemical structures of amine crosslinkers are shown in
without delineating the individual component reac- Fig. 1. Amine hydrogen equivalent weight (AHEW) as
tions.21–23 Monitoring of cure kinetics via mid-IR supplied of MPMD, polyetheramine, 4,4¢-DDM, and
(600–4000 cm1) is complicated because of overlapping 3,3¢-DDS are 29.34, 60, 51.10, and 63.26, respectively.
bands for epoxy–amine systems.24 On the other hand,
the near infrared (NIR) spectroscopy (4000–8000 cm1)
Characterization
spectrum of the epoxy-amine system is characterized by
distinct bands for epoxide, primary amine, phenyl,
Differential scanning calorimetry (DSC)
combined primary–secondary amine, and hydroxyl
groups.25–27 Besides, NIR spectroscopy is also used to
DSC was conducted to (i) select cure condition, (ii)
determine epoxy content and epoxy equivalent weight
determine Tg0 (when extent of epoxy reaction is zero),
of epoxy resins.28,29 The concentration of epoxy, primary
(iii) measure Tg (or Tg¥, when epoxy reaction is 100%),
amine, and secondary amine groups can be determined
(iv) determine activation energy of the epoxy–amine
from the NIR spectrum via Lambert–Beer’s law. The
reaction as well as the effect of core–shell rubber
extent of epoxy–amine reaction can then be quantified
(CSR) toughener on activation energy. DSC analysis
from the concentration of epoxy, primary amine, and
was conducted on a DSC Q 2000 from TA Instruments
secondary amine moieties.
and the data was processed via Universal Analysis 2000
Curing an epoxy prepolymer with curing agents of
software. Ten grams of epoxy prepolymer and stoichi-
various molecular structures yields epoxy thermosets of
ometric amount of amine crosslinker were weighed out
varying glass transition temperatures (Tgs). Four tetra-
in a scintillation vial and mixed in a centrifugal speed
functional crosslinkers were selected to react with a
mixer (FlackTek, Inc.) for 3–5 min at ambient condi-
commercial epoxy prepolymer at ambient temperature
tions at 2700 rpm. In the case of systems with tough-
to 200C and evaluated to quantify the extent of epoxy,
eners, CSR particles (loaded into the epoxy
primary amine, and secondary amine conversion as well
prepolymer at 5 wt% based on stoichiometric formu-
as side reactions, if any. In addition, the effect of core–
lation) were mixed at 100C at about 1800 rpm for 2 h,
shell rubber (CSR) toughener particles on the cure of
and cooled to ambient before blending with stoichi-
epoxy–amine blend was also investigated.
ometric amount of amine, as mentioned above. About
7.5 mg of the blend was weighed into a closed
aluminum pan. To determine the appropriate cure
Experimental condition, each sample was heated at 2C/min. To
determine Tg0, the epoxy–amine blend was analyzed
Materials via DSC at 10C/min. For determining the activation
energy, each blend was heated at multiple heating rates
Epoxy prepolymers used in this study are detailed in (1, 1.5, 2, 2.5C/min). To determine Tg¥, each epoxy–
Table 1. The basic chemical structures of epoxy pre- amine blend was cured in a convection oven at
polymers used in this investigation are shown in Fig. 1. different temperatures (shown in Table 2) and ana-
3,3¢-Diaminodiphenylsulfone (3,3¢-DDS) of 98% purity lyzed via DSC at a heating rate of 10C/min. Each DSC
was purchased from TCI. 4,4’-Diaminodiphenylmeth- analysis was conducted in a nitrogen environment.
ane (4,4¢-DDM) (97% pure) and 2-methylpentanedi- The average activation energy for each epoxy–
amine (99% pure) were purchased from Acros amine system was determined using the Kissinger
Organics and Sigma-Aldrich, respectively. Jeffamine equation, which is expressed as30:
D230 (polyetheramine) was supplied by Huntsman.    
b AR EK
ln ¼ ln þ ð1Þ
TP 2 EK RTP
Table 1: Detail of epoxides/epoxy prepolymers used
Epoxy Supplier Physical EEW Functionality where b is heating rate, A is preexponential factor, R is
prepolymers state (g/eq) universal gas constant, EK is activation energy of the
reaction, and TP is peak temperature at which the
DGEBA- Momentive Liquid 185–192 2
reaction rate is maximum. The plot of ln(b/TP2) vs 1/TP
based
gives a straight line. The activation energy was calcu-
TGAP-based Huntsman Liquid 95–106 3
lated from the slope of the straight line of this plot.

144
 J. Coat. Technol. Res., 11 (2) 143–157, 2014

CH3 OH CH3 O
H H
C CH CH2 O O CH2 CH CH2 O O CH2 C C
H O H
CH3 CH3 H
n

Diglycidyl ether of bisphenol-A (DGEBA)-based epoxy prepolymer

O
N
O
O
O

Triglycidyl m-aminophenol (TGAP)-based epoxide

H2N NH2
O
H2N NH2
CH3 CH3
x

2-Methylpentanediamine (MPMD) Polyetheramine

NH2
O
H2N CH2 NH2 S
O
H2N

4,4'-Diaminodiphenylmethane (4,4'-DDM) 3,3'-Diaminodiphenylsulfone (3,3'-DDS)

Fig. 1: Basic chemical structures of epoxy prepolymers and amine crosslinkers

values to develop Tg vs conversion (x) plot. The extent

Table 2: Dynamic DSC condition for the determination of reaction (pc) at the gel point often is expressed as32
of Tg¥ of epoxy–amine blend (same condition was
applied when system had CSR particles)
1
Sample Temperature (C) and time (h) pc ¼    1=2 ð4Þ
r fw;A  1 fw;B  1
DGEBA and MPMD RT (12 h) + 135C (2 h)
DGEBA and polyetheramine 60C (4 h) + 125C (2 h) where fw,A and fw,B are weight-average functionalities
DGEBA and 4,4¢-DDM 90C (4 h) + 200C (2 h) of A and B functional groups, respectively, and r is the
DGEBA and 3,3¢-DDS 125C (6 h) + 200C (2 h) stoichiometric imbalance. In this study, the value of
TGAP and 3,3¢-DDS 100C (6 h) + 200C (2 h) r for each system was 1 because of stoichiometrically
balanced epoxy–amine blend.

Tg at any extent of reaction was calculated employ-

Near IR (NIR) spectroscopy
ing Tg0 and Tg¥ in the following equation31:

Tg  Tg0 kx To prepare NIR specimens, amine was solubilized in

¼ ð2Þ epoxy prepolymer. MPMD and polyetheramine are
Tg1  Tg0 1  ð1  kÞx liquids and soluble in DGEBA-based epoxy prepoly-
mer at ambient. Stoichiometric amounts of MPMD
where x and k are extent of reaction and adjustable and polyetheramine were mixed individually with
parameter. k varies between 0 and 1. The value of DGEBA-based epoxy prepolymer using the same
k = 0.487 was found to be in good fit for bifunctional procedure as was applied for the preparation of DSC
DGEBA-based epoxy prepolymer system.31 The value samples. 3,3¢-DDS and 4,4¢-DDM are solids and
of k of an epoxy–amine system can be calculated using insoluble in DGEBA-based prepolymer at ambient.
an equation as31 Stoichiometric amount of 3,3¢-DDS was added to
preheated DGEBA-based epoxy prepolymer at
DCp1 Tg0 125C in an oil bath and stirred mechanically until
k¼ ¼ ð3Þ
DCp0 Tg1 the mixture turned transparent (30 min). Stoichiom-
etric blends of DGEBA-based epoxy prepolymer with
where DCp¥ and DCp0 are change in isobaric heat 4,4¢-DDM and TGAP-based epoxy prepolymer with
capacity at Tg¥ and Tg0, respectively. In our study, k 3,3¢-DDS were prepared similarly at 60 and 100C,
was calculated for each system using their Tg0 and Tg¥ respectively. To observe the effect of CSR particles on

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J. Coat. Technol. Res., 11 (2) 143–157, 2014

the cure, paraloid-powdered CSR particles were dis- Transmission Electron Microscopy (TEM)
persed mechanically in epoxy prepolymer as men-
tioned in the DSC sample preparation. Amine Particle size of core–shell rubber (CSR) materials was
crosslinkers were solubilized/blended in stoichiometric determined by TEM analysis on a JEOL JEM Trans-
amount employing the same procedure as mentioned mission Electron Microscope. Powder CSR materials
when the system did not have CSR particles. were embedded in an epoxy matrix and a solid sample
For NIR analysis, the required amount of epoxy–amine was sliced into thin slices of 70-nm thickness using a
blend was placed between two 32-mm salt plates using a diamond knife. The thin slices were stained with OsO4
0.2-mm Teflon spacer and loaded into a programmable solution.
thermal heating cell of a Nicolet 6700 FTIR Analyzer
from Thermo Scientific equipped with an InGaAs detec-
tor, CaF2 beam splitter, and a quartz-halogen source. Results and discussion
Absorption spectra were recorded between 4000 and
8000 cm1 (32 scans, resolution 4 cm1) by operating the Figure 2 shows DSC exotherms of stoichiometric
instrument in transmission mode and analyzed via blends of (a) DGEBA-based epoxy prepolymer and
OMNIC version 8.0 software. The epoxy, primary amine, MPMD, (b) DGEBA-based epoxy prepolymer and
and secondary amine concentrations were determined polyetheramine, (c) DGEBA-based epoxy prepolymer
from the areas under their respective bands using Lam- and 4,4¢-DDM, (d) DGEBA-based epoxy prepolymer
bert–Beer’s law while the total amine hydrogen concen- and 3,3¢-DDS, and (e) TGAP-based epoxy prepolymer
tration was calculated from the summation of primary and and 3,3¢-DDS. It was observed that the epoxy–amine
secondary amine concentrations. reaction in DGEBA-based epoxy prepolymer and
MPMD blend began at 10C while the same reaction
Background of application of NIR spectroscopy was found to occur at 35C in DGEBA-based epoxy
prepolymer and polyetheramine blend. The higher
Lambert–Beer’s law is expressed as33: reaction initiation temperature of polyetheramine with
DGEBA-based epoxy prepolymer relative to that of
  DGEBA-based epoxy prepolymer with MPMD is
I0 attributed to the presence of the polyether component
A ¼ log10 ¼ ebc ð5Þ
It in the polyetheramine backbone. The structural effect
of crosslinker which includes the spatial crowding,
where A, I0, It, e, b, c are absorbance, intensity of incident electron withdrawing/donating, amine hydrogen equiv-
radiation, intensity of transmitted radiation, molar alent weight has been discussed in the literature.34,35 In
extinction coefficient, or molar absorptivity MPMD, primary amine (–NH2) is connected to
(L mol1 cm1), path length of radiation passed primary carbon while amine (–NH2) is attached to
through the sample and molar concentration secondary carbon in the selected polyetheramine,
(mol L1), respectively. The molar extinction co-
efficient is a unique property of each material/
functional group and is widely used for quantitative 4.50
determination. Specifically measuring the epoxy and a
b
amine volume concentrations in an epoxy–amine c
mixture is a challenging task as varying combinations 3.50 d
and extent of reaction for the liquid epoxy blend with a e
Heat flow (mW)

crystalline solid but soluble amine. Besides, the physical 2.50

state of epoxy–amine blend shifts toward a glassy solid
from liquid. Equation 5 can be simplified to:
1.50
A ¼ ac ð6Þ
0.50
Exo

where a = eb, a is referred to as molar absorptivity

(kg mol1) and c is molar concentration in mol kg1
instead of mol L1. As molar absorbance (A) is an –0.50
additive property, equation (6) for n components can –20 10 40 70 100 130 160 190 220 250 280

be written as Temperature (°C)

X
Fig. 2: Dynamic DSC exotherms of (a) DGEBA-based
A ¼ A1 þ A2 þ A3 þ A4 þ   An
ð7Þ epoxy prepolymer and MPMD, (b) DGEBA-based epoxy
¼ a1 c 1 þ a2 c 2 þ a3 c 3 þ a4 c 4 þ    þ an c n prepolymer and polyetheramine, (c) DGEBA-based epoxy
prepolymer and 4,4¢-DDM, (d) DGEBA-based epoxy pre-
P polymer and 3,3¢-DDS and (e) TGAP-based epoxy prepoly-
where A is total absorbance (i.e., combined band mer and 3,3¢-DDS (each system was blended in
area) of components 1 to n. stoichiometric proportions and heated at 2°C/min)

146
 J. Coat. Technol. Res., 11 (2) 143–157, 2014

which may hinder nucleophilic attack of NH2 in 4600–4700 cm1 in aromatic amines, DGEBA-based
polyether amine to epoxide as a result of spatial epoxy prepolymer, and TGAP-based epoxy prepoly-
crowding. Lower amine hydrogen equivalent weight mer.
(AHEW) of MPMD (AHEW = 29) compared to the
selected polyetheramine (AHEW = 60) causes higher
concentration of epoxides and amines in stoichiometric Determination of epoxy, primary amine, secondary
formulation for a particular amount of blend. In amine, and total amine hydrogen concentration
addition, ether (–O–) in polyetheramine act as hydro-
gen-bond acceptor which slows down the nucleophilic Epoxy, primary amine, and secondary amine concen-
addition reaction between amine and epoxide.36,37 trations were determined from their respective peak
Epoxy–amine reaction in DGEBA-based epoxy pre- areas in their NIR spectra by applying Lambert–Beer’s
polymer blend with 4,4¢-DDM, DGEBA-based epoxy law. Each epoxy–amine system studied contains a
prepolymer system with 3,3¢-DDS, and TGAP-based phenyl band at 4622 cm1. The phenyl concentration
epoxy prepolymer blend with 3,3¢-DDS was found to in the epoxy–amine blend remains unchanged during
occur at 60C, 110C, and 95C, respectively. The cure. Due to this, each spectrum (NIR) was normalized
solid aromatic amines, 4,4¢-DDM and 3,3¢-DDS, are against standard peak at 4622 cm1 before applying
less nucleophilic than the aliphatic amine and required Lambert–Beer’s law to determine concentration. The
higher temperature to commence the reaction with the primary amine concentration in mixture was deter-
same epoxy functional prepolymer, DGEBA. Tri- mined from the area of the band at 5060 or 4950 cm1
functionality as well as tertiary amine moiety in as
TGAP-based epoxy prepolymer favored the epoxy–
amine reaction at lower temperatures compared to A1 ¼ apa1 cpa1 ð8Þ
DGEBA-based epoxy prepolymer and 3,3¢-DDS sys-
tem. Depending on the epoxy–amine reaction com- where, A1 is NH2 band area at 5060 or 4950 cm1, cpa1
mencing temperature, cure conditions for each system is NH2 concentration (mol kg1) and apa1 is molar
are mentioned in the NIR spectra figures of epoxy– absorptivity of NH2 band at 5060 or 4950 cm1 that
amine blends. was quantified from neat amine monomer spectrum at
Near IR spectra of MPMD, polyetheramine, 4,4¢- a sample thickness 0.20 mm. Aromatic amines show an
DDM, 3,3¢-DDS, DGEBA-based epoxy prepolymer, amine band where epoxides exhibit their epoxy band
and TGAP-based epoxy prepolymer are shown in around 4530 cm1. Epoxy concentration in the blend
Fig. 3. Characteristic primary amine bands around of epoxy prepolymer and aromatic amine was
4950 and 6580 cm1 were observed for the aliphatic determined from combined band area for the epoxy
amines, polyetheramine and MPMD.38 The aromatic and primary amine at 4530 cm1 using the simplified
amines, 3,3¢-DDS and 4,4¢-DDM-exhibited primary version of equation (7)
amine bands at around 4543, 5061, and X
6675 cm1.33,38,39 Characteristic bands for the epoxy A2 ¼ ae ce þ apa2 cpa2 ð9Þ
group of DGEBA-based epoxy prepolymer and P
TGAP-based epoxy prepolymer were noted around where, A2 is combined band area of epoxy and
4530 cm1. Bands observed around 6000 cm1 were primary amine groups at 4530 cm1, ae and ce are
attributed to the presence of –CH3, –CH2, and –CH molar absorptivity and concentration of epoxy group,
groups.38,39 Phenyl groups were observed at and apa2 and cpa2 are molar absorptivity and

0.60
a
b
Epoxy

0.50
c
d
0.40
Absorbance

e
Phenyl

f NH2 0.30

NH2 + NH 0.20
CH + CH2 + CH3
0.10

0.00
8000 7500 7000 6500 6000 5500 5000 4500 4000

Wavenumber (cm–1)

Fig. 3: Near infrared spectra of (a) MPMD, (b) polyetheramine, (c) 4,4¢-DDM, (d) 3,3¢-DDS, (e) DGEBA-based epoxy
prepolymer, and (f) TGAP-based epoxy prepolymer

147
J. Coat. Technol. Res., 11 (2) 143–157, 2014

concentration of primary amine group. ae was Concentration and conversion of epoxy, primary
determined from spectrum of neat epoxy prepolymers amine, secondary amine, and total amine hydrogen
at 0.20-mm thickness. Similarly, apa2 was obtained from
neat aromatic amine monomer spectrum of thickness NIR spectra were recorded for the individual cure of
0.20 mm. cpa2 is actually cpa1 for the same spectrum. DGEBA-based epoxy prepolymer blended with stoi-
Aliphatic amines, polyetheramine, and MPMD do not chiometric ratios of the amines, polyetheramine,
show any peak close to epoxy band 4530 cm1. Epoxy MPMD, 4,4¢-DDM, and 3,3¢-DDS. Figure 4 displays a
concentration in the epoxy prepolymer–aliphatic amine representative example of the NIR spectra obtained as
blend was thus determined applying the simplified a function of time and temperature during the cure of
version of equation (7) as: DGEBA-based epoxy prepolymer with MPMD. As
X expected, the epoxy and amine peak intensities
A2 ¼ ae ce : ð10Þ decreased while the hydroxyl peak intensity increased
concurrently with time because of epoxy–amine reac-
tion. The epoxy and amine peaks disappeared com-
Secondary amine concentration in the epoxy pre-
pletely under the selected cure conditions. The NIR
polymer amine blend was determined from the band at
spectra of other epoxy–amine systems (DGEBA-based
6500–6600 cm1 as below after rearranging the equa-
epoxy prepolymer with polyetheramine, 4,4¢-DDM,
tion (7)
and 3,3¢-DDS) are not displayed here but were
X qualitatively similar.
A3 ¼ apa3 cpa3 þ asa csa ð11Þ
Concentration and functional group a conversion as
P function of time and temperature during cure of
where, A3 is the combined band area of primary
DGEBA-based epoxy prepolymer with stoichiometric
amine and secondary groups, apa3 and cpa3 are molar
amount of MPMD are shown in Fig. 5. The data points
absorptivity and concentration of primary amine
at time 1 h represent the epoxy and amine concen-
group, and asa and csa are molar absorptivity and
trations before mixing (no epoxy–amine reaction).
concentration of secondary amine group. Secondary
Epoxy and primary amine concentrations decreased
amine concentration was assumed to be zero just after
rapidly during the first 5 h at ambient conditions,
mixing and apa3 was determined from equation (11)
resulting in conversion of 63.34 and 90.24%, respec-
when cpa3 = cpa1 for the same spectrum. Once, apa3 and
tively. The epoxy–amine reaction proceeded slowly
cpa3 are known, asa was obtained assuming that the
thereafter as the system had probably reached a
secondary amine does not react during the initial
diffusion limited state, i.e., vitrification. The system
experiments. The total amine hydrogen concentration
was cured at ambient condition (20C). Based on
in blend was calculated as
equation 4, epoxy conversion at the critical extent of
reaction at the gel point is about 57.70%. Tgs at 57.70
cta ¼ cpat þ csat ð12Þ and 63.34% epoxy conversions are supposed to be
28.20 and 37.89C (shown in Fig. 5c) based on equa-
where cpat, csat, and cta are primary, secondary, and tion 2. As Tg at 57.70–63.34% epoxy conversion is
total amine hydrogen concentrations, respectively, at higher than the reaction temperature, the system will
time t. have reached vitrification causing the reaction to

Epoxy
Absorbance
Phenyl
NH2 + NH

NH2
OH

8000 7500 7000 6500 6000 5500 5000 4500 4000

–1
Wavenumber (cm )

Fig. 4: Near infrared spectra of stoichiometric blend of DGEBA-based epoxy prepolymer and MPMD during cure at ambient
for 12 h and post-cure at 135°C for 4 h

148
 J. Coat. Technol. Res., 11 (2) 143–157, 2014

(a) 5.00 (b)

Epoxy 100%
Primary amine
Concentration (mol/kg) 4.00
Secondary amine
80%
Secondary amine (No rxn)

Conversion
3.00 Total amine H
60% RT 135°C

2.00 RT 135°C 40%

Epoxy
1.00 20% Primary amine
Secondary amine
Total amine H
0.00 0%
–2 0 2 4 6 8 10 12 14 16 –2 0 2 4 6 8 10 12 14 16
Time (h) Time (h)

(c) 130
Tg0 = –44.63°C
100 Tg∞ = 120.11°C

70
Tg (°C)

40

10

–20

–50
–0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Conversion (fraction)

Fig. 5: Concentration (a) and conversion (b) of epoxy, primary amine, secondary amine, and total amine hydrogen of
DGEBA-based epoxy prepolymer and MPMD stoichiometric blend during cure at ambient for 12 h and post-cure at 135°C for
4 h. (c) Plot of Tg vs fractional epoxy conversion (applying equation 2) of stoichiometric blend of DGEBA-based epoxy
prepolymer and MPMD. [Data at 21 h represents the preblend concentration where extent of reaction is zero and it was not
measured via NIR; data at 0 h represents first data obtained via NIR spectra of blend/solution after specimen preparation]

proceed very slowly after 63.34% epoxy conversion. conversions occurred at the same rate. These results
Secondary amine conversion was about 7% while indicate that the epoxy–amine reaction in this system is
primary amine conversion was about 40% in the first free from side reactions such as epoxide–epoxide
2 h at ambient condition. The secondary amines homopolymerization and hydroxyl-epoxide etherifica-
formed in situ from the reaction of epoxy and primary tion.
amine usually start to react with epoxide immediately. Does a DGEBA-based epoxy prepolymer and
At the initial stage of curing, the concentration of polyetheramine blend, which reacts at about 35C,
secondary amine is very low and the rate of secondary undergo side reaction during cure? Figure 6 shows
amine to epoxy reaction is lower than that of primary concentrations and conversion of epoxy, primary
amine to epoxy reaction; because of this, tracking of amine, secondary amine, and total amine hydrogen of
secondary amine conversion at the very initial stage of a stoichiometric blend of DGEBA-based epoxy pre-
cure is quite difficult. Beyond 2 h at ambient, the polymer and polyetheramine. During cure at 60C, a
secondary amine reached a maximum concentration rapid decrease in primary amine and epoxy concentra-
over the next 2 h while the conversion was 32.61%. tions was observed in the first 3 and 4 h, respectively,
The secondary amine conversion rate slowed consid- leading to conversions of 98.30 and 83.47%, respec-
erably after 5 h at ambient (conversion 40.38%). tively. Beyond this point, epoxy conversion slowed
Extending the cure to 12 h at ambient-yielded epoxy, leading to a conversion of 91.49% at the end of the
primary amine, and secondary amine conversion values next 2 h due to diffusion limited condition (vitrifica-
of 72.03, 95.24, and 47.29%, respectively. Post-curing at tion). Critical extent of reaction for DGEBA-based
135C resulted in conversions of epoxide, primary epoxy prepolymer and polyetheramine stoichiometric
amine, and secondary amine concentrations of 99.99, blend was 57.70% (based upon equation 3). Epoxy
99.24, and 99.91%, respectively, in 1 h. In addition, it conversion proceeded to 88.82% in 5 h at 60C, which
was noted that the epoxy group concentration was beyond the gel point. Tg of the system at 88.82%
decreased at the same rate as the total amine groups, epoxy conversion is expected to be 64.19C, shown in
confirming that the epoxy and total amine hydrogen Fig. 6c (based on equation 2). As Tg reached and

149
J. Coat. Technol. Res., 11 (2) 143–157, 2014

(a) Epoxy (b) 100%

4.00 Primary amine
Secondary amine
Concentration (mol/kg) Secondary amine (No rxn) 80%
3.00 Total amine H
60°C 125°C

Conversion
60%
2.00
40%
60°C 125°C Epoxy
1.00 Primary amine
20%
Secondary amine
Total amine H
0.00 0%
–2 –1 0 1 2 3 4 5 6 7 8 9 10 –2 –1 0 1 2 3 4 5 6 7 8 9 10
Time (h) Time (h)

(c) 90 Tg0 = –46.38°C

Tg∞ = 86.25°C
70

50
Tg (°C)

30

10

–10

–30

–50
–0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Conversion (fraction)

Fig. 6: Concentration (a) and conversion (b) of epoxy, primary amine, secondary amine, and total amine hydrogen of
DGEBA-based epoxy prepolymer and polyetheramine stoichiometric blend during cure at 60°C for 6 h and post-cure at
125°C for 4 h, (c) plot of Tg vs fractional epoxy conversion (applying equation 2) of stoichiometric blend of DGEBA-based
epoxy prepolymer and polyetheramine. [Data at 21 h represents the preblend concentration where extent of reaction is zero
and it was not measured via NIR; data at 0 h represents first data obtained via NIR spectra of blend/solution after specimen
preparation]

passed the cure temperature at 88.82% conversion, the reaction (57.70% epoxy conversion) at 90C in 2 h and
system vitrified and reaction moved slowly beyond this the Tg of the materials is supposed to be about
point. Secondary amine, i.e., the in situ product of 141.05C (shown in Fig. 7c) based on equation 2.
epoxy and primary amine reaction, was noted to react Naturally, Tg of the system after 2 h of cure was higher
with epoxy at 60C (about 30 min) and reached its than cure temperature, which led to vitrification at
maximum concentration by the end of 2 h (conversion about 88.85% epoxy conversion. The secondary amine
33.60%). Post-curing at 125C yielded epoxy, primary formed in situ started to react at 90C (about 30 min)
amine, secondary amine, and total amine conversions as noticed, reaching its maximum concentration in 1 h
of 99.95, 99.99, 99.53, and 99.76%, respectively, in 1 h. (conversion 48.83%), and increasing to 78.73% con-
Similar to the DGEBA-based epoxy prepolymer and version in the next 1 h. The secondary amine conver-
MPMD system, it was noted that the epoxy and total sion proceeded slowly thereafter, increasing to 81.11%
amine conversions proceeded at the same rate without conversion at the end of the next 2 h. Post-curing at
any accompanying side reactions. 200C resulted in epoxy and total amine hydrogen
A stoichiometric blend of DGEBA-based epoxy conversions of 99.41% in 1 h. The DGEBA-based
prepolymer and 4,4¢-DDM, in which the epoxy–amine epoxy prepolymer and 4,4¢-DDM system also did not
reaction starts at 60C, was set to cure at 90C and indicate the presence of any side reactions to the
the epoxy, primary amine, secondary amine, and total epoxy–amine reactions as epoxy and total amine
amine concentration and conversion during cure are hydrogen conversions proceeded at the same rate
shown in Fig. 7. The epoxy and primary amine reaction throughout the cure.
proceeded rapidly resulting in conversion values of A stoichiometric blend of DGEBA-based epoxy
88.85 and 99.42%, respectively, in 2 h at 90C. Epoxy prepolymer and 3,3¢-DDS, which started to react at
conversion proceeded to only 90.03% at the end of an 110C, was set to cure at 125C and the epoxy,
additional 2 h at 90C, which was attributed to vitri- primary amine, secondary amine, and total amine
fication. Indeed, DGEBA-based epoxy prepolymer concentration and conversion during cure are shown in
and 4,4¢-DDM blend passed the critical extent of Fig. 8. The primary amine moieties reacted rapidly,

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 J. Coat. Technol. Res., 11 (2) 143–157, 2014

(a) 5.00 (b)

Epoxy 100%
Primary amine
Concentration (mol/kg) 4.00 Secondary amine
Secondary amine (No rxn) 80%
Total amine H

Conversion
3.00 90°C 200°C
60%

2.00 40%
90°C 200°C Epoxy
1.00 20% Primary amine
Secondary amine
Total amine H
0.00 0%
–2 –1 0 1 2 3 4 5 6 7 8 –2 –1 0 1 2 3 4 5 6 7 8
Time (h) Time (h)

(c) 185
Tg0 = –13.88°C
155 Tg∞ = 174.63°C

125
Tg (°C)

95

65

35

–25
–0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Conversion (fraction)

Fig. 7: Concentration (a) and conversion (b) of epoxy, primary amine, secondary amine, and total amine hydrogen of
DGEBA-based epoxy prepolymer and 4,4¢-DDM stoichiometric blend during cure at 90°C for 4 h and post-cure at 200°C for
4 h. (c) Plot of Tg vs fractional epoxy conversion (applying equation 2) of stoichiometric blend of DGEBA-based epoxy
prepolymer and 4,4¢-DDM. [Data at 21 h represents the preblend concentration where extent of reaction is zero and it was
not measured via NIR; data at 0 h represents first data obtained via NIR spectra of blend/solution after specimen
preparation]

reaching 99.74% conversion in 2 h at 125C, while the DGEBA–DDS–DGEBA–DDS–DGEBA–DDS–DGEBA,

epoxy conversions proceeded to 81.62% by the end of etc., at 50% conversion of both total amine hydrogen
the first 3 h. The secondary amine concentration at and epoxy. In this system also, no side reactions were
30 min was almost equal to the amount of reacted noted as the epoxy and total amine conversions
primary amine. After 3 h at 125C, the reaction slowed proceeded at the same rate.
and reached 87.51% in the next 1 h. In the first 4 h at DGEBA-based epoxy prepolymer when cured indi-
125C, epoxy conversion reached 87.51%, which was vidually with stoichiometric amounts of MPMD,
quite past the gel point (57.70% conversion) and the Tg polyetheramine, 4,4¢-DDM, and 3,3¢-DDS at their
at that extent of reaction was expected to be 137.98C curing and post-curing condition did not undergo side
(based on equation 2). Thus, the Tg of the DGEBA- reactions like etherification. An epoxy prepolymer
based epoxy prepolymer and 3,3¢-DDS stoichiometric containing a tertiary amine moiety, i.e., TGAP-based
blend after 4 h of cure was higher than the curing tri-epoxide, was evaluated for cure with stoichiometric
temperature. This explained why the system reached amounts of 3,3¢-DDS. The NIR spectra during cure at
vitrification and reaction proceeded very slowly at 100C of TGAP-based epoxy prepolymer with stoichi-
about 87% conversion. Extended curing at 125C ometric amounts of 3,3¢-DDS is displayed in Fig. 9. As
resulted in an epoxy conversion of 90.18% by the expected, the epoxy, primary amine, and secondary
end of 6 h. Post-curing at 200C resulted in epoxy and amine peaks decreased in intensity while the secondary
total amine conversions of 99.09 and 99.10%, respec- hydroxyl group increased in intensity with time
tively, in 1 h. Theoretically, this results represent the because of epoxy–amine reaction. Importantly, the
trimer (DGEBA–DDS–DGEBA) but the molecular secondary amine peak did not decrease in intensity by
weight species in the system could be the average from the time the epoxy peak disappeared upon post-curing
a mixture of species, e.g., DGEBA, DGEBA–DDS– at 200C for 1 h, indicating the presence of side
DGEBA, DGEBA–DDS–DGEBA–DDS–DGEBA, reaction.

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J. Coat. Technol. Res., 11 (2) 143–157, 2014

(a) 5 Epoxy (b)

Primary amine 100%
4 Secondary amine
Concentration (mol/kg) Secondary amine (No rxn)
Total amine H 80%

Conversion
3
60% 125°C 200°C
125°C 200°C
2
40%
Epoxy
1 20% Primary amine
Secondary amine
Total amine H
0 0%
–2 –1 0 1 2 3 4 5 6 7 8 9 10 –2 –1 0 1 2 3 4 5 6 7 8 9 10
Time (h) Time (h)

200
(c)
175 Tg0 = –12.86°C
Tg∞ = 175.14°C
150

125
Tg (°C)

100

75

50

25

–25
–0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Conversion (fraction)

Fig. 8: Concentration (a) and conversion (b) of epoxy, primary amine, secondary amine, and total amine hydrogen of
DGEBA-based epoxy prepolymer and 3,3¢-DDS stoichiometric blend during cure at 125°C for 6 h and post-cure at 200°C for
4 h. (c) Plot of Tg vs fractional epoxy conversion (applying equation 2) of stoichiometric blend after 4 h of cure and 3,3¢-
DDS. [Data at 21 h represents the preblend concentration where extent of reaction is zero and it was not measured via NIR;
data at 0 h represents first data obtained via NIR spectra of blend/solution after specimen preparation]

The epoxy, primary amine, secondary amine, and ceeded to 99.91, 99.99, 83.16, and 91.58%, respectively,
total amine concentration and conversion during cure in 1 h. This indicated that the epoxy and primary
of a stoichiometric blend of TGAP-based epoxy amine groups reacted completely without complete
prepolymer and 3,3¢-DDS are displayed in Fig. 10. consumption of secondary amine and supported the
Epoxy concentration decreased rapidly in first 5 h at fact that epoxy groups participated in side reactions
100C resulting in conversion of 70.91%. Upon like etherification.
extended curing at 100C, the reaction proceeded at CSR particles are one of the potential tougheners
a slower rate leading to an epoxy conversion of 75.35% for epoxy thermosetting systems. The effect of CSR
at 6 h. Tg of this blend is supposed to be 110.54C at particles on the cure of epoxy–amine systems was also
73.73% epoxy conversion (based on equation 2). As Tg evaluated. A TEM image of CSR particles is shown in
of the blend at 71–75% epoxy conversion was close to Fig. 11. It was observed that CSR particles remained
cure temperature, the system gets vitrified and pro- agglomerated while the average individual particle size
ceeds slowly beyond 71% epoxy conversion. Primary was about 200 nm. Figure 12 shows conversion of
amine concentration decreased rapidly in the first 4 h epoxy and total amine hydrogen with and without CSR
at 100C yielding a conversion of 92.34% and conver- particles in the epoxy and amine blends. It was noticed
sion moved to 97.10% in next 1 h at the same cure that initially both epoxy and amine moieties reacted
condition. Detectable amount of conversion of sec- faster in CSR modified DGEBA-based epoxy prepoly-
ondary amine was noted in 30 min at 100C and mer and MPMD blend compared to the control system
reached a maximum concentration at 4 h resulting in a at a lower level of conversion. Besides, epoxy and
conversion of 36.90%. It was observed that epoxy and amine conversions proceeded at the same rate near
total amine hydrogen concentration decreased at the and beyond the vitrification for both with and without
same rate when epoxy–amine blend was cured at CSR particles in DGEBA-based epoxy prepolymer
100C. When the same system was post-cured at 200C, and MPMD systems. This indicated that CSR nano-
it was noticed that epoxy, primary amine, secondary particles accelerated the epoxy–amine reaction at
amine, and total amine hydrogen conversion pro- lower stage of conversion of DGEBA-based epoxy

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 J. Coat. Technol. Res., 11 (2) 143–157, 2014

NH2 + Epoxy

Absorbance
NH2

NH2 + NH

Phenyl
OH

8000 7500 7000 6500 6000 5500 5000 4500 4000

Wavenumber (cm–1)

Fig. 9: Near infrared spectra of stoichiometric blend of TGAP-based epoxy prepolymer and 3,3¢-DDS during cure at 100°C
for 6 h and post-cure at 200°C for 4 h

(a) Epoxy (b)

6.00 100%
Primary amine
Secondary amine
Concentration (mol/kg)

5.00
Secondary amine (No rxn) 80%
Total amine H
4.00 Conversion
100°C 200°C 60%
3.00 100°C 200°C

40%
2.00 Epoxy
Primary amine
1.00 20% Secondary amine
Total amine H
0.00 0%
–2 –1 0 1 2 3 4 5 6 7 8 9 10 –2 –1 0 1 2 3 4 5 6 7 8 9 10
Time (h) Time (h)

(c) 250
Tg0 = –25.54°C
200 Tg∞ = 204.05°C

150
Tg (°C)

100

50

–50
–0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Conversion (fraction)

Fig. 10: Concentration (a) and conversion (b) of epoxy, primary amine, secondary amine, and total amine hydrogen of
TGAP-based epoxy prepolymer and 3,3¢-DDS stoichiometric blend during cure at 100°C for 6 h and post-cure at 200°C for
4 h. (c) Plot of Tg vs fractional epoxy conversion (applying equation 2) of stoichiometric blend of TGAP-based epoxy
prepolymer and 3,3¢-DDS. [Data at 21 h represents the preblend concentration where extent of reaction is zero and it was
not measured via NIR; data at 0 h represents first data obtained via NIR spectra of blend/solution after specimen
preparation]

prepolymer and MPMD system at ambient. CSR post-curing temperature of 135C. The similar catalytic
nanoparticles had no effect on epoxy–amine reaction effect at lower conversion was noticed by other
of DGEBA-based epoxy prepolymer and MPMD researchers in polysulfone nanofibrous and core–shell
system beyond vitrification at ambient as well as at particles modified epoxy and amine blends.39,40 CSR

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J. Coat. Technol. Res., 11 (2) 143–157, 2014

nanoparticles were also observed to accelerate epoxy–

amine reaction at lower conversion ( £ 10%) of
DGEBA-based epoxy prepolymer and polyetheramine
system at 60C (Fig. 12b). Beyond this point (10%
conversion), CSR particles did not show any effect on
the epoxy–amine reaction up to vitrification as well as
at post-curing temperature. Similar catalytic effect
from CSR nanoparticles was noticed with DGEBA-
based epoxy prepolymer and 3,3¢-DDS system at 125C
(Fig. 12c) below 10% conversion. In this case too, CSR
particles did not affect the reaction from conversion
10% to vitrification at 125C; but it accelerated the
conversion at the initial level of post-curing tempera-
ture (200C). In the case of tertiary amine moiety-
containing epoxy prepolymer, TGAP and 3,3¢-DDS
blend, an effect of CSR nanoparticles on the cure at
lower epoxy conversion at 100C was also noted
(Fig. 12d). Beyond 15–20% conversion, CSR particles
did not affect the cure of TGAP-based epoxy prepoly-
mer and 3,3¢-DDS system even at the post-curing
condition at 200C. Activation energy of epoxy–amine
reaction was also determined using Kissinger equation
Fig. 11: TEM image of CSR particles embedded in an to determine the effect of CSR particles and the energy
epoxy matrix barrier values are shown in Table 3. A decrease in

(c)100% (d) 100%

80% 80%
Conversion
Conversion

60% 125°C 200°C 60%

100°C 200°C

40% 40% Epoxy 0% CSR

Epoxy 0% CSR
Epoxy 5% CSR
Epoxy 5% CSR 20%
20% Total amine H 0% CSR
Total amine H 0% CSR
Total amine H 5% CSR Total amine H 5% CSR
0% 0%
–2 0 2 4 6 8 10 –2 0 2 4 6 8 10
Time (h) Time (h)

(a) 100% (b) 100%

80% 80%
Conversion
Conversion

60% 60%
RT 135°C 60°C 125°C

40% 40%
Epoxy 0% CSR Epoxy 0% CSR
Epoxy 5% CSR 20% Epoxy 5% CSR
20%
Total amine H 0% CSR Total amine H 0% CSR
Total amine H 5% CSR Total amine H 5% CSR
0% 0%
–2 0 2 4 6 8 10 12 14 16 –2 0 2 4 6 8 10
Time (h) Time (h)

Fig. 12: Epoxy and total amine hydrogen conversion of (a) DGEBA-based epoxy prepolymer and MPMD stoichiometric
blend with and without CSR during cure at ambient for 12 h and post-cure at 135°C for 4 h. (b) DGEBA-based epoxy
prepolymer and polyetheramine stoichiometric blend with and without CSR during cure at 60°C for 6 h and post-cure at
125°C for 4 h. (c) DGEBA-based epoxy prepolymer and 3,3¢-DDS stoichiometric blend with and without CSR during cure at
125°C for 6 h and post-cure at 200°C for 4 h, and (d) TGAP-based epoxy prepolymer and 3,3¢-DDS stoichiometric blend with
and without CSR during cure at 100°C for 6 h and post-cure at 200°C for 4 h. [Data at 21 h represents the preblend
concentration where extent of reaction is zero and it was not measured via NIR; data at 0 h represents first data obtained via
NIR spectra of blend/solution after specimen preparation]

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 J. Coat. Technol. Res., 11 (2) 143–157, 2014

Table 3: Energy barrier of epoxy–amine systems ary amine and epoxy is low in comparison to the rate of
determined using the equation 1 (Kissinger plot) reaction of primary amine to epoxy. As a result, the
secondary amine conversion at the very initial stage of
Epoxy–amine systems Ea (kJ/mol) cure was thus undetectable. However, a detectable
Epon 828 and MPMD 56.32 ± 0.93
extent of reaction from secondary amine was observed
Epon 828 and MPMD + 5 wt% CSR 55.09 ± 0.35
in 1 h at ambient, 30 min at 60C, 30 min at 90C, 30 min
Epon 828 and JD 230 59.81 ± 1.55
at 125C, and 30 min at 100C in DGEBA–MPMD,
Epon 828 and JD 230 + 5 wt% CSR 55.58 ± 1.32
DGEBA–polyetheramine, DGEBA–4,4¢-DDM, DGE-
Epon 828 and 3,3¢-DDS 58.22 ± 1.64
BA–3,3¢-DDS, and TGAP–3,3¢-DDS, systems, respec-
Epon 828 and 3,3¢-DDS + 5 wt% CSR 55.95 ± 1.53
tively, during their initial cure. The DGEBA-based
MY 610 and 3,3¢-DDS 62.45 ± 0.26
epoxy prepolymer reacted at much slower rate after
MY 610 and 3,3¢-DDS + 5 wt% CSR 60.70 ± 0.85
achieving conversion levels of 63.34, 83.47, 88.85,
87.52% when cured individually with MPMD, polye-
theramine, 4,4¢-DDM, and 3,3¢-DDS systems, respec-
activation energy was observed for each of the systems tively, as the network restricted the mobility of the
with CSR particles, which also supported its catalytic reactive functional groups due to vitrification. TGAP, a
effect at low conversion. Interestingly, it was noticed tertiary amine moiety-containing epoxy prepolymer,
that core–shell particles did not affect the epoxy and reacted very slowly beyond 70.91% epoxy conversion at
amine conversions of DGEBA as well as TGAP-based 100C as a result of system vitrification, which accom-
epoxy prepolymer and amine systems cured at ambi- panied the diffusion limited state. Side reactions were
ent, 100, 125, 135, and 200C. In addition, it was not noted with the DGEBA-based epoxy prepolymer
observed that CSR particles did not induce side when cured individually with stoichiometric amount of
reactions in any of the epoxy–amine systems evaluated. MPMD, polyetheramine, 4,4¢-DDM, and 3,3¢-DDS even
The CSR particles had an average size of about at curing temperatures of Tg + 15C, Tg + 39C, Tg +
200 nm and exhibited three thermal Tgs at 77.39, 26C, Tg + 25C, respectively, as their epoxy conver-
35.89, and 62.21C (shown in electronic supplemen- sions were found to proceed at the rate of total amine
tary information, Fig. S1 DSC). Acid value titration via conversions over the entire cure period. On the other
ASTM D 1639 yielded an acid value of 1.12 mg/g hand, the cure of TGAP-based epoxy prepolymer with
of sample, which indicates the presence of 0.09 wt% 3,3¢-DDS was characterized by side reactions when post-
–COOH group or its equivalent in CSR materials. The cured at 200C as total amine conversion approached
high surface area because of nanosized particles and/or 91.58% while their epoxy conversions were 99.93%. It
the presence of detectable amount of acid groups in was noted that CSR particles accelerated the epoxy-
CSR particles could be the cause of acceleration in the amine reaction at lower epoxy–amine conversions;
epoxy–amine reaction rate. In addition, the Tg of however, they did not induce any side reactions. Overall,
77.39C makes CSR nanoparticles more mobile in an (i) self-etherification (e.g., hydroxyl–epoxy etherifica-
epoxy–amine blend, which in turn may accelerate the tion and/or epoxy–epoxy etherification) was not ob-
crosslinking reaction. Polysulfone nanofibrous mem- served under any cure conditions (even few degrees
branes and films were also noted to accelerate epoxy higher than Tg) when the epoxy prepolymer lacked a
curing rate at lower level of epoxy conversion due to tertiary amine moiety, (ii) self-polymerization was
enhanced network mobility.40 Epoxide surface-func- observed and quantified when tertiary amine moiety-
tionalized CSR materials were found to accelerate the containing epoxy prepolymer was cured at a few degrees
epoxy–amine reaction in a DGEBA-based epoxy resin below Tg (204C), (iii) due to the catalytic effect, core–
and m-phenylenediamine system.41 Carboxyl-termi- shell rubber particles accelerated epoxy–amine reaction
nated rubber was reported to increase the rate of at lower level of conversion, and (iv) NIR correlated well
epoxy conversion as a result of interaction between with the multifunctional cure chemistry and was utilized
carboxyl-terminated groups of rubber and epoxide ring as a definitive method for direct interrogation of epoxy
of epoxy prepolymer.42 and amine reactions during cure.

Acknowledgments The authors acknowledge the

Conclusions Office of Naval Research for their financial support
via Award No. N00014-07-1-1057.
NIR spectroscopy in conjunction with Lambert–Beer’s
law was employed to independently track epoxy–
primary amine and epoxy–secondary amine reactions.
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