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Comparison of Glass-Transition Temperatures for Epoxy Polymers Obtained

by Methods of Thermal Analysis

Article in Mechanics of Composite Materials · May 2020

DOI: 10.1007/s11029-020-09875-5

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Mechanics of Composite Materials, Vol. 56, No. 2, May, 2020 (Russian Original Vol. 56, No. 2, March-April, 2020)

COMPARISON OF GLASS-TRANSITION TEMPERATURES

FOR EPOXY POLYMERS OBTAINED BY METHODS

OF THERMAL ANALYSIS

O. V. Startsev,1* Yu. M. Vapirov,2 M. P. Lebedev,1 and A. K. Kychkin3

Keywords: glass-transition temperature, epoxy polymer, calorimetry, dynamic mechanical analysis,

thermomechanical analysis

In this review, the characteristic temperatures for epoxy polymers and epoxy matrices of fiber-reinforced
composites in the glass-transition ( α -transition) range determined using different methods of thermal analysis
(DSC, DMA, and TMA) are compared. The influence of loading frequency in the DMA method and of uniformity
of heating and postcuring of specimens in all the methods is revealed. The agreement between the glass-transition
temperatures given by different methods is achieved using the same characteristic points in experimental curves
and the same time parameters (the frequency of external actions, heating rate, and the uniformity of temperature
distribution in specimens in testing chambers).

Introduction

Epoxy compounds are widely used as polymeric matrices of dispersedly filled and fibrous composite materials
(CMs) of various purpose [1]. By varying the polymeric basis, hardeners, cure modes, micro- and nanoadditives, CMs
with a wide set of property parameters are obtained, the most important of which is the glass-transition temperature Tg
of epoxy matrices [2]. The necessity for measuring Tg is explained by two principal reasons. First, by this temperature,

1
V. P. Larionov Institute of Physicotechnical Problems of North of the Siberian Branch of the Russian Academy of Sciences,
Yakutsk, Russia
2
Federal State Budget Institution of Science “Institute of Natural-Technical Systems,” Sochi, Russia
3
M. K. Ammosov North-East Federal University, Yakutsk, Russia
*
Corresponding author; e-mail: startsevov@gmail.com

Translated from Mekhanika Kompozitnykh Materialov, Vol. 56, No. 2, pp. 337-356, March-April, 2020. Original
article submitted August 2, 2019; revision submitted February 4, 2020.

0191-5665/20/5602-0227 © 2020 Springer Science+Business Media, LLC 227

the maximum operation temperature of CM products is determined, which is close to the index of their deformational heat
resistance. Second, the glass-transition temperature is one of the most correct indicators of cure of epoxy polymers and
of their structural transformations. This fact is reflected in works of our domestic classics (Kargin, Kobeko, Frenkel,
Slonimskii, Perepechko, Bartenev, and Zelenev [3-5]). This temperature determines the transition of a cross-linked poly-
mer from the glassy to the high-elasticity state ( α -transition by the terminology of [3]), during which the segmental
mobility [3-5] “becomes unfrozen.” The temperature Tg is sensitive to the composition of epoxy resins, hardeners, and
modifiers [6-9], to the influence of disperse fillers [10-14], to the state of polymeric matrices in a CM including the inter-
face between carbon, glass [15-20], organic, and other fibrous fillers [21-27]. The characteristic temperatures of α -tran-
sition (onset, completion, mid-interval, etc. [28]) give information on changes in the segmental mobility of epoxy polymers
and epoxy matrices of CMs at thermal-humid actions [9, 10, 14, 29-33], during climatic aging [17, 22, 34], and in the
conditions of open space [26, 35, 36].
To measure Tg , widely used are such thermal analysis methods as the differential scanning calorimetry (DSC) [11,
12, 28, 29, 37-40] and its versions — the modulated differential scanning calorimetryю (MDSC) [29], thermomechanical
analysis (ТМА) [41-45], dynamic mechanical analysis (DMA) [46-49], and dielectric relaxation spectrometry (DRS) [3,
29, 37, 42, 44]. Widespread is the point of view the notion that Tg is determined not only by the molecular structure and
composition of the polymeric matrix, and the mode and degree of cure, but also by the measurement technique [23, 29, 41,
48, 50]. Authors of works [23, 32] believe that the values of Tg will differ if checked is the mobility of molecular chains
(DMA), the free volume (ТМА), or thermal effects (DSC). In [41], from the temperature dependences of the dynamic shear
modulus, the loss modulus and the mechanical loss tangent, three different glass-transition temperatures were found, but it
is not indicated which of them can be compared to the values of Tg given by the ТМА and DSC. In work [48], epoxy poly-
mers were studied by three thermal methods at different heating speeds of samples. In the opinion of authors of work [50],
the DMA and DSC methods always give different values of Tg for epoxy polymers. In [28], in analyzing the glass-transition
temperature of linear amorphous polymers, with the example of polymethylmethacrylate, by mechanical, thermal, electric,
optical, and other methods, it is shown, that the α -transition is a relaxation transition dependent on the frequency of an
external action and on the heating rate. If action frequencies and the heating rate are the same, Tg is independent of the
method of measurements. However, in the scientific literature, the point of view [51] explaining distinctions between the
values of Tg of amorphous polymers by different mechanisms of fixed processes in the DSC and DMA is still retained.
The purpose of our review is to compare the α -transition temperatures in separately cured epoxy polymers and
matrices of the CMs measured by different methods of thermal analysis in order to establish a uniformity in treating the
temperatures revealed. The task of our review is to compare the sensitivities of different methods to find the limits of vit-
rification and to substantiate the selection of the temperature between the limits of α -transition, which has to considered
as the glass-transition temperature of an epoxy polymer. For this purpose, sections in which systematized data on the stan-
dard methods for measuring Tg of epoxy polymers are included in this review, values of this temperature are analyzed by
different methods of thermal analysis, and the influence of vibration frequency in DMA methods, heating rates, and precure
effects are determined.

1. Standards for Determining the Glass-Transition Temperature of Epoxy Polymers by Methods of Thermal Analysis

In review [29], the DSC, ТМА, and DMA methods, laying at the basis of thermal analysis of polymers, are con-
sidered. The principles, methodical bases, schemes, and examples of measurements, including those for thermosetting
materials, are expounded. Authors of work [42] have compared the sensitivity of DSC, modified DSC, ТМА, DMA, and
dielectric spectrometry methods in determining Tg of thermosetting plastics and revealed the advantages of DMA. Accord-
ing to the data given in [45], the DMA is 10-100 times more sensitive to changes in physical parameters occurring at the
glass-transition temperature than other methods.

228
 E Ti E tan 
Ttan 
T0 Tf

 E
 E
 tan 
Tm

Te Tr
T

Fig. 1. Characteristic temperatures of α -transition of epoxy polymers regulated by ISO 6721-11 (2012) [61].

The methodical basis of measuring Tg of epoxy polymers and epoxy matrices of CMs are the ASTM [52-58] and
ISO [59-61] standards. In the group of ASTM standards, the most informative is ASTM E1356 [52], regulating the mea-
surement of six characteristic temperatures α -transition by the DSC method:
T0 — the temperatures of a deviation from the first base line approximating the linear variation in the thermal flow
with growing temperature in the glassy state;
T f — the temperature of the extrapolated initial temperature of α -transition as the intersection point of the first
base line and the line extrapolating the linear variation in the thermal flow in the region of α -transition;
Tm — the temperatures of the average point determined at the half-jump of the normalized thermal flow;
Ti — the temperature of an inflection point corresponding to the temperature of peak of the temperature derivative
of thermal flow in the region of α -transition;
Te — the temperature of extrapolated final temperature of α -transition as the intersection point of the line ex-
trapolating the linear variation in the thermal flow in the region of α -transition and the second base line in the region of
high-elasticity state;
Tr — temperatures of the last return to the second base line.
The characteristic temperatures listed can also be determined the МDSC method — a variant of the traditional DSC
one, in which the usual linear heating is combined with a temperature modulation [29, 43]. A sinusoidal temperature
modulation is routinely used, which leads to modulation of the resulting thermal flow. As a result, three signals arise — the
overall thermal flow, equivalent to the signal of the usual DSC, a reversible thermal flow related to the change in the heat
capacity of sample, and an irreversible thermal flow responsible for kinetic transitions, for example, in the precure reaction,
which gives additional information on properties of epoxy polymers in the region of α -transition [43].
Some similar in their content standards [53-58] decree that the ТМА and DMA methods be used to determine only
the extrapolated initial temperature T f , the temperature Tm of middle point, and the extrapolated final temperature Te .
ISO standards [59, 61] correct the drawbacks of ASTM standards [53-58]. By the DMA method, directed is the
determination of all six indicated characteristic temperatures of α -transition from temperature dependences of the dy-
namic elastic moduli E ′ and the dynamic loss moduli E ′′ : T0 (1), T f (2), Tm (3), Ti (4), Te (5), and Tr (6). One more
temperature, Ttanδ (7), is determined from the position of maximum of the tangent tanδ of mechanical losses (Fig. 1 [61]).
The ASTM and ISO standards are compared in [47]. According to ISO 11357-2 [60], Tg recommended to deter-
mine by the DSC method as Ti from the deflection point of step of the thermal flow, but two its drawbacks are noted. A
portion of some milligrams may not reflect the properties of all volume of a material. The step of a thermal flow is expressed
well not always, and its parameters are ambiguous. When using the TMA method according to ASTM E 1545 [55] and
ISO 11359:2 [59], Tg is found from the intersection point. According to ASTM D 7028 the advantage of DMA is its
higher resolution [58], because a heating / cooling rate of 3°С/min is used instead of 10°С/min in the DSC. As the best
criterion of Tg , recognized is the inflection point in the temperature dependence of the dynamic elastic modulus, E ′ ,

229
which corresponds to the temperature of peak of the dynamic loss modulus E ′′ . The DMA method is convenient, because
changes in the parameters are always well expressed. It is mentioned that the values of Tg determined from the inflection
point of E ′(T ) and the peak of tanδ can differ by 40°С. The DMA method is convenient owing to the possibility of
changing the vibration frequency, heating rate, and the deformation way of samples. However, by comparing different
thermal methods, it has been shown that the scatter of Tg measurements in the DMA method is greater than in the DSC
method owing to errors in temperature measurements.
It is necessary to note that, to determine the glass-transition temperature of unreinforced polymer materials by
the DMA method, the national standard GOST Р 56753-2015, an analogue of ISO 6721-11 [61], operates in the Russian
Federation. One more national standard, GOST Р 57739-2017, is intended for measuring the glass-transition temperature
of polymer CMs. The basis of this standard is ASTM D 7028 [58]; however, in this Russian standard, regulated is only
the determination of the quantities T f and Ttanδ of the possible seven characteristic α -transition temperatures, which
limits and narrows the possibilities of its application.

2. Comparison of Glass-Transition Temperatures of Epoxy Polymers Measured by Different Methods

The numerous examples of determination of the values of Tg by the methods of DSC [6, 9-14, 27, 32, 38, 39, 43,
47, 48, 50, 62-71], ТМА [9, 11, 15, 26, 38, 48, 72, 73], and DMA [7, 9-18, 20-24, 30, 32-35, 38, 39, 43, 44, 48, 50, 62,
65-68, 70, 71, 73-81] show great discrepancies between them. Let us consider some characteristic examples in which, for
various epoxy polymers or CM epoxy matrices, Tg is measured by two or three methods of thermal analysis [9, 11, 12,
14, 15, 23, 38-44, 47, 48, 62, 65, 67-71, 73].
In [9], the moisture-caused plasticization of an epoxy polymer on the basis of tetraglycidyl ether of methylene-
dianiline and a NARMCO 5208 diamino diphenylsulfone is investigated by three methods. The sensitivity of the DSC
method turned out to be insufficient to reveal the α -transition for dry or moistened samples. By the ТМА method, it was
found that Tg = 217°С. The DMA method gave the temperature of 250°С. The reason for such a significant discordance
is measuring different characteristic temperatures: T f by the ТМА method and Ttanδ by the DMA method, which is close
to Te and Tr (see Fig. 1). The values found depended on the rate of samples temperature variations at their heating or
cooling.
Authors of work [11] investigated the α -transition of a DGEBA-based epoxy polymer filled with Al 2O 3
nanoparticles. In the absence of the nanofiller, the DSC method showed that Tm = 163°С and the DMA method — that
Ttanδ = 170°С. With increasing content of the nanoparticles to 4%, Tm decreased by 6°С, but Ttanδ increased by 11°С.
The temperature T f of ТМА-transition at 170°С did not change in the presence of the nanoparticles. The reasons for
such distinctions can be explained by unequal heating rates and the influence of sample sizes. Similar results were also
obtained in [12], where mixes of an epoxy resin with 5-20% butadiene-nitrile rubber with clay nanoparticles were in-
vestigated. In the presence of 5% nanoparticles, DMA- Tg increased by 11°С. For each composition, DSC- Tg was by
22-25°С lower, because it coincided with the beginning α -transition. When nanoparticles of surface-active organic clays
were added to a DGEBA-based epoxy polymer [14], the DMA method showed a decrease in Ttanδ to 13°С, and it ampli-
fied with moistening, but the DSC method did not reveal any difference.
For the epoxy binder of a carbon plastic [15], the ТМА- Tg determined according to ASTM 1545 [55], at heating
rate of 3°С/min, was T f = 119°С. For the same material, DSC- Tg was found at 163°С, because it characterized the tem-
perature Tm according to ASTM D3418 [53] at a heating rate of 20°С/min.
In work [23], attempts to achieve identical values of Tg in epoxy carbon plastics, using DMA, ТМА, and DSC
methods and varying the heating rate of samples according to ISO 6721 [61], did not give desirable results because of
different characteristic temperatures, indicated by ISO ( Ti , Ttanδ , and Tm ), were measured. However, it was proved that
the best convergence could be achieved by varying the thickness of samples to decrease the errors of temperature mea-
surements. The main cause for such errors is the lag of measured temperature of the samples, which depends on their size,

230
the arrangement of temperature sensors, and heating rate [38]. To lower this influence, in [38], using three thermal meth-
ods, the same heating rate of 5°С/min was chosen, at which, for a well cured epoxy polymer, the coincidence of tem-
peratures T f was achieved at 123°С, measured by the standard ТМА and DMA methods at a lowered frequency of 0.1 Hz.
The DSC method determined this temperature as the middle point Tm of α -transition, since the real temperature was
lower because of the temperature gradient, which was rather high at the heating rate of 5°С/minutes.
In [39], ASTM standards [52, 57] were used to find the characteristic temperatures of α -transition for an epoxy
polymer by the DMA and DSC methods. The beginning T f of the transition at 66°С was determined from the change in
the value of E ′ , Ti = 100°С corresponded to the position of the peak of E ′′ , and Ttanδ = 117°С coincided with the high-
temperature limit of α -transition when the value of E ′ reached the plateau of high-elasticity. Parallel DSC-measurements
revealed an insignificant, smeared in temperature, change of the thermal flow, complicating a correct estimation of the
corresponding characteristic temperatures.
In [40], recommendations of the ASTM and ISO standards for DSC and DMA measurements of epoxy polymers
are compared. The technique for finding the characteristic temperatures of α -transition by the beginning and termination
of intersection, by the middle of the interval, and by the inflection point in the G ′ , G ′′ , and tanδ graphs is expounded.
It is noted that the best agreement with the data of DSC measurements is achieved using the temperature of peak of the
loss modulus instead of loss tangent. It is concluded that, to within 10°С, the values of Tg determined by the middle point
of the step of thermal flow, and by the temperature of the peak of G ′′ are equivalent.
A detailed comparison of thermal methods for measuring Tg is carried out in [41-44, 47]. In opinion of the authors
of [41, 47], finding this parameter by the DSC method from the inflection point of the specific heat capacity is less reli-
able, because of the insufficient sensitivity and small sizes of samples. It is recommended to use the ТМА and DMA and,
as in [40, 47], to find Tg by the intersection point of the straight lines approximating the transition and by the positions
of maximum of G ′′ and tanδ . The termination of α -transition is not discussed. In [42], considering the five methods of
the thermal analysis, the preference it is given to the DMA. Equivalence of the values of Tg of epoxy polymer found from
the data of DMA and of temperature-modulated DSC is proved in [43]. Attempts to achieve a similar agreement for the
classical DGEBA-based polymer when using the methods of DMA and dielectric spectrometry [44] and Ttanδ were unsuc-
cessful because of the insufficient resolution of the dielectric loss tangent. To improve the convergence of results of the
measurements by different thermal methods, it is necessary to take into account the influence of sample heating rate [47].
The influence of the chemical structure of eight epoxy polymers on Tg was investigated by three thermal meth-
ods in [48]. Because of the low sensitivity of DSC, it was possible to measure Tg only for two polymers. For both of
them, the value of Tg found by the DMA was higher than that given by the ТМА, but the reasons for this distinctions
were not commented.
In [62], the results of interlaboratory measurements for 14 epoxy polymer variants by the methods of DMA and
DSC are presented. Samples with different degrees of cure were tested after their keeping at room temperature during 7,
30, and 100 days. By the DMA method, the characteristic temperatures T f , Ti , and Ttanδ were determined at the frequen-
cies of 1 and 5 Hz and heating rates of 2 and 3°С/min (see Fig. 1), and they were compared with the temperature Tm
determined by the DSC method at heating rate of 10°С/min from the position of the middle point of step of the normalized
thermal flow. The conclusion is made that the about affinity of values of T f and Tm are close, which cannot be considered
correct, because the frequency of mechanical vibrations in the DMA and distinctions in the heating rate in the two meth-
ods compared was not taken into account. Such an account is performed in [65]. For the epoxy the polymers investigated
in [13, 79], the values of Ttanδ measured on a torsional pendulum at from the temperature of the peak of decay of me-
chanical losses (an analogue of tanδ ) and Tm determined by the method of DSC at the temperature corresponding to the
half-step of the specific heat capacity [8] were compared. The excess of Ttanδ above Tm by 10-15°С was explained by
the influence of vibration frequency in DMA measurements. However, this comparison is also inadequate, because Ttanδ
usually coincides with the high-temperature limit of the α -transition of epoxy polymers [19, 61], but Tm coincides with
its middle [60]. The best coincidence, even at a varying vibration frequency [67, 70] and distinctions in the heating rate [68,
70, 71], is achieved by comparing Ti (DMA) and Tm (DSC) [67-71, 73].

231
 As already mentioned in the Introduction, thermosetting epoxy systems are frequently investigated by the methods
of dielectric relaxation spectrometry. “Defreezing” of the segmental mobility at the transition of cross-linked polymers from
the glassy to the high-elasticityе state greatly influences the change of the real and imaginary parts of complex dielectric
permeability. [3]. The temperature of α -transition of epoxy systems is determined by the methods of dielectric spectrom-
etry from the maximum of the dielectric loss factor ε′′ in the range of frequencies from 10−4 to 106 Hz [3, 37, 42]. For
example, according to the data in [29], the temperature of the ε′′ -peak in the DGEBA-based epoxy polymer at a frequency
of 0.1 Hz is –17°С. An increase in the frequency of electric field to 104 Hz increases the temperature of this peak to 0°С.
The temperatures of ε′′ -maxima of the of dielectric loss factor correspond to the temperatures of E ′′ - and G ′′ -maxima of
the dynamic mechanic loss moduli if the influence of heating rate of samples and frequencies are taken into account. This
effect is a consequence the relaxationого character of the dielectric α -transition and is comparable to the influence of the
frequency of dynamic mechanical vibrations [44]. Thus, by the dielectric spectrometry, it also is possible to estimate the
temperatures of the beginning and termination α -transition by analogy with ASTM E1356 [8]. For example, a graph-
ical processing of the ε′′ peak at the frequency of 104 Hz for an uncured DGEBA epoxy polymer showed that T f = –20,
Ti = 0, and Tr = 20°C [29]. On curing the DGEBA polymer by 3,3’-diaminodiphenylsulfone, the temperatures T f = 150,
Ti = 185, and Tr = 220 °C, determined by the peak of dielectric losses, coincide with the similar characteristic temperatures
of DMA parameters to within 5°C [44].
Good examples of measuring Tg for thermosets by several thermal methods are works [66, 82]. In [82], the cure
process of an RTM6 epoxy polymer was investigated at a constant temperature of 160°C. By the DMA method, it was
established that, during its isothermal holding, the glass-transition temperature measured at a vibration frequency of 1 Hz,
grew from 100 to 180°C for 50 min, and then remained constant. Measuring the parts of complex dielectric permeability
in the range from 100 Hz to 1 MHz and determining the glass-transition temperature as Tm by extrapolation to the fre-
quency of 1 Hz, authors established that the precure came to the end in 53 min, which confirmed and refined the result of
DMA. In more detail, the precure process was characterized, using the МDSC method, by changes in heat capacity of the
polymer and revealing its lowering in the interval from 50 to 65 min of holding.
Thus, a correct comparison of the characteristic temperatures α -transitions by thermal methods is impossible
without taking into account the heating rate of samples and the frequency of dynamic mechanical vibrations.

3. Influence of Vibration Frequency in DMA Methods

The frequency dependence of the characteristic temperatures α -transition for epoxy polymers by using DMA
methods is investigated in [20, 31, 37, 62, 65, 67, 75, 77, 81]. For its quantitative estimation, the following relations are
used [37]:
 E 
f = f 0 exp  − a , (1)
 k BTg 
 

 Ea 
f = f0  − , (2)
 k B (Tg − Tgs ) 
 
where f is vibration frequency; f 0 is a multiplier; Ea is the activation energy; k B is the Boltzmann constant; Tg is the
temperature corresponding to the maximum of loss modulus, which is assumed as the glass-transition temperature of a poly-
mer; Tgs is the glass-transition temperature in the static regime (in the absence of vibrations). Besides Eqs. (1) and (2), simi-
lar relations following from the Williams–Landel–Ferry equation [45] can also be used.
The validity of Eqs. (1) and (2) follows from the fact that ln f is a linear function of 1/ Tg or 1/( Tg – Tgs ). An ex-
ample is shown on Fig. 2, when the characteristic temperature Ti of epoxy matrix of a KMKS-1.80 glass-fiber reinforced
plastic, measured with the help of a torsional pendulum [20], is approximated by Eqs. (2) and shows an increase in Ti from

232
 ln f, Hz
2.0

1.5

1.0

0.5

0.5
1/(TgTgs ), K1
0.12 0.14 0.16 0.18

Fig. 2. Temperature Tg of the epoxy matrices of a КМКС-1.80 glass-fiber plastic vs. deformation
frequency of sample: dots — measurements [20]; the line — approximation by Eq. (2).

132 to 140°С when the vibration frequency grows from 0.73 to 9.6 Hz. The temperature Tgs = 128°C coincides with that in
the quasi-static deformation of samples [20] within ±1°C.
It was found in [31] that, with increasing vibration frequency of glass-fiber-reinforced plastic samples from 0.3 to
100 Hz [31], the temperatures Ti and Ttanδ of its polymeric matrix grew by 25°С. Distinctions of 1 and 5 Hz in the vibration
frequency, at the interlaboratory control [62], showed 3-7°C distinctions in Ttanδ . In a DGEBA-based carbon-fiber plastic
with an epoxy matrix, a similar increase in Ti and Ttanδ gave 13 and 14°C when the vibration frequency increased from
0.316 to 31.6 Hz [75]. For an EP45NT epoxy polymer, with increasing the frequency of its bending vibrations from 1 to
30 Hz, the temperatures T f and Ti grew by 35°С, whereas the temperature Ttanδ rised by 10°С [77], which has to be taken
into account in choosing the characteristic temperature of α -transition. Processing DMA results of a C2H5-TGDDM-based
epoxy polymer by Eq. (1) showed [81], that effective activation energy of α -transition found from Ttanδ measurements (924
kJ/mol) was higher that obtained from Ti measurements (793 kJ/mol).
Thus, with account of the fact that Tg depends on vibration frequency, allows one, when using DMA methods, to
bring in significant corrections in establishing the equivalence of the characteristic temperatures of α -transition found by
the methods of thermal analysis.

4. Influence of Heating, Precure, and Thermal Inertia of Samples

When measuring Tg of epoxy polymers by the methods of thermal analysis, the heating rate V of samples in the
chambers of measuring devices usually are chosen at a level of 1-10°С/min, which corresponds to the requirements of
ASTM [52-58] and ISO [59-61] standards. Such a practice complicates the comparison of the values of Tg found, because
this temperature greatly depends on the value of V , as it has been established, for example, in works [6, 23, 37, 47, 63, 66,
74, 75-77]. This law is true for results of the measurements performed by the DSC [6, 47, 63, 66], DMA [23, 37, 47, 74-77],
and ТМА [3, 37] methods. For example, an increase in V from 2 to 10°С/min raises the temperatures T f , Ti , and Tm of
epoxy polymers and CM epoxy matrices by 6-13°С [23, 37, 63, 80], 18-35°С [6, 76], and even by 42-45°С [6, 63], which
is shown on Fig. 3.
In most cases (see Fig. 3), Tg as a function of V is well approximated by the linear relation

Tg = Tg 0 + θ V , (3)

where Tg0 is the glass-transition temperature, extrapolated to the infinitesimal heating rate; θ is a proportionality factor
dependent on the chemical structure and composition of the epoxy polymer.

233
 Tg, K
600

550

500

450

400

350
V, K/min
0
5 10 15 20

Fig. 3. Influence of heating rate V of samples on the glass-transition temperature Tg of epoxy

polymers: dots — literature data [63] (○), [77] (□), [80] (●), [76] (◊), and [6] (∆); lines — approxi-
mation by Eq. (3).

In work [83], the parameter θ was determined as the product of thermal resistance and thermal capacity of
sample. If the heating of an epoxy polymer is accompanied by precure, an analysis of modelless kinetics of this process
by the methods used in [84-86] gives a linear relation between the logarithm of heating rate of sample and the return
temperature, which is frequently used to characterize thermosetting epoxy mixes.
In work [66], the connection between the vitrification temperature as a function of cooling rate V (DSC method)
and modulation frequency of the dynamic vitrification temperature Tα (МDSC method) is determined. For a DGEBA
epoxy resin cured by polyetheramine Tα can exceed Tg by some degrees. The relation V = 2π faδ T establishes an inter-
relation between V (cooling rate), f (the frequency of temperature modulation), and δ T (the vibrations of temperature
modulation) ( a is a material constant). The equivalence of Tg and Tα is reached at D = log q − log ω = 0.41–0.44 ( ω = 2π f ).
In order to avoid the errors caused by different heating rates, it is wise to compare the characteristic temperatures
of α -transition, found by different methods of thermal analysis, by employing the unified index Tg0 . However, when
using Eq. (3), it is necessary to take into account the important feature of thermal analysis methods — manifestation of
the precure effect during heating samples.
Numerous examples have demonstrated that the values of the characteristic temperatures of α -transition found by
the methods of thermal analysis depend on the degree of cure of epoxy polymers [7, 30, 35, 50, 62-64, 72, 75, 87]. The
precure at heating samples is clearly revealed by the DSC [62-64,87], DMA [7, 30, 35, 50, 75], and ТМА [72] methods. The
temperature Tg in relation to the degree of cure (degree of conversion of groups) p is described by the function [87]

Tg = Tg∞ − K (1 − p ) , (4)

where Tg° is the vitrification temperature at full cure; K is a constant specific for each polymer, namely,

EnTg∞
K= , (5)
M mon

which depends on the molecular weight M mon of monomer, the elementary increment E , and the number n of the end
groups falling on the unit a monomer.
Another known relation connecting Tg with the degree p of cure is [88]

Tg 1 − (1 − e ) p
= , (6)
Tg0  Tg0 
1 − 1 − ∞ b p
 Tg 
 

234
 , min
6

1
Tg0, K
300 350 400 450 500

Fig. 4. Proportionality factor θ vs. glass-transition temperature Tg0 at infinitesimal heating rate
determined by Eq. (3).

where Tg0 is the vitrification temperature of an uncured polymer; Tg° is the vitrification temperature at full cure; b is an
empirical parameter [88]. Equations (4) and (6) and other similar ones [89, 90] connect the character of Tg functions with
the segmental mobility of fragments of the polymer system. Therefore, when comparing the characteristic temperatures
of α -transition of epoxy polymers using different methods of thermal analysis, it is important to take into account the
heating / cooling rate of and precure effects and to choose the same characteristic temperature of α -transition in Eqs. (4)
and (6), for example, Ti . Therefore to estimate the influence of precure, Tg as a function of heating temperature [7, 63,
87] and heating duration [30, 50, 75] is analyzed. To measure Tg¥ , a repeated scanning is employed [35, 64, 72].
One more feature of the thermal methods of analysis is the effect of thermal inertia of samples, manifesting itself
as the lag of sample temperature behind the temperature in the measuring chamber [21, 24, 38, 47, 68, 71, 74-76, 80, 91,
92], which influences results of measurements. According to the data in [47], the distinction between the temperature at
the center of sample and near to its surface is 6°С. Because of temperature gradients along the sample, dependent on its
thickness and heat conduction [21, 47, 74, 80, 92], the errors in measurements make up 5-10°С for T f , 7-25°С for Ti ,
and even reach 40°С at high heating rates [76]. In DMA measurements [71] at a heating rate of 3°С/min, the center of a
sample is by 30°С cooler than its edges (at a distance of 7.5 mm from its support). Even at a 10-mm distance between
supports, the temperature gradient along the sample makes up 6°С/mm. The measurement accuracy grows at calibration
of thermal sensors [38, 68]. To reach the temperature of 171°С at the heating rate of 300°С/min, a 14.4°С overheating is
needed [91]. An effective method of temperature regulation, which reduces the temperature gradient of samples in the
measuring chamber of torsional pendulum with a rate of 0.1°С/mm, is considered in [24].
In view of the results presented, it is possible to explain the dependence of the parameter θ appearing in Eq. (3)
on the value of Tg0 . For DGEBA-based epoxy polymers of eight structures investigated by the DSC method at heating
rates from 2.5 to 10°С/min, changes in the values of Tg determined from the beginning, end, and maximum of the peak
of thermal flow were compared [6]. The shifts in values of T f from variation in V were much smaller than those in the
shifts of Te . These and similar results [23, 37, 63, 76, 87] are shown on Fig. 4.
As is seen from the data of Fig. 4, the proportionality factor θ in Eq. (3) also depends on the chemical structure
and structure of epoxy polymer and grows with Tg0 . The increasing scatter of the values θ with growing Tg0 , marked by
the dashed lines on Fig. 4, is explained by growing errors caused by the thermal inertia of samples at increasing tem-
peratures.

235
Conclusion

In the present work, the results found for the characteristic temperatures in the regions of vitrification ( α -transi-
tion) of epoxy polymers and epoxy matrices of polymer composite materials determined by widespread methods of thermal
analysis have been compared. The influence of vibration frequency in the method of dynamic mechanical analysis, and of
the heating rate and uniformity and precure of samples in all methods on the temperatures determined was analyzed. It is
shown that equivalence of the vitrification temperature determined by these methods can be reached using identical char-
acteristic points of experimental curve and time parameters of experiments (the frequency of external actions and the heat-
ing rate and uniformity of samples in the measuring chambers of devices).

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