J Therm Anal Calorim
DOI 10.1007/s10973-015-4670-5
Assessment of polyamide-6 crystallinity by DSC
Temperature dependence of the melting enthalpy
Coraline Millot1,2 • Louise-Anne Fillot2 • Olivier Lame1 • Paul Sotta2
Roland Seguela1
Received: 4 February 2015 / Accepted: 22 March 2015
 Akadémiai Kiadó, Budapest, Hungary 2015
Abstract This study addresses the question of the crys-
tallinity determination of PA6 by means of DSC in the case
when structural changes occur over a very large tem-
perature domain during the heating scan. The temperature
dependence of the melting enthalpy is then of crucial im-
portance for determining the amount of crystalline phase
involved in the various processes, and thus the initial
crystallinity. Both DSC and WAXS measurements have
been carried out of a PA6 sample submitted to various
thermal treatments in order to identify the crystalline forms
and the temperature-induced structural changes. The
melting enthalpy dependence on temperature of PA6 was
computed from heat capacity data of the solid and liquid
borrowed from literature data tables. Similar computations
were performed for PA66 which is likely to exhibit ana-
logous structural changes during DSC analysis.
Keywords Polyamide-6  Melting enthalpy  DSC 
WAXS  Crystallinity
& Olivier Lame
olivier.lame@insa-lyon.fr
Roland Seguela
roland.seguela@insa-lyon.fr
1
MATEIS, UMR 5510 CNRS - INSA de Lyon, Lyon Tech La
Doua, 69621 Villeurbanne, France
2
LPMA, UMR 5268 CNRS - SOLVAY, 85 avenue des Frères
Perret, 69192 Saint-Fons, France
•
Introduction
Semi-crystalline polymers display a structural hierarchy
that is strongly sensitive to processing conditions and
thermo-mechanical treatments. The crystal weight fraction
or crystallinity, Xc, is particularly processing dependent
owing to texturing and chain orientation effects. This
phenomenon has an impact on the material macroscopic
behavior since the intrinsic properties of the crystalline and
amorphous phases are generally quite different [1–3].
Rapid cooling after melt processing generally makes Xc
lower than its maximum value, noticeably in the case of
polymers having low crystallization kinetics. This may be
detrimental for the physical characteristics and use prop-
erties of manufactured parts. In the case of polymers
having a glass transition temperature above room tem-
perature, crystallization may even be completely inhibited
upon fast cooling.
The quantitative determination of the crystallinity of a
semi-crystalline polymer after thermo-mechanical pro-
cessing is mandatory for understanding its properties.
Several methods are commonly used in this aim: differ-
ential scanning calorimetry (DSC), density measurements,
X-ray scattering, infrared and Raman spectroscopy, and
nuclear magnetic resonance [4]. DSC is the easiest and
most largely used one. This method relies on the mea-
surement of heat that must be provided to the material for
the melting of its crystalline phase during heating at con-
stant rate. A major drawback of this method is that ther-
modynamically unstable phases present in the initial
material can take advantage of the heating to reorganize
into stable ones during the DSC scan. Therefore, the final
melting endotherm does not provide information on the
actual structure of the material since it combines the
123

melting of both the initial crystals and the reorganized
ones.
Aromatic semi-crystalline polymers, some aliphatic
polyesters and aliphatic polyamides [5, 6], are typical
polymers undergoing restricted crystallization under fast
cooling. During the heating scan of the DSC analysis, cold
crystallization may take place above the glass transition
temperature (Tg). Provided that the DSC baseline was
properly adjusted prior to the analysis, it is quite easy to
determine the amount of matter involved in the melting and
the cold crystallization processes. Computing the actual
crystallinity of the original material is then straightforward.
This computation is generally carried out by assuming
that the specific heat of fusion, or melting enthalpy DHm  ,
and the specific heat of crystallization, DHc  , of the 100 %
crystalline material have the same absolute value at the
equilibrium temperature of fusion, Tm  . This would be
theoretically true if the two processes occurred in the same
temperature range. However, the temperature gap between
cold crystallization and melting may be very large, typically
100 C or more for the kind of polymers previously men-
tioned. Moreover, the specific heat of melting, or crystal-
lization, strongly depends on temperature due to the different
T-dependences of the heat capacities of the solid and the
liquid [7]. A significant depression of DHm  can be observed
below Tm  , as already reported for several polymers [5, 8].
Therefore, an accurate determination of the crystallinity re-
quires an analytical expression for the DHm  ðTÞ relationship.
In spite of rather fast crystallization kinetics, incomplete
crystallization of aliphatic polyamides may occur upon
quenching from the melt. This is evidenced by the occurrence
of crystal reorganization effects during subsequent heating
just above Tg. Khanna and Kuhn [6] have argued on the re-
liability of DSC for determining the crystallinity of poly-
amides, particularly in the case of poorly crystallized samples
that precisely may exhibit structural reorganization events
during the heating scan, including cold crystallization just
above Tg. These authors have also pointed out that the melting
enthalpy of nylons is likely to exhibit a T-dependence [6].
The impact of crystallinity on the mechanical properties
of polyamides [9–11] makes its accurate determination a
crucial issue. In continuation of Khanna and Kuhn’s paper
[6], the present work deals with the practical assessment of
polyamide-6 crystallinity by taking into account the
DHm  ðTÞ relationship when structural changes occur far
below the melting point during the DSC scan [12–16].
Experimental
The polyamide-6 (PA6), otherwise nylon-6, under inves-
tigation is an industrial grade from Solvay. The number
average molecular weight is Mn & 31 kg mol-1, and the
123
C. Millot et al.
polydispersity index Ip & 1.86. The material was received
in the form of 1.6-mm-thick injection-molded plates stored
into tightly sealed bags just after processing in order to
prevent moisture absorption.
Four different thermal treatments were performed on
samples of about 5 mg that were inserted into hermetic
DSC pans in order to prevent moisture uptake prior to
treatment and pollution by the silicon oil during of the
thermal treatment bath:
• Quenching was carried out by dropping one of these
sealed samples into an ice water bath at 0 C imme-
diately after melting in an oven at 270 C for 10 min in
order to erase memory effect [17].
• Isothermal crystallization at 213 C for 24 h was
performed by plunging the sample in a thermo-
regulated silicon oil bath after melting for 10 min in
the oven at 270 C.
• Isothermal annealing at 200 C for 30 min of quenched
samples was made in the same oil bath.
• Isothermal annealing at 80 C for 30 min of quenched
samples was also performed in order to better under-
stand the crystalline changes involved in the cold
crystallization process.
Differential scanning calorimetry (DSC) was performed
on a Q2000 apparatus from TA Instrument at a heating rate
of 10 C min-1. The temperature and heat flow scales were
calibrated using high purity indium and zinc samples. The
thermally treated samples in their closed DSC pans were
directly used in the DSC measurements.
Wide-angle X-ray scattering (WAXS) experiments were
carried out on the BM02 beamline at ESRF (European
Synchrotron Radiation Facility, Grenoble, France) equip-
ped with a CCD camera from Princeton Instrument, using a
wavelength k = 0.154 nm. The thermally treated samples
were extracted from the hermetic pans just before the
WAXS measurements. Corrections of the 2D frames were
routinely performed using the bm2img software of ESRF.
Azimuthal integration of the isotropic 2D patterns was
carried out by means of the Fit2D software.
Results and discussion
It is worth to briefly review the most common crystal forms
of PA6 in relation to thermal treatments. The monoclinic a-
form is the most stable one, generally obtained from qui-
escent melt at crystallization temperatures Tc [ 150 C
[14, 18–20]. The pseudo-hexagonal c-crystals can be ob-
tained from the quiescent melt at Tc \ 150 C [14, 18–21].
Fiber spinning from the melt at low or moderate spinning
rates is also well known to generate c-crystals [22–24].
However, spun fibers may contain defective c-crystals that
Assessment of polyamide-6 crystallinity by DSC
display an early melting and then undergo recrystallization
in the a-crystal form during the heating scan [22].
Films cast on cold rolls exhibit the so-called meso-
morphic phase or mesophase, otherwise b-form, that is
hardly distinguishable from the c-form by means of X-ray
scattering. This metastable mesophase also undergoes re-
organization into the a-crystal form during the heating scan
[14, 16, 19].
Yet, it is not clear from literature data whether the b-
form and the defective c-form are actually different kinds
of ill-ordered crystals or just two different views of the
same species (see Murthy [19], Kolesov et al. [16] and
Auriemma et al. [25]).
To sum up, in spite of the fairly good knowledge of the
morphogenesis of the various PA6 crystal forms, the
situation remains unclear in many cases.
Thermal and structural behavior of PA6
Figures 1 and 2 report the DSC heating traces and the WAXS
intensity profiles of PA6 samples submitted to the various
thermal treatments. Regarding the DSC data first, Fig. 1
shows that quenching at 0 C partially prevents crystalliza-
tion of the sample as can be seen from the cold crystallization
exotherm at 55 C, i.e., just above the temperature range of
55.0 °C
Quenched at 0 °C
15.3 J g–1
Heat flow/W g–1
Quenched at 0 °C + annealed at 80 °C
Quenched at 0 °C + annealed at 200 °C
202.0 °C
Isotherm at 213 °C
Exo
1 W g–1
Endo
0 50 100 150
Temperature/°C
Fig. 1 DSC heating traces of PA6 samples after various thermal
treatments
the glass transition. Then, a broad melting endotherm occurs
with a peak temperature T m peak  216  C. It is to be noticed
that complete (or nearly complete) amorphization has been
reported for PA6 thin films, according to the height of the
heat capacity jump at the glass transition [6, 26]. This re-
sulted in a cold crystallization peak with greater amplitude
than in the present case, which means that amorphization is
partial for the present quenched PA6 sample. Moreover, the
above-mentioned works also reported the observation of a
weak and broad exotherm extending from the cold crystal-
lization up to the final melting. This was ascribed to the
occurrence of a gradual reorganization of the amorphous
material into crystal, and/or perfectioning of the formerly
grown crystals [6, 26]. In the present quenched PA6 sample,
such kind of broad exotherm appears beyond the cold crys-
tallization peak up to about 120 C (see top curve in Fig. 1).
The origin of this phenomenon will be further discussed in
the ‘‘Concluding discussion’’ section.
Isothermal annealing at 80 C of the quenched sample
suppresses the cold crystallization phenomenon due to the
annealing-induced crystallization. In addition, it results in a
shift of the melting endotherm up to Tpeak
m & 220 C. The
faint exotherm pointing at 190 C is relevant to reorgani-
zation processes of probably unstable crystals. This phe-
nomenon has been commonly observed in PA6 samples
Isotherm at 213 °C Quenched at 0 °C
+ annealed at 80 °C
Quenched at 0 °C
+ annealed at 200 °C Quenched at 0 °C
56.2 J g–1
Intensity/arbitrary units
216.5 °C
221.0 °C
230 °C
200 250 10 15 20 25 30 35
Scattering angle 2θ /°
Fig. 2 WAXS intensity profiles of PA6 samples after various thermal
treatments
123
 C. Millot et al.

and largely discussed elsewhere in relation to processing information on the (020) reflection is given in this latter
condition [27]. work, so that no clear-cut conclusion can be made.
Isothermal crystallization at 213 C, as well as anneal-
ing at 200 C, no longer lead to cold crystallization. In both
cases, the shift of the melting peak to higher temperature Temperature dependence of the PA6 melting
indicates a better thermal stability of the crystallites, due to enthalpy
more favorable growth conditions. Concerning isothermal
crystallization at 213 C, the DSC trace reveals a unique The large gap (of the order of 160 K) between the cold
and rather narrow melting peak with Tpeak & 230 C. This crystallization exotherm and the final melting endotherm
m
suggests the melting of a-crystals after Kyotani and Mit- raises the question of the T-dependence of the melting (or
suhashi’s study [18]. In contrast, the DSC trace of the crystallization) enthalpy of 100 % crystalline PA6, which
sample annealed at 200 C exhibits a double endotherm is important for determining the index of the material by
suggesting the melting of two kinds of crystallites either of DSC. For any kind of physical or chemical transformation,
the same crystal form but having two different crystal the temperature dependence of the enthalpy is given by
thickness or of different kind, namely a- and c-crystals, Kirchhoff’s law, which takes the following form in the case
melting respectively in the major endotherm at of melting enthalpy
Z
Tpeak
m & 221 C and in the minor one at Tpeak m & 202 C.
DHm ðT2 Þ  DHm ðT1 Þ ¼ DCp dT ð1Þ
The next WAXS data support the second hypothesis. The
occurrence of a small amount of c-crystals upon annealing
where DCp is the difference of the heat capacities of the
at 200 C for 30 min is consistent Kyotani and Mit-
material in the final and initial states at every temperature
suhashi’s [18] regarding the PA6 crystallization kinetics.
over the range (T1 - T2).
Regarding the WAXS data, the intensity profiles of
The T-dependence of the melting enthalpy, that also
Fig. 2 confirm that the sample isothermally crystallized at
applies to the crystallization enthalpy, can be determined
213 C is in the a-crystal form as evidenced by the (200)
from Eq. 1 provided that the heat capacities of the liquid
and (002/020) reflections located at 2h & 20 and
and the solid can be extrapolated over the temperature
2h & 24, respectively [28]. The WAXS data for the
range (Tg  –Tm  ). Computations were performed by Wun-
sample annealed at 200 C show the characteristic (002/
derlich [8] in the case of polyethylene and by Seguela [5] in
200) reflections of the c-form at 2h & 22, between the
the case of poly(ethylene-terephthalate) and poly(aryl-
two major reflections of the a-crystal form. Besides, the
ether-ether-ketone). Such computations are based on the
characteristic (020) reflection of the c-form is clearly ob-
experimental heat capacity data reported by Wunderlich
served at 2h & 10.5 [29]. It is to be noticed that, except
et al. [32, 33] for a number of semi-crystalline polymers.
for the last one, the angular positions of the various re-
Worth noticing is that the term ‘‘solid’’ includes crystalline
flections may be slightly different from literature data due
and glassy materials for which the heat capacities are as-
to different degrees of crystal perfection inducing varia-
sumed identical, for all polymers [32, 33]. As a matter of
tions in the unit cell parameters [30].
fact, slight differences of Cp data between the two solid
Regarding the sample quenched at 0 C, the very broad
states have only been observed at very low temperature,
scattering halo without sharp reflection suggests amor-
i.e., below 100 K. This comment also applies for the var-
phous and/or mesomorphic b-form. After annealing at
ious crystalline forms of PA6 that may display slight dif-
80 C, a narrowing of this broad scattering occurs ac-
ferences in Cp values also assumed to be negligible in
companied by a fairly well-resolved reflection on the right-
comparison with the DCp between solid and liquid. A well-
hand side having an apex at 2h & 21. This is a priori
known property in favor of this assumption is that the a and
consistent with cold crystallization into the c-form of PA6
c crystals of PA6 practically have the same enthalpy of
as reported by Khanna and Kuhn [6]. However, the present
melting at their respective melting points [8, 34].
WAXS data display only a weak (020) reflection charac-
Regarding PA6, experimental data of the heat capacities
teristic of the c-form at 2h & 10.5. This may indicate that
of the liquid and the solid, Cp,l and Cp,s, respectively, are
cold crystallization generates a relatively disordered form
available from the above-mentioned data tables. The
of c-crystals, otherwise a kind of b-mesophase. A parallel
computed polynomial fittings are the followings:
can be made with a similar study on quenched PA6 sub-
mitted to annealing at various temperatures by Kolesov and • for the liquid in the range 320–600 K:
Androsch [31]. These authors claimed for a cold crystal- Cp;l ¼ 0:001348 T þ 1:9793 in J g1 K1 ð2Þ
lization into b-mesophase that gradually transforms into a-
crystals during the DSC heating scan. Unfortunately no • for the solid in the range 70–310 K:

123
Assessment of polyamide-6 crystallinity by DSC

Cp;s ¼ 0:004502 T þ 0:1387 in J g1 K1 ð3Þ Temperature/°C

50 100 150 200 250

Figure 3 shows the PA6 experimental heat capacity data 240

together with the fitted polynomial plots according to
Eqs. 2 and 3. 220
Taking the above linear relationships for Cp,l and Cp,s

Melting enthalpy/J g–1

and assuming linear extrapolation over the whole tem- 200
perature range, the specific melting enthalpy of 100 %
crystalline PA6 at any temperature between Tg  and Tm  180
can be written from Eq. 1 as
160
DHm  ðPA6Þ ¼ 03:03 þ 1:8406T
 0:001577T 2 in J g1 ; with T in K ð4Þ
140 PA 66
The integration constant of Eq. 4 was determined by PA 6
using literature data for the enthalpy of fusion 120
DHm  & 230 J g-1 [8] of 100 % crystalline PA6 at
Tm  = 533 K. Though several different values have been 100
reported for DHm  (PA6), the above-mentioned value is 300 350 400 450 500 550
rather consensual. Temperature/K
The variation curve of DHm for PA6 as a function of
Fig. 4 Melting enthalpy, DHm , versus temperature of 100 % crys-
temperature is plotted in Fig. 4 according to Eq. 6. The
talline PA6 and PA66
roughly twofold increase in DHm between Tg  and Tm  is
surprisingly large and has never been mentioned so far in slow cooling of droplets dispersed in a polyethylene matrix
the literature. Only Sanchez et al. [35] mentioned the DHc which occurs about 50 C below that of bulk PA6 under
depression of PA6 in the case of the crystallization under similar conditions.
Considering the occurrence of crystal phase transfor-
mations during the DSC heating scan from Tg to Tm, one
Temperature/°C may wonder whether the difference in T-dependence of
–200 –100 0 100 200 300 DHm for the c-form and a-form crystals should be con-
3.0 sidered. This questioning can be alleviated by taking into
account the experimental evidence that the two forms have
very close DHm  values [8, 34].
2.5
Heat capacity/J g–1 K–1

Temperature dependence of the PA66 melting

2.0 enthalpy

Cpl
Cps
Polyamide-66 (PA66) is structurally close to PA6 and
1.5
Cps exp displays very similar thermal and thermo-mechanical
Cpl exp properties due to equivalent densities of H-bonds and
1.0 similar crystallinity. Moreover, as does PA6, PA66 may
display unstable crystal forms that reorganize into more
0.5
stable ones upon heating above Tg [12, 13].
Tg Tm Heat capacity values for PA66 are available from data
tables of Wunderlich et al. [32, 33]. The fitted polynomials
0.0 for Cp,l and Cp,s are the following ones
0 100 200 300 400 500 600
• for the liquid in the range 330–600 K:
Temperature/K
Cp;l ¼ 0:002069T þ 1:5517 in J g1 K1 ð5Þ
Fig. 3 Temperature variations of the heat capacities of the liquid,
Cp,l, and the solid, Cp,s, for PA6 obtained by curve-fitting of the • for the solid in the range 230–320 K:
experimental data from Ref. [31] (dashed curves are linear
extrapolations) Cp;s ¼ 0:005012T  0:0397 in J g1 K1 ð6Þ

123

Using Eqs. 1, 5, and 6, the temperature dependence of
the melting enthalpy of 100 % crystalline PA66 is then
given by the relation
DHm  ðPA66Þ ¼ 200:05 þ 1:5914T
 0:0014715T 2 in J g1 ; with T in K
ð7Þ
taking DHm  = 230 ± 70 J g-1 [5] at Tm  = 553 K. This
value of DHm  for PA66 is very close to that of PA6
[36, 37]. However, it should be noticed that the literature
data display a very large dispersion in the range
160–300 J g-1 [5].
The DHm variation with temperature for PA66 is plotted
in Fig. 4 between Tg and Tm  according to Eq. 7. From
 account the temperature dependence of the enthalpy of
Fig. 4, it appears that DHm of PA66 increases by a factor
1.5 between 323 and 538 K, i.e., a smaller effect than that
observed for PA6. The amplitude of this effect, however,
depends on the choice of the DHm  value of PA66 in the
range 160–300 J g-1.
Computation of PA6 crystallinity
From a practical standpoint, the two annealed PA6 samples
in Fig. 1 and the isothermal one display a melting en-
dotherm that does not exceed 30 K in width, and not other
thermal transition. In such cases, it is worthless making a
DHm correction in consideration of experimental errors and
reproducibility. In contrast, the quenched PA6 sample ex-
hibits cold crystallization just above Tg for which T-de-
 shown that the melting enthalpy of 100 % crystalline PA6
pendence of DHm is no longer negligible in regard to the
huge T-range between this process and the melting.
First, disregarding the temperature dependence and
 
taking a constant value DHm = DHc  = DHm  =
230 J g-1 whatever the temperature at which occurred the
two events, the total enthalpy of transformation DHc ?
DHm is computed by using the recommended linear inter-
polation of the baseline from the onset of the cold crys-
tallization up to the end of the melting [6, 31]. Then it
comes
Xc ¼ ðDHc þ DHm Þ=DHm  ¼ 40:7=230 ¼ 0:18 ð8Þ
Considering secondly the significant depression of the
specific heat of crystallization at the peak temperature of
the cold crystallization exotherm, Eq. 4 gives |DHc (55 C)
 
| = 131 J g-1. This huge drop of DHc  as compared to
DHm  is worth being taken into account. In such circum-
stances, the crystallinity can be computed as
Xc ¼ DHc =DHc  ð55  CÞ þ DHm =DHm  ð216  CÞ
¼ ð15:3=131Þ þ ð56:2=230Þ ¼ 0:13 ð9Þ
This latter value of the crystallinity is significantly lower
and certainly more correct than the one previously
123
C. Millot et al.
computed without considering the T-dependence of the
specific enthalpy of both fusion and crystallization of
100 % crystalline PA6. A more rigorous way of computing

Xc would be to consider the T-dependence of DHm and

DHc over the whole temperature range, not just in the T-
domains of the major transformations, i.e., cold crystal-
lization and melting. The incidence is insignificant as
compared to the computation made in Eq. 9.
Considering annealed and isothermally crystallized
samples, both exhibit thermal phenomena beyond 180 C
upon heating, either exo- or endothermic. Figure 4 shows
that in the temperature range [180 C–Tm], the deviation of
 
DHm ðTÞ and DHc ðTÞ from DHm  does not exceed 10 %.
In such instance, one may consider useless to take into
both fusion and crystallization for the computation of
crystallinity.
Concluding discussion
Rapidly cooled or quenched bulk PA6 undergoes partial
amorphization. Upon heating, cold crystallization occurs at
about 20 K above Tg. The crystalline phase that develops
thereof proved to be in the b-form, in agreement with
observations from Kolesov and Androsch [31]. Very gra-
dual re-organization into more stable forms occurs upon
heating up to the melting that finally occurs at about 160 K
above the cold crystallization exotherm. In parallel, it is
hugely depends on temperature in the (Tg   Tm  ) range. If
not taken into account, this phenomenon entails an erro-
neous estimation of the crystallinity from DSC. A similar
temperature dependence is shown for the melting enthalpy
of 100 % crystalline PA66.
Khanna and Kuhn [6] as well as Kolesov and Androsch
[31] have reported the occurrence of a broad exotherm
following the cold crystallization upon heating, and span-
ning up to about 180 C. This phenomenon was claimed to
be the footprint of a gradual increase in crystallinity of the
material and/or perfectioning of the ill-ordered crystals
initially grown during the cold crystallization process
(likely in b-form). In the present context of a strong T-
dependence of both the melting and the crystallization
enthalpies of PA6, i.e., DHm ðTÞ and DHc ðTÞ, the above
observation could be attributed in part to the gradual in-
 
crease in both DHm ðTÞ and DHc ðTÞ during the heating-
induced perfecting process. Indeed, the crystals that melt at
T1 with a melting enthalpy DHm (T1) recrystallize subse-
quently at T2 [ T1 with a heat of crystallization DHc(T2)
such that |DHc(T2)| [ DHm(T1) so that the resulting heat
balance is exothermic. In this instance, there would be no
Assessment of polyamide-6 crystallinity by DSC
increase in crystal content, but just an increase in crystal
perfection accompanied with higher melting point and
higher DHm . This does not mean that an increase in crystal
content could not occur in parallel. However, the two
phenomena could be hardly distinguished from each other
if occurring concomitantly.
It is to be noticed that the present approach relies on the
assumption that all solid forms of PA6, i.e., the glass and
the various crystal polymorphs, obey the same Cp variation
with temperature, in first approximation. The Cp difference
between the various solid forms is indeed negligible in
comparison with the DCp = Cp,s - Cp,l that is under con-
cern in Eq. 1. In contrast, the relevance of the present
approach has been previously demonstrated for other
polymers which display either a strong melting point de-
pression or a large temperature gap between crystallization
and melting. For instance, ethylene-based polymers and
copolymers may display Tm depression involving sig-
nificant DHm depression with respect to DHm  due to
structural defects in the chains that promote small and
imperfect crystals [38, 39]. As already pointed out in the
introduction, poly(ethylene-terephthalate) and poly(aryl-
ether-ether-ketone) [5] may exhibit cold crystallization
after fast cooling from the melt, in a similar way as PA6.
This process takes place far below Tf  so that DHc is
strongly depressed with respect to DHc  . In both cases, the
effect is great enough to be taken into account for crys-
tallinity calculations.
Acknowledgements The authors gratefully acknowledge the
Rhone-Alpes Region for the grant of a doctoral fellowship to C. Millot
(Academic Research Communities—Energies Division). The Euro-
pean Synchrotron Radiation Facility (Grenoble, France) is also ac-
knowledged for time allocation on the BM02 beamline for the WAXS
experiments. The authors are indebted to Dr. C. Rochas (CERMAV,
Grenoble) for assistance in the WAXS experiments and working of
the data.
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