Received: 26 February 2018 | Accepted: 3 April 2018

DOI: 10.1002/pcr2.10005

REVIEWS

Crystallization, recrystallization, and melting of polymer crystals

on heating and cooling examined with fast scanning calorimetry

Yoshitomo Furushima1 | Christoph Schick2,3 | Akihiko Toda4

1
Materials Characterization Laboratories, Toray Research Center Inc., Otsu, Shiga 520-8567, Japan
2
University of Rostock, Institute of Physics and Competence Centre CALOR, 18059 Rostock, Germany
3
Kazan Federal University, Kazan 420008, Russian Federation
4
Graduate school of Integrated Arts and Sciences, Hiroshima University,
Higashi-Hiroshima 739-8521, Japan

Correspondence
Yoshitomo Furushima, Materials
Abstract
Characterization Laboratories, Toray Fast scanning calorimetry (FSC) has been used to investigate the kinetics of nonisothermal crystal-
Research Center Inc., lization, isothermal crystallization, and melting for semicrystalline polymers (ie, poly(butylene
3–7, Sonoyama 3-chome, Otsu,
terephthalate, polyphenylene sulfide, and isotactic polypropylene). The scanning rate dependence
Shiga 520-8567, Japan.
Email: Yoshitomo_Furushima@trc.toray.co. of enthalpy of melt-crystallization, cold-crystallization, and recrystallization obtained from FSC are
jp quantitatively explained on the basis of Ozawa’s method. For isothermal kinetics, FSC allows to
obtain the annealing-temperature dependence of crystallization half-time in a wide range of the
Funding information
supercooling without any unwanted nucleation or crystallization during cooling. The effect of addi-
Grants-in-Aid for Scientific Research –
KAKENHI, Grant/Award Number: tives for nonisothermal or isothermal crystallization was also considered in this article. In addition,
JP16H04206; Ministry of Education and hyphenated technique of FSC and polarized optical microscopy clearly shows the differences in
Science of the Russian Federation, Grant/
crystallization kinetics and morphologies.
Award Number: 14.Y26.31.0019)

KEYWORDS
crystallization, fast scanning calorimetry, melting, recrystallization

1 | INTRODUCTION slow heating; hereafter the term, recrystallization, includes reorganiza-

Differential scanning calorimetry (DSC) is a common method for study-
ing crystallization and melting of polymers.[1] However, the tempera-
ture range for direct isothermal crystallization studies is limited to
regions close to the melting temperature, where crystallization pro-
ceeds slowly. Lower temperatures cannot be reached because crystalli-
zation starts upon cooling, even using the highest possible cooling rate
of the DSC. A similar limitation exists is the case of nonisothermal crys-
tallization; applicable scanning rates of conventional DSC are only up
to few K s21.[2] Therefore, in many cases, it is difficult to suppress the
effect of unwanted nucleation and crystallization during cooling.
Regarding the investigation of melting kinetics, multiple melting peaks
obtained from calorimetric measurements are a well-known feature of
semicrystalline polymers. [3,4]
Metastability of chain-folded polymer
crystals is one of the reasons of this complicated behavior due to
recrystallization and/or reorganization to more stable crystals during
tion. Therefore, it is difficult to estimate the zero-entropy-production
melting (ZEP) temperature using conventional DSC. Here, ZEP melting
is the melting of a metastable chain-folded polymer crystal without any
increase in entropy (ie, cold-crystallization, recrystallization, and super-
heating) during heating.[1]
Fast scanning calorimetry (FSC) is a powerful method to overcome
these limitations.[5–10] A nonadiabatic FSC method based on a chip cal-
orimeter was developed at the University of Rostock[11–13] while a
comparable commercial instrument was developed by Mettler-Toledo:
the Flash DSC 1.[8–10] The feature of fast temperature scanning of FSC
allows investigating crystallization, reorganization, and melting kinetics
quantitatively. The application of FSC has been successful in the scru-
tiny of these issues for polyamide (PA),[14–17] poly(acrylonitrile)
(PAN),[18] poly(E–caprolactone) (PCL),[19–21] polyethylene (PE),[22–25]
poly(ether ether ketone) (PEEK),[26–28] poly(ethylene terephthalate)
(PET),[29,30] poly(butylene terephthalate) (PBT),[31–37] poly(trimethylene

Polymer Crystallization. 2018;e10005. wileyonlinelibrary.com/journal/pcr2 V

C 2018 Wiley Periodicals, Inc. | 1 of 10
https://doi.org/10.1002/pcr2.10005
2 of 10 | FURUSHIMA ET AL.

FIGURE 1 Schematic representation of the three types of nonisothermal crystallization of polymers

terephthalate) (PTT),[38,39] poly(L-lactic acid) (PLLA),[40] isotactic poly- Figure 2 shows FSC traces on heating at a rate of 10 000 K s21 for
propylene (iPP),[32,41,42] polyphenylene sulfide (PPS),[43] isotactic poly- PBT with 0.1 wt% talc (hereafter talc-PBT). The endotherm due to
[44,45] [46,47]
styrene (iPS), poly(vinylidene fluoride) (PVDF), or polyvinyl melting becomes smaller as the previous cooling rate increases. At a
alcohol (PVA).[48] previous cooling rate of 50 000 K s21, samples show only glass transi-
In this article, we review kinetic studies on polymer crystallization tion. This means that the crystallization and even nucleation is fully
(nonisothermal or isothermal) and melting focusing on PBT, PPS, and suppressed during the previous cooling and the heating measurement.
iPP. The original works summarized in this article refer to Refs. 35, 36, At a previous cooling rate between 5000 and 50 000 K s21, exothermic
and 43. peaks due to cold-crystallization can be seen between 380 K and
440 K at heating with 10 000 K s21. The cold-crystallization peak area
2 | NONISOTHERMAL CRYSTALLIZATION is dependent on the number of nuclei before heating. Above the critical

Three types of nonisothermal crystallization process are mentioned in

this section. Figure 1 shows schematic image of nonisothermal crystalli-
zation of polymer. Melt-crystallization proceeds during cooling from
melt. Cold-crystallization is defined as the crystallization proceeding
above the glass transition temperature during heating from the glassy
state. The rather low heating rate employed in conventional DSC often
causes structural changes of metastable crystals into more stable struc-
tures during heating. This phenomenon is called recrystallization. Quan-
titative analysis of the kinetics of nonisothermal crystallization requires
a very wide range of cooling and heating rates (ie, from 1022 to 106 K
s21). Combination of DSC and FSC fulfills this request and allows
studying nonisothermal crystallization kinetics in a previously not
accessible scanning rate range.

2.1 | Melt-crystallization on cooling

To determine the critical cooling rate to suppress crystallization, the
sample is heated once to the molten state and then cooled at different
cooling rates. The heating measurements are also carried out with dif-
F I G U R E 2 Apparent heat capacity as function of temperature for
ferent scanning rates.
talc-PBT samples quenched at different cooling rates. The curves
First, the relation between heat of fusion and previous cooling rate were obtained upon heating at a rate of 10 000 K s21. (Repro-
is discussed for the quantitative understanding of melt-crystallization. duced from Ref. 35, with permission from Wiley Periodicals, Inc.)
FURUSHIMA ET AL.
FIGURE 3 Crystallinity as function of previous cooling rate from
the melt for PPS (green square), PBT (blue diamond), talc-PBT (red
diamond), and iPP with glass fiber (purple triangle). Lines represent
the result of fitting using Equation 15
cooling rate to suppress crystallization, the cold-crystallization enthalpy
depends on the number of active nuclei and the time for growth con-
trolled by the heating rate. The cold-crystallization enthalpy can be
considered to be a relative measure of the number of nuclei present
prior to the heating scan. The same behaviors were also observed for
PCL,[19–21,49] PA6,[50] and PA11.[51]
The crystallinity, /, is calculated as follows:
DHtotal
/5 (1)
DH0m
where DHtotal is the observed total heat of fusion, and DH0m is the heat
of fusion for the perfect and infinite large crystal at the actual melting
temperature. To be exact, crystallinity determination as described
above is known to be inadequate, because the temperature depend-
ence of heat of fusion and intersection between the baseline and the
trace are not considered in Equation 1. However, these influences for
calculating the crystallinity are often negligible; the limiting factor as
regards accuracy is the instability of the calorimeter.[52] The relation
FIGURE 4 Schematic representation of overall crystallization process. The original idea quoted from Ref. 20
| 3 of 10
between crystallinity and previous cooling rate is plotted in Figure 3.
As a reference, the results for PPS,[43] PBT,[35] and iPP with glass fiber
(GF) are also plotted in the figure. The critical cooling rate to
suppress crystallization, bcritical, is 40 K s21 for PPS, 2000 K s21 for
PBT, 7000 K s21 for talc-PBT, and 10 000 K s21 for iPP with GF.
Despite of the polymer species, crystallinity decreases with
increasing the previous cooling rate. It seems that the cooling rate
dependence of crystallinity shows two different areas. At low cooling
rate, decrease in crystallinity seems to be proportional to logarithm of
previous cooling rate. After that, at higher cooling rate, crystallinity
decrease exponentially with increasing previous cooling rate. In the
next section, we shortly summarize the nonisothermal crystallization
behavior quantitatively.
2.2 | Quantitative understanding of nonisothermal
crystallization kinetics
Figure 4 shows schematic route of crystallization. Firstly, it requires a
certain amount of nuclei to start crystallization. In general, nucleation
occurs on cooling from melt. Fast enough cooling avoids measurable
growth of crystals starting from heterogeneous nuclei on cooling of
bulk samples and enforces homogeneous nucleation at high supercool-
ing. Primary crystallization proceeds from available homogeneous and
heterogeneous nuclei. Subsequently, after sufficient annealing, the
sample space will be filled up with spherulites or other crystalline mor-
phologies. For longer annealing, the crystalline morphology slowly gets
perfected (secondary crystallization), often resulting in a linear increase
of crystallinity with the logarithm of annealing time. As is the case for
melt-crystallization, both primary and subsequent secondary crystalliza-
tion proceed in most semicrystalline polymer at slow cooling using con-
ventional DSC. In the case of fast cooling using FSC, we can control
crystallinity of the sample in a wide range. Based on the above men-
tioned crystallization mechanism, we succeed to describe the cooling
rate dependence of total enthalpy change (which is in proportion to
the crystallinity) using Ozawa model.[53–55]
4 of 10 | FURUSHIMA ET AL.

In terms of final crystallinity of primary crystal after the cooling In Figure 3, there seems to be a secondary crystallization process
process, /end, Kolmogorov’s interpretation of the Avrami model of on slow cooling; cooling rates below 1000 K s21 for talc-PBT. For the
crystallization is as follows: evolution of total crystallinity with cooling rate in Figure 3, we add the
secondary crystallization (crystal perfection) term, /2nd, as follows[56]:
/end 512exp½2/0end  (2)
 
DT
where /0end represents the degree of transformation counted with the /2nd 5A logðDtÞ  A log  2A flogðbcool Þ2logðb2nd Þg (13)
bcool
allowance of the overlap of the crystalline domains. For the case of
heterogeneous nucleation with domain size, D, /0end is represented as where b2nd is the characteristic cooling rate of secondary crystalliza-
tion. We assumed that A is constant and independent of temperature.
/0end 5I0 ½Dð0; tend Þd (3)
We further assume that the secondary crystallization is fully sup-
with constant I0 and d of 1, 2, 3. With the rate of domain growth, dD/ pressed above the characteristic cooling rate of secondary crystalliza-
dt 5 V(T), D(0, tend) can be rewritten as follows: tion b2nd. Then, taking into account Equations 12 and 13, the cooling
ð tend ð TH rate dependence of total enthalpy change in Figure 3 is fitted by the
Dð0; tend Þ5 V ðT Þdt5 V ðT ÞdT ðbcool Þ21 5vðTH ; TL Þðbcool Þ21 (4)
0 TL following function:
        
and bc n b 1 b 2b2nd
DHtotal 5C2Bexp 2 2A log cool 3 12 cool
bcool b2nd 2 jbcool 2b2nd j
/0end 5I0 ½Dð0; tend Þd 5I0 ½vðTH ; TL Þd ðbcool Þ2d (5) (14)
where bcool represents cooling rate and TH and TL are the highest and where A, B, and C are constants. As mentioned before, it is suggested
lowest temperatures of the temperature scan during the cooling process. that secondary crystallization proceeds only at slow cooling rates.
m(TH, TL) is the domain size between TH and TL. Then /end is rewritten as Note, in the previous study, the cooling rate dependence of the crystal-
"   #
bc d linity was described using a simple phenomenological model with
/end 512exp 2 with d 51; 2; 3 (6)
bcool generic crystallization function and retardation function.[57] The form
of the functions is different from the present equation.
where bc is the characteristic cooling rate of domain growth derived
For example, the b2nd/bc was 0.68 for talc-PBT. The bc was
from heterogeneous nucleation and is represented as
1473 K s21. Compared with the critical cooling rate to suppress the
ð TH
bc 5I0 =d crystallization during cooling, bcritical, the bc is slower. As shown in
1
V ðT ÞdT for heterogeneous nucleation: (7)
TL
Equations 6 and 10, the bc is integral to the overall domain growth
Homogeneous nucleation is more likely the case for crystallization rate. Therefore, the bc is related to both of the crystal growth rate and
at fast cooling. In the case of homogeneous nucleation, /0end in Equa- nucleation rate during cooling. On the other hand, the bcritical is related
tion 2 is then indicated as only to the beginning of the formation of nuclei on cooling. It is worth
ð tend
comparing both rates. The bc/bcritical value is 0.1 and 0.2 for PBT and
/0end 5 IðsÞ½Dðs; tend Þd ds (8)
0 talc-PBT, respectively. The obtained n was 1.7 for PBT and 2.5 for talc-
with homogeneous nucleation rate I and PBT.[35] It seems that those differences in crystallization kinetics, in the
ð tend ð Ts presence or absence of talc, are due to the difference in nucleation
Dðs; tend Þ5 V ðT Þdt5 V ðT ÞdT ðbcool Þ21 5vðTs ; TL Þðbcool Þ21 (9)
s TL density.

Then, /end is represented as follows:

2.3 | Cold-crystallization
 ð TH 
/end 512exp 2bcool 2ðd11Þ IðTs Þ½vðTs ; TL Þd dTs One can observe faster overall crystallization due to enhanced primary
TL
"   # (10) nucleation when heating from the glassy state and crystallizing at low
bc d11
512exp 2 temperature than on cooling from the melt. Such low-temperature
bcool
crystallization is called cold-crystallization.[1] As already shown in Figure
where bc is the characteristic cooling rate of domain growth and is rep-
2, at a previous cooling rate between 5000 and 50 000 K s21, exother-
resented as
mic peaks due to cold-crystallization can be seen in talc-PBT. In this
ð TH 1 =d11
section, taking PBT and talc-PBT as an analogy, we introduce the rela-
bc 5 IðTs Þ½vðTs ; TL Þd dTs for homogeneous nucleation:
TL tion between enthalpy of cold-crystallization and scanning rate (ie,
(11) measurement heating rate or previous cooling rate).
As a result, final crystallinity can be summarized as follows: As seen in Figure 3, in the previous cooling rate range above
   
bc n 2000 K s21 of PBT, crystallinity becomes zero; namely, there are no
/end 512exp 2 (12)
bcool crystals in the sample. This means that the homogeneous and hetero-
where n 5 d for heterogeneous nucleation and n 5 d 1 1 for homoge- geneous nuclei, which may have been formed during the cooling pro-
neous nucleation. Furthermore, Equations 7 and 11 represent the bc of cess, did not grow to a measurable size during cooling.[19–21,25] At this
heterogeneous and homogeneous nucleation, respectively. range of cooling rate, cold-crystallization can be observed depending
FURUSHIMA ET AL. | 5 of 10

ð TH
/0end 5bheat 2ðd11Þ IðTs Þ½vðTH ; Ts Þd dTs (18)
TL

The heating rate dependences of DHcc at previous cooling rates of

10 000 and 50 000 K s21 are shown in Figure 6 for both PBT samples.
Heating rate dependences of DHcc of PBT coincides with that of talc-
PBT at 10 000 and 50 000 K s21; it seems that talc does not affect the
cold-crystallization during heating. For the heating run at 10 000 K s21,
nuclei formed on cooling act as preexisting seeds for crystallization,
that is, I0 in Equation 16, so that the crystallization is the fastest. On
the other hand, for the heating at 50 000 K s21, crystallization starts
from pure supercooled liquid without homogeneous nuclei. Only addi-
tional heterogeneous nuclei introduced by the talc particles are pres-
ent. Under those conditions, the enthalpy of cold-crystallization on
heating can also be written in the same way as described in Equation
FIGURE 5 Enthalpy of cold-crystallization for PBT as function of
14 with heating rate, bheat, as follows:
previous cooling rate from the melt. Each symbol represents the
result obtained from different heating rate (ie, 䊊 of 2500 K s21, 䉱         
bc n b 1 b 2b2nd
of 5000 K s21, w of 10 000 K s21, and 䉲 of 20 000 K s21) DHcc 5C2Bexp 2 2A log heat 3 12 heat
bheat b2nd 2 jbheat 2b2nd j
(19)
on the heating rate. This means nuclei does not contribute to the total
with the following bc
enthalpy change; however, they can grow into crystals during heating.
Figure 5 shows the relation between enthalpy of cold-crystallization ð TH 1 =d
(DHcc) and previous cooling rate for PBT. At heating rate of 50 000 K bc 5 IðTs Þ½vðTH ; Ts Þd dTs (20)
TL
s21, DHcc becomes zero. Under this situation, cold crystallization during
As shown in Figure 6, crystallization during cooling and that during
heating is fully suppressed since there is not enough time for measura-
heating after previous cooling rate of 50 000 K s21, both start from
ble crystal growth starting from a small number of heterogeneous or
supercooled liquid without preexisting nuclei. Even so, the crystalliza-
homogeneous nuclei. At heating rate of 5000 and 10 000 K s21, the
tion on heating was faster at the same scan rate and not influenced by
DHcc gradually decreases with increasing the previous cooling rate. This
talc. This is due to the hysteresis of temperature scan, namely due to
corresponds to the decrease in the number of nuclei formed during the
the difference between Equations 11 and 20. During cooling, sample
cooling process. Finally, DHcc becomes either saturated or zero, mean-
passes the temperature range of homogeneous nucleation in the final
ing no nuclei formed on cooling. The DHcc is due to the growth of crys-
stage, while during heating, the temperature range is passed in the ini-
tals formed during the heating process and the behavior strongly
tial stage, so that the cold-crystallization from the glass on heating can
depends on heating rate. At heating rate of 2500 K s21, DHcc shows
start with a large number of homogeneous nuclei and becomes faster
constant value independent of the previous cooling rate. Nucleation
than the crystallization from the melt on cooling.
and subsequent cold-crystallization proceed during slow-heating. The
similar behavior was observed for talc-PBT. It is said that above-
mentioned nucleation process is also occurred in the talc-PBT.
Heating rate dependence of crystallinity of cold-crystallization
(cold-crystallinity) can also be written in the same way as mentioned in
Equations 2–12 with heating rate, bheat, as follows:
ð tend ð TH
Dð0; tend Þ5 V ðT Þdt5 V ðT ÞdT ðbheat Þ21 5vðTH ; TL Þðbheat Þ21
0 TL
(15)

and

/0end 5I0 ½Dð0; tend Þd 5I0 ½vðTH ; TL Þd ðbheat Þ2d (16)

for heterogeneous nucleation. On heating, the nuclei can be also the

ones formed during the previous cooling.
And for homogeneous nucleation,
ð tend ð TH
Dðs; tend Þ5 V ðT Þdt5 V ðT ÞdT ðbheat Þ21 5vðTH ; Ts Þðbheat Þ21 (17)
s Ts
F I G U R E 6 Enthalpy of cold-crystallization as function of heating
and rate for PBT and talc-PBT. The lines are fitted by Equation 19
6 of 10 | FURUSHIMA ET AL.

F I G U R E 8 Schematic description of the progress of melting and

recrystallization during heating

DHhigh2T
/recryst: 5
DHtotal

where DHtotal is the total enthalpy change, DHhigh is the melting

enthalpy of the recrystallized crystals and is obtained from peak sepa-
F I G U R E 7 FSC curves of PBT crystallized at 340 K for 100 s.
ration of high-T peak in Figure 7. Figure 9 shows the heating rate
Heating rate was ranged from 10 000 to 100 000 K s21.
(Reproduced from Ref. 36, with permission from Elsevier Ltd.) dependence of recrystallinity. The behaviors are similar with drastic
increase with decreasing scanning rate and subsequent log|bj depend-
2.4 | Recrystallization ence at even lower scanning rates. For the kinetics of crystallization
from the melt and that of cold-crystallization, similar fitting equation as
The recrystallization behavior has also been examined in a quantitative
above of Equation 19 can be derived. As plotted by red line in Figure 9,
manner by the comparison of the characteristic scanning rate deter-
the recrystallinity has been successfully determined as a function of
mined by the Ozawa’s method. Measurements of FSC with wide range
heating rate.
of heating rate allow analyzing recrystallization kinetics. Figure 7 shows
Figure 10 summarizes the scanning rate dependence of normalized
the heating rate dependence of melting behavior for the PBT prepared crystallinity for PBT. Table 1 summarizes the fitting parameters for
at the annealing temperature of 340 K for 100 seconds. Heating rate those processes. Compared with the melt-crystallization and cold-
dependence of melting temperature shows the double melting peaks crystallization kinetics, it is confirmed in a quantitative manner that the
(low-T and high-T) on the FSC curves. The enthalpy of low-T peak recrystallization kinetics is the fastest process. This is because many
increases with increasing heating rate. In addition, the peak temperature crystals which are not fully disordered during heating act as nuclei.
of low-T peak also increases with increasing heating rate due to super- Present result supports the previous estimation that recrystallization
heating. For the high-T peak, meanwhile, enthalpy decreases with should be faster than initial crystallization due to large difference in
increasing heating rate, and the peak temperature first decreases and nuclei densities.[30,58] On the other hand, for cold-crystallization, a very
reaches to a constant temperature at faster heating rates. Finally, the high number of nuclei is formed, too, when passing the maximum of
high-T peak disappears at a heating rate of 100 000 K s21. Note that homogenous nucleation. Therefore, for recrystallization faster than
independent of heating rate, the total enthalpy change (DHtotal), which is cold-crystallization even under much smaller supercooling, there should
the sum of enthalpy of low-T peak (DHlow) and that of high-T peak be additional accelerating factors such as the existence of largely
(DHhigh), is constant. These results strongly suggest that the high-T peak ordered melt which can recrystallize quickly.[40]
is assigned to the melting of recrystallized crystals and the low-T peak is
attributed to the melting of isothermally formed original crystals.
Figure 8 shows schematic description of the progress of melting
and recrystallization during heating. Double melting peak observed on
the FSC curve at slow heating rate can be understood in the following
way. Melting of original crystals and recrystallization proceed simulta-
neously during slow heating. Finally, the recrystallized crystal melts at
higher temperature than the original one. As a result, double melting
peak was observed on FSC curve at slow heating. Recrystallization is a
very rapid process and the critical heating rate to suppress recrystalliza-
tion during heating is 100 000 K s21 for PBT crystals prepared by
annealing at 340 K for 100 seconds.
Considering the quantitative recrystallization kinetics, we define F I G U R E 9 Relation between recrystallinity and heating rate.
the recrystallinity as follows: (Reproduced from Ref. 36, with permission from Elsevier Ltd.)
FURUSHIMA ET AL. | 7 of 10

FIGURE 10 Scanning rate dependence of normalized crystallinity.

Red filled-circle indicates heating rate dependence of recrystallinity
for PBT crystallized at 340 K for 100 seconds. The results of cool- FIGURE 11 FSC curves for isothermally crystallized PBT at 450 K.
ing rate dependence of melt-crystallinity (blue), heating rate (Reproduced from Ref. 35, with permission from Wiley Periodicals,
dependence of cold-crystallinity from glass (green) are also shown Inc.)
in the figure. (Reproduced from Ref. 36, with permission from
Elsevier Ltd.) Avrami index of overall crystallization, and A2nd is a secondary crystalli-
zation parameter.[56] The latter part of the secondary crystallization
3 | ISOTHERMAL CRYSTALLIZATION term is used to adjust it to zero before primary crystallization half-time.
KINETICS Figure 13 shows the crystallization half-time (t1/2) over the anneal-
ing temperature (Tiso) for PBT and talc-PBT. A bimodal curve with two
In this section, we summarize isothermal crystallization from super- minima is observed. This finding is in agreement with previous observa-
cooled liquid state. FSC allows suppressing nucleation during cooling tions for PBT.[31–35,37] The t1/2 is not influenced by the talc below Tiso
from the melt to isothermal annealing temperature. Figure 11 shows of 340 K. As Wurm et al. mentioned,[33] this behavior is expected
the FSC heating curves of PBT after annealing at 450 K for different because homogenous nucleation is dominant in this temperature range,
times. Enthalpy of fusion increases with annealing time due to the crys- and growable homogeneous nuclei are present. Simultaneous growth
tal growth during the isothermal process. Figure 12 shows the total of all these homogeneous nuclei immediately results in a space-filling
enthalpy change (DHtotal) of isothermally crystallized samples plotted semicrystalline morphology.[59,60] The low temperature regime can
against annealing time at Tiso of 450 K. The DHtotal increases with time therefore be assigned to crystallization via homogeneous nucleation.
due to primary and secondary crystallization.
The Kolmogorov-Johnson-Mehl-Avrami equation and the logarith-
mic increase in the secondary stage were supposed to fit the data of
Figure 12 to obtain crystallization half-time.[54–56]
" ( !n )# ( )
t t
DHtotal 5DHmax 12exp 2 ln2 1A2nd log
t1 =2 t1 =2
! (22)
1 t2t1 =2
3 11
2 jt2t1 =2 j

where DHmax is the enthalpy change at the end of primary crystalliza-

tion, t is the annealing time, t1/2 is the crystallization half-time, n is the

T AB LE 1 Fitting parameter of Equations 14 and 19 for PBT (Repro-

duced with permission from Ref. 36, with permission from Elsevier
Ltd.)

C B A n bc b2nd

Recrystallization 0.74 0.96 0.05 1 29 000 10 000

FIGURE 12 Annealing time dependence of total enthalpy change
Cold-crystallization 0.91 0.96 0.15 3 4000 - for PBT and talc-PBT at a crystallization temperature of 450 K.
(Reproduced from Ref. 35, with permission from Wiley Periodicals,
Melt-crystallization 0.83 0.83 0.26 1.9 200 -
Inc.)
8 of 10 | FURUSHIMA
FIGURE 13 Annealing temperature dependence of crystallization
half-time for PBT and talc-PBT. (Reproduced from Ref. 35, with
permission from Wiley Periodicals, Inc.)
On the other hand, the high temperature regime represents crystalliza-
tion via heterogeneous nucleation. Here, the number of homogeneous
nuclei is orders of magnitude lower, and crystallization after heteroge-
neous nucleation dominates. The addition of talc as heterogeneities,
which act as nuclei, speeds up the overall crystallization rate.
It is noteworthy that although the t1/2 is not influenced by the talc
at isothermal temperatures between 300 and 340 K. Molecular dynam-
ics simulation for the early stage of homogeneous nucleation suggests
that the chains forming the nuclei showed bundle-like aggregates. Fur-
thermore, the chains that form the nuclei, as a whole, took chain-
folded conformations.[61,62] This result suggests that the dynamics of
the whole polymer chain affects the kinetics of forming the homogene-
ous nuclei. Therefore, it could be thought that talc suppresses the
dynamics of the molecular chain near the glass transition temperature.
To investigate the influence of homogeneous nucleation at 280 K
on the crystallization at the second annealing at 450 K, Tammann’s
FIGURE 14 POM image of isothermal crystallized PBT and its talc
composites
ET AL.
two-stage nuclei formation and growth approach with FSC was
applied.[19,63] This approach is advantageous in order to investigate
homogeneous nucleation within experimentally accessible time scales.
Homogeneous nuclei can be formed at low temperatures (in this study,
at 280 K), which then grow at sufficiently higher temperatures (in this
study, at 450 K). As shown in Figure 12, pre-annealing at 280 K for
1000 seconds shortens the crystallization time at 450 K for PBT (not
for talc-PBT). The t1/2 of pre-annealing at 280 K is shown in Figure 13
as open symbol. This result suggests that at heating with 50 000 K s21
homogeneous nuclei formed at 280 K do not melt/disorder until
450 K, and enhanced crystal growth at the isothermal process at 450 K
for PBT. On the other hand, for talc-PBT, a clear difference is not
observed either with or without the pre-annealing at 280 K. It may
indicate, for talc-PBT, the nuclei melt/disorder below 450 K during the
heating. We can also think of a possibility that the functional groups of
the talc surface might depress the mobility of the PBT chain and sup-
press the nucleation at 280 K. The t1/2 at 460 K after the same pre-
annealing at 280 K is also carried out. At Tiso of 460 K, the half-time
crystallizations are almost same regardless of the presence or absence
of pre-annealing at 280 K for both PBT and talc-PBT. For PBT, it seems
the nuclei melt/disorder between 450 and 460 K during the heating,
which is 170–180 K higher than the nucleation temperature.
Figure 14 shows polarization optical microscope (POM) image for
isothermally crystallized PBT samples. The samples were isothermally
crystallized for 400 seconds at 330 K or 410 K (which are chosen from
two minima temperature at the bimodal dependence of t1/2 as shown
in Figure 13). Note the annealing time of 400 seconds is long enough
to progress secondary crystallization. At 330K where homogeneous
FIGURE 15 Annealing temperature dependence of half-time crys-
tallization for PPS. POM image of isothermal crystallized PPS for
400 seconds at 1208C (left) and 2208C (right). (Reproduced from
Ref. 43, with permission from Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.)
FURUSHIMA ET AL.
nucleation occurs, there are no spherulites for both PBT samples. On
the other hand, at 410 K, spherulites were observed for both samples,
and the size is smaller for talc-PBT. This means the nucleation density
is higher for talc-PBT.
Monomodal shape can be seen in the annealing temperature
dependence of crystallization half-time for PPS (see Figure 15). POM
images of PPS samples in Figure 15 were isothermally crystallized at
120 or 2208C for 400 seconds. At an isothermal temperature of 2208C,
the radius of spherulites is 30–40 lm. At 1608C, the radius of spheru-
lites decreases to about 20 lm. Finally, at 1208C, spherulites with a
radius of around 10 lm were observed on the surface between sample
and sensor.
4 | CONCLUSIONS
FSC is a relatively new type of DSC instrument. It has been developed
to obtain the behavior of materials at fast heating and cooling rates.
The wide heating and cooling rate range enables the investigation of
nonisothermal crystallization and isothermal crystallization of semicrys-
talline polymers. First, the heat of fusion after cooling was discussed
for the quantitative understanding of melt-crystallization on cooling.
Despite polymer species, crystallinity decreases with increasing cooling
rate. The cooling rate dependence of crystallinity showed two distinc-
tive areas. Heating rate dependence of cold-crystallization and recrys-
tallization on heating also showed similar behavior. The scanning rate
dependence of enthalpy of melt-crystallization, cold-crystallization, and
recrystallization obtained from FSC are quantitatively explained in the
same model on the basis of Ozawa’s method.
FSC allows suppressing nucleation during cooling from the melt to
isothermal annealing temperature. We can obtain the annealing-
temperature dependence of crystallization half-time in a wide range of
the supercooling without any unwanted nucleation or crystallization
during cooling. A bimodal curve with two minima was observed for
PBT and talc-PBT, while for PPS the curve was monomodal. Tam-
mann’s two-stage nuclei formation and growth approach with FSC was
applied for PBT samples and confirmed that the homogeneous nuclei
formed at 280 K were still active for crystallization at much higher tem-
perature at 450 K. Combined analyses of FSC and other experiments
(ie, optics or mechanics) for crystallization kinetics awaits future
investigation.
AC KNOWLE DGME NT S
This work was financially supported by Toray Research Center, Inc.,
Japan. Part of this work was supported by the Grants-in-Aid for Sci-
entific Research – KAKENHI (JP16H04206). CS acknowledges finan-
cial support from the Ministry of Education and Science of the
Russian Federation (Grant 14.Y26.31.0019).
OR CID
Yoshitomo Furushima http://orcid.org/0000-0003-0705-184X
Christoph Schick http://orcid.org/0000-0001-6736-5491
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