Accepted Manuscript

Characterization of polymers based on differential scanning calorimetry based

techniques

Joanna Drzeżdżon, Dagmara Jacewicz, Alicja Sielicka, Lech Chmurzyński

PII: S0165-9936(18)30383-2
DOI: https://doi.org/10.1016/j.trac.2018.10.037
Reference: TRAC 15301

To appear in: Trends in Analytical Chemistry

Received Date: 27 July 2018

Revised Date: 27 September 2018
Accepted Date: 31 October 2018

Please cite this article as: J. Drzeżdżon, D. Jacewicz, A. Sielicka, L. Chmurzyński, Characterization of
polymers based on differential scanning calorimetry based techniques, Trends in Analytical Chemistry,
https://doi.org/10.1016/j.trac.2018.10.037.

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 ACCEPTED MANUSCRIPT
Characterization of polymers based on Differential Scanning Calorimetry
based techniques

Joanna Drzeżdżon1, Dagmara Jacewicz1, Alicja Sielicka2,3, Lech Chmurzyński1*

1
Faculty of Chemistry, University of Gdansk, Wita Stwosza 63, 80-308 Gdansk, Poland

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2
Department of Biochemistry, Medical University of Gdansk, Gdansk, Poland
3
Structural Heart Research & Innovation Laboratory, Carlyle Fraser Heart Center, Division

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of Cardiothoracic Surgery, Emory University, Atlanta, USA.

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Abstract

Polymers have a wide range of applications, in the production of packaging, medical

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and the automotive industries. Due to the ample and large-scale usage of polymers in various
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industries, scientists are now looking for novel polymer materials with thermoplastic
properties or with the high mechanical strength while, maintaining a lightweight.
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Differential Scanning Calorimetry (DSC) based techniques such as conventional DSC,

Parallel-Nano DSC (PNDSC), MicroElectroMechanical Systems (MEMS)-DSC, Modulated-
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Temperature DSC (MTDSC), Infrared (IR)-heated DSC, Gas Flow-Modulated DSC

(GFMDSC), High-Performance (HPer) DSC, Pressure Perturbation Calorimetry (PPC), Flash
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DSC and Self-Referencing DSC (SRDSC) are frequently used to study and analyze the
thermal properties of polymer materials. These techniques allow researchers to determine
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melting temperatures, polymorphic transformations and decompositions. This review

highlights the recent developments within the field of DSC applications, which show new
possibilities in the applications of DSC for physicochemical analysis.
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Keywords: Differential scanning calorimetry; Pressure perturbation calorimetry; Polymers;

Polymorphic transformations; Thermal properties

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* Corresponding author. Tel: +48 58 523 50 61; fax: +48 58 523 54 72
E-mail address: lech.chmurzynski@ug.edu.pl (L. Chmurzyński)
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1. Introduction
The first construction and principles of operation of the Differential Adiabatic
Scanning Microcalorimeter (DASM) were reported in 1964 [1]. From that moment, the
Differential Scanning Calorimetry (DSC) technology has developed rapidly. The analysis of
the differences between the response to heating of the sample and reference cells allows to
minimize the influence of the solvent and other factors on the thermal effects during the

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measurement [1]. The development of the DSC method was based on the miniaturization of
measuring cells to increase the sensitivity of the method [2]. The progress of research in this

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direction has been crowned with the fact that in 2010 the Miniaturized Ceramic Differential
Scanning Calorimeter (MC-DSC) was implemented and reported [2]. MC-DSC with a

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crucible and an oven has the following dimensions: 11 mm × 39 mm × 1.5 mm [2].
Techniques based on DSC are very important in polymer science. DSC is used to
measure and analyze the reaction of polymers to heat. The properties such as the heat

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capacity, the temperature of glass transition, the crystallization temperature, the melting
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temperature characterize the polymer materials (Fig. 1.). Based on the obtained DSC curve
the previously mentioned properties of polymers are investigated [3]. The use of DSC in the
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polymer studies serves to determine the transition enthalpy, the degree of crystallinity and the
thermal conductivity of polymer materials [3]. These listed quantities are associated with
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melting ranges for polymers, but DSC is also used in research on the release of polymer
strains, e.g. the studies on the mesophase transition, the quality control of strains and
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determination of purity [3]. The development of DSC-based methods has contributed to the
fact that nowadays there is the wide range of DSC scanning from 1 µK · s-1 to 1 MK · s-1 at
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maximum heating and cooling [4]. The level of scanning in DSC is dependent on the polymer
being tested [4]. The semicrystalline polymers and the choice of scan rates in DSC for these
polymers are considered a special case in the DSC studies, because the phase transitions are
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time-dependent [4]. Despite the progress of DSC methods, there are still a few gaps in the
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literature related to polymer research problems, e.g. the multiple peaks in the melting curve
analysis.
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Fig. 1. Applications of DSC.
This review is focused on the following techniques: conventional DSC, Parallel-Nano

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DSC (PNDSC), MicroElectroMechanical Systems (MEMS)-DSC, Modulated-Temperature
DSC (MTDSC), Infrared (IR)-heated DSC, Gas Flow-Modulated DSC (GFMDSC), High-

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Performance (HPer) DSC, Pressure Perturbation Calorimetry (PPC), Flash DSC and Self-
Referencing DSC (SRDSC). We examine the latest progression in the field of DSC- based
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techniques. We also identify the knowledge gaps in the characterization of polymers using a
variety of DSC techniques.
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2. Conventional DSC
The “Conventional DSC“ is the basic method of DSC techniques, involving the
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measurement of heat transfer using a comparison of a sample containing test material with a
reference sample. During the measurement, a constant rate of heating or cooling is maintained
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[5]. DSC is used in the identification of polymeric materials based on their properties such as
melting point, glass transition and crystallization. DSC analysis is very often supported by
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thermogravimetry (TG). Often, when polymers are tested, the last transition is below the
operational range of most conventional DSCs, so this technique may not work and one
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method of extended DSC must be used [4].

Recently DSC curves for 600 different polymers along with commercial data have
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been added to the existing the KIMW library (KIMW Testing & Analysis Association) which
is helpful for researchers [5]. Unfortunately, this library is available only for the Identify
program – a data analysis software from TG and DSC [5]. The Identify program allows for
easy comparison of the curve resulting from measuring the sample with the curve in the
database. As of 2017, the limitations of the KIMW library have been slightly reduced. An
ambiguous interpretation of the measurement signal has been somewhat offset by combining
two types of measurements such as an improved search system in the database [5]. In our
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opinion, it is necessary to extend the findings in the Identify program because the ideal
overlap of the curves is very dependent on the measurement conditions, and even this depends
on the type of crucible in which the measurement is made and on the lid.
By analyzing reports on the development of DSC methods in polymer research, it is
worth noting that in 2016 Tan and Torkelson reported the designing of polymer nanotubes
using DSC technique [6]. DSC has been used to study changes in the glass transition

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temperature of poly(methyl methacrylate) (PMMA) in the form of nanotubes, which are
additionally supported in templates from anodized aluminum oxide (AAO). The motivation

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for the research conducted by Tan and Torkelson was that modifications to the matrix surface
affect the thermal stability of polymeric materials. It was shown that the molecular weight

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change of the polymer correlates with the change in the thickness of the nanotube walls. The
thickness of the polymer nanotubes is strictly dependent on the radius of gyration (Rg) of the
polymeric material [6]. These studies led to determine the formula showing the relationship

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between Rg and the thickness of the nanotube, which is as follows [6]:
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ttube ≈ 2 Rg + 9 nm (1)
The DSC technique was used to confirm the dependence of limitations on Tg value changes,
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and the results show that Tg-confinement effects decrease as follows: α-Al2O3 films > γ-Al2O3
lamps > sput-Al2O3 films > Si/SiOx foils [6].
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In addition to research on the PMMA polymer, which is widely used industrially as

acrylic glass, the DSC method was used to study the properties of other polymer groups also
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used in industry, e.g. polymers and copolymers being derivatives of poly(1,4-butylene 2,5-
furandicarboxylate) (PBF) [7]. The tested polymer family has applications in the electronics
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and automotive industry because the studied polymers are within the group of thermoplastic
elastomers. The group of copolymers and polymers based on PBF was studied by the
conventional DSC method in order to investigate thermal and crystallization properties. The
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series of co-polyesters of poly(1,4-butylene 2,5-furandicarboxylate)-co-poly((poly(ethylene

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glycol))2,5-furandicarboxylate) (PBF/PEGF) (based on PBF) has been obtained by

introducing different molar amounts of PEG relative to PBF [7]. The results obtained by DSC
show that PBF and PEGF have Tg equals 71.1 °C and -35.8 °C, respectively, while the studied
family of co-polyesters PBF/PEGF has Tg in the range form -43.1 °C to -35.4 °C [7].
Moreover, the values of cold crystallisation temperature (Tcc) were determined only for the
co-polyesters containing the same molar content of PBF and PEGF or when the molar content
PEGF was greater than the number of PBF moles in the co-polyester [7]. Tcc is 0.22 °C for
the molar ration PBF/PEGF = 50/50 and -26.0 °C for the molar ration PBF/PEGF = 34/66 [7].
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The endothermic peaks on the co-polyester thermograms indicate Tm. The Tm values for the
various co-polyesters are very dependent on the molar ratio of PBF and PEGF in such a way
that the molar content of PEGF higher than PBF in the co-polyester causes the Tm of co-
polyester to be close to Tm for PEGF [7]. It is interesting that PBF / PEGF obtained and
tested come from renewable sources, which is in line with trends in modern chemistry. We
think that it is worth to do this type of research, because it is a kind of reconciliation of the

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industrial chemistry development with the protection of the environment.
The conventional DSC method is used to the advanced characterization of molecularly

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imprinted polymers (MIP) [8]. MIP as the recognition elements are the topic of the
contemporary research because they have tridimensional cavities binding of analyte which is

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the target of the studies. They are potential substitutes for many recognition elements. The
replacement of antibodies is one of the applications of MIP. The results of the studies on
thermal properties of MIP show that they are thermally stable up to 250 °C [8].

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Carbamazepine (CBZ) is often used as a model template in the DSC studies of MIP.
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Nonimprinted polymers bind less carbamazepine compared to MIP [8]. Examining the MIP
after bonding with CBZ, the endothermic peak at 190 °C is observed on the DSC
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thermograms as an effect of CBZ melting [8].

Although many polymer samples can be tested with conventional DSC, unfortunately
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it has numerous limitations. One limitation is that thermal transitions are often related with
other processes such as the enthalpic relaxation at the glass transition. In this setting, polymer
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samples must be studied with other methods such as extension of DSC.

3. Parallel-Nano DSC (PNDSC)
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The Parallel-Nano DSC was patented by Vlassak and McCluskey in 2007 [9]. PNDSC
was created to study the materials at the nanoscopic scale, which conventional DSC does not
achieve Another reason for the introduction of PNDSC was the limitations of conventional
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DSC for testing nanomaterials. Heating in the PNDSC method is performed in a specific order
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[9]. In this method a set of samples can be simultaneously analyzed which reduces the time
for the entire experiment. This is possible by the calorimetric cell system in which the heating
speed in this method can be as high as 104 K/s [10]. Achieving such a high temperature is
obtained by using low weight sensors. The advantage of PNDSC such as obtaining a high
heating rate is the opportunity to study the kinetics of phase transformations. One of the ways
to increase the sensitivity of temperature measurement in the PNDSC method is the addition
of vanadium(II) oxide. It is caused by the thermal coefficient of resistivity which is 2 %/K for
vanadium(II) oxide [9].
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The development of the PNDSC method has led to a method called Parallel Nano-
Scanning Calorimeter (PNSC) [11]. It is the connection effect of nanocalorimetry and
combinatorics. For the first time, the sensitivity of PNSC was examined by McCluskey and
Vlassak using thin indium film [11]. PNSC measurements can be conducted within a wide
temperature range between room temperature up to 900 °C [11]. The PNSC method is very
sensitive, which is confirmed by the high resolution of the nanocalorimeter which is equal 10

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nJ/K while the PNDSC resolution is 10 pJ/K [11]. Thin-film samples are tested with high
throughput by the PNSC method. Another advantage of the PNSC technique is the ability to

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quickly synthesize many samples through the thin film growth technique. In this way, PNSC
allows the creation of a sample library to be very fast. For polymer science the PNSC has

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applications in the thin-film dewetting of polymers [11]. The characterization of polymers by
the PNSC method allows for the determination of energy values corresponding to thermal
transformations.

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The efficiency in the PNSC method needs to be highlighted due to the fact that many
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samples containing different materials can be measured simultaneously. It is also worth noting
the high temperature capabilities of PNSC.
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4. MicroElectroMechanical Systems DSC (MEMS DSC)

MEMS DSC is the integrated system of miniaturized sensors and actuators [12].
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MEMS DSC were introduced to avoid measurement limitations of the conventional DSC
method. MEMS -DSC is a method based on the polymers, and it is mainly used for liquid
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phase investigations. A silicon-based MEMS DSC is also known, but unfortunately it has
many disadvantages such as frequent damage to free-standing structures by high measurement
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temperatures, an expensive production process for the production of silicon-based materials

[13]. For this reason, a polymer-based MEMS DSC is used more commonly. MEMS DSC
allows for the analysis of biomolecular interactions [12]. The thermodynamic properties of
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biomolecules and their thermal activity can be examined by MEMS DSC [12]. The
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calorimetric microcells in MEMS DSC are usually composed of polydimethylsiloxane. The

thermal isolation during MEMS DSC testing is ensured due to the low thermal conductivity of
the polymeric material and through the use of gaps through air which can penetrate and play
the role as an isolation [12]. The thermodynamic parameters obtained by MEMS DSC are
compatible with the literature data, e.g. for RNase A and lysozyme [12]. It is possible to
determine the total enthalpy of the biomolecule conversion using this method. MEMS DSC
has several advantages such as a very high sensitivity of sensors, very quick response to
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heating processes during the measurement, and monitoring of temperature changes in real
time [13].
MEMS DSC can be integrated with Isothermal Titration Calorimetry (ITC) [14]. The
advantage of such a combined system is the use of a polymer that has a low thermal
conductivity. The existing ITC devices without MEMS DSC do not give the full
characterization of thermodynamic properties of the reaction systems. Recently, the literature

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reports that MEMS DSC is used to inter alia to study the stability of proteins [15]. It is worth
noting that in the MEMS DSC test samples as small as 1 µ L are sufficient

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In our view, MEMS DSC solves the problem of conventional DSC related to the
investigation of the structural and biomolecular transitions. Interesting future directions of

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MEMS DSC include improvements to change the noise level of measurements in power unit
from nW to pW [16]. This would enable monitoring of the signal from a single cell during the
molecular interaction studies by MEMS DSC.
5. Modulated DSC (MDSC)
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MDSC is the another improved version of conventional DSC. It has the advantages of
DSC but disadvantages of conventional DSC have been removed except the longer
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measurement time in the case of MDSC. The quasi-isothermal heating is maintained during
the MDSC measurement, and the changes in the thermal activity of the polymers can be
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traced and analyzed even during various kinetic processes or reactions. We have highlighted
in our review two types of MDSC: modulated-temperature and gas-flow modulated DSC.
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5.1. Modulated-Temperature DSC (MTDSC)

The name MTDSC is covered by the copyright of TA Instrument. In most cases, a
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sinusoidal temperature change is used in this technique. The advantage of MTDSC in relation
to conventional DSC is the ability to better investigate the transformation of components of a
certain mixture under the influence of temperature, which changes may overlap in a given
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temperature range. MTDSC allows for the separation of overlapping signals, which makes
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this method a great tool for studies. MTDSC was previously used only in the frequency range
from 0.001 Hz to 0.1 Hz, however, in 2015, MTDSC was extended for use in very low and
high frequencies [17]. Now the literature reports that the measurements using MTDSC are
possible for frequencies between 10-5 Hz and 150 Hz [17].
The thermodynamic properties of polymers are studied by MTDSC [18, 19]. Glass
transitions, heat capacity, and polymer melting are mainly measured by the method of
MTDSC. Recently, MTDSC has been used to study polymer solar cells [20]. It provides the
possibility to predict the stability of polymer microstructures. MTDSC allows to determine Tg
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values of the pure compound and the mixtures of the compounds with the bulk-heterojunction
structures (BHJ) [20]. The BHJ type compounds are used in the production of photovoltaics
which are the subject of the study in recent years of many research groups [20]. It is a very
important topic because photovoltaics are a renewable energy source and contributes to the
environmental protection.
5.2. Gas Flow-Modulated DSC (GFMDSC)

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Another variation of the MDSC method is GFMDSC. In this method the flowing gas
affect the thermal activity of the test and the reference sample. Recently, GFMDSC method

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was used to characterize phosphorus- and sulfur-containing aromatic polyimides with a high
refractive index [21]. Nitrogen was used for these tests. For polyimides the temperatures at

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5% and 10% weight loss have been determined by GFMDSC. Polyimides only loses its
weight at temperatures above 450 °C [21]. The results of the GFMDSC measurements show
that for polyimides the values of Tg are in the temperature range from 210 °C to 265 °C.

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It should be noted that in the case of polymers-based glass solutions, such samples
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may contain a large portion of the absorbed water which causes evaporation during heating
and disturbance of signals during DSC measurements. For this reason, the identification of the
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peak corresponding to the Tg peak is difficult, however, this problem can be solved using the
MDSC method.
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6. Infrared-heated DSC (IR-heated DSC)

IR-heated DSC is also called heat-flux DSC. The IR-heated DSC measuring device in
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addition to the DSC sensors includes a set of tubular IR lamps [22]. The measurements
obtained from IR-heated DSC are more accurate than conventional DSC because the IR
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method takes into account the asymmetry of the sensors [23]. An additional advantage of the
IR-heated DSC is the fact that the measurements take into account the possible differences in
the heating rate of the test sample compared with the reference sample. A device to IR-heated
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DSC is equipped with a thermal resistor, which is configured to provide adequate heat flux
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during tests. In this method, calorimeters with a heating rate of 2000 °C · min-1 are known
[23].
The thermal behaviour of polypropylene in isotactic and crystalline form has been
examined using heat-flux DSC [24]. The influence of sample mass and the heating rate (β) on
the thermal activity of polypropylene was checked. While examining polypropylene, Toda
has presented in an interesting way the influence of change in the peak of the melting
temperature of the polymer in relation to βz where "z" denotes the power (Fig. 2.) [24].
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Fig. 2. The plots showing the dependence of β with the temperature difference (Tpeak - Tmelt)
where Tpeak = the melting temperature and Tmelt = the zero-entropy-production melting
temperature.

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An unconventional approach was the use of the IR-heated DSC method for testing
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materials used for thermal energy storage (TES) [25]. The heat capacity of TES has been
determined. These type of measurements were conducted in the temperature ranges between -
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20 °C and 500 °C [25]. During these studies using high scan rates, the DSC equipment must
be stabilized, otherwise the results obtained within the first two minutes of measurement are
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incorrect and error-prone [26].

7. High-Performance DSC (HPer DSC)
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The HPer DSC is the high-speed calorimetry. A special application of the HPer DSC
is the study of kinetic processes related to the thermal activity of polymers. The HPer DSC
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technique allows for the analysis of the metastability of polymers [27, 28]. For example,
polypropylene (PP), polyoxymethylene (POM) and polyamide-6 (PA6) were tested using this
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method [28]. More precisely, the melting behaviour of PP, POM and PA6 was examined by
HPer DSC. PP reorganization processes have been investigated on the basis of different rates
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from 5 °C/min to 250 °C/min. PP begins to melt at a temperature of 160°C [28]. Higher
cooling rates are associated with less crystalline enthalpy. The results of the studies carried
out by Poel and Mathot show that for POM higher heating rates cause the melting point of
POM to occur at higher temperature values. The cooling of PA6 in stages allows different
crystal structures of PA6 to be obtained [28].
The detection and quantification of polymer samples is performed using HPer DSC
[29]. Often, the full characterization of polymers is tested using a combination of two
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methods: HPer DSC and high-temperature-HPLC [29]. For one of the tested polypropylene
copolymers fractions, the studies have shown that melting starts at 120 °C. This is due to the
presence of short polypropylene chains.
The HPer DSC technique does not require large amounts of test samples. For this
reason, very small amounts of substances eliminate the conformational changes of substances
under the influence of heat, recrystallization and other processes. Unfortunately, sometimes

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due to the nature of the polymers studied, the HPer DSC is not enough, and the DSC
technique with an even higher scanning rate, e.g. Flash DSC, must be applied. A very high

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scanning rate prevents disruptions caused by the reorganisation processes such as
recrystallization.

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8. Pressure Perturbation Calorimetry and DSC (PPC DSC)
In PPC DSC method, the heat changes are measured as the effects of pressure changes
and thermodynamic properties of the studied systems. The application of PPC DSC is based

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on the examining the thermal phase transitions, membrane packing and volumetric properties
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[30]. The enthalpy change related with the transition process of the sample is determined
using PPC DSC. The thermoresponsive polymers showing the lower critical solution
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temperature are examined towards their phase transition temperatures using PPC DSC [31].
The thermoresponsive polymers behave in aqueous solutions as shown in Fig. 3 [31].
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Fig. 3. The schematic representation of the impact of temperature changes on behavior of

hydrated thermoresponsive polymers in aqueous solutions.
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Zhang et al. determined the cloud point temperatures (Tcp) using PPC DSC for
thermoresponsive polymers [31]. The Tcp parameter describes the temperature at which the
polymer solution changes from the "clear" solution to the cloudy solution. The measurement
was carried out using the heating rate 0.5 °C · min-1. For the studied thermoresponsive
polymers the transition from coils to globules (shown in Fig. 3.) is the endothermic process.
The cause of this phenomenon may be the breaking of the characteristic hydrogen bonds

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between the polymer and the solvent.
9. Flash DSC

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An extremely interesting advantage of the Flash DSC method is the fact that it allows
for the analysis of reorganization processes, which previously could not be measured. The

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tests can be carried out in the temperature range from -95 °C to 1000 °C. In 2017 Treviño-
Quintanilla and co-workers reported the results regarding the non-isothermal crystallization of
the polyethylene (HDPE) resins [32]. The specific melting enthalpy has been determined by

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Flash DSC. The different cooling rates in the range from 50 to 4000 °C/ s were used for the
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studies of thermal activity of HDPE. The crystallization temperature decreases with the higher
cooling rate [32]. The isothermal studies of HDPE also show the same dependence the
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between crystallization temperature and the cooling rate.

Moreover, Li and co-workers used Flash DSC to study the nucleation kinetics of
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polymers [33]. This innovative use of Flash DSC is worth discussing because the method
proposed by Li and co-workers is effective in studying nucleation kinetics for polymers,
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irrespective of their crystallization rates. The crystal nucleation is the first step of the
crystallization process. The studies of poly(L-lactic acid) (PLLA) and poly(D-lactic acid)
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(PDLA) by Flash DSC at the 0.5 °C/s rate show that the blends of PLLA/PDLA the beginning
of the melting process affects the nucleation process [33]. The crystallization enthalpy for the
sample of PLLA/PDLA is 2.0 µJ. Additionally, the results of these studies confirm that the
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presence of a heterogeneous nucleus in the tested cell accelerates the cold crystallization and
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shortens the nucleation time during crystallization. Flash DSC allows for the study of kinetics
of crystallization using different cooling rates.
10. Self-Referencing DSC (SR DSC)
The SR DSC method is a low-cost DSC and is used for analyses on an industrial scale.
The temperature range for SR DSC measurements is 50 °C – 1000 °C [34]. In this method,
the furnace used for heating is round and a circular plate is placed in it, through which the
heat flow takes place [34]. These kind of the studies allows a low energy transition to be
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determined. The temperature gradient is calculated as the difference between the sample
temperature and the reference temperature.
The amorphous polyethylene terephthalate (PET) was examined by SR DSC in order
to examine the thermal behaviour and physical aging of PET [34]. In order to study the
thermal activity of PET, the samples are heated in the range from 50 °C to 270 °C. The
heating rate of PET samples is 10 °C/s. In addition, the physical ageing of polymers such as

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PET can be tested using SR DSC. The physical ageing of PET has been monitored at 65 °C
[34]. The studies on PET have shown that using the SR DSC method, measurements with

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higher sensitivity are obtained using the thinnest possible plate. In addition, the lower the
thermal conductivity of the material from which the plate was made, the measurements are

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more accurate and the SR DSC method is more sensitive.
11. Conclusions
The DSC-based techniques are the powerful tools to characterize and analyse the thermal

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behaviour of synthetic and natural polymers, allows to study the interaction of polymers and
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proteins. Summing up the methods collected in this review, the main advantages and
disadvantages of the DSC-based methods for studies of thermal properties of polymers are
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summarized in Table 1.

Table 1. Summary of major advantages and disadvantages of methods based on DSC

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Method Major advantages Major disadvantages

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conventional DSC relatively fast, ease of sample measurement of total heat

preparation corresponding to overlapping
processes
Parallel-Nano DSC small amounts of material for polymers in only nano-
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tested scale
MicroElectroMechanical biomolecular interactions change in properties of
Systems DSC studies materials after transferring
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them to microscale
Modulated DSC separation of overlapping
slow data collection
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processes
Infrared-heated DSC fast heating and cooling a lot of IR energy is needed
of sample to achieve right heating rate
of sample
High-Performance DSC monitoring dynamics of
thermo- dependent
processes; expensive method
it can imitate conditions such
as in rotational molding
Pressure Perturbation it allows testing of
impact of several parameters
Calorimetry and DSC volumetric parameters of
on method sensitivity
polymers; fully automated
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Flash DSC extremely fast heating and silicone oil used in this
cooling of sample method can be absorbed by
polymers
Self-Referencing DSC wide temperature range of dependence of sensitivity of
measurements method on thickness of plate

The preparation of polymers as well as techniques for their study are the subject of

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research conducted by scientists [35-37]. Nowadays, the new non-metallocene complex
compounds of chromium(III) and oxovanadium(IV) are synthesized, because they may play

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the role of catalysts for polymerization [38-47]. The development of polymerization on the
industrial scale is currently associated with the development of methods for testing the

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properties of polymeric materials. The DSC-based methods still have some limitations,
although these methods have evolved and improved over the last few years. In our opinion,
over the next few years DSC methods will be further developed in terms of increased

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sensitivity and miniaturization [48-50].
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Acknowledgements
This work was supported by the National Science Centre, Poland under Grant number
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2015/19/N/ST5/00276.
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References
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Characterization of polymers based on Differential Scanning Calorimetry
based techniques

Joanna Drzeżdżon1, Dagmara Jacewicz1, Alicja Sielicka2,3, Lech Chmurzyński1*

1
Faculty of Chemistry, University of Gdansk, Wita Stwosza 63, 80-308 Gdansk, Poland

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2
Department of Biochemistry, Medical University of Gdansk, Gdansk, Poland
3
Structural Heart Research & Innovation Laboratory, Carlyle Fraser Heart Center, Division

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of Cardiothoracic Surgery, Emory University, Atlanta, USA.

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Highlights

• The latest progression in the field of DSC- based techniques.

•
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The knowledge gaps in the characterization of polymers using DSC techniques.
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• The miniaturization of measuring cells to increase the sensitivity of DSC.
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