Article

Polymers and Polymer Composites

2021, Vol. 29(9S) S11­–S18
Thermal analysis of polymer blends ª The Author(s) 2020
Article reuse guidelines:

and double layer by DSC sagepub.com/journals-permissions

DOI: 10.1177/0967391120984606
journals.sagepub.com/home/ppc

Pooja Saxena1 , Prashant Shukla2 and MS Gaur3

Abstract
Differential Scanning Calorimetry (DSC) is considered one of the most adaptable thermal analysis characterization
techniques. It can be applied to polymers and their blends, composites, multilayer to study various thermodynamic
processes like glass transition temperature (Tg), specific heat capacity and other related kinetic properties and also clarify
the material structure, morphology and crystallinity of polymers. In the present paper we have reported thermal analysis
of Polymethyl methacrylate (PMMA), Polyvinylidene fluoride (PVDF), Polysulfone (PSF), PVDF-PSF blend and PVDF-
PMMA double-layer samples using DSC technique. Attempts have been made to calculate the Tg and interpret the
corresponding changes that have been observed on blending PVDF with PSF and double-layer formation with PMMA.
Blending of PVDF with PSF results the change in Tg of PSF and the occurrence of a single peak confirms the proper
miscibility of the two polymers. DSC plot of double layer also proved to be in confirmation about the formation of PVDF-
PMMA double layer and demonstrated a significant change in its thermal behavior.

Keywords
DSC, blends, double layer, glass transition, phase change

Received 28 November 2019; accepted 14 November 2020

Introduction
Polymer and their blends have always been the thrust area of research and development for many researchers 1,2 as well
as industrial community so that the characteristic defects and faults of a particular polymer can be managed or
minimized using blending or double-layer formation technique. Similar techniques are also used to develop new
polymeric materials which could have more scientifically attractive properties and further can be utilized in other
fields of applications. This research work is more focused on the blending of the two polymers and its layered
formation. Before we start the processing of polymer blends and mixing any, one should have the basic idea of their
physical compatibility. The latter can be defined as the appreciation of the overall blend composition and its properties
at the macroscopic scale and it depends on various factors like miscibility, the morphology of the blend, their propor-
tions etc. Thus, the final properties of the resulting blend and layering depend on the degree of miscibility between its
components, composition, solvent, and morphology of the polymer system.3 The miscibility and preliminary affinity
between two polymers can be checked by the study of change in the glass transition temperature (Tg) after blending. The
appearance of single glass transition temperature (Tg) peak in polymer blends shows the miscible behavior of two
polymers and more than one peak glass transition peak reflects the partially miscible or immiscible behaviors of two or

1
G.L. Bajaj Institute of Technology and Management, Greater Noida, Uttar Pradesh, India (affiliated to Dr. A. P. J. Abdul Kalam Technical University,
Lucknow, Uttar Pradesh, India)
2
Amity Institute of Advanced Research and Studies (M & D), Amity University, Noida, Uttar Pradesh, India
3
Department of Physics, Hindustan College of Science and Technology, Farah, Mathura, Uttar Pradesh, India (affiliated to Dr. A. P. J. Abdul Kalam
Technical University, Lucknow, Uttar Pradesh, India)

Corresponding author:
Pooja Saxena, G.L. Bajaj Institute of Technology and Management, Greater Noida 201307, Uttar Pradesh, India (affiliated to Dr. A. P. J. Abdul Kalam
Technical University, Lucknow, Uttar Pradesh, India).
Email: [email protected]
S12
2 Polymers and Polymer Composites 29(9S)
Polymers XX(X)

more polymers.4 The different methods used to describe the glass transition temperature (Tg) are available in many
books and publications by researchers which is mainly based on the heat flux measurement over a wide range of
temperature by differential scanning calorimeters.5
A thermal investigation method called DSC is used to reveal the thermal changes in polymers, for example, the melting
point temperature (Tm) and the glass transition temperature (Tg). The melting point and glass transition temperature of
many polymers are available from standard compilations values, and DSC measurements specify probable polymer
degradation by dropping of the estimated melting point (Tm) which depends upon the molecular weight of the polymer.
Thus lower grade polymers will likely to have lower melting points than reference with higher molecular weights. It can
also be utilized to assess various polymers and drugs concentrations. This is probably due to the wide range of temperature
accessible over which a mixture of compounds melts is dependent on their comparative amounts. This effect occurs due to
a phenomenon which is known as freezing point depression, which generally occur when a different solvent is added to a
polymer mix. As a result, an impure substance melts over a wide range and shows a widen peak at a temperature much
lower than that of the pure substance as studied and reported in literature by Brydson et al.6
The method was developed by a team of researchers ES Watson and MJ O’Neill in year 1960 and commercially
introduced in 1963 in Pittsburgh Conference on “Analytical Chemistry and Applied Spectroscopy.”Wunderlich7 and
Dean8 dealt with the technique DSC which was developed coined to measures energy directly and allows precise
measurements of heat capacity by the sophisticated instrument. The basic principle underlying this method is that once
the sample undergoes a physical transformation like phase transitions, more or less heat will required to flow than
reference so as to maintain the same temperature. The amount of heat that should flow to the sample depends on the
type of process whether it is endothermic or exothermic. When the difference of heat flow between the sample and
reference is observed, differential scanning calorimeters would be able to measure the amount of heat absorbed or released
throughout such transitions. DSC can also be utilized to observe more sensitive physical changes, like glass transitions.9,10
It is wide utilized in industrial settings as a high quality control instrument due to its ability in evaluating sample purity and
for finding out chemical compound action. It can even be used to observe fusion and crystallization events as well as glass
transition temperatures (Tg). O’Neill11 used DSC to check oxidation and other chemical reaction. In addition to this glass
transition temperature, Tg may be defined as the temperature at which the polymer structure changes into a viscous liquid
or becomes rubbery on being heated. It is the temperature at which amorphous polymers acquires the properties of glassy
state like being brittle, stiff and rigid on cooling. This temperature can be used to identify the polymers. It generally
depends on the chemical structure of the polymer and the mobility of polymeric chains which generally lies between
170 K and 500 K for most of the synthetic polymers. The two class of polymers behaves in different ways like amorphous
polymers shows Tg whereas crystalline polymers exhibit a Tg along with melting temperature Tm since semi-crystalline
polymers have crystalline as well as amorphous part. The transition from glassy to rubbery state brings a considerable
change in the physical property of the polymer like change in hardness, volume, percent elongation to break and Young’s
modulus. Tg can be determined by using a very sensitive and reliable technique called DSC (Differential Scanning
Calorimetry) or DTA (Differential Thermal Analysis). This technique can be work for both amorphous as well as
semi-crystalline materials. Both of the thermal analysis methods either DSC or DTA produces exothermic and endother-
mic transitions peaks with providing thermal variations and indicate phase changes.12 There are various factors which
affect the glass transition temperature like13,14

a. Chemical Structure of the polymer which includes Molecular weight, molecular structure, polar group and
chemical cross linking.
b. Mixing of plasticizer in polymer increases the free volume in the material structure and thus the polymer chains can
move around at lower temperatures resulting in decrease in Tg of a polymer.
c. Increase in water content or moisture leads to the formation of hydrogen bonds with polymeric chains and brings
more gap between polymeric chains. Hence increases the free volume gives lowers the glass transition temperature
(Tg).
d. This further describes the higher value of entropy for the amorphous material and lower value for crystalline
material. The higher value of entropy indicates the high value of glass transition temperature (Tg).
e. High Tg may also due to increase in surrounding pressure due to decrease in free volume.
f. Some other factor may include film thickness, interaction in polymer bonds and flexibility of polymer chain.

Glass transition peak might be seen at the level where the temperature of amorphous solid is found to be increased.
These changes mark as a step in the baseline of the recorded DSC signal. Since the sample is undergoing a change in
heat capacity; thus no recognized phase change occurs as discussed by Brydson et al.6 The amorphous solid becomes
less viscous with the increase in temperature with the increasing value of resistive frictional forces. Eventually the
particles may acquire to have enough volume to freely move and to organize them into a crystalline structure course of
action and termed as crystallization temperature (Tc). This progress of stage from indistinct strong to crystalline strong
is an exothermic procedure, and results in the presence of top in the DSC sketch. As the temperature expands,
the sample reaches to its melting temperature (Tm). The melting process results to get an endothermic peak in the
Saxena et al. S13
3

DSC curve. DSC technique has been proved to be a vital tool in producing phase diagrams for various chemical systems
and phase transition in the various systems and it also has the ability to determine transition temperatures and
enthalpies.
DSC analysis does not require large samples, numerous control or extensive method involvement make it more
advantageous. These are few advantages offered by this powerful thermal analytical tool, which has been proven to have
much more measurement capability than just determining a melting point. This paper reports a DSC study on PVDF-
PMMA double layer and films of blends of PVDF and PSF that were prepared in different ratios by weight percentage. For
all blend ratios used for PVDF: PSF (80:20, 70:30 and 60:40), the DSC test describes the miscibility behavior by observing
the glass transition temperature in polymer blends and composites.
A lot of work has been reported on single polymer thin films and researchers have produced the results that helped in
gaining a better insight into the molecular processes and phase transition in these polymers.15,16 The effects of interfacial
phenomenon on electrical behavior have attracted the attention of many researchers and open new areas of research in
understanding the polymeric insulating materials. The polymeric interfaces strongly acts as charge-carrier trapping sites in
double-layered heterogeneous polymeric system and blends.17 Therefore, it has become essential to study the effect of
interfaces in polymers blends and double layer since most practical insulators comprises of several insulators and
semiconductors. PMMA and PSF used in the present research work belongs to amorphous and PVDF to semi-
crystalline class of polymers having different glass transition temperatures and structural morphologies. However, the
studies on various mechanisms of blend and layered structures are yet to be completely explored. Thus, it became
evocative to investigate the role of polymer-polymer interface in polymeric double-layer and blend samples. Therefore,
the present work proposes to undertake the extensive and careful thermal studies in a distinct combination of double-layer
and polyblend of polar, amorphous and semi-crystalline polymers for which studies are scarce in available literature. The
aim of this paper is to study and verify the miscibility of the blends and double layer using theoretical and experimental
characterization methods.

Experimental
PMMA, PVDF, PSF, PVDF-PSF polyblend and PMMA-PVDF double-layer samples were prepared by utilizing the
arrangement developed technique.18-21 The commercial PVDF [Solef 1015 PVDF Powder], PMMA [BDH Ltd., England]
and PSF [UDEL P1700 PSF Pellets] used were supplied by Redox India Pvt. Ltd. To prepare PMMA, PVDF and PVDF-
PSF polyblend samples, the solution of the required polymer(s) with desired concentration was prepared in a common
solvent N, N, dimethylformamide (DMF) at 50 C using an indigenously made hot plate magnetic stirrer. The solution was
kept at 50 C for a period of 1 hr and then kept at room temperature for 2 hrs to end up the solution that becomes
homogeneous. The optically plane cleaned glass plate at ambient temperature was then kept immersed in the polymer
solution for about 90 min but at the same temperature for about 10 min for PMMA. The plate was then gradually removed
from the arrangement, leaving a uniform micron thin polymer film on the plate. The dried polymer samples on glass plate
were kept at room temperature outgassing in air at 60 C at 0.0134 Pa (105 torr) for a further period of 12 hrs to expel the
traces of any leftover solvent. Polymer film is then gently peeled off from the glass plate. Polyblend films with different
polymer ratios by weight were formed using two polymers PVDF & PSF. The weight proportion of PVDF: PSF as wt% is
varied as 80:20, 70:30 and 60:40 respectively. The prepared thin films of PMMA and PVDF were then stacked one over
the other and compressed together under a compression molding machine at a temperature of 65 C and pressure of
2500 lbin2 (17.25 MPa) to yield double-layer samples with PMMA on one side and PVDF on the other. Thus PVDF,
PMMA and PVDF-PMMA double-layer samples are prepared. All polymer samples were kept different vacuum desic-
cators; loaded up with silica gel to keep them safe from environmental humidity. The circular shaped polymer samples
thus prepared were having diameter of 5 cm and thickness 35–50 mm.
Differential Scanning Calorimetry (DSC) experiments were carried out for all single, blend and double-layered
samples with Perkin Elmer Differential Scanning Calorimeter-Pyris 6 DSC at USIC, Delhi University, New Delhi in
an inert atmosphere of argon gas flowing at the rate of 25 cc/min. which has accuracy of +2 C. The polymer thin film
samples were cut into small pieces and were kept in aluminum pans. The samples were weighed in a microbalance. The
weight of the free polymer film sample piece (PMMA, PVDF, PMMA-PVDF double layer and PVDF-PSF polyblend in
ratio by wt% as 80:20, 70:30, 60:40) used for the DSC measurements varied from 1.5 to 3.8 mg. Alumina was taken as
reference material. The temperature range scanned was 30–300 C. The rate of heat flow was kept constant to be 3 C/min.
All polymeric samples were subjected to two DSC thermal scans with similar temperature range and heating rate. The first
DSC thermal scan was just for the removal of residual solvents, and erase the thermal history of the polymer. The reported
DSC thermal scans are from second cycle of heating. Several batches comprising 12–15 samples were prepared. These
batches were prepared separately for PVDF, PMMA, PVDF-PMMA double layer and polyblend samples of PVDF-PSF in
different ratios by weight as 80:20, 70:30 and 60:40 respectively. Sample for investigation were randomly chosen from
their respective batch. Experiments were repeated for four to five times for a particular type of sample, chosen differently
from its batch on every experimental cycle. All the experimental observations were reproducible and carried out with
S14
4 Polymers and Polymer Composites 29(9S)
Polymers XX(X)

Figure 1. DSC thermogram of PMMA sample.

Figure 2. DSC thermogram of PVDF sample.

accuracy having the standard deviation to the mean value of +3%. The DSC sketches were obtained for polymer sample
as a function of temperature.

Results
Thermal characterization of polymeric blend and double-layered samples was performed using DSC (Figures 1, 2 and 3)
represents DSC plot for PMMA, PVDF and PVDF-PMMA double-layered sample respectively. It is observed that PMMA
sample has a single peak at 106.8 C which signifies its glass transition temperature. Several researchers have reported
comparative Tg in PMMA.22-24 The DSC plot recorded for PVDF shows the melting temperature of PVDF which
corresponds to a peak at 163.2 C. However, PVDF has ultra-low glass transition temperature.25-27 The occurrence of a
single transition at 165.6 C in DSC plot for double-layered sample, confirms the formation of double layer.
The experimental results indicated that the Tg for double-layered polymer sample is higher in comparison to PMMA or
PVDF taken individually. This can be discussed on the basis of the amount of free volume in double-layered polymer
sample. Doolittle27 Turnbull and Cohen et al.28,29 experimentally illustrated the concept of free volume to a wide variety
of disordered solids. The availability of free volume in a polymer matrix system facilitates the higher probability for the
movement of its molecular segment. By laminating PMMA and PVDF, one on top of the other; the structure of the voids
present in both the polymer matrix is disrupted, consequently the free volume of the resultant polymer matrix decreases.
This decrease in free volume restricts the mobility of the chains forming a compacted structure and therefore more energy
is required to activate the segmental motion of the polymer chains. Hence, the double-layer sample uncovers a compara-
tively higher Tg.
Further, DSC study is also carried out to investigate the effect of PSF in PVDF-PSF blend, with different concentra-
tions, on the value of Tg. The results for pure polymer and their blends with different compositions by wt% (weight
Saxena et al. S15
5

Figure 3. DSC thermogram of PVDF-PMMA double-layered samples.

Figure 4. DSC thermogram of polysulfone sample.

Figure 5. DSC thermogram of PVDF-PSF (80–20) blend sample.

percentage) are shown in Figures 4–7. Figure 4 shows the DSC plot for Polysulfone (PSF), where the Tg is found to be
185 C. The DSC results for PVDF-PSF blend samples with different compositions viz. 80:20, 70:30 and 60:40 respec-
tively are shown in Figures 5–7. The Tg is found out to be 163.1 C, 164.5 C and 168.6 C respectively. It is also observed
that the Tg value increases with decreasing PVDF composition in the blend samples.
S16
6 Polymers and Polymer Composites 29(9S)
Polymers XX(X)

Figure 6. DSC thermogram of PVDF-PSF (70–30) blend sample.

Figure 7. DSC thermogram of PVDF-PSF (60–40) blend sample.

Table 1. The glass transition temperature (Tg) analyzed experimentally using DSC and calculated theoretically using Eq. 1.

Polymer/Blend Tg (calculation) Tg (DSC)

PVDF/PSF (80/20) 167.0� C 163.1� C

PVDF/PSF (70/30) 169.0� C 164.5� C
PVDF/PSF (60/40) 171.1� C 168.6� C

The Tg for polymer blend has been calculated by using an approximate relationship between Tg for blend samples and
composition as given by the sample (rule of mixture) for binary mixture by Fried30 in Equation 1
1 W1 W2
¼ þ ð1Þ
Tg Tg1 Tg2

where, W1 and W2 are the weight fraction of two polymers used, having glass transition temperature Tg1 and Tg2
respectively. From these calculations, the value of Tg’s for the above blend compositions observed are listed below in
Table 1.
It is seen that the calculated values of Tg for polymer blends are slightly higher than those found by DSC technique for
all the compositions but are well with in +3% admissible range of experimental errors. It has been reported that Tg’s
behavior for polymer blends has been used as a measure of miscibility. The appearance of a single peak at a temperature
Saxena et al. S17
7

intermediate between the Tg of pure polymer is indicative of molecular homogeneity, while the appearance of multiple
peaks reflects phase separation of the blend’s components.31,32 In the present study the DSC technique averment the state
of miscibility by recording a single sharp Tg for polymer blends and double layer.

Conclusion
The thermo-analytical technique DSC has obtained valuable information about the phase transitions and Tg for PVDF-
PMMA double-layer and PVDF-PSF polyblend samples. The experimental results were found to be in close confirmation
with amorphous nature of PMMA and semi-crystalline nature of PVDF. The results also revealed that PVDF-PMMA
double layer is characterized by a single Tg peak at higher temperature, as compared to that of PMMA or PVDF which
confirms the formation of double layer with reduced free volume availability, due to disrupted geometry of the voids
present in parent polymer matrix i.e. PMMA or PVDF. Hence, to activate the restricted segmental motion of the polymeric
chains, more energy is required, causing a higher glass transition temperature. DSC also revealed the complete miscibility
of PVDF and PSF in case of polyblend samples. This was also found to be in good agreement with the result calculated
from Fried formula for binary mixtures and hence confirms the reported behavior of the discussed heterogeneous
polymeric systems.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of this article.

ORCID iD
Pooja Saxena https://orcid.org/0000-0002-0977-5721

References
1. Seong DW, Yeo J and Hwang SH. Fabrication of polycarbonate blends with poly(methyl methacrylate-co-phenyl methacrylate)
copolymer: miscibility and scratch resistance properties. J Ind Eng Chem 2016; 36: 251–254.
2. Balart R, López J, Garcı́a D, et al. Recycling of ABS and PC from electrical and electronic waste. effect of miscibility and previous
degradation on final performance of industrial blends. Euro Polym J 2005; 41(9): 2150–2160.
3. Marwat ZK and Baloch MK. Solvent induced miscibility between polymers, and its influence on the morphology, and mechanical
properties of their blends. Euro Polym J 2015; 66: 520–527.
4. Fekete E, Foldes E and Pukanszky B. Effect of molecular interactions on the miscibility and structure of polymer blends. Euro
Polym J 2005; 41(4): 727–736.
5. Khan I, Chohan M and Mazumder M. Polymer Blends. In: Functional Polymers- Polymers and Polymeric Composites: A
Reference Series. Cham: Springer, 2018.
6. Brydson JA. Plastics materials. 7th edn. Oxford: Butterworth-Heinemann, 1999.
7. Wunderlich B. Thermal analysis. Cambridge: Academic Press, 1990, pp. 137–140.
8. Dean JA. The analytical chemistry handbook. New York, NY: McGraw Hill Inc., 1995, pp. 15.1–15.5.
9. Pungor E. A practical guide to instrumental analysis. Boca Raton: CRC Press, 1995, pp. 181–191.
10. Douglas A, Skoog F, Holler J, et al. Principles of instrumental analysis. 5th edn. New York, NY: Thomson Learning, 1998,
pp. 905–908.
11. O’Neill MJ. The analysis of a temperature-controlled scanning calorimeter. Anal Chem 1964; 36(7): 1238–1245.
12. Jansen JC. Glass transition temperature (Tg). In: Drioli E and Giorno L (eds) Encyclopedia of membranes. Berlin: Springer, 2015.
13. Qian Z, Cao Z, Galuska L, et al. Glass transition phenomenon for conjugated polymers. Macromol Chem Phys 2019; 220: 1900062.
14. Dudowicz J, Freed KF and Douglas JF. The glass transition temperature of polymer melts. J Phys Chem B 2005; 109:
21285–21292.
15. Xin R, Zhang J, Sun X, et al. Polymorphic behavior and phase transition of poly(1-Butene) and its copolymers. Polymers 2018;
10(5): 556–589.
16. Paramita J R and Kohji T. Phase-transition behavior of a crystalline polymer near the melting point: case studies of the ferroelectric
phase transition of poly(vinylidene fluoride) and the b-to-a transition of trans-1,4-polyisoprene. Polymer 2013; 45: 1107–1114.
17. Shukla P and Gaur MS. Investigation of electrical conduction mechanism in double-layered polymeric system. J Appl Polym Sci
2009; 114(1): 222–230.
18. Saxena P and Gaur MS. Electrical conduction mechanism of polyvinylidenefluoride (PVDF)–polysulfone (PSF) blend film.
J Electrostat 2009; 67: 844–849.
19. Saxena P and Gaur MS. Thermally stimulated depolarization study in polyvinylidenefluoride–polysulfone polyblend films. J Appl
Polym Sci 2010; 118(6): 3715–3722.
S18
8 Polymers and Polymer Composites 29(9S)
Polymers XX(X)

20. Saxena P, Gaur MS and Khare PK. Effect of blending with polysulfone on thermally stimulated discharge behavior of polyviny-
lidenefluoride films. Polym Plast Technol Eng 2009; 48(4): 415–422.
21. Saxena P, Gaur MS, Shukla P, et al. Relaxation investigations in polysulfone: thermally stimulated discharge current and dielectric
spectroscopy. J Electrostat 2008; 66: 584–588.
22. Mathur V and Sharma K. Thermal response of polystyrene/poly methyl methacrylate (PS/PMMA) polymeric blends. Heat Mass
Transfer 2016; 52: 2901–2911.
23. Nam JE, Keun LJ and Mauldin TC. Isothermal physical aging of thin PMMA films near the glass transition temperature. Polym Bull
2010; 65(8): 825–835.
24. Kabomo MT and Blum FD. Glass transition behaviour of PMMA thin films. Polym Prep 2001; 42(2): 67–68.
25. Ruan L, Yao X, Chang Y, et al. Properties and applications of the b phase poly(vinylidene fluoride). Polymers 2018; 10: 228–254.
26. Mandal A and Nandi AK. Physical properties of poly(vinylidene fluoride) composites with polymer functionalized multiwalled
carbon nanotubes using nitrene chemistry. J Mater Chem 2011; 21: 15752–15763.
27. Doolittle AK.Studies in Newtonian flow. II. The dependence of the viscosity of liquids on free space. J Appl Phys 1951; 22(12):
1471–1475.
28. Turnbull D and Cohen MH. Free volume model of the amorphous phase: glass transition. J Chem Phys 1961; 34(1): 120–125.
29. Cohen MH and Turnbull D. Molecular transport in liquids and glasses. J Chem Phys 1959; 31(5): 1164–1169.
30. Fried JR. Polymer science and technology. 2nd edn. India: Prentice Hall, 2005.
31. Merfeld GD and Paul DR. Polymer blends volume 1: formulation. New York, NY: John Wiley and Sons Inc., 2000.
32. Aseeri J, Alandis NM, Mekhamer W, et al. Miscibility studies of polystyrene/polyvinyl chloride blend in presence of organoclay.
Open Chem 2019; 17(1): 927–935.