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FTIR-ATR spectroscopic, thermal and microstructural studies on

polypropylene-glass fiber composites

Renata Caban

PII: S0022-2860(22)00838-9
DOI: https://doi.org/10.1016/j.molstruc.2022.133181
Reference: MOLSTR 133181

To appear in: Journal of Molecular Structure

Received date: 30 November 2021

Revised date: 22 April 2022
Accepted date: 26 April 2022

Please cite this article as: Renata Caban , FTIR-ATR spectroscopic, thermal and microstruc-
tural studies on polypropylene-glass fiber composites, Journal of Molecular Structure (2022), doi:
https://doi.org/10.1016/j.molstruc.2022.133181

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FTIR-ATR spectroscopic, thermal and microstructural studies on polypropylene-glass
fiber composites
Renata Caban1
1
Czestochowa University of Technology, Department of Materials Engineering, 19 Armii
Krajowej Ave., 42-200, Czestochowa, Poland, e-mail: renata.caban@pcz.pl

KEYWORDS: polymer composites, polypropylene, glass fiber, FTIR, thermal properties

Highlights
 The functional groups in the chemical structure of the composites were identified
 The degree of crystallinity was determined by differential scanning calorimetry (DSC)
 The annealing contributes to an increase in crystallinity
 The size of polypropylene spherulites was determined by optical method

Graphical abstract

ABSTRACT
This study presents the results of examinations of polypropylene-glass fiber composites.
Polypropylene matrix composites containing 30% and 50% glass fiber were tested. Part of the
material was subjected to heat treatment consisting of annealing. Depending on how
polymeric materials are obtained, their physical and mechanical properties change over a wide
range. Their understanding and interrelation between each other depend on accurate
quantitative structural assessment at both the chain and elemental cell microstructural levels
and the supramolecular level. FTIR-ATR technique was used to identify the characteristic
functional groups present in the chemical structure of polypropylene and composites based on
its matrix. Structure analysis at the supramolecular level was performed using differential
scanning calorimetry (DSC) and temperature microscopic examinations. These examinations
allowed for the evaluation of thermal parameters such as melting point and crystallization
temperature of the polymer matrix in the composites studied. Furthermore, by analyzing the

1
values of thermal effects determined using the DSC method, it was possible to determine the
degree of crystallinity. A deeper understanding of the interdependence between the structure
and properties of polymers allows to predict the characteristics of the final product and
enables optimization of technological processes.

1. INTRODUCTION
Polypropylene and its composites have been widely used in many engineering applications as
an alternative to metallic products. In recent years, glass fiber reinforced polymer matrix
composites have become a promising research area for the development of advanced
engineering materials [1,2]. As a traditional thermoplastic material, polypropylene has been
widely used in daily life and industry due to its excellent heat resistance, good dimensional
stability, processing properties, non-toxicity, and low prices. However, polypropylene still
requires mechanical improvement to expand its applications as construction plastics. Glass
fiber reinforced polypropylene is one of the most popular ways to solve this problem [3,4,5].
Glass fibers are the most commonly used reinforcing fibers as they effectively improve the
mechanical strength of the polymer matrix [6, 7]. Glass fibers are characterized by low prices,
high tensile strength, excellent corrosion resistance, and good insulation properties. From the
point of view of composite construction, glass fibers are the basic load-bearing element of the
composite while the polymer matrix is the binder that connects the fibers and ensures the
distribution of the external load between them. An additional task of the matrix is also to
protect the composite against external factors. It also participates to a small extent in the
transfer of internal loads [8,9]. The main determinants of the properties of a composite are the
properties of its individual components. The quality of the composite is determined by the
internal structure of the polymer matrix and the type of the reinforcing phase. Isotactic
polypropylene can occur in four polymorphic forms: monoclinic α form, hexagonal β form,
triclinic γ form and mesomorphic phase (smectic form) [10, 11]. In our own work [12],
examining the structure of polypropylene-glass fiber composites by X-ray, diffraction
reflections were found from polymorphic types of polypropylene: α (monoclinic), β
(hexagonal) and smectic phase. Moreover, changes in intensity of the reflex (300) which
come from the  form show that this form is less stable than monoclinic form. Equally
important effects on the properties and structure have the content of the fiber reinforcing the
polymeric matrix, its shape, and adhesion occurring at the fiber-matrix interface [13,14,15].
Injection molding processes are often used to produce polymer composites with glass fiber
[16,17]. Properties of polymeric molded pieces can be improved by using heat treatment that
2
allows for increasing the degree of crystallinity. Heat treatment consisting of annealing at a
specific temperature leads to significant changes in the structure of the polymer matrix
composites. Remodeling of crystalline structures and increase in the amount of crystalline
phase in the polymer matrix is observed. A higher degree of crystallinity has a positive effect
on changes in mechanical, thermal, and functional properties of products [12,18]. Regardless
of how polymeric materials are obtained, their physical and mechanical properties change
over a wide range. Their understanding and interrelation between each other depend on
accurate quantitative structural assessment at both the chain and elemental cell microstructural
levels and the supramolecular level [19,20,21,22]. This leads to the necessity to conduct
research with several methods allowing for the characterization of the structure not only in
qualitative but also quantitative terms and, consequently, the evaluation of the effect of the
structure on the physical properties of composite materials. The structure of polypropylene is
crystalline-amorphous, while better properties are obtained when the spatially ordered
crystalline phase is prevalent in the structure. Reviewing the literature, usually X-ray
diffraction (XRD) [5, 23] or differential scanning calorimetry [24, 20] (DSC) are the most
commonly used methods to determine the crystallinity of polymers. Also density
measurements [25], Raman spectroscopy and also Fourier transform infrared spectroscopy
(FTIR) are used to determine the orientation and structure development of crystalline regions
of polymers [26]. Fourier transform infrared (FTIR) spectroscopy is a technique for
characterizing the microstructure of polymers at the molecular level, is widely used to
characterize the conformational changes of polymer chains. In addition, FTIR spectroscopy is
often used to analyse the crystallization kinetics of semicrystalline polymers during
crystallization [27, 28], and also to distinguish crystalline forms [29] and for the analysis of
changes in orientation of the crystalline and amorphous phases during deformation of
polymers [20, 30]. The aim of the present study was to perform the spectroscopic structure
analysis and thermal and microscopic examinations of polypropylene-glass fiber composites
before and after annealing.

2. MATERIALS AND EXPERIMENTAL PROCEDURE

This work presents the results of investigations of composites made of the granulates by
Polimarky (Rzeszow, Poland). These granulates contained polypropylene - Malen P J – 400
produced by Petrochemia Płock and glass fibres with E symbol. The glass fibres with final
length 6 mm were covered by silane preparation. Samples for investigations were prepared by

3
means of injection with Krauss – Maffei injection machine (KM65 – 160C1 type). The
investigations encompassed the composites on the polypropylene matrix which contained
30% and 50% of the glass fibre (GF). For the comparison purposes the matrix material was
also tested. Part of the material was processed by heat treatment in the form of annealing at
the temperature of 130 °C in the air. Annealing rate amounted to 0,015 °C/s, annealing time
900 s per mm of the sample thickness, cooling rate 0,010 °C/s. The symbols of individual
specimens and content percentage of glass fibres are presented in Table 1.

Table 1. Designations of specimens used in study

Specimen,
PP PP-a PP70/GF30 PP70/GF30-a PP50/GF50 PP50/GF50-a
“a” – samples after annealing
Content of glass fibre content,
- - 30 30 50 50
%

The chemical structure of polypropylene and glass fiber reinforced polypropylene composites
was studied using a SHIMADZU Irraffinity-1s Fourier transform infrared spectrophotometer
(FTIR) and the method of attenuated total reflectance (ATR). Spectroscopy research samples
were cut out of the strength samples. They were in form of cuboids with measurements of
2x2x1 mm. Samples surfaces were flat, smooth, and tightly adhered to the crystal's surface.
The spectra were recorded in the measurement range of 400 to 4000 cm-1 at 60 scans per
measurement. The resolution of the camera was 2 cm-1. The testing of thermal properties
using the DSC method for polypropylene composites with glass fibre was performed using a
PC 200 Netzsch scanning microcalorimeter [31]. Preparations for DSC testing were cut out
perpendicularly to the direction of flow of the polymeric material from the samples obtained
through injection. The samples were firstly heated to 200 °C and held for 4 min to eliminate
the thermal history, and then cooled to 20 °C with a rate of 15 °C/min, after that the samples
were subsequently heated to 200 °C at the same rate for the second run. The tests were carried
out in a nitrogen atmosphere (Figure 1).

The physical transformation temperatures and the degree of crystallinity of the specimens
were determined using PC 200 Netzsch software. The software enabled analysis of the sample
melting process and evaluation of the area between the thermographic curve and the baseline
for the occurrence of endothermic reflex. Indium was used as a model, with the sample weight
ranging from 8 to 10 mg. The test samples were weighed with a SARTORIUS balance with
weighing accuracy of 0.01 mg, internal calibration and a closed measuring chamber. The

4
value of the degree of crystallization was calculated according to (1) considering the
measured melting enthalpy.

H p
Sk   100%
H k (1)

where:
Sk – degree of crystallinity, %
ΔHp – melting enthalpy of the tested material,
ΔHk – melting enthalpy of a completely crystalline material.
The melting heat for PP was assumed to be 209 J/g [32,33].

Temperature microscopic examinations were carried out using a set for microscopic
observation of phase transitions (Mettler Toledo FP82HT heating table, Polam 113 polarizing
microscope, Panasonic KR-222 video camera). They allowed for the observation of the
melting and crystallization processes occurring in the specimens studied. Fine chips taken
from the specimen core for strength testing were heated from room temperature to 210°C at a
rate of 15°C/min. Observation of the melting process allowed for optical determination of the
melting point (observable melting of the specimen). The specimens were then cooled from
210°C to room temperature at a rate of 15°C/min. During cooling, the crystallization process
of the matrix from the melt was observed and the crystallization temperature was determined
optically. The next stage of the research was to perform microscopic examinations. After the
crystallization, the microstructure was observed using Polam-113 polarizing microscope.
Observations were made in unpolarized ordinary light and polarized light at 200x
magnification.

3. RESULTS AND DISCUSSION

The results of spectroscopic examinations (FTIR-ATR) of polypropylene and polypropylene-
glass fiber composites before and after annealing is presented in Fig.2.
Analysis of FTIR-ATR spectra allowed for the identification of characteristic functional
groups occurring in the chemical structure of polypropylene and composites based on its
matrix. In one unit of PP molecule chain are tree atoms of carbon, in the form of different
groups: -CH2, -CH- and –CH3. Each of them is correlated in IR spectra with the suitable

5
absorption peak by definite wavenumber values (Figure 2). The proper characteristic,
concerning this correlation is presented in Table 2.

Table 2. FTIR absorption of specimens used in study [34÷39, 44, 45]

Wave number, cm-1 Absorbing group Type of vibration
2950 CH3 asymmetrical stretching
2915 CH2 asymmetrical stretching
2860 CH3 symmetrical stretching
2837 CH2 symmetrical stretching
1457 CH3 asymmetrical bending
1376 CH3 symmetrical bending
1356 CH2 wagging vibration
CH wagging vibration
1166 C-C asymmetrical stretching
CH3 asymmetrical rocking
C-H wagging vibration
998 CH3 asymmetrical rocking
974 CH3 asymmetrical rocking
C-C asymmetrical stretching
898 CH3 asymmetrical rocking
C-C asymmetrical and
symmetrical stretching
841 CH2 rocking vibration
809 CH2 rocking vibration
1060 Si-O asymmetrical stretching in
the silicon-oxygen
tetrahedron
455 Si(Al)-O-Si bending vibration

The absorption peaks occurring at wave numbers 1166 cm-1, 998 cm-1, 974 cm-1, 841 cm-1 are
peaks characteristic of isotactic partially crystalline polypropylene [36]. Many publications
have focused on the absorbance characteristics of polypropylene [30,35,37,38,39]. The peak
occurring at 998 cm-1 corresponds to the crystalline phase of polypropylene [40]. Since
crystals  and  polypropylene have similar spectra [30] the height of this peak, should be
seen as a measure of the overall crystallinity of the sample and cannot be partitioned for phase
 and . In contrast, the peak at 974 cm-1 is attributed to both amorphous and crystalline
regions of the polymer [20]. Kilic et al. [41] showed that the absorbance ratio at A997/A972 is
linearly related to polymer density and therefore can be used to measure the degree of
crystallinity of a polymer. Lanyi et al. [40] presented a methodology for determining the
degree of crystallinity using the ratio of the maksimum peak heights at 998 cm-1 and 974 cm-1
determined from FTIR measurements versus the degree of crystallinity that was determined
by X-ray. In contrast, the ascending peak at 841 cm-1 is associated with crystallization of
polypropylene [28] and is generally used as a probe to monitor the crystallization process of
iPP [42, 43]. Analyzing the FTIR - ATR spectra, especially the spectra of glass fiber and
polypropylene, one can see a clear effect of modification of the polymer matrix of the

6
composites studied the introduced glass fiber. FTIR spectroscopic studies confirmed the
presence of glass fiber in the composites and increased chemical effect with increasing
amount of glass fiber in PP composites. The wide absorption band recorded in the composite
specimens before and after annealing with a maximum around 1060 cm-1 corresponds to
asymmetric Si-O stretching vibrations in the silicon-oxygen tetrahedron, while the peak at a
wave number of 455 cm-1 indicates bending vibrations [44,45].

Differential thermal analysis was also used. The results of the analysis using differential
scanning calorimetry are presented in Table 3 and Figures 3,4.

Table 3. Results of DSC examinations

Samples Degree of Melt temperature Melt temperature Crystallization Crystallization
crystallinity, % range, ˚C – peak max., ˚C temperature temperature - peak
range, ˚C max, ˚C
PP 51 108176 166 11899 108
PP-a 67 96177 166 123108 109
PP70/GF30 31 115178 167 122116 118
PP70/GF30-a 33 116178 168 124117 117
PP50/GF50 23 126178 168 127117 117
PP50/GF50-a 24 130176 167 128115 117

Analysis of the DSC results revealed that the melting point (maximum of endothermic reflex)
and crystallization temperatures (maximum of exothermic reflex) in the polypropylene/glass
fiber composites are shifted towards higher values compared to the matrix material. Earlier
results of X-ray diffraction analysis [12], showed the presence of polymorphic varieties of
polypropylene in the composites studied: ,  and smectic phase. However, the analysis of
endothermic curves does not highlight the presence of polymorphism. The endothermic
reflection observed in Figure 3 corresponds to the melting of the monoclinic  polypropylene
phase. According to Janicki [46], this reflection is characteristic of non-isothermal
crystallization and indicates recrystallization occurring after the initial melting of the sample.
The melting curves lack a clear thermal effect coming from the  polypropylene phase. The
reason for this may be that the heating rate (15˚C/min) used in this study was too high.
Addition of glass fiber as a filler decreased the degree of crystallinity of the specimens
studied. The highest value was recorded for pure polypropylene. As the glass fiber content
increased, a decrease in the degree of crystallinity was recorded (31% for the sample
PP70/GF30 and 23% for the sample PP50/GF50, respectively). Heat treatment by annealing
the specimens led to an increase in the degree of crystallinity compared to unheated material.

7
Mulle et al. [24] conducting DSC investigations of glass fiber - reinforced polypropylene
laminates, noticed that annealing of the samples at the temperature 80˚C increases the degree
of crystallinity of the tested materials. Franciszczak et al. [5] examining the influence of
polymer matrix crystallinity on the mechanical properties of short fibre composites also
noticed an increase in the degree of crystallinity after annealing. Similar tendency was
observed in own research [12, 46] as well as in other publications [47, 48]. As a result of
heating, the mobility of macromolecules increases, and fragmentation of crystalline structures
(mainly spherulites) occurs. These tiny elements of crystalline structures become new nuclei.
New spherulites are formed from the nuclei, mainly in the form of crystalline plates called
lamellae, and as a result of ordering some of the macromolecules of the non-crystalline phase.
Already during heating, some macromolecules of the non-crystalline phase were ordered
while increasing the proportion of crystalline phases. Growth of spherulites can occur by
radial spreading evenly in all directions or by branching, starting from the nucleus.
Temperature microscopic studies were performed to complement the DSC studies. The
examinations carried out in polarized light allowed for the optical determination of the
melting point (during heating) and the crystallization temperature of the polymeric matrix
(during cooling). In the microscopic method, the melting point is the temperature at which the
most crystallized crystallites disintegrate and the last traces of crystallinity disappear [49].
The results of these examinations are presented in Table 4.

Table 4. Melting point and the range of crystallization temperature of the materials
determined using the microscopic method
Samples Melt temperature, ˚C Crystallization Crystallization
temperature range, ˚C temperature,°C
PP 166 122110 110
PP-a 167 125115 115
PP70/GF30 167 123119 119
PP70/GF30-a 168 125118 118
PP50/GF50 167 128119 119
PP50/GF50-a 166 128115 115

Both polypropylene and polypropylene matrix composites specimens exhibited features of

crystalline objects by depolarizing light. This made it possible to observe the forming
crystalline structures observed as colored objects on the black background of the amorphous
liquid. The course of crystallization of polypropylene is shown in Figure 5, whereas Figure 6

8
presents the course of crystallization of the composite containing 30% of glass fiber after
annealing.
The crystallization of both polypropylene and its matrix composites reinforced with glass
fibers occurred very quickly from the appearance of the first nuclei to the crystallization of the
entire specimen. Crystallization of the specimens after annealing proceeded at slightly higher
temperatures. It is difficult to distinguish single spherulites, in the microphotographs showing
the course of crystallization of composites containing 30% of glass fiber after heat treatment.
(Figure 6). The reason for this is the high content of glass fibers in the specimen material.
Glass fibers cause significant image blurring and distortion. This makes it impossible to
determine the size of the resulting crystalline structures. Nevertheless, it can be concluded that
the crystallites are formed in large numbers throughout the specimen, but they are not large.
This is due to the glass fibers, whose content in the specimen material limits their growth.
Investigations using a polarizing microscope allowed for the observation of the
supramolecular structure of polypropylene and glass fiber reinforced composites (Figures 7,
8). In the case of polypropylene, the structure was regular and ordered. Polypropylene
spherulites ranged in size from 20 to 490 m (Figure 7.).

For composites containing glass fibers, the amount of reinforcing phase makes it difficult to
specify individual spherulites. Their presence is indicated only by the depolarization of the
light in the examined material. Figure 8 shows the polypropylene/glass fiber composite after
annealing of PP70/GF30-a and the boundary zone of the preparation. Crystalline structures in
the form of spherulites that are not optically distorted by the glass fibers contained in the
specimen can be noticed. This may indicate that such structures are present throughout the
specimen, but cannot be directly observed due to the high glass fiber content. The size of the
spherulites in the composites studied is not very large (about 20 m).

4. CONCLUSION
The study of the structural properties of semi-crystalline polymers is critical to understanding
the relationship between structure and properties and provides valuable information necessary
to control the microstructure during product manufacturing. Fourier transform infrared
spectroscopy (FTIR-ATR) is a highly sensitive technique for used for the characterization of
the microstructure of polymers at the molecular level and has been widely used to characterize
conformational changes of polymer chains. Analysis of FTIR-ATR spectra allowed for the

9
identification of characteristic functional groups occurring in the chemical structure of
polypropylene and composites based on its matrix. The peaks occurring at wave numbers:
1166 cm-1, 998 cm-1, 974 cm-1, 841 cm-1, are characteristic of partially crystalline isotactic
polypropylene. The peak occurring at 998 cm-1 corresponds to the crystalline phase of
polypropylene, while the peak occurring at 974 cm-1 is attributed to both the amorphous and
crystalline regions of the polymer. One of the clear differences in the spectra of polypropylene
and composites based on its matrix is the occurrence of a broad absorption band with a
maximum of about 1060 cm-1, confirming the presence of glass fibers in the composites
studied. Thermal parameters such as melting point and crystallization temperature of the
polymer matrix in the composites studied, determined by DSC and optical methods, are
comparable. An increase in the glass fiber filler content shifts the melting point and
crystallization temperature to higher values compared to the matrix material. The endothermic
reflection on the melting curve, corresponds to the melting temperature of the monoclinic 
polypropylene phase. Based on the obtained DSC results and their analysis, it was found that
the addition of the filler in the form of glass fibers reduced the degree of crystallinity of the
specimens studied. Annealing of specimens contributed to an increase in the degree of
crystallinity. The degree of crystallinity determined by DSC decreases with increasing glass
fiber content in the composites, with higher values of the degree of crystallinity determined for
annealed samples. After annealing, the proportion of crystalline phases present in the polymer
matrix increased. A similar trend was observed by determining the degree of crystallinity by
X-ray diffraction analysis [12].The composites studied were characterized by a spherulitic
supramolecular structure. The size of polypropylene spherulites evaluated by the optical
method ranged from 20 to 495 m. Glass fibers significantly reduced the growth of
spherulites, which were formed in large amounts throughout the volume of composite
specimens. Their size in the composites studied is not very large (about 20 m).
Credit Author Statement
Caban Renata: Conceptualization, Investigation, Formal analysis, Writing – review &
editing.
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

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Figure 1. DSC examinations of the PP50/GF50% composite

Figure 2. FTIR-ATR spectra of the studied materials: 1-PP, 2-PP – a, 3 – PP70/GF30, 4

PP70/GF30 – a, 5 – PP50/GF50, 6- PP50/GF50- a, 7 – GF, 8 –GF -a

Figure 3. DSC thermograms of the specimens (melting curve): 1 - PP, 2 – PP70/GF30, 3

– PP50/GF50
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Figure 4. DSC thermograms of the specimens after annealing (crystallization curve): 1 –
PP-a, 2 – PP70/GF30-a, 3 – PP50/GF50-a

Figure 5. Crystallization of polypropylene

Figure 6. Crystallization of PP70/GF30-a composite

Figure 7. Microstructure of polypropylene: a) unpolarized light, b) polarized light

Figure 8. Microstructure of PP70/GF30-a composite: a) unpolarized light, b) polarized

light

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