Journal of Molecular Structure 1264 (2022) 133181

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

FTIR-ATR spectroscopic, thermal and microstructural studies on

polypropylene-glass fiber composites
Renata Caban
Czestochowa University of Technology, Department of Materials Engineering, 19 Armii Krajowej Ave., 42-200, Czestochowa, Poland

a r t i c l e i n f o a b s t r a c t

Article history: This study presents the results of examinations of polypropylene-glass fiber composites. Polypropylene
Received 30 November 2021 matrix composites containing 30% and 50% glass fiber were tested. Part of the material was subjected to
Revised 22 April 2022
heat treatment consisting of annealing. Depending on how polymeric materials are obtained, their phys-
Accepted 26 April 2022
ical and mechanical properties change over a wide range. Their understanding and interrelation between
Available online 27 April 2022
each other depend on accurate quantitative structural assessment at both the chain and elemental cell
Keywords: microstructural levels and the supramolecular level. FTIR-ATR technique was used to identify the char-
Polymer composites acteristic functional groups present in the chemical structure of polypropylene and composites based
Polypropylene on its matrix. Structure analysis at the supramolecular level was performed using differential scanning
Glass fiber calorimetry (DSC) and temperature microscopic examinations. These examinations allowed for the evalu-
FTIR ation of thermal parameters such as melting point and crystallization temperature of the polymer matrix
Thermal properties
in the composites studied. Furthermore, by analyzing the values of thermal effects determined using the
DSC method, it was possible to determine the degree of crystallinity. A deeper understanding of the in-
terdependence between the structure and properties of polymers allows to predict the characteristics of
the final product and enables optimization of technological processes.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction tect the composite against external factors. It also participates to

a small extent in the transfer of internal loads [8,9]. The main de-
Polypropylene and its composites have been widely used in terminants of the properties of a composite are the properties of
many engineering applications as an alternative to metallic prod- its individual components. The quality of the composite is deter-
ucts. In recent years, glass fiber reinforced polymer matrix com- mined by the internal structure of the polymer matrix and the
posites have become a promising research area for the develop- type of the reinforcing phase. Isotactic polypropylene can occur in
ment of advanced engineering materials [1,2]. As a traditional ther- four polymorphic forms: monoclinic α form, hexagonal β form, tri-
moplastic material, polypropylene has been widely used in daily clinic γ form and mesomorphic phase (smectic form) [10,11]. In
life and industry due to its excellent heat resistance, good dimen- our own work [12], examining the structure of polypropylene-glass
sional stability, processing properties, non-toxicity, and low prices. fiber composites by X-ray, diffraction reflections were found from
However, polypropylene still requires mechanical improvement to polymorphic types of polypropylene: α (monoclinic), β (hexago-
expand its applications as construction plastics. Glass fiber rein- nal) and smectic phase. Moreover, changes in intensity of the re-
forced polypropylene is one of the most popular ways to solve flex (300) which come from the β form show that this form is
this problem [3–5]. Glass fibers are the most commonly used rein- less stable than monoclinic form. Equally important effects on the
forcing fibers as they effectively improve the mechanical strength properties and structure have the content of the fiber reinforc-
of the polymer matrix [6,7]. Glass fibers are characterized by low ing the polymeric matrix, its shape, and adhesion occurring at the
prices, high tensile strength, excellent corrosion resistance, and fiber-matrix interface [13–15]. Injection molding processes are of-
good insulation properties. From the point of view of compos- ten used to produce polymer composites with glass fiber [16,17].
ite construction, glass fibers are the basic load-bearing element of Properties of polymeric molded pieces can be improved by us-
the composite while the polymer matrix is the binder that con- ing heat treatment that allows for increasing the degree of crys-
nects the fibers and ensures the distribution of the external load tallinity. Heat treatment consisting of annealing at a specific tem-
between them. An additional task of the matrix is also to pro- perature leads to significant changes in the structure of the poly-
mer matrix composites. Remodeling of crystalline structures and
increase in the amount of crystalline phase in the polymer matrix
E-mail address: [email protected]

https://doi.org/10.1016/j.molstruc.2022.133181
0022-2860/© 2022 Elsevier B.V. All rights reserved.
R. Caban Journal of Molecular Structure 1264 (2022) 133181

is observed. A higher degree of crystallinity has a positive effect on

changes in mechanical, thermal, and functional properties of prod-
ucts [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 [19–22]. This leads to the necessity to conduct research with
several methods allowing for the characterization of the struc-
ture not only in qualitative but also quantitative terms and, conse-
quently, the evaluation of the effect of the structure on the physi-
cal properties of composite materials. The structure of polypropy-
lene 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 [20,24] (DSC) are the Fig. 1. DSC examinations of the PP50/GF50% composite.
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 400 to 4000 cm−1 at 60 scans per measurement. The resolution
to determine the orientation and structure development of crys- of the camera was 2 cm−1 . The testing of thermal properties us-
talline regions of polymers [26]. Fourier transform infrared (FTIR) ing the DSC method for polypropylene composites with glass fiber
spectroscopy is a technique for characterizing the microstructure was performed using a PC 200 Netzsch scanning microcalorime-
of polymers at the molecular level, is widely used to character- ter [31]. Preparations for DSC testing were cut out perpendicularly
ize the conformational changes of polymer chains. In addition, FTIR to the direction of flow of the polymeric material from the sam-
spectroscopy is often used to analyze the crystallization kinetics of ples obtained through injection. The samples were firstly heated
semicrystalline polymers during crystallization [27,28], and also to to 200 °C and held for 4 min to eliminate the thermal history, and
distinguish crystalline forms [29] and for the analysis of changes then cooled to 20 °C with a rate of 15 °C/min, after that the sam-
in orientation of the crystalline and amorphous phases during de- ples were subsequently heated to 200 °C at the same rate for the
formation of polymers [20,30]. The aim of the present study was second run. The tests were carried out in a nitrogen atmosphere
to perform the spectroscopic structure analysis and thermal and (Fig. 1).
microscopic examinations of polypropylene-glass fiber composites The physical transformation temperatures and the degree of
before and after annealing. crystallinity of the specimens were determined using PC 200 Net-
zsch software. The software enabled analysis of the sample melt-
ing process and evaluation of the area between the thermographic
2. Materials and experimental procedure curve and the baseline for the occurrence of endothermic reflex.
Indium was used as a model, with the sample weight ranging from
This work presents the results of investigations of composites 8 to 10 mg. The test samples were weighed with a SARTORIUS bal-
made of the granulates by Polimarky (Rzeszow, Poland). These ance with weighing accuracy of 0.01 mg, internal calibration and
granulates contained polypropylene - Malen P J – 400 produced a closed measuring chamber. The value of the degree of crystal-
by Petrochemia Płock and glass fibres with E symbol. The glass fi- lization was calculated according to (1) considering the measured
bres with final length 6 mm were covered by silane preparation. melting enthalpy.
Samples for investigations were prepared by means of injection
H p
with Krauss – Maffei injection machine (KM65 – 160C1 type). The Sk = · 100% (1)
investigations encompassed the composites on the polypropylene Hk
matrix which contained 30% and 50% of the glass fiber (GF). For where:
the comparison purposes the matrix material was also tested. Part Sk – degree of crystallinity,%
of the material was processed by heat treatment in the form of Hp – melting enthalpy of the tested material,
annealing at the temperature of 130 °C in the air. Annealing rate Hk – melting enthalpy of a completely crystalline material.
amounted to 0,015 °C/s, annealing time 900 s per mm of the sam- The melting heat for PP was assumed to be 209 J/g [32,33].
ple thickness, cooling rate 0,010 °C/s. The symbols of individual Temperature microscopic examinations were carried out using a
specimens and content percentage of glass fibres are presented in set for microscopic observation of phase transitions (Mettler Toledo
Table 1. FP82HT heating table, Polam 113 polarizing microscope, Panasonic
The chemical structure of polypropylene and glass fiber rein- KR-222 video camera). They allowed for the observation of the
forced polypropylene composites was studied using a SHIMADZU melting and crystallization processes occurring in the specimens
Irraffinity-1 s Fourier transform infrared spectrophotometer (FTIR) studied. Fine chips taken from the specimen core for strength test-
and the method of attenuated total reflectance (ATR). Spectroscopy ing were heated from room temperature to 210 °C at a rate of
research samples were cut out of the strength samples. They were 15 °C/min. Observation of the melting process allowed for opti-
in form of cuboids with measurements of 2 × 2 × 1 mm. Sam- cal determination of the melting point (observable melting of the
ples surfaces were flat, smooth, and tightly adhered to the crystal’s specimen). The specimens were then cooled from 210 °C to room
surface. The spectra were recorded in the measurement range of temperature at a rate of 15 °C/min. During cooling, the crystal-

Table 1
Designations of specimens used in study.

Specimen,“a” – samples after annealing PP PP-a PP70/GF30 PP70/GF30-a PP50/GF50 PP50/GF50-a

Content of glass fiber content,% – – 30 30 50 50

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R. Caban Journal of Molecular Structure 1264 (2022) 133181

Table 2
FTIR absorption of specimens used in study [34–41].

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 CH wagging vibrationwagging vibration
1166 C-CCH3 C–H asymmetrical stretchingasymmetrical rockingwagging vibration
998 CH3 asymmetrical rocking
974 CH3 C–C asymmetrical rockingasymmetrical stretching
898 CH3 C–C asymmetrical rockingasymmetrical 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

lization 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 un-
polarized 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 dif-
ferent groups: -CH2 , -CH- and –CH3 . Each of them is correlated in
IR spectra with the suitable absorption peak by definite wavenum-
Fig. 3. DSC thermograms of the specimens (melting curve): 1 - PP, 2 – PP70/GF30,
ber values (Fig. 2). The proper characteristic, concerning this corre- 3 – PP50/GF50.
lation is presented in Table 2.
The absorption peaks occurring at wave numbers 1166 cm−1 ,
998 cm−1 , 974 cm−1 , 841 cm−1 are peaks characteristic of iso-
tactic partially crystalline polypropylene [36]. Many publications should be seen as a measure of the overall crystallinity of the sam-
have focused on the absorbance characteristics of polypropylene ple and cannot be partitioned for phase α and β . In contrast, the
[30,35,37–39]. The peak occurring at 998 cm−1 corresponds to the peak at 974 cm−1 is attributed to both amorphous and crystalline
crystalline phase of polypropylene [42]. Since crystals α and β regions of the polymer [20]. Kilic et al. [43] showed that the ab-
polypropylene have similar spectra [30] the height of this peak, sorbance 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. [42] presented a methodology for de-
termining the degree of crystallinity using the ratio of the maksi-
mum peak heights at 998 cm−1 and 974 cm−1 determined from
FTIR measurements versus the degree of crystallinity that was de-
termined by X-ray. In contrast, the ascending peak at 841 cm−1 is
associated with crystallization of polypropylene [28] and is gener-
ally used as a probe to monitor the crystallization process of iPP
[44,45]. Analyzing the FTIR - ATR spectra, especially the spectra of
glass fiber and polypropylene, one can see a clear effect of modifi-
cation of the polymer matrix of the composites studied the intro-
duced glass fiber. FTIR spectroscopic studies confirmed the pres-
ence of glass fiber in the composites and increased chemical ef-
fect with increasing amount of glass fiber in PP composites. The
wide absorption band recorded in the composite specimens be-
fore and after annealing with a maximum around 1060 cm−1 cor-
responds 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 [40,41].
Differential thermal analysis was also used. The results of the
Fig. 2. FTIR-ATR spectra of the studied materials: 1-PP, 2-PP – a, 3 – PP70/GF30, 4 analysis using differential scanning calorimetry are presented in
PP70/GF30 – a, 5 – PP50/GF50, 6- PP50/GF50- a, 7 – GF, 8 –GF -a. Table 3 and Figs. 3 and 4.

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R. Caban Journal of Molecular Structure 1264 (2022) 133181

Table 3
Results of DSC examinations.

Degree of Melt temperature Melt temperature – Crystallization Crystallization

Samples crystallinity,% range, °C peak max., °C temperature range, °C temperature - peak 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

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: α , β and smectic phase. However, the
analysis of endothermic curves does not highlight the presence of
polymorphism. The endothermic reflection observed in Fig. 3 cor-
responds to the melting of the monoclinic α 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 β 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 high-
est 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 speci-
Fig. 4. DSC thermograms of the specimens after annealing (crystallization curve): 1
mens led to an increase in the degree of crystallinity compared
– PP-a, 2 – PP70/GF30-a, 3 – PP50/GF50-a.
to unheated material. Mulle et al. [24] conducting DSC investiga-
Analysis of the DSC results revealed that the melting point tions of glass fiber - reinforced polypropylene laminates, noticed
(maximum of endothermic reflex) and crystallization temperatures that annealing of the samples at the temperature 80 °C increases
(maximum of exothermic reflex) in the polypropylene/glass fiber the degree of crystallinity of the tested materials. Franciszczak

Fig. 5. Crystallization of polypropylene.

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R. Caban Journal of Molecular Structure 1264 (2022) 133181

Fig. 6. Crystallization of PP70/GF30-a composite.

et al. [5] examining the influence of polymer matrix crystallinity portion of crystalline phases. Growth of spherulites can occur by
on the mechanical properties of short fiber composites also no- radial spreading evenly in all directions or by branching, starting
ticed an increase in the degree of crystallinity after annealing. Sim- from the nucleus.
ilar tendency was observed in own research [12,46] as well as in Temperature microscopic studies were performed to comple-
other publications [47,48]. As a result of heating, the mobility of ment the DSC studies. The examinations carried out in polarized
macromolecules increases, and fragmentation of crystalline struc- light allowed for the optical determination of the melting point
tures (mainly spherulites) occurs. These tiny elements of crystalline (during heating) and the crystallization temperature of the poly-
structures become new nuclei. New spherulites are formed from meric matrix (during cooling). In the microscopic method, the
the nuclei, mainly in the form of crystalline plates called lamellae, melting point is the temperature at which the most crystallized
and as a result of ordering some of the macromolecules of the non- crystallites disintegrate and the last traces of crystallinity disap-
crystalline phase. Already during heating, some macromolecules of pear [49,50]. The results of these examinations are presented in
the non-crystalline phase were ordered while increasing the pro- Table 4.

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R. Caban Journal of Molecular Structure 1264 (2022) 133181

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

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

Table 4 glass fibers in the specimen material. Glass fibers cause significant
Melting point and the range of crystallization temperature of the materials de-
image blurring and distortion. This makes it impossible to deter-
termined using the microscopic method.
mine the size of the resulting crystalline structures. Nevertheless,
Crystallization it can be concluded that the crystallites are formed in large num-
Melt temperature Crystallization
bers throughout the specimen, but they are not large. This is due
Samples temperature, °C range, °C temperature, °C
to the glass fibers, whose content in the specimen material limits
PP 166 122÷110 110 their growth.
PP-a 167 125÷115 115
Investigations using a polarizing microscope allowed for the ob-
PP70/GF30 167 123÷119 119
PP70/GF30-a 168 125÷118 118 servation of the supramolecular structure of polypropylene and
PP50/GF50 167 128÷119 119 glass fiber reinforced composites (Figs. 7 and 8). In the case of
PP50/GF50-a 166 128÷115 115 polypropylene, the structure was regular and ordered. Polypropy-
lene spherulites ranged in size from 20 to 490 μm (Fig. 7).
For composites containing glass fibers, the amount of reinforc-
Both polypropylene and polypropylene matrix composites spec- ing phase makes it difficult to specify individual spherulites. Their
imens exhibited features of crystalline objects by depolarizing presence is indicated only by the depolarization of the light in the
light. This made it possible to observe the forming crystalline examined material. Fig. 8 shows the polypropylene/glass fiber com-
structures observed as colored objects on the black background of posite after annealing of PP70/GF30-a and the boundary zone of
the amorphous liquid. The course of crystallization of polypropy- the preparation. Crystalline structures in the form of spherulites
lene is shown in Fig. 5, whereas Fig. 6 presents the course of crys- that are not optically distorted by the glass fibers contained in
tallization of the composite containing 30% of glass fiber after an- the specimen can be noticed. This may indicate that such struc-
nealing. tures are present throughout the specimen, but cannot be di-
The crystallization of both polypropylene and its matrix com- rectly observed due to the high glass fiber content. The size of the
posites reinforced with glass fibers occurred very quickly from the spherulites in the composites studied is not very large (about 20
appearance of the first nuclei to the crystallization of the entire μm).
specimen. Crystallization of the specimens after annealing pro-
ceeded at slightly higher temperatures. It is difficult to distinguish 4. Conclusion
single spherulites, in the microphotographs showing the course
of crystallization of composites containing 30% of glass fiber after The study of the structural properties of semi-crystalline poly-
heat treatment (Fig. 6). The reason for this is the high content of mers is critical to understanding the relationship between struc-

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R. Caban Journal of Molecular Structure 1264 (2022) 133181

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