Characterization of polymer materials using FT-IR and DSC

techniques

Pere Pagès
Departamento de Ciencia de Materiales, Universitat Politècnica de Catalunya. Colom,
11, 08222-Terrassa. Spain
[email protected]

1. Introduction
In this chapter the autor realise various studies about the structural
characterisation of polymer materials, using the Infrared spectrophotometry (FT-IR) and
the Differential Scanning Calorimetry (DSC) techniques.
Results obtained by means of both techniques are in all the cases
complementaries in order to achieve a better comprensiveness about the structure of the
polymers.
2. Part one: FT-IR and DSC study of HDPE structural changes and mechanical
properties variation when exposed to weathering aging during canadian winter
This work studies the influence of the climatic conditions during the Canadian
winter using high-density PE (HDPE) samples exposed to weather conditions during
different periods of time. Under these conditions, it is reasonable to think that the
chemical changes caused by the climatic degradation will at first sight be due to
photochemical reactions (sunlight) and, to a lesser extent, to hydrolytic reactions
(environmental moisture). FT-IR was used to study the microstructural changes.
Similarly, many of these microestructural modifications are thought to originate some
changes in the crystalline content. As is well known, crystallinity is closely related to
the macroscopic properties of the polymer and this knowledge is fundamental in
engineering applications. Therefore, another objective of this work is the study of the
crystallinity variation of the polymer subjected to drastic environmental conditions by
using two techniques: FTIR and DSC. The variation of the mechanical properties of
HDPE exposed to the indicated climated conditions was also analyzed.
2.1. Experimental

2.1.1. Materials
HDPE (HDPE 2909, Du Pont Canada) is a thermoplastic polymer with the
following properties: density 960 kg/m3 and melting flow index 1.35 g/min.
2.1.2. Preparation of HDPE Samples
Samples were prepared in a mold according to ASTM D-638 (type V). The
HDPE, previously milled and screened, was compacted in a mold at 3 MPa pressure for
20 min at room temperature. Then it was heated to 1500C and pressure increased to 3.2
MPa for 20 min. Demolding was accomplished by slowly quenching the mold until
room temperature to prevent bubble formation.
122 PERE PAGÈS

2.1.3. Environmental Conditions

Samples were weather exposed during different periods of time: 0, 15, 30, 60
and 90 days. Figure 1 shows the daily data about minimum and maximum temperatures
during the time studied. In addition to the low temperatures there is a very accentuated
difference of temperature between day and night (i.e., thermal fatigue). As a result,
treatments can be considered as doubly drastic.
2.1.4. Analytical Techniques
Microstructural changes in the HDPE were determined by FTIR
spectrophotometry. In relation to the variation of crystallinity, two instrumental an-
alytical techniques were used: FTIR and DSC.
FTIR Spectrophotometry
A Nicolet 510 M with CsI optics was used to obtain the FTIR spectra. The
method to prepare the samples consisted of dispersing the surface of the finely divided
sample (9 mg) in a matrix of KBr (300 mg), followed by compression at 167 MPa to
compact the pellet.
To evaluate microstructural changes undergone by the HDPE samples, the
pertinent spectra were obtained for each of the treatment periods (from 0 to 90
days). Based on the spectral recordings, called "basic," the variations that
occurred were analyzed: formation/disappearance, increase/decrease, and
displacement of the various bands. To evaluate these differences, subtraction
between the various spectra was used by enlarging the spectrum zones that
give better information, 775-1540 and 1600-1800 cm [1].

Figure 1. Maximum and minimum values of HDPE temperature during the exposure
period to environmental conditions.

These zones include and surpass the spectral zones used in previous works to
study the PE aging [2].
Concerning the crystallinity, the literature indicates that it was first determined
by the ratio of the absorption intensities at 1303 cm-1 corresponding to the amorphous
phase of the solid and melted states [7]. This method implies incertitude as the
absorption coefficients in both states are not the same. A procedure based on a universal
calibration constant and on the measure of the absorption intensity at 1303 cm-1 of the
amorphous phase was later developed. Unfortunately, this method can only be applied if
the film density and thickness are known [8].
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 123

Zerbi et al. [9] recently suggested the use of spectral bands corresponding to the
bending vibrations: 1474 and 730 cm-1 (crystalline phase) and 1464 and 720 cm-1
(amorphous phase). This procedure was selected for this work as the preparation
technique in pellets provides intense absorptions in such spectral bands while the
absorption at 1303 cm-1 gives low intensity due to the high crystallinity of the HDPE.
Therefore, mainly two spectral zones were analysed:
600-800 cm-1 (containing the bands 720 and 730 cm-1) and 1400-1550 cm-1
(containing the bands 1464 and 1474 cm-1).

DSC
This technique was used to support the results of crystallinity obtained by FTIR.
A DSC 30 Mettler analyzer, with liquid nitrogen, capable of reaching a maximum
sensitiveness of 0.4 mJ/s per each 100 divisions of the recording paper was used to
obtain the thermograms. The sample weight varied between 2.0 and 3.0 mg. Weights
sufficiently small were selected to prevent heat transfer problems, such as was already
proved in previous thermogravimetric studies [10]. The heating rate was 20 K/min,
which means a balanced compromise between the measuring speed and the peak
resolution. The temperature range analysed was 50-200ºC. The temperature and energy
calibration was achieved by means of In, Pb, and Zn standards, under identical ana-
lytical conditions of the HDPE samples.
2.1.5. Mechanical Properties
The tensile strength, elasticity modulus, and impact energy were determined by
standardized procedures to study the influence of aging on the mechanical properties.
2.1.6. Analysis of Chemical Changes
With the spectral subtractions of the different samples exposed during various
periods of time, taking as reference the nondegradated HDPE sample, tables were
prepared in which the most relevant results are shown. Table 1 shows the most
significant bands studied and their distinctive functional group. Table 2 defines the
behavior of all the bands specified that are listed according to generated, transformed, or
invariable functional groups as the result of the exposure undergone during a period of
15 days. The progress of the microstructural phenomena of configuration as the ex-
posure time increased is shown in Table 3.
A comparative study with the results found by D'Esposito and Koening [2]
shows a significant coincidence in most of the bands studied, although some discrepant
bands also occur. These discrepant values are corroborated by characteristic and original
bands pertaining to the region of 1700-1800 cm-1 that were not included in the above-
mentioned work, even though these bands are confirmatory of groups obtained within
the range 750-1425 cm-1.
124 PERE PAGÈS

Table 1. Spectral FTIR Bands Studied

Wave
Number Functional Groups Type of Vibration
-1
(cm )

(1) 900 RR’C=CH2 C-H rocking

(2) 909 RCH=CH2 C-CH2 out of plane bending

(3) 971 (trans) R’CH=CHR =C-CH bending, R and R’ are alkyl

groups

(4) 990 RCH=CH2 =C-H out of plane bending, related to

(2)

(5) 1068 RCH2-CHOH-CH2R’ C-O stretching, corresponding to a

secondary alcohol, R and R’ are groups
with insaturations

(6) 1131 RCH2-COH(CH3)-CH2- C-O stretching,corresponding to a

tertiary alcohol

(7) 1177 -CH(CH3)2 C-C stretching and C-C-H bending

(8) 1368 -C(CH3)3 Doblet in C-H bending

(9) 1360 -CO-CH3 -CH3 symmetric vibration in a ether

(10) 1375 -CH3 C-H symmetric bending

(11) 1410 RCH2-CO-CH2R -CH2- scissoring

(12) 1653 (cis) R’CH=CHR Terminal bond vibration where R and R’

are alkyl chains

(13) 1692 R-CO-OR’ C=C stretching where R and R’ are

vinyl groups

(14) 1738 R-CO-OR’ C=O stretching where R and R’ are

alkyl groups
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 125

Table 2 Functional Groups Resulting from HDPE Aging for 15-Day Exposure
Time (by FTIR)

Spectral Bands (cm-1) Generated Groups

(7) 1177 -CH(CH3)2
(8) 1368 -C(CH3)3
(9) 1360 -CO-CH3
(10) 1374 -CH3
(11) 1410 R-CH2-CO-CH2-R’
(13) 1692 R-CO-OR’
(14) 1738 R-CO-OR’

(2) 909 R-CH=CH2

(12) 1653 RHC=CHR’ (cis), terminal insaturations
related to (2) Unchanged Groups

(1) 900 R’RC=CH2

(3) 971 (trans) RCH=CHR’
(4) 990 RCH=CH2
(5) 1068 RCH2-CHOH-CH2R’
(6) 1131 -CH2-C(CH2R)OH-CH2

Table 3 Types of Spectral Bands Resulting from HDPE Aging for 15, 60, and 90-Day
Exposure Time to Environmental Conditions (by FTIR)

15 Days

Intensity Increase,
Intensity Increase, Transformed Unchanged Intensity
Generated
Groups (cm-1) (cm-1)
groups (cm-1)

900, 1177, 1368, 1375, 1360,

909, 990, 1953 971, 1068, 1131
1410, 1692, 1738

60 Days

900,971,1368,1375,1360,
909,990,1068,1683 1177,1410
1131,1692,1738

90 Days

900,971,1368,1375,1360,
909,990,1068,1653 1177,1410
1131,1692,1738
126 PERE PAGÈS

On comparing the results of the first 15 and 30 days of exposure, the trend
followed by the increase bands (generation of groups) and the decrease bands
(transformation of groups) remain unchanged. Bands at 900 and 990 cm-1 initially
belonging to the invariant group are incorporated, respectively, to the increase and de-
crease blocks. Results at 60-days degradation confirm the previously mentioned values.
The characteristic block of transformed groups was increased by the incorporation of an
invariant band while the characteristic block of generated groups did not change. In
view of these results, it was confirmed that the microstructural changes undergo
alterations during the first 60 days of exposure, thus becoming stable.
The results confirm the microstructural configuration modifications occurring in
the polymeric chains. Such modifications are defined by a series of mechanisms
involved in the HDPE degradation:

1. chain breaking with the formation of characteristic groups (methyl, terbutyl,

iaopropyl, and end insaturations) due to homolytic and heterolytic dissociations
reflected in the positive evolution banda (900, 1177, 1368, 1375, and 1678 cm-1);
2. chain branching with generated groups defined by bands 1177, 1368, and 1375
cm-1 and with transformed groups (909, 990, and 1653 cm-1) that confirm these
modifications;
3. crosslinks between polymeric chains caused by additive reactions on double
linkages. The characteristic groups defining this type of modification appear in
the negative evolution bands (909 and 1653 cm-1);
4.oxidation phenomena defined by the positive evolution bands (1760, 1410, 1692,
and 1675 cm-1) and involving the formation of peroxides, alcohol groups, and
carboxylic groups.

To summarize this study, Table 4 shows the evolution of the different

characteristic bands that define every phenomenon occurring in the configurational
variations and their relationships to the various exposure times.
2.1.7. Crystallinity Variation
The empirical relation proposed by Zerbi et al. [9] was used to evaluate
crystallinity:

1 − I a / Ib
X = 1.233 .100
I
1+ a
Ib
where X is the percentage of the amorphous content, Ia and Ib the intensities of
absorption in the bands of 730 and 720 cm-1 or, alternatively, at 1474 and 1464 cm-1,
respectively. The constant 1.233 corresponds to the relations of intensity bands of fully
crystalline HDPE.
Table 5 illustrates the variation of the HDPE amorphous and crystalline content
as a function of the exposure time and the calorimetric features (initial and final melting
temperatures and the melting enthalpy). Results show relevant discrepancies according
to the spectral bands selected for the evaluation of the content in both the amorphous
and crystalline phases. The intensity ratio 730/720 cm-1 leads to random results for
crystallinity without the possibility of establishing the level of degradation in terms of
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 127

its duration. In addition, the crystallinity varies in the range 71.5-76.6%, values too low
for the HDPE, which is a highly crystalline polymer. The density and also the melt flow
index of HDPE confirm that it is a material prepared with a Phillips-type catalyst,
whose crystallinity is around 90% [11]. The conclusion from these facts is that the
measurement of crystallinity through the bands 730/ 720 cm-1 is not adequate. On the
contrary, the bands 1474/1464 cm-1 indicates that the crystallinity progressively
decreases, while the weathering exposure time increases, from 98 to 95%. Moreover,
these values are rather similar to the HDPE ones of this study. On the other hand, the
calorimetry study that follows supports the validity of using the bands 1474/1464 cm-1.
In effect, from the thermograms obtained it is clear (see Table 5) the melting enthalpy
decreases (i.e., crystallinity decrease) as the exposure time increases. This article has
demonstrated that aging is caused by specific chemical transformations undergone by
the polymeric chains.

Table 4 HDPE Microstructural Variations as a Function of Exposure Time (by FTIR)

Chains Breaking
Days 900 cm-1 971 cm-1 1177 cm-1 1368 cm-1 1374 cm-1
15 inv inv + ++ inv
30 + inv + ++ +
60 ++ + ± ++ ++
90 ++ ++ ± ++ ++

Chain Branching
900 909 971 990 1177 1368 1374 1653
15 inv - inv inv + ++ inv ---
30 + -- inv - + ++ + ---
60 ++ --- + - ± ++ ++ --
90 ++ --- ++ - ± ++ ++ -

Oxidation Phenomena
1360 cm-1 1410 cm-1 1692 cm-1 1738 cm-1
15 + + ++ ++
30 ++ + +++ ++
60 +++ ± +++ ++
90 ++ ± ++ +++
Inv, unchanged; (+) increase; (-) decrease; (±) slight increase.

These reactive phenomena decrease the linear character of the polymeric chains
caused by the formation of bulky groups, which leads to an increase of the amorphous
content. Therefore, the crystallinity results found by DSC are in accordance with those
recorded by FTIR in the bands 1474/1464 cm-1. Figure 2 proves the actual linear
relation between the melting enthalpy and the HDPE crystallinity degree. This
correlation indicates that per each 1% of less crystallinity due to the aging process, the
melting enthalpy decreases by 3.8 J/g. By extrapolation of the straight line at 100%
crystallinity, a melting enthalpy of 229.0 J/g is obtained, corresponding to the fully
crystalline HDPE.
128 PERE PAGÈS

Table 5 Variation of HDPE Amorphous and Crystalline Contents (by FTIR),

Temperatures, and Melting Enthalpy (by DSC) as a Function of Exposure Time

Spectral Bands
Ia= 730 cm-1 Ia=1474 cm-1
Ib= 720 cm-1 Ib=1464 cm-1
Initial and
Melting Melting
Exposure Amorphous Crystalline Amorphous Crystalline Temperatures Enthalpy
Time Content Content Content Content (ºC) (J/g)
(Days) (%) (%) (%) (%)
0 28.10 71.90 2.02 97.98 126.7-149.8 221.4
15 28.52 71.48 3.76 96.24 127.3-145.9 215.3
30 26.98 73.02 4.16 95.84 127.1-145.2 212.8
60 26.35 73.65 4.80 95.20 126.3-145.7 211.2
90 27.38 72.62 4.88 95.12 123.6-142.1 210.7

Figure 2 Relation between melting enthalpy and crystallinity of HDPE.

Table 6 shows the evolution of the mechanical properties studied. The decrease
of the impact energy caused by the formation of bulky groups, imparting stiffness to the
polymeric chains, is remarkable. The rest of the mechanical properties evaluated (tensile
strength and Young's modulus) do not vary significantly with exposure, something to be
expected as their characteristics basically depend on crystallinity. To be noted is that the
HDPE crystallinity varies not more than 3% (environmental exposure of 90 days).

2.2. Conclusions part one

HDPE undergoes aging when submitted to drastic climatic conditions such as

the Canadian winter: low temperature and sharp temperature changes between day and
night (i.e., intense thermal fatigue). This aging becomes apparent by a series of
chemical changes in the polymeric chains and a progressive decrease of HDPE
crystallinity if the weathering exposure time increases.
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 129

The study of the spectral bands of samples degradated during different

weathering exposure times demonstrated the existence of a series of microstructural
modifications: chain breaking, chain branching, crosslinking, and oxidation. These con-
figuration changes obviously influence the polymer crystallinity that was evaluated by
quantifying the absorption intensity FTIR in two spectral bands: one characteristic of
the amorphous phase and another of the crystalline phase. Two zones of the spectrum
corresponding to vibrations of deformation, 730/720 cm-1 and 1474/1464 cm-1 were ana-
lyzed. The use of the bands 1474/1464 cm-1 was appropriate for the evaluation of
crystallinity while the bands 730/720 cm-1 yielded random and too low results (71-77%
with respect to the values that should be obtained for HDPE prepared with a Phillips-
type catalyst, usually higher than 90%). Consequently, the use of the latter bands to
evaluate the percentage of the polymer crystalline character was rejected. The results of
DSC ratify the results accomplished by FTIR at 1474/1464 cm-1, as the melting
enthalpy, and therefore crystallinity, decrease with the weathering exposure time.
Similarly, a linear relation between the melting enthalpy and crystallinity was made
evident in such a way that 1% less crystallinity involves a 38 J/g decrease of the melting
enthalpy. By application of this straight line and extrapolation at 100% crystallinity, a
value of 229.0 J/g for the melting enthalpy was found, which should correspond to an
ideal, fully crystalline HDPE. The property most affected by aging phenomena is the
impact energy owing to the stiffness of the polymeric chains. The other mechanical
properties evaluated (tensile strength and elasticity modulus) remain almost constant as
they basically depend on the crystalline content of the polymer that decreases
approximately 3% after 90 days of weathering exposure.

Table 6 Variation of HDPE Mechanical Properties as a Function of Exposure Time

Exposure Time Tensile Strength Young’s Modulus Impact Energy

(Days) (MPa) (GPa) (mJ)
0 23.1 1.46 80.6
15 24.5 1.49 70.2
30 22.6 1.53 64.9
60 22.6 1.52 41.9
90 23.6 1.40 37.7

3. Part two: natural and artificial aging of polypropylene-polyethylene

copolymers
It is known that exposing polymeric materials to environmental and artificial
atmospheres changes their properties and external appearances with some modification
of their surfaces. Several chemical reactions, induced by irradiation with sunlight, take
place because of the chromophoric groups present in the polymer and the consequent
ability of the polymer to absorb ultraviolet light Photoreactions are usually induced
when polymer materials are damaged, causing embrittlement and color changes [12-14].
For the prevention of these phenomena, several methods have been developed. One of
the most important is stabilizing the polymers with additives (i.e., antioxidants and light
stabilizers).
130 PERE PAGÈS

To develop effective formulations, we must first know the causes and

mechanism of the degradation. Fourier transform infrared (FTIR), differential scanning
calorimetry (DSC), and scanning electron microscopy (SEM) are techniques used to
evaluate the degradation process of polymeric materials. One of the earliest works
performed with FTIR spectrophotometry was based on a study of PFT films exposed to
high temperatures [15]. More recently, several studies on the artificial aging of
different polymers were carried out, and their effects were quantified by FTIR
spectrophotometry and photoacoustic FTIR [14, 16-18].
In this article, we report on aging-induced changes in the structural and thermal
properties of polypropylene (PP)-polyethylene (PP)-based copolymers that were used as
seats in the Olympic stadium of Barcelona, Spain. The samples were exposed to natural
aging by weather for 2.5 years and to artificial aging by exposure to radiation from a
xenon lamp for 5000 h, which is considered to be equivalent to 2.5 years of
environmental exposure [19].
3.1. Experimental
The analyzed material was a PP-rich (~95 wt %) PP-PE copolymer
manufactured by Repsol and marketed as PB 140. It was a block copolymer with short
PE chains grafted to PP. The composition (95% PP) was chosen for its mechanical
properties, that is, the high degree of toughness. Several additives were added to the
base material. Table 7 shows a list of the various samples, which differed in the types
and quantities of the additives employed.
The additives were antioxidants (Tinuvin 770, Irganox BZ15, Bioxid Kronos CL
2220, and Quimasorb 944) and colorants (blue Cromoftal A3R, red Cromoftal DPP-BO,
violet Cinquasia R RT 891D, Iagacolor 10401, Byferrox 110, and Iagacolor 415).

Table 7. Description of the Additives Present in the Studied Copolymers

Sample Additives

A Tinuvin 770, Igamoz BZ15, Quimasorb 944, Cromoftal A3R, Bioxid

Kronos CL 2220

B Tinuvin 770, Quimasorb 944, Cromoftal DPP-BO, Cinquasia R RT 891D

C Tinuvin 770 Igarnoz BZ15, Quimasorb 944, Iagacolor 10401 Bioxid

Kronos CL 2220

D Tinuvin 770, Quimasorb 944, Iagacolor 415, Byferrox 110

The coupled samples A-B and C-D were prepared with different combinations
of coloring additives according to the main industrial process. Samples A and B were
subjected to artificial aging performed in a xenon test 450 chamber, with a xenon arc
lamp as the radiating light source for the simulation of natural aging. The artificial aging
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 131

time was 5000 h (equivalent to 2.5 years of natural aging). The samples were labeled as
A-5000 and B-5000, respectively. Samples C and D were aged under natural climatic
conditions for 2.5 years and were labeled C-2.5 and D-2.5, respectively.
The structural changes and thermal properties of the PP-PE copolymers were
measured with FTIR spectrophotometry and DSC techniques. A Nicolet 510M
spectrometer with CsI optics was used to obtain the FTIR spectra, with a resolution of 2
cm-1 and with an average of 50 scans. Pellets were prepared by the dispersion of the
surfaces of finely divided samples (3 mg) in a matrix of KBr (300 mg), followed by
compression at 167 MPa.
To determine changes in the FJJR spectra, several authors [14, 18, 20] chose a
particular band as a reference to avoid deviations between spectra produced by samples
of different weights or thicknesses. The absorption related to this band is known as the
reduced or compensated absorption. In this work, the spectral reference band chosen
was at 2840 cm-1 and was due to methylene symmetric stretching vibrations.
The thermal behavior of the samples was analyzed with DSC. The
measurements were made with a Mettler TA4000 thermoanalyzer coupled with a low-
temperature (nitrogen coil) DSC 30 apparatus. The calibration of the temperatures and
energies was made with standard samples of In, Pb, and Zn under the same conditions
used in the sample analysis. The measurements were made with dry air as a purging gas
at a flow rate of 20 mL/mm. The heating rate was 10 K/min, a good compromise
between the measurement rate and the endothermic melting peak resolution. The sample
mass was about 2.5 mg, small enough to prevent the problems caused by heat- and
mass-transfer limitations. Several experiments were performed to ensure the
reproducibility of the results, with the samples heated to 600, 300, or 1850C.
The microstructures of the samples were characterized by SEM in a Zeiss DSM
960 A apparatus. The resolution was 3.5 nm, the acceleration voltage was 15 kv, and the
working distance was 10-20 mm. The samples were sputtered previously with C with a
K 550 Emitech instrument. The aim was to observe microstructural changes arising
from the degradation phenomena related to the aging processes, as well as the effects of
the thermal treatments applied to the material.

Table 8. Variation of Reduced Absorbance Avarage Values of All Samples as a

Funtion of Artificial Aging and Natural Aging.
132 PERE PAGÈS

3.2. Results and discussion

We analyzed the characteristic spectral bands of the polymer that were more
greatly modified during the aging process. The results are shown in Table 8. The
chemical groups related to these bands are carbonyl groups (1735 cm-1), ether (1167 cm-
1
), nonsaturated bonds (1650 cm-1), methylene (1460 cm-1), and methyl (1378 cm-1).
There are also three bands related to the structural characteristics: configuration isomer-
ism and conformational order (812, 901, and 976 cm-1) The evolution of these latter
bands allowed us to determine structural and configurational changes.

Figure 3. FTIR spectra of samples C and D exposed to natural aging in the spectral
range 1025-1380 cm-1

3.2.1. Study of Natural Aging by FTIR

Figure 3 shows the spectral range 1025-1380 cm-1 for samples C and D exposed to
natural aging. The 1168 cm-1 band, associated with the C-O-C group, shows a tendency
to increase in aged samples, suggesting the formation of ether groups. Moreover, the
FTIR spectrum of sample D-2,5 has three bands at 1235, 1194, and 1080 cm-1 (marked by
arrows) and two shoulders, one at 1294 cm-1 and another at 1154 cm-1 (marked by
arrows), associated with transitions of the crystalline phase. These spectral differences be-
tween the aged and nonaged samples show that the crystallinity of sample D was more
affected by the aging process. Sample C was less affected by aging, showing only small
spectral changes (the 1235 cm-1 band and the shoulder at 1154 cm-1).
Figure 4 shows the spectral range 750-1050 cm-1 corresponding to samples C
and D not aged and naturally aged. The absorbance of the 812-, 976-, and 998-cm-1
bands, related to conformational and configurational changes, is higher in aged samples
than in nonaged ones. Moreover, the presence of the bands marked by arrows makes it
evident that some changes were produced. The spectral band at 901 cm-1 moved to 912
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 133

cm-1, and this short shift was attributed to the background changes generated by
conformational modifications. Likewise, a small shoulder appears at 941 cm-1, and two
peaks appear at 1015 and 1035 cm-1 (associated with the stretching vibrations of -C-O-C
and –C-O-H, respectively). Both peaks appear as a result of the oxidative process that
originated during natural aging.
3.2.2. Study of Artificial Aging by FTIR
Samples A and B were subjected to artificial aging in the xenon test chamber for
5000 h. The spectra of aged and nonaged samples are shown in Figures 5 and 6. The
changes detected in both materials (A and B) are very similar. Nevertheless, these
changes are not as important as they are for the materials subjected to natural aging for
2.5 years (C and D).
The spectra corresponding to the samples artificially aged (A and B), illustrated
in Figure 4, show that degradation phenomena are lower than in the previous case. In
the artificially aged samples, only a slight increase in the band absorbances associated
with the configuration order was detected. We can conclude, therefore, that exposure to
weather leads to more aggressive degradation than that produced by exposure to the
homogeneous conditions employed in the xenon test chamber in our study.
3.2.3. Comparison of Natural and Artificial Aging by FTIR
A comparative study of both types of aging processes (natural and artificial) is
shown in Figure 7. An increase of the ester and ketone groups (1735 and 1717 cm-1)
was detected. This increase was greater in the materials subjected to natural aging.
Samples C were the most affected by carbonyl group formation.

Figure 4 FTIR spectra of samples C and D exposed to natural aging in the spectral
range 750-1050 cm-1. Bands marked with arrows are related to large spectral changes.
134 PERE PAGÈS

Figure 5 FTIR spectra of samples A and B exposed to artificial aging in the spectral
range 1025-1380 cm-1

Figure 6 FTIR spectra of samples A and B exposed to artificial aging in the spectral
range 750-1050 cm-1. Bands marked with arrows are related to large spectral changes.
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 135

Comparing samples C and A (Fig. 7), which only differed in the pigment used
and the type of aging, we can observe that natural aging is far more aggressive than
artificial aging.
The formation of ether groups related to the 1168-cm-1 band (Figs. 3 and 5) is
not clear in the artificially aged samples This difference in the evolution of these groups
must be influenced by parameters difficult to reproduce in artificial aging in a xenon test
chamber (e.g., sudden changes of temperature and humidity, rain, and sea proximity).
Furthermore, it is also difficult to reproduce the interactions of these parameters with
the pigment used and the ability to react at high temperatures, mainly with sulfurous
compounds [21] arising from pollution.

Figure 7 Reduced absorbance results of spectral bands associated with the carbonyl
group in all aged samples.

There are several bands related to the double bonds. The one that can best help
to define the evolution of the aging process is the 1650-cm-1 band, associated with the
stretching vibrations of -C=C- The tendency of this band to diminish in the aged
samples, as shown in Table 8, is similar in all samples. Nevertheless, it is remarkable
that samples artificially aged presented a decrease of 46%; compare this to 33% for the
naturally aged ones. The double bonds are generated in the first steps of the aging
process, reacting subsequently to produce branching, crosslinking, or both.
The samples exposed to natural aging had a lower percentage of double bonds
but higher crosslinking. That is reflected in the configurational changes shown by the
evolution of the main bands associated with the tacticity of PP (976, 901, and 812 cm-1)
[22] in Figures 4 and 6.
The decline of every band, shown in Figure 8, occurred for all (naturally or
artificially) aged samples. The spectral band most sensitive to the changes in the
configuration order is the 976-cm-1 band, associated with ν(CC) in the chain and with
yr(CH3).
136 PERE PAGÈS

Figure 8 Reduced absorbance corresponding to spectral bands associated with

configurational isomerism (976, 901, 812 cm-1) for all aged samples.

Likewise, the tendency of the methyl (1378 cm-1) and methylene (1460 cm-1)
groups to diminish was observed in all samples and in both aging processes. The results
are given in Figure 9, which shows the evolution of the 1460- and 1378-cm-1 bands. The
greatest decrease occurred in the naturally aged ones (being more important in C than in
D). The breaking of the group combined with the carbon in the natural aging process is
widely accepted because this labile carbon easily becomes a free radical through
elimination reactions [23, 24] when ultraviolet radiation is present. Moreover, in most
of the degradation processes of polyolefins, there is a decrease in the number of
methylene groups these phenomena help to confirm that macromolecular chains suffer
homolytic and heterolytic breakage [25]. In this work, as shown in the results listed in
Table 8 and Figure 9, a methylene decrease was also detected.
.

Figure 9 Reduced absorbance corresponding to spectral bands associated with methyl

and methylene groups (1460 and 1378 cm-1) for all aged samples
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 137

Figure 10 DSC curves corresponding to newly manufactured samples (A, B, C and D)

and the aged samples (A-5000, B-5000, C-2.5, and D2.5).

A chain break leads to the generation of terminal methyl groups, of which an

increase would be expected, but our data revealed a decrease. This apparent
contradiction is due to the fact that the number of methyl groups generated by chain
scission is lower than the number of methyl groups that disappear in the formation of
free radicals in tertiary carbons. The radicals generated present a high reactivity and
provoke the rapid formation of nonsaturated bonds, which act as precursors in the
formation of branching and crosslinking processes.
This transformation in the configurational order also appeared in samples A and
B, although it was always present as a minor change.

3.2.4. Comparison of Natural and Artificial Aging by DSC and SEM

Figure 10 shows the DSC thermograms of the samples, and Table 9 shows the
characteristic thermal parameters of the melting and degradation processes.
In the calorimetric study performed by DSC (heating up to 6000C), several
processes associated with melting and thermal decomposition (beginning after fusion)
were detected. As shown in Table 9, the decomposition process of the naturally aged
samples (C and D) began at lower temperatures than in other samples. The difference
between the melting onset temperature (T0) for the decomposition process of artificially
aged samples A and B and the nonaged samples was as low as 1-20C, whereas the
difference was greater for C and D samples (natural aging), being as high as 25-27ºC.
These differences also existed in the melting peak temperature (Tp) for the melting
process. The decrease in the decomposition and melting temperatures is associated with
shorter polymeric chains and a lower thermal stability of the material.
In the naturally aged samples (C and D), the melting enthalpy presented a clear
decrease (ca. 40%) in comparison with the nonaged ones (Table 9). The enthalpy
decrease was intrinsically associated with a loss of the crystalline fraction of the
copolymer, as previously shown by FTIR.
138 PERE PAGÈS

Table 9 Characteristics of Melting and Thermal Decomposition Processes

The calorimetric changes detected in the artificially aged samples (A and B)

were lower than those observed in naturally aged ones. The melting enthalpy (ΔH)
diminished by about 14% in the A samples and by about 4% in the B samples.
Previous studies on the crystallization kinetics of samples A and B led to the
conclusion that these processes may be very sensitive to the presence of additives.
These results are confirmed in this work through the spectrophotometric and
calorimetric studies. Nevertheless, in samples C and D, natural aging produced
modifications of a larger magnitude than the use of different additives did.
The superficial morphology of aged samples depends on the type of aging. The
surface of the samples aged by weather presented a scale structure, whereas the
artificially aged surfaces preserved the original morphology, with the exception of
several modified zones.
Another difference was detected when the samples were subjected to a thermal
treatment followed by cooling to the crystallization temperature. The structure after the
solidification process became porous (Fig. 11, top). Samples A and B, newly
manufactured or after aging, presented similar morphologies, without preferential
orientations, but the crystallization of samples C and D produced a micelle distribution
(Fig. 11, bottom). This difference in behavior is related more to the presence of different
additives than to degradation. Additive particles can act as nucleation centers of
heterogeneous degradation. It appears that macroscopic structure modifications
produced by natural and artificial degradation occur on the surface because an analysis
of the internal areas of several broken samples did not show any differences between
aged and nonaged samples.
3.3. Conclusions
From the results obtained, it can be stated that natural aging produces
configurational and conformational changes of a higher order than artificial aging.
Oxidative processes are present in both kinds of aging. The main changes are the
formation of carbonyl groups, the scission of hydrocarbonated chains, the formation of
free radicals in tertiary carbons, and the initial formation of nonsaturated bonds
followed by the progressive participation of these bonds in branching and crosslinking
reactions.
The differences in behavior between the samples subjected to the same type of
aging could be attributed to the presence of different commercial additives. For sample
C, the combination of three types of antioxidants led to a synergistic effect that
improved its stability against natural aging. Also, the catalytic effect of some colorants
appeared in the results obtained.
 CHARACTERISATION OF POLYMER MATERIALS USING FT-IR AND DSC TECHNIQUES 139

Figure 11 Micrographs corresponding to B-5000 artificial aging (top) and C-2.5

natural aging (bottom).

DSC corroborated several of these results. The Samples naturally aged showed a
greater loss of crystallinity than those subjected to the xenon test. The melting enthalpy
diminished by about 40% in the naturally aged samples and by only about 14% in the
artificially aged samples.
The morphology obtained during the crystallization process was clearly different
in samples subjected to both types of aging. This fact could be attributed to the additives
used and to the differences between the aging processes.
The intended equivalence between the two types of aging processes has to be
reviewed because the heterogeneous conditions in which natural aging occurs (e.g.,
environment, salinity content, ram, and pollution) produce a greater and more extensive
effect than those of the xenon test.
140 PERE PAGÈS

References
1. Tabb, D. L. and Koening, J. L. Macromolecules, 8, 929 (1975).
2. D'Esposito, L. and Koening, J. L. Fourier Transform Infrared Spectroscopy, Vol. 1,
Ferraro, J.R. and Basile, L. J. Eds., Academic Press, New York, 1978, p. 73.
3. Musto, P.; Karasaz, F. E. and Macknight, W. J. Polymer, 34(14), 2934 (1993).
4. Delprat, P. and Gardette, J. L. Polymer, 34(5), 903 (1978).
5. Carrasco, F.; Kokta, B. V.; Arnau, J. and Pages, P. Composites, 33(2), 46 (1993).
6. Pagès, P.; Arnau, J.; Carrasco, F.; and Gironés, J. 6th Mediterranean Congr. Chem.
Eng., Barcelona, Book of Abstracts, Vol. II, Ed. Departamento de Prensa y
Publicaciones, Fira de Barcelona, Barcelona, 1993, p.729.
7. Nikitin, V. N. and Pokrovskii, E. L. Doklady Akad. Nauk SSSR, 95, 109 (1954).
8. Tobbin, M. C. and Carrano, M. J. J Polym. Sci., 24, 93 (1957).
9. Zerbi, G.; Galiano, G.; Fanti, N. D. and Baini, L. Polymer, 30, 2324 (1989).
10. Carrasco, F. Thermochim. Acta, 213, 115 (1993).
11. Alguer, M. S. M. Polymer Science Dictionary, Elsevier, New York, 1989, p. 344.
12. Kaczmarek, H. Polymer 1996, 37, 189.
13. Carrasco, F.; Pagés, P.; Pascual, 8.; Colom, X. Eur Polym J 2001, 37, 1457.
14. Colom, X.; García, T.; Suñol, J J.; Saurina, J.; Carrasco, F. J. Non-Cryst Solids
2001, 287, 308.
15. Esposito, L.; Koening, J. L. In Applications of Fourier Transform Infrared lo
Synthetic Polymers and Biological Macromolecules; Ferraro, 1 R.; Basile, L. J.,
Eds.; Academic: New York, 1978; Vol. 1, Chapter 2.
16. Caykara, T.; Guven, O. Polym Degrad Stab 1999, 65, 225.
17. Chiaotore, O.; Troasarelli, L.; Lazzari, M. Polymer 2000, 41, 1657.
18. Irusta, L.; Fernández-Berridí, M. J. Polymer 1999, 40, 4821.
19. EN 13206:2001; Annex A, Point 8.10.
20. Romeu, J.; Pagès, P.; Carrasco, F. Rev Plást Mod 1997, 74, 255.
21. Schnabel, W. Polymer Degradation Principles and Practical Applications; Hanser:
New York, 1981.
22. Bower, D. I.; Maddams, W. F. The Vibrational Spectroscopy of Polymers;
Cambridge University Press: Cambridge, England, 1989.
23. Vollhardt, C. Organic Chemislry; Freeman: New York, 1987.
24. Linstromberg, W. W. Organic Chemistry: A Brief Course; Heath: Lexinglon, MA,
1979.
25. Pagès, P.; Carrasco, F.; Saurina, 1.; Colom, X. J Appl Polym Sci 1996, 60, 153.