Accepted Manuscript

FTIR analysis on aging characteristics of ABS/PC blend under

UV-irradiation in air

Jiarong Li, Fu Chen, Long Yang, Long Jiang, Yi Dan

PII: S1386-1425(17)30353-0
DOI: doi: 10.1016/j.saa.2017.04.075
Reference: SAA 15128
Spectrochimica Acta Part A: Molecular and Biomolecular
To appear in:
Spectroscopy
Received date: 4 December 2016
Revised date: 23 April 2017
Accepted date: 25 April 2017

Please cite this article as: Jiarong Li, Fu Chen, Long Yang, Long Jiang, Yi Dan , FTIR
analysis on aging characteristics of ABS/PC blend under UV-irradiation in air,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2017), doi:
10.1016/j.saa.2017.04.075

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 ACCEPTED MANUSCRIPT

FTIR Analysis on Aging Characteristics of ABS/PC Blend

under UV-irradiation in Air

Jiarong Li, Fu Chen, Long Yang, Long Jiang*, Yi Dan*

State Key Laboratory of Polymer Materials Engineering of China (Sichuan University),
Polymer Research Institute of Sichuan University, Chengdu 610065, China
*Correspondence: jianglong@scu.edu.cn, danyichenweiwei@163.com

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ABSTRACT: Fourier Transform Infrared Spectroscopy (FTIR) is adopted to study the aging
characteristics of poly(acrylonitrile–butadiene–styrene)/polycarbonate (ABS/PC) blend under

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UV-irradiation in air by analyzing the variation of the three main absorbance at about 967cm ,
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1720cm and 3420cm associated with carbon-hydrogen bonds belonging to 1,4 butadiene,

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carbonyl and hydroxyl groups, respectively. Results indicate that, under UV-irradiation in air,
the photo-oxidation of the blend is not a simple combination of the photo-oxidation of
corresponding ABS and PC themselves and takes place predominantly at the ABS component.
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Due to the interaction between the two components and the Fries rearrangement taken place
in the PC component during the UV-irradiation in air, the ABS/PC blends behave higher
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photo-stability than ABS has.

Key Words: ABS/PC blend; UV-irradiation; Structure change; FTIR analysis

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INTRODUCTION
Poly(acrylonitrile–butadiene–styrene)/polycarbonateblends(ABS/PC blends) are widely used
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in demanding applications such as automotive parts, home appliances, consumer electronics

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and 3D printing. ABS is sensitive to light since the presence of the double bonds in butadiene
[1-3]
unit, resulting in an obvious deterioration in structure and performance . Though ester
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groups in the backbone of PC is susceptible to moisture environment, particularly under an

[4]
acidic condition, PC has a relative stability to light . For ABS/PC blends, to reveal the problem
whether the coexistence of the two polymer components would result in different aging
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tendency from either single polymer has a great significance for the application of this polymer
blend. Fourier transform infrared spectroscopy(FTIR) is a fast and accurate analytic tool of
following the structural change occurring throughout the polymer aging since it can detect the
change of the absorption of typical groups and then to study the kinetic process involved in
[5,6,7]
natural and accelerated weathering . However, most of the studies focused on the
single-component polymer system and minimal FTIR data concerned with the
multi-components polymer system. In this study, the FTIR technique will be applied to detect
the structure change of the two-components polymer system, i.e., ABS/PC blend which will be
aged by photo-oxidation, and then to reveal the influence of PC on the ABS during the
photo-oxidation aging.
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EXPERIMENTAL
Materials
The polymers used in the investigation were poly(acrylonitrile–butadiene–styrene)(ABS, 301)
pellets supplied by Lanzhou Petrochemical Company (Lanzhou, China) and polycarbonate(PC,
injection grade 6109) pellets purchased from Chongqing Changfeng Chemical Factory
(Chongqing, China). Chloroform(analytical grade) was purchased from Chengdu Kelong
Chemical Factory (Chengdu, China).

Sample preparation

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The ABS pellets and the PC pellets with different mass ratios of ABS:PC (g:g) (ABS:PC=100:0,
70:30, 50:50, 30:70, and 0:100 ) were dissolved into chloroform. 24h latter, the ABS/PC blend

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solutions with 8% concentration were produced. By spinning coating the blends solutions
using a KW-4A spin coater (Institute of microelectronics, Chinese academy of sciences,

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China), the ABS/PC blend films were prepared. After dried in a vacuum oven at 60℃ for 24h,
the ABS/PC blend film samples with different components and with an average thickness of
30m were obtained, which were denoted as ABS, blend 7-3, blend 5-5, blend 3-7, and PC
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respectively, corresponding to the above mass ratios of ABS:PC.

Photo-oxidation aging test

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The film samples were suspended to the bracket in an ultraviolet irradiation chamber
(Guangzhou Biaogeda laboratory instrument equipment company, China) with a light intensity
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of 0.55W/m @340nm in air at 25±1℃ for photo-oxidation aging test. A certain irradiation time
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later, samples were taken out for FTIR characterization, then back to the irradiation chamber
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for continuing to undertaken irradiation. The total irradiation time was 96h.
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FTIR characterization
Chemical structure changes during photo-oxidation aging were characterized by transmission
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FTIR spectra obtained on a Nicolet iS10 (Thermo Fisher Scientific inc., USA) instrument.
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Collecting parameters were set as follows: resolution 4cm , the wave number range was from
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4000cm to 400cm , 32 scans were performed and averaged per spectrum to improve the
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signal-to-noise ratio.

RESULTS AND DISCUSSION

Before investigating structure change of the ABS/PC blend after aging test, the FTIR
spectroscopic characteristics of the original ABS (as shown in Figure 1a), PC (as shown in
Figure 1b) and ABS/PC blend ( blend 5-5, in which the mass ratio of ABS to PC was 50:50)
were detected first and the results are given in Figure 2.

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Figure 1 Schematic molecular structure of (a) ABS and (b) PC.

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Figure 2 FTIR spectra of ABS, PC and ABS/PC blend in the range of 4000-500cm-1

From Figure 2, the stretching vibrations of aromatic and aliphatic C-H in ABS are clearly seen
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in the range of 3200-3000cm and 3000-2800cm , respectively. Characteristic absorption of
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acrylonitrile unit represented by the C≡N bond appears at about 2237cm . The absorption at
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1638cm represents stretching vibration of C=C double bond from butadiene units, while the
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stretching vibration of aromatic ring from styrene unit appears at 1495cm . The deformation of
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C-H for hydrogen atoms attached to alkenic carbons is seen at 967cm for 1,4 butadiene units
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and 911cm for 1,2 butadiene units. Different from the ABS, the PC molecule has a
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characteristic carbonate linkage behaving an infrared absorption of carbonyl group at near

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1772cm , a stretching vibration of C–O bond around 1200cm and an absorption of methyl
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group in the range of 2800-3000cm . From the FTIR spectrum of blend 5-5, peaks at
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2237cm , 1772cm and 967cm , 911cm signify that the blend is composed of ABS and PC
polymer components.

Figure 3 displays FTIR spectra of ABS, PC and blend 5-5 irradiated by UV light for different
hours.

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(a) (b)

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(c)
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Figure 3 FTIR spectra of (a) ABS, (b) PC, and (c) blend 5-5 before and after irradiated for different hours

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In Figure 3(a), increased absorptions in the hydroxyl (3650-3200cm ) and carbonyl
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(1850-1650cm ) regions are clearly seen, indicating a production of oxygen-containing groups
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in the chemical structure of ABS during the irradiation. In the absorb region (1400-1000cm ) of
C-O stretching vibrations, an important increase in the absorbance is observed though the
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peak positions are not clearly visible. However, the FTIR spectrum, as shown in Figure 3(b), of
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PC is hardly seen having any change, even after irradiated for 96h, no obvious difference
between the irradiated sample and the original sample can be found, suggesting a relative
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stability of the PC to UV light. After irradiated for different hours, blend 5-5 produces not only
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hydroxyl group but also carbonyl group, showing an absorption not only in 3650-3200cm but
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also in 1850-1650cm (Figure 3(c)), as has been seen in the spectra of ABS(Figure 3(a)). The
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lower absorbance may be from the less content of ABS component in the blend.

In order to understand the influence of both the ABS and the PC on the structure change of the
ABS/PC blends during the irradiation, three absorb regions, i.e., the hydroxyl absorb region
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(3650-3200cm ), the carbonyl absorb region (1850-1650cm ) and the absorb region of
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deformation vibrations of C-H bonds attached to alkenic carbons under 1000cm , will be
focused on and the spectra change in these three absorb regions will be discussed in detail in
the following.

Figure 4 gives FTIR spectra of ABS, blend 7-3, blend 5-5, blend 3-7, and PC before and after
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irradiated for different hours in the region of 3650-3200cm .

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(a) (b)

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(c) (d)
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(e)
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Figure 4 FTIR spectra of (a)ABS, (b)blend 7-3, (c)blend 5-5, (d)blend 3-7 and (e)PC in the region of
3650-3200cm-1 before and after irradiated for different hours. Arrows indicate the changing trend of corresponding
absorption

From Figure 4, it can be seen that the un-irradiated ABS sample(Figure 4a) shows no
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absorption nearby 3420cm , while the irradiated ABS samples (Figure 4a) show absorption at
this position and, with the irradiation, the absorb intensity increases, behaving as that the
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absorb peaks at 3420cm gradually form, which is assigned to the multiple contributions from
alcohol and acid groups. Those spectra also show that, with the irradiation, the peak height at
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3420cm rises up gradually until irradiated for 80h, indicating that the photo-oxidation aging
process of ABS becomes stable after 80h. For PC sample (Figure 4e), however, almost no

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absorption at 3420cm appears even for samples irradiated for different hours, indicating that
no hydroxyl groups generate during the irradiation. Different from PC, the ABS/PC blends
(Figure 4b, 4c, and 4d) show a similar change trends of the absorption with the irradiation time
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as ABS, i.e., for each blend, the absorbance at 3420cm increase with the increase of
irradiation time and retains a stable value after irradiated for 80h.

From Figure 4, it can also be seen that with the increase of PC component the absorbance at
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3420cm decreases, indicating a decrease of hydroxyl groups coming from the
photo-oxidation aging of the ABS. Does the PC component enhance the UV-resistance of ABS

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component? To answer this question, the variation of the absorbance of samples at 3420cm
was further analyzed by comparing the testing value and the calculating value which was

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calculated by the following equation (1) basing on the composition of the blends, and the
results are given in Figure 5.

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A= AABS  wABS + APC  wPC (1)
where, A, AABS and APC represent the calculated absorbance of blend, the tested absorbance
of ABS and the tested absorbance of PC respectively under same irradiating conditions, while
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wABS and wPC are the mass fraction of ABS and PC respectively in the blend.
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(a) (b)
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(c)
Figure 5 Comparison of absorbance of ABS/PC blends at 3420 cm-1 between the tested values and the calculated
value: (a) blend 7-3, (b) blend 5-5, (c) blend 3-7

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Figure 5 clearly shows that the tested absorbance of blends at 3420cm is smaller than the
calculated values, indicating that the practical production of hydroxyl group in the ABS/PC
blend is less than that in the single ABS component and hence indicating that the PC
component restrains the photo-oxidation of the ABS component. From blend 7-3 (Figure 5a) to
blend 5-5 (Figure 5b) and then to blend 3-7 (Figure 5c), differences between the tested
absorbance and the calculated absorbance become larger and larger, further suggesting that
the photo-oxidation of ABS/PC blends is not the simple combination of the photo-oxidation of
corresponding ABS and PC themselves but the interaction between the two polymer

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components. Introducing more PC component in the blend leads to a more enhancement in
the UV-resistance of ABS component. Under UV-irradiation, Fries rearrangement taken place
in the PC component results in a formation of aromatic ketone product which should be

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responsible for the enhancement in the UV-resistance of the ABS/PC blends when compared
to the ABS itself.

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Figure 6 displays absorb spectra of samples in the range of 1850-1650cm , an indication of
carbonyl stretching vibration. It can be seen that the un-irradiated ABS sample(Figure 6a)
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shows no absorption at 1720cm , while the irradiated ABS samples show absorption nearby
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this position and, with the irradiation, an increase in absorbance at 1720cm is observed,
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which is assigned to the aliphatic carbonyl species from aliphatic carboxyl acids, ketones or
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aldehydes. The absorbance at 1720cm also goes to stable after 80h of irradiation as same as
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absorbance at 3420cm though the former has an obvious increase in the first 24h of
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irradiation and the latter takes more time (32h) to get an obvious increase, further indicating
that the photo-oxidation aging process of ABS becomes stable after 80h. Much different from
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ABS, PC samples (Figure 6e) are hardly seen having absorption at 1720cm even it has been
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irradiated for 96h, indicating that, during the irradiation, no any carbonyl group forms in the PC
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molecules, while the absorption at 1773cm is assigned to the stretching vibration of carbonyl
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in ester group of PC. Introducing PC component to the ABS, the formed ABS/PC blends show,
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during the irradiation, a variable absorption at 1720cm but invariable absorption at 1773cm ,
implying that the ABS component undertaken a damage by the irradiation but the PC
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component is stable to the irradiation, and, with the increase of PC component in the blend,
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the increase of absorbance at 1720cm decreases, indicating a suppression of PC component
to the structure destroy of ABS component under the irradiation, which is also proved by the
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comparison of the tested absorbance and the calculated absorbance at 1720cm in Figure 7
where the tested absorbance is smaller than the calculated absorbance and the difference
between the tested value and the calculated value increases with the increase of the PC
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component as same as what has been done for the absorption at 3420cm (Figure 5). If there
is no any interaction between ABS and PC, the characteristic absorbance of ABS/PC blend at
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1720cm should depend on the mass fraction of the two components as given in equation 1,
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the difference between the tested absorbance and the calculated absorbance at 1720cm

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indicates an interaction between ABS and PC and hence the restriction of PC to the
photo-oxidation of ABS.

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(a) (b)

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(c) (d)
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(e)
Figure 6 FTIR spectra of (a) ABS, (b-d) ABS/PC blends and (e) PC in the region of 1850-1650cm-1 before and
after irradiated for different hours. Arrows indicate the changing trend of corresponding absorption

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(a) (b)

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(c)
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Figure 7 Comparison of absorbance of the ABS/PC blends at 1720cm-1 between the tested values and the calculated
values. (a) blend 7-3; (b) blend 5-5; (c) blend 3-7
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Figure 8 shows the C-H stretch of hydrogen atoms linked to carbons of the 1, 2 butadiene at
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911cm and of the 1,4 butadiene at 967cm . For ABS, both of the two bands gradually
weaken with the increase of irradiation time, corresponding to the gradual enhancement in the
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absorption of oxygen-containing groups at 3420cm and 1720cm as shown in Figure 4a and
Figure 6a respectively and indicating a disappearance of the butadiene units after the
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irradiation. For the blends 7-3, 5-5 and 3-7, the two bands show a same variation tendency
with the irradiation as that of ABS does but the absorbance decreases with the increase of PC
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component. By analyzing the variation of the absorb peaks at 911cm and 967cm more
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carefully, it is found that the decrease rate of the absorbance at 967cm is more pronounced
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than that at 911cm , which is in good agreement with the results previously reported and is
[8]
explained by the stability of the free radicals formed .

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(a) (b)

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(c) (d)

Figure 8 FTIR spectra of (a)ABS and (b-d)ABS/PC blends in the region of 1000-900cm-1 before and after irradiated for
different hours. Arrows indicate the changing trend of corresponding absorption
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Since the PC macromolecule has no absorption at 967cm from 1,4 butadiene units as
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showed in its FTIR spectrum (Figure 1), the calculated absorbance (A) of blends at 967cm is
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obtained by the following equation (2) just basing on the mass fraction of ABS in the blend.
A= AABS  wABS (2)
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where, AABS represents the absorbance of ABS at 967cm , wABS is the mass fraction of ABS in
the blend.
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Figure 9 shows that, in the 96h of irradiation, the tested absorbance of blends at 967cm is
bigger than the calculated absorbance, corresponding to a smaller tested absorbance at both
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3420cm (Figure 5) and 1720cm (Figure 7) when comparing the calculated absorbance at
these two positions. This also suggests that the introduction of PC component can slow down
the photo-oxidation of ABS though it could not prevent this process.

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(a) (b)

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(c)
Figure 9 Comparison of absorbance of the ABS/PC blends at 967cm-1 between the tested values and the
calculated values (a) blend 7-3; (b) blend 5-5; (c) blend 3-7
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CONCLUSIONS
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In this work, the Fourier Transform Infrared Spectroscopy technique is used to follow the
variation of structure of ABS/PC blends during the UV-irradiation in air by detecting the spectra
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change in main three absorb regions, i.e., the hydroxyl absorb region (3650-3200cm ), the
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carbonyl absorb region (1850-1650cm ) and the C-H stretch regions of hydrogen atoms linked
-1 -1
to carbons of the 1, 2 butadiene at 911cm and of the 1,4 butadiene at 967cm . The
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photo-oxidation of the blend takes place predominantly at the ABS component. Introduction of
PC can restrain the photo-oxidation of the ABS because of the interaction between the two
components and because of the aromatic ketone from the Fries rearrangement taken place in
the PC component. The ABS/PC blends have higher photo-stability than ABS has.

ACKNOWLEDGEMENTS
The authors gratefully acknowledge the National Natural Science Foundation of China (No.
50533080 and No. 51133005) for financial support of this research.

REFERENCES
[1]Yu Z, Li Y, Zhao Z, Wang C, Yang J, Zhang C. Polym. Eng. Sci. 2009, 49, 2249.
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[2] Polli H, Pontes LA, Araujo A, Barros JM, Fernandes V. J. Therm. Anal. Calorim. 2009, 95,
131.
[3] Santos RM, Botelho GL, Machado AV.J. Mater. Sci. 2013, 49, 508.
[4] Yuli Zhou, Yi Dan, Long Jiang, Guangxian Li. Polym. Degrad. Stab. 2013, 98, 1465.
[5] Bower, D. I.; Maddams, W. F. The Vibrational Spectroscopy of Polymers; Cambridge
University Press: Cambridge, United Kingdom, 1992.
[6] J.G. Bokria, S. Schlick. Polymer.2002, 43, 3239.
[7] Vipin V. Rajan, Roy Wäber, Jürgen Wieser. J. Appl. Polym. Sci. 2012, 124, 3988.

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[8] Santos RM, Botelho GL, Machado AV.J. Appl. Polym. Sci. 2010, 116, 2005.

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Graphical abstract
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Highlights
 FTIR technique is used to follow the structure change of ABS/PC
blend during the UV-irradiation in air and then to study the aging
characteristics of the ABS/PC blend.
 The photo-oxidation of the ABS/PC blend takes place predominantly at the
ABS component and the introduction of PC can restrain the photo-oxidation of

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ABS.
 The ABS/PC blend behaves higher photo-stability than ABS has.

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