materials

Article
The Effects of UV Light on the Chemical and
Mechanical Properties of a Transparent
Epoxy-Diamine System in the Presence
of an Organic UV Absorber
Saeid Nikafshar 1 , Omid Zabihi 2, *, Mojtaba Ahmadi 3 , Abdolreza Mirmohseni 1 ,
Mojtaba Taseidifar 4 and Minoo Naebe 2, *
1 Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51666, Iran;
s_nikafshar@yahoo.com (S.N.); a.mirmohseni@hotmail.com (A.M.)
2 Institute for Frontier Materials, Deakin University, Geelong, Burwood, VIC 3125, Australia
3 Department of Chemical Engineering, Isfahan University of Technology, Isfahan 84156/83111, Iran;
mojtaba.ahmadi@ce.iut.ac.ir
4 School of Physical, Environmental & Mathematical Sciences, UNSW, Canberra, ACT 2610, Australia;
m_taseidifar@yahoo.com
* Correspondence: ozabihi@deakin.edu.au (O.Z.); minoo.naebe@deakin.edu.au (M.N.);
Tel.: +61-4-6957-0372 (O.Z.); +61-3-5227-1410 (M.N.)

Academic Editor: Lioz Etgar

Received: 16 December 2016; Accepted: 3 February 2017; Published: 14 February 2017

Abstract: Despite several excellent properties including low shrinkage, good chemical resistance,
curable at low temperatures and the absence of byproducts or volatiles, epoxy resins are susceptible
to ultra violet (UV) damage and their durability is reduced substantially when exposed to
outdoor environments. To overcome this drawback, UV absorbers have been usually used to
decrease the rate of UV degradation. In this present study, the effects of UV light on the chemical,
mechanical and physical properties of cured epoxy structure, as well as the effect of an organic
UV absorber, Tinuvin 1130, on the epoxy properties were investigated. Chemical changes in
a cured epoxy system as a result of the presence and absence of Tinuvin 1130 were determined
using Fourier transform infrared spectroscopy (FT-IR) analyses. The effect of Tinuvin 1130 on the
surface morphology of the epoxy systems was also investigated by scanning electron microscopy
(SEM) imaging. Additionally, the glass transition temperatures (Tg ) before and during UV radiation
were measured. After an 800 h UV radiation, mechanical test results revealed that the lack of
the UV absorber can lead to a ~30% reduction in tensile strength. However, in the presence of
Tinuvin 1130, the tensile strength was reduced only by ~11%. It was hypothesized that the use of
Tinuvin 1130, as an organic UV absorber in the epoxy-amine system, could decrease the undesirable
effects, arising from exposure to UV light.

Keywords: epoxy resin; UV absorber; photodegradation process; Tinuvin 1130

1. Introduction
Nowadays, various polymeric materials are commercially available and used in many applications
such as protective coatings, civil engineering materials, aerospace composites, automotive fields,
and marine industries [1–4]. The durability of materials is a key factor for many applications which
affects the performance of polymer-based materials. The sun is the major source of energy for
the earth and emits a vast range of wavelengths in which only ultraviolet (UV) light, visible and
infrared light (IR) reach the earth [5]. Ozone layer filters emit UV wavelengths from 100 to 315 nm.

Materials 2017, 10, 180; doi:10.3390/ma10020180 www.mdpi.com/journal/materials

Materials 2017, 10, 180 2 of 18

Definitely, the ozone layer completely eliminates UVC (100–280 nm) and most of UVB (280–315 nm)
and only UVA (315–400 nm) and a small amount of UVB reach the earth [6]. The UV radiations
are harmful to polymers, a phenomenon known as photodegradation is initiated which affects the
physical, mechanical and chemical properties of polymers [7–11]. UV light of sunlight forms free
radicals on the surface of polymer-based materials [12]. These radicals are extremely active in attacking
the polymeric structures. The energy of UV light is usually higher than the chemical bonds strength
e.g., C–C, O–O, H–O, and C–N in polymers. Therefore, these chemical bonds are prone to break and
photodegradation occurs [13]. Other environmental factors including humidity, oxygen, temperature,
and pollutants can intensify the rate of photodegradation significantly [14–16].
To avoid or reduce photodegradation, inorganic and organic UV absorbers, as well as stabilizers
have been used [17–19]. The mechanism of these UV absorbers against UV light varies from one
material to another. Inorganic UV absorbers often scatter light, while organic UV absorbers convert UV
light to heat, higher wavelengths, and radical interceptors (HALS), capturing free radicals [16,19,20].
Compared with inorganic UV absorbers, organic UV absorbers have higher efficiency but they have
less durability due to their evaporation and migration to the surface of polymers [21,22]. In addition,
inorganic UV absorbers such as ZnO and TiO2 have broad absorptions in the UV range and even in
the visible range, whereas organic UV absorbers only absorb specific wavelengths in the UV range and
almost do not have any absorptions in the visible range. It is clear that organic UV absorbers are in high
demand and suitable for clear and transparent coatings and polymers [23,24]. Moreover, polymeric
coatings with organic UV absorbers, compared with inorganic UV absorbers, are more flexible and have
a lower glass transition temperature (Tg ). Although epoxy systems have great chemical and mechanical
properties, since they are applied in many applications even in the outdoor environment, durability and
performance of epoxy structure is reduced dramatically. Herein, yellowing, cracking, and reduction
of mechanical properties are inevitable aspects [25]. Epoxy resins possess aromatic groups with
a strong absorption in the UV range (about 300 nm). This makes epoxy structures vulnerable to UV
degradation [26]. When oxygen molecules in the air are exposed to UV light radiation, oxygen radicals
are produced. Radicals are also formed from broken bonds, which are highly reactive and have a very
short life [27]. These formed radicals attack the surface of the epoxy coatings and react with them.
There are various mechanisms proposed for UV degradation of cured diglycidyl ether bisphenol A
(DGEBA), as presented in Figure 1.
Currently, several organic UV stabilizers with different maximum absorption bonds are
produced commercially. According to the chemical structures of organic UV stabilizers, they can
be divided into three categories: benzotriazoles, benzophenones, and hindered amine light
stabilizer (HALS). They have different reactions with UV light. When benzotriazoles are exposed
to UV light, they, as organic UV absorbers with aromatic parts, can behave in the three following
ways: changing the conformational structure, emitting higher wavelength, and converting UV light to
heat [24]. The two conformations of a benzotriazole compound, (2(2-hydroxyphenyl)2H-benzotriazole),
with UV light are shown in Figure 2. The [H] conformation of the molecule, which directly inclines
itself to the hydrogen bonding, has the ortho-hydroxyl group aligned to the cisoid arrangement,
while the ortho-hydroxyl group is aligned in a transoid arrangement in another isomer [N]. In the
[H] isomer, UV light (350 nm) is converted to heat, while in the [N] isomer, UV light is emitted as
a longer wavelength [20]. When a benzophenone compound is exposed to UV light, it is excited to the
single state and the proton of the hydroxyl group is transferred to the carbonyl group. The efficiency
of benzophenones for absorbing UV light is lower than that of benzotriazoles [11]. On the other
hand, HALSs do not absorb UV light yet they act as polymer degradation inhibitors. They either
stop or at least slow down the degradation reaction rate by scavenging produced radicals [28].
Organic stabilizers are produced under the commercial name of Tinuvin. For instance, Tinuvin 5151,
Tinuvin 326, Tinuvin 328, and Tinuvin 1130 are based on benzotriazoles with different substituents,
while Chimassorb 81 is based on benzophenone. It is worth mentioning that Chimassorb 944 and
Tinuvin 770 are classified as HALSs.
Materials 2017, 10, 180 3 of 18
Materials 2017, 10, 180 3 of 18

CH3 CH3
UV, O2
C O CH2 C O C

CH3 CH3 O
photo-Fries CH3
rearrangement
C C

CH3 O
OH
Oxidation of phenoxy part

OH O
UV
O CH CH2 O CH2 CH CH2 + H
O
UV
O CH2 CH + CH2 O CH3 + CO

Hydroxy group reactions

UV, O2
2 O CH2 CH CH2 O

OH

2 O CH + O CH

O OH

Formation of phenyl format

CH3 O CH2 CH CH2 CH3

O CH2 CH CH2
UV N C CH2
OH N CH CH2 OH
O CH2 CH CH2 O CH2 CH CH2

OH OH

O CH2 CH CH2 CH3

UV, O2 N C CH2 + OH
OH
O CH2 CH CH2
O
(a) OH (b)

O CH2 CH CH2 O CH2 CH CH2

OH N C CH3 OH N C CH2
O CH2 CH CH2 O CH2 CH CH2
O O
OH OH

+ CH2 + CH3
Formation of amide

Figure
Figure 1.
1. Various mechanisms of
Various mechanisms of UV
UV degradation
degradation in
in the
the epoxy
epoxy system.
system.
Materials 2017, 10, 180 4 of 18
Materials 2017, 10, 180 4 of 18

hv' hv
N N N N N N N
hv'' N heat
N H N H
N N
300 nm 350 nm
O O O O
H H

[N] [H]

Figure2.2.The
Figure Thereaction
reactionbetween
between aa benzotriazole
benzotriazole compound
compoundand
andUV
UVlight.
light.

Actually, through modification of the chemical structure of UV absorbers, various UV

Actually,with
absorbers through modification
different maximum of the chemical
bonds can be structure of UV [20,29].
synthesized absorbers, UVvarious
absorbersUV absorbers
can be
with different maximum bonds can be synthesized [20,29]. UV absorbers
distinguished by absorption bonds, the phase of materials, melting points, multiple colors, and can be distinguished
bymiscibility.
absorptionTherefore,
bonds, the based phase of materials,
on polymers types andmelting points, multiple
their structures, colors,of and
several types miscibility.
UV absorbers
Therefore, based on polymers types and their structures, several
can be used. In recent studies, UV performance of different organic UV absorbers in polymers has types of UV absorbers can
be been
used.investigated.
In recent studies, UV performance
Tinuvin 1130 and Tinuvin 5151 of different
were used organic
as UV UV absorbers
absorbers in water-borne
in clear polymers has
been investigated.
coatings Tinuvin 1130blends)
(acrylic-polyurethane and Tinuvin
and it 5151 were used
was found as UV absorbers
that Tinuvin 1130 was morein clear water-borne
effective than
Tinuvin(acrylic-polyurethane
coatings 5151 in terms of protection against
blends) andUV it light
was [19].
found Tinuvin
that 1577
Tinuvin was added
1130 was into more
polyethylene
effective
terephthalate
than Tinuvin 5151 (PET)in and
termsit ofwas found that
protection addition
against UV of lightTinuvin
[19]. 1577
Tinuvineffectively
1577 was reduced
addedthe into
photodegradation
polyethylene of PET (PET)
terephthalate [30]. Jiaandet it
al.was
[31]found
reportedthathigh UV stability
addition of Tinuvin of polypropylene
1577 effectively with the
reduced
theaddition of Tinuvin of
photodegradation 328.
PET The effect
[30]. ofal.
Jia et Tinuvin 384 on high
[31] reported the isocyanate
UV stability type of acrylated urethane
of polypropylene with the
oligomer was investigated by Lee and Kim [32] and they observed
addition of Tinuvin 328. The effect of Tinuvin 384 on the isocyanate type of acrylated urethane oligomer an improvement in
photodegradation. Liu et al. [33] investigated the effect of four types
was investigated by Lee and Kim [32] and they observed an improvement in photodegradation. of UV stabilizers e.g., Tinuvin 326,
LiuChimassorb 81, Tinuvin 770,
et al. [33] investigated and Chimassorb
the effect of four types 944ofonUVethylene-octene
stabilizers e.g.,copolymer.
Tinuvin 326, They found that81,
Chimassorb
the UV performance of Tinuvin 770 and Chimassorb 944 was higher than that of Chimassorb 81 and
Tinuvin 770, and Chimassorb 944 on ethylene-octene copolymer. They found that the UV performance
the UV performance of Tinuvin 326 was the lowest.
of Tinuvin 770 and Chimassorb 944 was higher than that of Chimassorb 81 and the UV performance of
In this study, the photodegradation process of epoxy in the presence and absence of Tinuvin 1130
Tinuvin 326 was the lowest.
was investigated and the chemical as well as mechanical properties were studied. Since epoxy resins
In this study, the photodegradation process of epoxy in the presence and absence of Tinuvin 1130
have a high amount of aromatic rings in their structures which can absorb UV light around 300 nm,
was investigated and the chemical as well as mechanical properties were studied. Since epoxy resins
Tinuvin 1130 was selected as a UV absorber working at UV light in the ranges of 300–350 nm and
have a highnm
350–390 amount of aromatic
optimally. It was rings
believedin their
that structures which can
this UV absorber couldabsorb UV polymeric
protect light around 300 nm,
matrices
Tinuvin
against UVA and UVB ranges. In addition, Tinuvin 1130 which is a viscous liquid can be applied asand
1130 was selected as a UV absorber working at UV light in the ranges of 300–350 nm a
350–390 nm optimally.
UV absorber for epoxyIt was believed
resin without that this UV
using any absorber
solvents couldwhichprotect polymericaffect
may negatively matricesthe against
final
UVA and UVB
mechanical ranges. In
properties addition,
of the epoxy. Tinuvin
Moreover, 1130 which
Tinuvin is aalmost
1130 viscous doesliquid can be
not have anyapplied
absorptionas ainUV
absorber for epoxy resin without using any solvents which may negatively
the visible area; therefore, it can be used for transparent polymeric structures. To the best of our affect the final mechanical
properties
knowledge, of the epoxy.
there have Moreover,
been no reportsTinuvin 1130 almost
investigating does not
chemical, have any
physical, andabsorption
mechanicalin the visible
properties
area; therefore,
of epoxy with it can
and be used
without for transparent
Tinuvin 1130 as UVpolymeric
absorber instructures.
the literature.To the best of our knowledge,
there have been no reports investigating chemical, physical, and mechanical properties of epoxy with
and2. without
Experimental
Tinuvin 1130 as UV absorber in the literature.

2.1. Materials
2. Experimental
Liquid diglycidyl ether of bisphenol A (DGEBA, Epon 828, Hexion, Columbus, OH, USA) with
2.1. Materials
an epoxy equivalent weight of 185–192 g/eq was supplied from E.V Roberts. Epikure F205 was
purchased from Hexion
Liquid diglycidyl used
ether of as a curing A
bisphenol agent. This curing
(DGEBA, Epon agent was based
828, Hexion, on isophorone
Columbus, diamine
OH, USA) with
an (IPDA)
epoxy which was further
equivalent weightmodified to cure
of 185–192 g/eqthewas
epoxy resin at from
supplied room E.V
temperature.
Roberts. Tinuvin
Epikure1130
F205was
was
Materials 2017, 10, 180 5 of 18

purchased from Hexion used as a curing agent. This curing agent was based on isophorone diamine
Materials 2017, 10, 180 5 of 18
(IPDA) which was further modified to cure the epoxy resin at room temperature. Tinuvin 1130 was
obtained from
obtained from CibaCiba Specialty
Specialty Chemicals
Chemicals (Basel,
(Basel, Switzerland). The chemical
Switzerland). The chemical structures
structures of
of DGEBA,
DGEBA,
IPDA, and Tinuvin 1130 are shown in Figure
IPDA, and Tinuvin 1130 are shown in Figure 3. 3.

O CH3 CH3 O
H2C CH CH2 O C O CH2 CH CH2 O C O CH2 CH CH2
CH3 OH CH3
n
Diglycidyl ether of bisphenol A (DGEBA)

NH2

H3C CH2NH2

H3C CH3

Isophorone diamine (IPDA)

HO

N 50%

CH2CH2CO(OCH2CH2)6-7 OH

HO

N
38%
N

CH2CH2CO (OCH2CH2)6-7 O

H-(OCH2CH2)6-7 OH 12%

Tinuvin 1130

Figure
Figure 3.
3. Chemical
Chemical structures
structures of
of diglycidyl
diglycidyl ether
ether of
of bisphenol
bisphenol A
A (DGEBA),
(DGEBA), isophorone
isophorone diamine
diamine (IPDA)
(IPDA)
and Tinuvin 1130.
and Tinuvin 1130.

2.2. Methods
2.2. Methods
The average epoxy molar mass (EMM) of Epon 828 according to the manufacturer was 188 g/eq.
The average epoxy molar mass (EMM) of Epon 828 according to the manufacturer was 188 g/eq.
The amine hydrogen molar mass (AHMM) of Epikure F205, which was employed as a curing agent,
The amine hydrogen molar mass (AHMM) of Epikure F205, which was employed as a curing agent,
was reported to be 105 g/eq. Therefore, each amine hydrogen reacts with one epoxy group and the
was reported to be 105 g/eq. Therefore, each amine hydrogen reacts with one epoxy group and the
stoichiometric ratio of the curing agent to epoxy resin for curing reaction can be determined
stoichiometric ratio of the curing agent to epoxy resin for curing reaction can be determined according
according to AHMM/EMM = 0.56. To prepare samples, 10 g of epoxy resin was stirred with 5.6 g of
to AHMM/EMM = 0.56. To prepare samples, 10 g of epoxy resin was stirred with 5.6 g of Epikure F205.
Epikure F205. All samples were prepared according to the obtained ratio of 1:0.56 epoxy resin and
F205, respectively, and only the quantity of Tinuvin 1130 in the samples was altered. Tinuvin 1130
was yellow to light, an amber, viscous liquid, and the proposed amount of Tinuvin 1130, according
to its manufacturer, was 3% for an epoxy resin. This amount of Tinuvin 1130 was high because the
UV degradation process can be accelerated with decreasing thickness of the coating, and
Materials 2017, 10, 180 6 of 18

All samples were prepared according to the obtained ratio of 1:0.56 epoxy resin and F205, respectively,
and only the quantity of Tinuvin 1130 in the samples was altered. Tinuvin 1130 was yellow to light,
an amber, viscous liquid, and the proposed amount of Tinuvin 1130, according to its manufacturer,
was 3% for an epoxy resin. This amount of Tinuvin 1130 was high because the UV degradation process
can be accelerated with decreasing thickness of the coating, and consequently, it needed to be used
in a higher quantity [34]. For FTIR spectroscopy and UV-visible spectroscopy analyses, DGEBA,
Epikure F205, and 3% Tinuvin 1130 (only for sample B) were mixed for 3 min, coated onto
a polyethylene sheet and after 8 h at 25 ◦ C, the formed coating was separated from the
polyethylene sheet. The thickness of the coating was ~0.5 mm, and the coating was cut into small
pieces of about 2 × 2 cm and stored in a dark place for 7 days at 25 ◦ C. This was mainly due to the
fact that some samples had UV absorbers (sample B) which were sensitive to light. Samples were
labeled as A1 , A2 , A3 , A4 and B1 , B2 , B3 , and B4 and placed under UV light. Subscribes 1, 2, 3, and 4
meant that samples were exposed to UV light for 0, 250, 500, and 800 h, respectively. To measure
the glass transition temperature (Tg ), 5 mg of each prepared film samples for Fourier transform
infrared (FT-IR) spectroscopy analysis, before and after UV radiation (various exposed time 250, 500,
and 800 h), was put into an aluminum pan. Samples for tensile test and Izod impact were prepared
as follows: DGEBA, Epikure F205 and 3% Tinuvin 1130 (only for sample B) were stirred for 3 min
and the mixture was then poured into a silicon mold. To complete the curing reaction, the samples
were cured for 8 h at room temperature, and then specimens were removed from the mold and kept
in a dark place at room temperature for 7 days. Epoxy resin, Epikure F205, and 3% Tinuvin 1130
(only for sample B) were mixed for 3 min and then the mixture was poured onto eight aluminum
plates, following that the pull-off strength was measured for each prepared coated sample on the
aluminum plates. Each sample was tested four times and the average was reported. The surfaces of
the prepared epoxy films were also studied by scanning electron microscopy (SEM, MIRA3 FEG-SEM,
Tescan, Brno, Czech Republic). Hitachi F40T10/BL UVB lamp 40 W with a length of 120 mm was
used for radiation (Hitachi, Tokyo, Japan). The lamp, installed in a fully closed aluminum box,
started to emit wavelength ranging from UV to visible, but the main emitted wavelength was around
290–320 nm (UVB). Samples were placed under the UV light radiation with 5 cm distance from
the lamp. To regulate the temperature, a fan was placed on one side of the aluminum box and the
temperature was kept at about 25 ◦ C during UV radiation. The photodegradation process continued
for 800 h. Before radiation and after certain time periods e.g., 250, 500, and 800 h various tests were
performed on the samples.

2.3. Analysis Techniques

FT-IR analyses were conducted using a Tensor 27 (Bruker, Billerica, MA, USA) with 40 scan
average at a resolution of 4 cm−1 . In this study, FT-IR spectroscopy was used to study the functional
groups and chemical structures of samples before and after UV radiation. To measure the absorption
in UV and visible ranges (200–400 and 400–700 nm), a UV-visible spectrophotometer was utilized
(Shimadzu UV-1700 pharmaspec, Shimadzu, Kyoto, Japan). Differential scanning calorimetry (DSC)
analyses (Linseis PT10, Linseis, Robbinsville, NJ, USA) were used to determine Tg . For each sample,
a non-isothermal test at a heating rate of 10 ◦ C/min was carried out at a temperature ranging from 0
to 150 ◦ C under a nitrogen flow of 40 mL/min. A tensile strength test was conducted according to
ASTM D638 with a Shimadzu 20 kN-testing machine. Specimen dimensions were selected according
to type 1 of ASTM (165 × 19 × 3.2 mm3 ). The crosshead speed was 2 mm/min. At least five samples
for each condition were tested. A Posi test AT-M from Deflesco was used to measure pull-off strength
according to ASTM D4541. Measurements were performed after 0, 250, 500, and 800 h UV radiation.
At least five measurements were conducted. To evaluate the effect of UV light on the Izod impact
strength of samples, five samples from each specimen were prepared. The dimensions of samples were
63.5 × 12.7 × 7.2 mm3 , according to ASTM D256 using a Zwick/Roell 6103 impact tester (Zwick/Roell,
Ulm, Germany). The test was carried out after 0, 250, 500, and 800 h UV radiation. This test was
Materials 2017, 10, 180 7 of 18

repeated five times for each sample. To study the effect of UV light on the morphology of the epoxy
samples, epoxy coatings were examined using SEM (MIRA3 FEG-SEM, Tescan). Samples were gold
coated and an accelerating voltage of 5.00 KV was employed.

3. Results and Discussion

As presented
Materials 2017, 10, 180in
Figure 4, Tinuvin 1130 had two absorption peaks at 305 and 345 nm and was
7 of 18
used as an organic UV absorber for this work. Because Tinuvin 1130 does not have any absorption
in the
the visible
visible area
area (400–700
(400–700nm),
nm),ititcan
canbebeused
usedinintransparent
transparentpolymers
polymers like epoxy.
like epoxy.Based
Basedonon
further
further
investigation, it was determined that Tinuvin 1130 as an organic UV absorber played a major in
investigation, it was determined that Tinuvin 1130 as an organic UV absorber played a major role role
in protecting
protectingthe
theepoxy
epoxystructure against
structure UVUV
against light. Experimentally,
light. it is proposed
Experimentally, that Tinuvin
it is proposed 1130 can
that Tinuvin 1130
cannot
notonly
onlypreserve
preserve the chemical
the chemical properties
propertiesbutbut
cancan
also prevent
also preventor or
at at
least reduce
least thethe
reduce drop
dropin in
thethe
mechanical
mechanical properties.
properties.

Figure 4. The UV-visible spectrum of Tinuvin 1130.

Figure 4. The UV-visible spectrum of Tinuvin 1130.

3.1. FT-IR Analysis

3.1. FT-IR Analysis
FT-IR
FT-IRspectroscopy
spectroscopyisisaacommon common methodmethod for evaluating chemical
for evaluating chemicalchanges
changesduringduring thethe
UVUV
degradation process in epoxy and polymeric systems [18,35–38]. The effects of
degradation process in epoxy and polymeric systems [18,35–38]. The effects of UV light on the epoxy UV light on the epoxy
structure
structurecancan
be be
studied
studiedbybyFT-IR.
FT-IR.Figure
Figure5 shows
5 showsFT-IR spectra
FT-IR of sample
spectra of sample A (epoxy
A (epoxy resin, Epikure
resin, Epikure F205)
before and after 250, 500, and 800 h of UV radiation. To study the photodegradation
F205) before and after 250, 500, and 800 h of UV radiation. To study the photodegradation phenomenon,
two areas of FT-IR −1 (area 1) −1
phenomenon, twospectra
areas ofshould carefully
FT-IR spectra be considered.
should carefully beThe areas of The
considered. 1600–1800
areas ofcm 1600–1800 cmand
3200–3700 − 1
(area 1) cm (area 2) are
and 3200–3700 cmrelated
−1 (areato2)carbonyl groups
are related to and hydroxyl
carbonyl groups groups, respectively
and hydroxyl [39,40].
groups,
Before UV irritation
respectively [39,40].(0Before
h), theUV absorption
irritation (0intensity in areas 1intensity
h), the absorption and 2 (carbonyl
in areas 1and
and hydroxyl
2 (carbonylgroups)
and
hydroxyl groups) was low, while after 250-h UV irradiation, the absorption
was low, while after 250-h UV irradiation, the absorption intensity in areas 1 and 2 increased. intensity in areas 1 and 2
increased.
After Afterthe
increasing increasing the UV time
UV irradiation irradiation
to 500time to level
h, the 500 h,ofthe level of absorption
absorption bands in bands
area 1 inandarea 1 2
area
and
still area 2 still
increased. increased.
According According
to the proposed to mechanisms
the proposedinmechanisms
Figure 3, morein Figure 3, more
carbonyl carbonyl groups
and hydroxyl and
arehydroxyl
generated groups
during areUVgenerated
degradation.duringIt UV degradation.
is clear that afterIt250
is clear
and 500thathafter
of UV 250 and 500 absorption
radiation, h of UV
radiation, absorption in the mentioned areas (areas 1 and 2) were
in the mentioned areas (areas 1 and 2) were enhanced, indicating the photodegradation process. enhanced, indicating the
photodegradation process. After increasing the UV radiation time to 800
After increasing the UV radiation time to 800 h, not only absorption bands in areas 1 and 2 increasedh, not only absorption
butbands in areas 1 and 2 increased but also an absorption
also an absorption band in the range 2400–3400 cm−1 band in the range 2400–3400 cm−1 appeared
appeared which was attributed to carboxylic
which was attributed to carboxylic acid groups [40]. It can be said that after 800 h UV radiation, more
acid groups [40]. It can be said that after 800 h UV radiation, more carboxylic acid groups were formed,
carboxylic acid groups were formed, which can be considered as an advanced UV degradation step.
which can be considered as an advanced UV degradation step. As seen in Figure 6, after 250 and 500 h
As seen in Figure 6, after 250 and 500 h of UV radiation, no significant changes were observed in the
of UV radiation, no significant changes were observed in the absorption intensity of carbonyl and
absorption intensity of carbonyl and hydroxyl areas in sample B which contains 3% Tinuvin 1130.
hydroxyl areas in sample B which contains 3% Tinuvin 1130. In this sample, after 800 h UV radiation,
In this sample, after 800 h UV radiation, absorption intensities in the 1600–1800 and 3200–3700 cm−1
absorption intensities in the 1600–1800 and 3200–3700 −1 areas (carbonyl and hydroxyl groups)
areas (carbonyl and hydroxyl groups) increased slightly.cm
This level of degradation was a preliminary
increased
step in slightly.
which sample This level of did
B still degradation
not reachwas the aadvanced
preliminary UVstep in whichstep.
degradation sample B stillBdid
Sample wasnot
reach the advanced
protected against UV UV degradation
degradationup step. Sample
to 800 B was protected
h of radiation against
as a result UV degradation
of Tinuvin up to 800 h
1130. The absorption
intensities of carbonyl and hydroxyl functional groups (areas 1 and 2) in Figures 5 and 6 further
confirmed the role of Tinuvin 1130 as a UV absorber.
Materials 2017, 10, 180 8 of 18

of radiation as a result of Tinuvin 1130. The absorption intensities of carbonyl and hydroxyl functional
groups (areas
Materials
Materials 1 and
2017,
2017,10, 2) in Figures 5 and 6 further confirmed the role of Tinuvin 1130 as a UV8absorber.
10,180
180 8ofof18
18

Figure
FigureFigure5.5.FT-IR
5. FT-IR spectra
spectra
FT-IR ofofsample
of sample
spectra AA(epoxy
sample A(epoxy resin
(epoxyresin and
andEpikure
resinand EpikureF205)
Epikure F205)after
F205) 0,0,250,
after
after 0,250,500,
250, and
500,
500, 800
800h800
andand hofofh of
UV
UV radiation.
radiation.
UV radiation.

FigureFigure
Figure 6.6.FT-IR
6. FT-IR FT-IR spectra
spectraspectraofofsample
of sample B B(epoxy
sample B(epoxy
(epoxyresin and
andEpikure
resinand
resin EpikureF205
Epikure F205with
F205 with
with3%
3%Tinuvin
3%Tinuvin1130)
1130)
Tinuvin after
after
1130) 0,0,250,
after 250,
0, 250,
500, and
andh800
500,800
500, and of hUV
800 hofofUV
UVradiation.
radiation.
radiation.

The
Theoptical
opticalimages
imagesof
ofsamples
samplesAAand
andBBafter
after0,0,250,
250,500,
500,and
and800
800hhUV
UVradiation
radiationare
areshown
shownin
in
The
Figureoptical images of samples A and 500 B after 0, radiation
250, 500, and clearly
800 h UV radiation are shown in
Figure 7.7. In
In sample
sample A, A, yellowing
yellowing after
after 500 hh UV
UV radiation was
was clearly seen
seen and
and the
the yellowing
yellowing
Figureintensity
7. In sample
intensity reached
reached A,the
yellowing
thehighest after
highestlevel 500
afterh
levelafter 800UV
800 hhradiation
of
ofUV was clearly
UVradiation.
radiation. Whileseen
While onlyand
only afterthe
after 800yellowing
800 UV,aaintensity
hhofofUV, low
low
reachedintensity of yellowing was seen in sample B, indicating an effective protection of sample B against of
the
intensityhighest
of level
yellowing after
was 800
seen h
inof UV
sample radiation.
B, While
indicating an only after
effective 800 h
protectionofofUV, a
samplelow B intensity
against
yellowing
UV wasdue
UVlight
light seen
due totoin
the sample
the organicB,
organic UV
UVindicating
absorber an effective
absorber(Tinuvin
(Tinuvin protection of sample B against UV light due to
1130).
1130).
the organic UV absorber (Tinuvin 1130).
Materials 2017, 10, 180 9 of 18
Materials 2017, 10, 180 9 of 18

Figure7.
Figure 7. Optical
Optical images
images of
of samples
samples A
Aand
andBBafter
after0,0,250,
250,500,
500,and
and800
800hhof
ofUV
UVradiation.
radiation.

3.2. UV-Vis
3.2. UV-Vis Analysis
Analysis
UV-Visiblespectroscopy
UV-Visible spectroscopy has has been
beenused
usedto tostudy
studythe theUV UVdegradation
degradationprocess,process, particularly
particularly for for
transparent polymers and coatings [19,39,41]. Due to the presence
transparent polymers and coatings [19,39,41]. Due to the presence of several aromatic groups in of several aromatic groups in the
epoxy
the structure,
epoxy structure, the absorbance
the absorbance intensity in theinUV
intensity therange
UV range(200–320 nm) was
(200–320 nm)high.
was As canAs
high. be can
seenbe in
Figure 8a, when the epoxy coating was exposed to UV light
seen in Figure 8a, when the epoxy coating was exposed to UV light radiation, the UV intensityradiation, the UV intensity was very
highvery
was at first.
highHowever, after 250 after
at first. However, and 500250 hand of 500
UV hradiation, the absorbance
of UV radiation, level waslevel
the absorbance reduced
was
because because
reduced the aromatic groupsgroups
the aromatic were derogated
were derogated or hadorundergone
had undergone rearrangements.
rearrangements. AfterAfter
800 800
h, the
h,
absorbance intensity, in comparison to 250 and 500 h, was
the absorbance intensity, in comparison to 250 and 500 h, was increased due to the formation ofincreased due to the formation of
carboxylic acids. Certainly, this was an advanced UV degradation
carboxylic acids. Certainly, this was an advanced UV degradation step, forming phenyl formate step, forming phenyl formate
carboxylic acid
carboxylic acid groups
groups in in which
which the the phenyl
phenyl groups
groups were were in in resonance
resonance and and consequently
consequently caused caused
intensification of the reduced absorbance. According to Figure 8b, by adding Tinuvin 1130 as aa UV
intensification of the reduced absorbance. According to Figure 8b, by adding Tinuvin 1130 as UV
absorber, the
absorber, the domain
domain of of the
the UVUV absorbance
absorbance was was extended
extended from from 200 200 toto 400
400 nmnm which
which was was almost
almost
complete absorbance in the UV range. Absorption behaviors
complete absorbance in the UV range. Absorption behaviors of sample B in the UV area were of sample B in the UV area were
comparatively contrary to the sample A. After UV radiation for
comparatively contrary to the sample A. After UV radiation for 250 and 500 h, the absorbance intensity250 and 500 h, the absorbance
intensity increased,
increased, and after 800 andhafterof UV 800radiation,
h of UV radiation,
the absorbance the absorbance intensity decreased.
intensity decreased.
A spectro-colorimeter is usually used for evaluating
A spectro-colorimeter is usually used for evaluating color changes in color changes inpolymers
polymers[42,43].
[42,43]. InIn this
this
work, in order to evaluate color changes in the samples under UV
work, in order to evaluate color changes in the samples under UV radiation, the area under the visible radiation, the area under the
visible(400–700
range range (400–700 nm) absorption
nm) absorption spectrum spectrum
was used. wasInused. In fact,this
fact, using using this method,
method, color changes
color changes can be
can be interpreted as quantitative data. These results obtained from
interpreted as quantitative data. These results obtained from analyzing data by OriginPro 8.6 softwareanalyzing data by OriginPro 8.6
software
are presentedare in presented
Table 1. in As Table
can be1.seen,As can be seen,
the visible the(400–700
area visible area (400–700 nm)
nm) increased with increased
increasingwith UV
increasing UV radiation time in the sample A, indicating color changes
radiation time in the sample A, indicating color changes in the sample. Moreover, the color change in the sample. Moreover, the
color change from sample of A to A was significantly high and
from sample of A3 to A4 was significantly high and severe yellowing occurred. On the other hand,
3 4 severe yellowing occurred. On the
other
the areahand, the area
of sample of sample
B (with TinuvinB (with Tinuvin
1130) even after1130)800 even
h ofafter
UV 800 h of UV
radiation did radiation
not change did drastically.
not change
drastically. Tinuvin 1130 not only caused slow UV degradation but
Tinuvin 1130 not only caused slow UV degradation but also prevented the advanced UV degradation also prevented the advanced UV
degradation step from occurring. The area of sample B (before UV
step from occurring. The area of sample B1 (before UV radiation) in the visible range was larger than
1 radiation) in the visible range
wasof
that larger than that
A1 because of A1 because
Tinuvin 1130 is Tinuvin
a yellow1130 is a yellow
to light, to light, liquid
amber viscous amberand viscous
when liquid
it was and whentoit
added
the mixture of the epoxy resin and Epikure F205, the absorbance intensity in the visible range visible
was added to the mixture of the epoxy resin and Epikure F205, the absorbance intensity in the of the
range ofB,the
sample sample
before UVB,radiation,
before UVwas radiation,
higherwas thanhigher
that ofthan
the that of the
sample A sample
(without A Tinuvin
(without1130).Tinuvin 1130).
Materials 2017, 10, 180 10 of 18
Materials 2017, 10, 180 10 of 18

Figure 8. (a) UV-Vis spectra of sample A (epoxy resin and Epikure F205) after 0, 250, 500, and 800 h of
Figure 8. (a) UV-Vis spectra of sample A (epoxy resin and Epikure F205) after 0, 250, 500, and 800 h of
UV radiation; (b) UV-Vis spectra of sample B (epoxy resin and Epikure F205 with 3% Tinuvin 1130)
UV radiation;
after 0, 250,(b) UV-Vis
500, spectra
and 800 h of UVofradiation.
sample B (epoxy resin and Epikure F205 with 3% Tinuvin 1130)
after 0, 250, 500, and 800 h of UV radiation.
Table 1. The areas under the visible range (400–700 nm) spectra of samples A (epoxy resin and
TableEpikure
1. TheF205)
areasand B (epoxy
under theresin andrange
visible epikure(400–700
F205 withnm)
3% Tinuvin
spectra1130) after 0, 250,
of samples 500, and resin
A (epoxy 800 h and
UV F205)
Epikure radiation.
and B (epoxy resin and epikure F205 with 3% Tinuvin 1130) after 0, 250, 500, and 800 h
UV radiation. Sample Area Sample Area
A1, 0 h 32.9 B1, 0 h 33.53
Sample A2, 250 hArea35.29 BSample
2, 250 h 33.98Area
A1 , 0 A
h 3, 500 h32.9
38.12 B3B, 1500
, 0 hh 34.2533.53
A2 , 250Ah4, 800 h35.29
64.94 BB42, ,800
250hh 36.5533.98
A3 , 500 h 38.12 B3 , 500 h 34.25
3.3. Tg Evaluation A4 , 800 h 64.94 B4 , 800 h 36.55

The Tg was defined as the temperature at which the mechanical properties of polymer changed
3.3. Tradically
g Evaluation
due to the internal movements of the polymer chains [44]. Tg is one of the most important
properties
The Tg was indefined
the evaluation
as theof performanceat
temperature ofwhich
polymers,
the which depends
mechanical on severalofparameters
properties e.g.,
polymer changed
molecular weight, branching degree, crosslink degree, bulking substituents, curing temperature,
radically due to the internal movements of the polymer chains [44]. Tg is one of the most important
and the polarity of constituents [45–47]. Figure 9 shows Tg values for samples A and B after 0, 250,
properties in the evaluation of performance of polymers, which depends on several parameters e.g.,
500, and 800 h of UV irradiation. It was observed that in sample A (free from UV absorber), with
molecular weight,
increasing branchingtime,
UV irradiation degree, crosslinkand
Tg increased, degree, bulking
after 800 h of UVsubstituents,
irradiation (Acuring temperature,
4), it reached its
and the polarity
maximum of constituents
value. While in sample [45–47]. Figurecontains
B, which 9 shows Tg values
Tinuvin 1130, for
the samples
increase A of and B after 0,
Tg values
250, 500, and 800
continued but htoof UV irradiation.
a lesser It was observed
extent. The increment thatthe
in Tg during in UV
sample A (freeprocess
degradation from UV madeabsorber),
the
with increasing UV irradiation time, Tg increased, and after 800 h of UV irradiation (A4 ), it reached
epoxy coatings brittle. Therefore, after 800 h of UV irradiation, sample B had higher flexibility as a
result of a value.
its maximum lower UV degradation
While in sampleprocess, compared
B, which to sample
contains A [19].1130,
Tinuvin Increase
the inincrease
Tg due tooftheTgUVvalues
radiation
continued butistorelated
a lesserto extent.
formationTheof increment
polar groupsinwhich can hinder
Tg during the UVchain movementsprocess
degradation and act as an the
made
epoxyinternal plasticizer
coatings brittle.[48]. Increasing
Therefore, Tg reduced
after 800 h oftheUVmobility of the polymeric
irradiation, sample B chains, demonstrating
had higher flexibility as
the significant contribution of Tinuvin 1130 to the protection of epoxy coating against UV light.
a result of a lower UV degradation process, compared to sample A [19]. Increase in Tg due to the
UV radiation is related to formation of polar groups which can hinder chain movements and act as
an internal plasticizer [48]. Increasing Tg reduced the mobility of the polymeric chains, demonstrating
the significant contribution of Tinuvin 1130 to the protection of epoxy coating against UV light.
Materials 2017, 10, 180 11 of 18
Materials 2017, 10, 180 11 of 18

Figure 9.
Figure 9. T
Tgg of
ofsamples
samplesA Aand
andBBasasaa function
function of
of UV
UV irradiation
irradiation time
time (A:
(A: epoxy
epoxy resin
resin and
and Epikure
Epikure F205,
F205,
B: epoxy resin and Epikure F205 with 3% Tinuvin 1130), (A1: 0 h, A2: 250 h, A3: 500 h,A3:
B: epoxy resin and Epikure F205 with 3% Tinuvin 1130), (A1: 0 h, A2: 250 h, A4:500
800 h,
h,
A4: 0800
B1: h, B1:
h, B2: 2500 h,
h, B3:
B2: 500
250 h,
h, B4:
B3: 500
800 h,
h UVB4: irradiation
800 h UV irradiation
time). time).

3.4. Tensile
3.4. Strength
Tensile Strength
The tensile
The tensile test
test was
wasconducted
conductedtotoevaluate
evaluatethe theeffect
effectofofUVUVlight
lightononthe mechanical
the mechanical properties
properties of
the epoxy polymer [49]. It was hypothesized that polymeric chains and
of the epoxy polymer [49]. It was hypothesized that polymeric chains and branches were destroyed branches were destroyed by
UVUV
by radiation,
radiation,affecting
affectingthethemechanical
mechanical performance
performance ofof
thetheepoxy
epoxypolymers.
polymers.As Asshown
shownin inTable
Table 2,2,
increasing UV irradiation time decreased the tensile strength and modulus
increasing UV irradiation time decreased the tensile strength and modulus of sample A (epoxy resin of sample A (epoxy resin
and Epikure
and Epikure F204).
F204). Nonetheless,
Nonetheless, it it seemed
seemed thatthat the
the tensile
tensile modulus
modulus was was not
not affected
affected significantly
significantly by by
UV light. After 800 h of UV radiation, tensile strength and elongation at break
UV light. After 800 h of UV radiation, tensile strength and elongation at break reduced dramatically. reduced dramatically.
For example,
For example, after
after 800
800 h,
h, tensile
tensile strength
strength andand elongation
elongation at at break
break of of sample
sample A A were decreased by
were decreased by
~30% and ~35%, respectively. As reported in Table 2, decreases in tensile
~30% and ~35%, respectively. As reported in Table 2, decreases in tensile strength and elongation strength and elongation at at
break for
break for sample
sample A A after
after 500
500 h h of
of UV
UV radiation
radiation were
were accelerated.
accelerated. ThisThis could
could be
be due
due toto the
the advanced
advanced
UV degradation step occurring in this sample. The incorporation of Tinuvin 1130 (sample B)led
UV degradation step occurring in this sample. The incorporation of Tinuvin 1130 (sample B) ledtotoa
significant slow decrease in tensile strength and elongation at break. After
a significant slow decrease in tensile strength and elongation at break. After 800 h of UV exposure, 800 h of UV exposure, the
tensile
the strength
tensile andand
strength thethe
elongation
elongation at break
at breakwere
weredecreased
decreased only
onlybyby11.94%
11.94%andand8.62%,
8.62%,respectively.
respectively.
Therefore, Tinuvin 1130 slowed down the UV degradation
Therefore, Tinuvin 1130 slowed down the UV degradation rate considerably. rate considerably.
Chaochanchaikuland
Chaochanchaikul andSombatsompop
Sombatsompop [50][50] studied
studied the of
the effect effect of Tinuvin
Tinuvin P on mechanical
P on mechanical properties
properties
of of PVC chloride)
PVC (polyvinyl (polyvinylwith chloride) with UV irradiation.
UV irradiation. It was reported It was reported
that that
after 720 after
h of UV720 h of UV
irradiation,
irradiation, elongation at break was decreased by 21.01% which was
elongation at break was decreased by 21.01% which was more than twice higher than that reported more than twice higher than
that
in thisreported
study. In in another
this study.study,In Tinuvin
another 622 study,wasTinuvin
added into622 vulcanized
was added ethylene
into vulcanized
propylene ethylene
diene
propylene diene monomer rubber (EPDM) and after 672 h of UV irradiation,
monomer rubber (EPDM) and after 672 h of UV irradiation, the tensile strength and elongation the tensile strength and
at
elongation at break were reduced by 15.38%
break were reduced by 15.38% and 67%, respectively [51]. and 67%, respectively [51].

Table 2.
Table 2. The
The effect
effect of
of UV
UV light
light on
on tensile
tensile strength,
strength, tensile
tensile modulus,
modulus, and
and elongation
elongation at
at break.
break. Sample
Sample A
A
(epoxy resin and Epikure F205) and Sample B (epoxy resin and Epikure F205 with 3% Tinuvin
(epoxy resin and Epikure F205) and Sample B (epoxy resin and Epikure F205 with 3% Tinuvin 1130). 1130).

Time Exposure Tensile Strength Tensile Modulus Elongation at Break

Sample Time Exposure Tensile Strength Tensile
Sample to UV Light (MPa) (MPa) Modulus Elongation
(%) at Break
A1 to UV 0Light
h (MPa)
29.12 ± 2.4 (MPa)
1756 ± 11.5 1.75 ± 0.33(%)
A1 A2 0250
h h 29.12 ±±3.5
27.87 2.4 17501756 ± 11.5
± 61.8 0.15 ± 0.33
1.69 ± 1.75
A2 A3 250 hh
500 27.87 ±±1.4
25.39 3.5 17491750 ± 61.8
± 45.4 0.93 ± 0.15
1.42 ± 1.69
A3 A4 500 hh
800 25.39 ±±2.9
20.25 1.4 17471749 ± 45.4
± 51.1 0.67 ± 0.93
1.13 ± 1.42
A4 B1 8000hh 20.25 ± 2.9
29.06 ± 6.9 1747 ±
1757 ± 74.7 51.1 1.74 ± 0.91 ± 0.67
1.13
B1 0h 29.06 ± 6.9 1757 ± 74.7 1.74 ± 0.91
B2 250 h 28.38 ± 3.7 1755 ± 32.4 1.74 ± 0.42
B2 250 h 28.38 ± 3.7 1755 ± 32.4 1.74 ± 0.42
B3 500 h 27.22 ± 2.5 1756 ± 63.9 1.63 ± 0.51
B3 500 h 27.22 ± 2.5 1756 ± 63.9 1.63 ± 0.51
B4 B4 800
800 hh 25.59
25.59 ±±1.7
1.7 17511751
± 46.4
± 46.4 1.59 ± 0.37
1.59 ± 0.37
Materials 2017, 10, 180 12 of 18

Materials 2017, 10, 180 12 of 18

3.5. Izod Impact Strength
3.5. Izod10
Figure Impact
showsStrength
the impact of Izod strength of samples A (epoxy resin and Epikure F205) and
B (epoxyFigure
resin 10
and Epikure F205 of
shows the impact with
Izod3% Tinuvin
strength 1130) versus
of samples A (epoxy UV radiation
resin time.
and Epikure In and
F205) sample
B A,
UV irradiation
(epoxy resinreduced IzodF205
and Epikure impact
withstrength.
3% TinuvinAfter 800
1130) h of UV
versus exposure,
radiation Izod impact
time. strength
In sample A, UVof the
irradiation
samples A and reduced Izod impact
B were reduced strength.and
by 22.52% After 800 h
9.04%, of exposure,UV
respectively. Izod impact
light strength
caused cracksof and
the tore
samples Achains,
up polymeric and B were reduced
resulting by 22.52%
in the andof
reduction 9.04%,
Izodrespectively. UV light
impact strength. caused cracks
Nevertheless, UV and tore
irradiation
up polymeric
damaged samplechains,
B less,resulting in thethe
confirming reduction
positiveof role
Izod of
impact strength.
Tinuvin 1130Nevertheless,
as an organic UVUV irradiation
absorber in
damaged sample B less, confirming the positive role of Tinuvin 1130 as an organic UV absorber in
epoxy resin. Attwood et al. [52] investigated the effect of UV light on the Izod impact strength of
epoxy resin. Attwood et al. [52] investigated the effect of UV light on the Izod impact strength of
polyolefin blends before and after 800 h of UV irradiation. It was reported that Izod impact strength
polyolefin blends before and after 800 h of UV irradiation. It was reported that Izod impact strength
was reduced
was reducedroughly by 25%
roughly as aasresult
by 25% of UV
a result exposure.
of UV exposure.Other studies
Other studieshave
havealsoalsoshown
shown thatthat UV
UV light
decreased
light decreased noticeably the Izod impact strength of various polymeric systems [52,53]. Accordingto the
noticeably the Izod impact strength of various polymeric systems [52,53]. According
results
to presented
the results in Figure 10,
presented after 800
in Figure 10,hafter
of UV800irradiation in the presence
h of UV irradiation of Tinuvin
in the presence 1130, Izod
of Tinuvin impact
1130,
strength
Izodwas decreased
impact strength only by 9.1%. only by 9.1%.
was decreased

Figure
Figure 10. Izod
10. Izod impact
impact strengthofofsamples
strength samples AA (epoxy
(epoxyand andEpikure
EpikureF 205) andand
F 205) B (epoxy resinresin
B (epoxy and and
Epikure F205 with 3% Tinuvin 1130) after 0, 250, 500, and 800 h of UV irradiation.
Epikure F205 with 3% Tinuvin 1130) after 0, 250, 500, and 800 h of UV irradiation.

3.6. Pull-Off Strength

3.6. Pull-Off Strength
Hydroxyl groups in epoxy resin are responsible for adhesion [54]. Therefore, any changes in the
Hydroxyl
concentration groups in epoxygroups
of hydroxyl resin are responsible
in the for adhesion
epoxy structure [54]. Therefore,
cause change in pull-offany changes
strength. Asin the
concentration
presentedof inhydroxyl
Figure 1, groups
during UVin the epoxy structure
degradation, some of cause change in
the primary pull-offgroups
hydroxyl strength. As presented
entered into
reaction
in Figure and were
1, during UVconverted to other
degradation, functional
some groups [9,15].
of the primary According
hydroxyl groupsto Table 3, increasing
entered UV and
into reaction
were irradiation
converted time diminished
to other functionalpull-off
groups strength
[9,15]. of sample A.
According to It was3,postulated
Table increasingthat, during UV time
UV irradiation
degradation,
diminished hydroxyl
pull-off groups,
strength as major
of sample A.adhesive agents, were
It was postulated either
that, destroyed
during or involved in hydroxyl
UV degradation, side
reactions. It was evident that when the concentration of hydroxyl groups was reduced, the pull-off
groups, as major adhesive agents, were either destroyed or involved in side reactions. It was evident
strength decreased. It is worth mentioning that after 800 h of UV radiation (A4), pull-off strength
that when the concentration of hydroxyl groups was reduced, the pull-off strength decreased. It is
decreased significantly, arising from the progress of UV degradation to the advanced stage. On the
worth mentioning
other that in
hand, changes after 800 h
pull-off of UVfor
strength radiation
sample B(A 4 ), pull-off
were strength
not as extreme as decreased
for sample A, significantly,
again
arising from the progress of UV degradation to the advanced stage. On
indicating the protective influence of Tinuvin 1130 over UV damage. Kielmann and Mai the other hand, changes
[55] in
pull-off strengththe
examined foreffect
sample ofB UV
werelight
not asonextreme as for sample
thermosetting A, again
N-methylol indicating
melamine the protective
(NMM) and
influence of Tinuvin 1130(PF)
phenol-formaldehyde overwith
UVand damage.
without Kielmann and Mai
UV absorbers. [55]tests
Pull-off examined the effect
on samples of UV
revealed that light
UV absorbers had
on thermosetting a positive melamine
N-methylol effect regarding
(NMM) adhesion
and of epoxy matrix to the aluminum
phenol-formaldehyde (PF) withsurface.
and without
UV absorbers. Pull-off tests on samples revealed that UV absorbers had a positive effect regarding
adhesion of epoxy matrix to the aluminum surface.
Materials 2017, 10, 180 13 of 18

Materials 2017, 10, 180 13 of 18

Table 3. The results of pull-off strength samples A (DGEBA and Epikure F 205) and B (DGEBA and
Table 3. The results of pull-off strength samples A (DGEBA and Epikure F 205) and B (DGEBA and
Epikure F 205 with 3% Tinuvin 1130) after 0, 250, 500, and 800 h UV irradiation.
Epikure F 205 with 3% Tinuvin 1130) after 0, 250, 500, and 800 h UV irradiation.
Sample
Sample Pull-OffStrength
Pull-Off Strength (MPa)
(MPa)
A1, 00 h
A1, h 4.42±±0.4
4.42 0.4
A2, 250 hh
A2, 250 4.33 ±
4.33 ± 0.40.4
A3, 500 h 4.04 ± 0.1
A3,
A4, 500
800 hh 4.04
3.52±±0.10.3
A4,
B1,800
0 hh 3.52
4.4 ±±0.3
0.3
B1,250
B2, 0 hh 4.35± ±
4.4 0.3
0.1
B3, 250
B2, 500 hh 4.21±±0.1
4.35 0.3
B4, 800 h 4.12 ± 0.4
B3, 500 h 4.21 ± 0.3
B4, 800 h 4.12 ± 0.4
3.7. SEM Morphology
3.7. SEM Morphology
To study the effect of UV on the surface morphology of epoxy samples, SEM imaging
was Toconducted.
study theThe surfaces
effect of UVof onsamples A (DGEBA
the surface morphology and of Epikure
epoxy Fsamples,
205) and SEMB (DGEBA and
imaging was
Epikure F 205 with 3% Tinuvin 1130) after 0, 250, 500, 800 h of UV radiation
conducted. The surfaces of samples A (DGEBA and Epikure F 205) and B (DGEBA and Epikure F 205 are shown in Figure 11.
As
withshown in Figure
3% Tinuvin 11(A
1130) 1 ), 0,
after the250,
surface of epoxy
500, 800 h of UVbefore UV radiation
radiation are shown was in fairly
Figuresmooth, but after
11. As shown in
250 h of UV radiation some nodes appeared on the surface attributed to
Figure 11(A1), the surface of epoxy before UV radiation was fairly smooth, but after 250 h of UV the generation of volatile
compounds,
radiation someleading
nodesto appeared
the formation of ripples
on the surface(Figure 11(A2to)).the
attributed After 500 h of UV
generation exposure,
of volatile the surface
compounds,
was covered
leading to thewith small cracks
formation of ripplesas seen in Figure
(Figure 11(A211(A 3 ). As
)). After 500the h exposure time increased
of UV exposure, to 800
the surface wash,
surface cracks became wider and deeper, indicating severe damage (Figure
covered with small cracks as seen in Figure 11(A3). As the exposure time increased 4to 800 h, surface 11(A )). For samples
containing
cracks became Tinuvin
wider1130,
and no crackindicating
deeper, was observed after
severe 250 and
damage 500, and
(Figure 11(Aeven 800 h of UV radiation,
4)). For samples containing

Tinuvin 1130, no crack was observed after 250 and 500, and even 800 h of UVexposure
as can be seen in Figure 12. This difference in surface morphology after UV radiation, was
as due to
can be
the presence of Tinuvin 1130. There were some visible nodes on the surface
seen in Figure 12. This difference in surface morphology after UV exposure was due to the presence after 500 and 800 h of
UVTinuvin
of exposure. It was
1130. Thereassumed
were some thatvisible
UV radiation
nodes on resulted in relocation
the surface after 500ofand
organic
800 hUV absorbers
of UV from
exposure. It
structure to the surface. Moreover, the SEM images further confirmed the
was assumed that UV radiation resulted in relocation of organic UV absorbers from structure to the mechanical properties
discussed
surface. previously.
Moreover, the SEM images further confirmed the mechanical properties discussed previously.

A1 A2

Figure 11. Cont.

Materials 2017, 10, 180 14 of 18
Materials 2017, 10, 180 14 of 18
Materials 2017, 10, 180 14 of 18

A3 A4
A3 A4
Figure 11. Scanning
Scanning electronmicroscopy
microscopy (SEM) images of sample A (DGEBA and Epikure F 205)
Figure
Figure 11.11. Scanningelectron
electron microscopy(SEM) (SEM)images
imagesof sample A (DGEBA
of sample and and
A (DGEBA Epikure F 205)
Epikure F after
205)
after
(A (A(A
1 ) 0; 1) 0; (A2) (A
) 250; 250; (A
3 ) (A 3) 500;
500; and
and (A 4 ) (A
8004) h
800
UVh irradiation.
UV irradiation.
after (A1) 20; (A2) 250; 3) 500; and (A4) 800 h UV irradiation.

B1 B2
B1 B2

Figure 12. Cont.

Materials 2017, 10, 180 15 of 18
Materials 2017, 10, 180 15 of 18

B3 B4
12. SEM images of sample B (DGEBA and Epikure F 205 with 3% Tinuvin 1130) after (B11) 0;
Figure 12.
(B22) 250; (B33)) 500;
(B 500; and
and (B
(B44))800
800hhUV
UVirradiation.
irradiation.

4. Conclusions
4. Conclusions
In summary,
In summary, this this study
study indicated
indicated that
that Tinuvin
Tinuvin 1130,
1130, asas an
an organic
organic UV
UV absorber,
absorber, is is an
an effective
effective
compound to decrease and even stop UV degradation in a cured epoxy-diamine
compound to decrease and even stop UV degradation in a cured epoxy-diamine system. FT-IR analyses system. FT-IR
analyses that,
showed showed that,
after anafter
800-han 800-h UV radiation,
UV radiation, an advanced
an advanced UVUV degradation
degradation stepoccurred
step occurredin in the
the
epoxy system without Tinuvin 1130, leading to formation of carboxylic
epoxy system without Tinuvin 1130, leading to formation of carboxylic acids. However, in the acids. However, in the
presence of
presence of Tinuvin
Tinuvin 1130,
1130, UV
UV damage
damage could
could not
not progress
progress wellwell and
and it
it remained
remained at at the
the early
early stages.
stages.
UV-Vis spectroscopy revealed that the epoxy system containing Tinuvin 1130
UV-Vis spectroscopy revealed that the epoxy system containing Tinuvin 1130 had a little yellowing had a little yellowing
after 800
after 800 h,
h, whereas
whereas the the pure
pure epoxy
epoxy system
system reached high levels
reached high levels of
of yellowing
yellowing after
after the
the same
same duration.
duration.
On comparison
On comparisonofoftensile
tensilestrength,
strength,pull-off
pull-off strength,
strength, andand Izod
Izod impact
impact strength
strength afterafter UV radiation,
UV radiation, it
it was
was found that Tinuvin 1130 effectively maintained the mechanical properties
found that Tinuvin 1130 effectively maintained the mechanical properties of the epoxy resin against of the epoxy resin
against
UV light.UV
SEM light. SEMalso
images images also demonstrated
demonstrated that no
that no cracks werecracks
seen were
on theseen on the
surface surface of
of samples samples
containing
containing
Tinuvin 1130Tinuvin 1130800
even after even
h ofafter
UV 800 h of UV
exposure, exposure,
while while on
on the surface ofthe surface
samples of samples
without Tinuvinwithout
1130,
Tinuvin 1130, cracks were produced after 500 h of UV radiation and the surface
cracks were produced after 500 h of UV radiation and the surface was completely destroyed after 800 h was completely
destroyed
of after 800 h of UV radiation.
UV radiation.

Acknowledgments: The
Acknowledgments: Theauthors
authorswould
wouldlikelike to gratefully
to gratefully thank
thank the University
the University of Tabriz
of Tabriz for the financial
for the financial support
for this research
support project. project.
for this research
Author Contributions: The
Author Contributions: The study
study was
was conceived
conceived and
and designed
designed by
by S.N.
S.N. Experiments were conducted
Experiments were conducted by
by S.N.
S.N.
Data and results were analyzed by S.N., O.Z., M.A., and M.T. with the support of A.M. and M.N. S.N. wrote the
Data and results were analyzed by S.N., O.Z., M.A., and M.T. with the support of A.M. and M.N. S.N. wrote the
first draft manuscript. All the authors reviewed and revised the manuscript to its final form.
first draft manuscript. All the authors reviewed and revised the manuscript to its final form.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
References
References
1. Zarras, P.; Goodman, P.A.; Stenger-Smith, J.D. Functional polymeric coatings: Synthesis, properties,
1. Zarras,
and P.; Goodman,
applications. P.A.; Stenger-Smith,
Res. Perspect. Funct. MicroJ.D. Functional
Nanoscale Coat. polymeric coatings: Synthesis, properties, and
2016. [CrossRef]
2. applications. Res. Perspect. Funct. Micro Nanoscale Coat. 2016, doi:10.4018/978-1-5225-0066-7.ch004.
Hensher, D.A. Fiber-Reinforced-Plastic (FRP) Reinforcement for Concrete Structures: Properties and Applications;
2. Hensher,Amsterdam,
Elsevier: D.A. Fiber-Reinforced-Plastic
The Netherlands, (frp) Reinforcement for Concrete Structures: Properties and Applications;
2016.
Elsevier: Amsterdam, The Netherlands, 2016.
3. Mirmohseni-Namin, A.; Nikafshar, S.; Mirmohseni, F. Increasing toughness and tensile strength of an
epoxy-diamine system using an inorganic ultra-accelerator. RSC Adv. 2015, 5, 53025–53035.
Materials 2017, 10, 180 16 of 18

3. Mirmohseni-Namin, A.; Nikafshar, S.; Mirmohseni, F. Increasing toughness and tensile strength of
an epoxy-diamine system using an inorganic ultra-accelerator. RSC Adv. 2015, 5, 53025–53035. [CrossRef]
4. Singh, P.; Kharwar, P.K.; Gautam, V.K.; Yadav, M.S.K. Physical and mechanical characterization of epoxy
based polymer composites for marine industry. Imp. J. Interdiscip. Res. 2016, 2, 608–613.
5. McKeen, L.W. The Effect of UV Light and Weather on Plastics and Elastomers; William Andrew: Norwich, NY,
USA, 2013.
6. Solar and Ultraviolet Radiation. Available online: https://www.ncbi.nlm.nih.gov/books/NBK304366/
(accessed on 16 December 2016).
7. Ghasemi-Kahrizsangi, A.; Neshati, J.; Shariatpanahi, H.; Akbarinezhad, E. Improving the UV degradation
resistance of epoxy coatings using modified carbon black nanoparticles. Prog. Org. Coat. 2015, 85, 199–207.
[CrossRef]
8. Suits, L.D.; Hsuan, Y.G. Assessing the photo-degradation of geosynthetics by outdoor exposure and
laboratory weatherometer. Geotext. Geomembr. 2003, 21, 111–122. [CrossRef]
9. Grassie, N.; Guy, M.I.; Tennent, N.H. Degradation of epoxy polymers. Part 5—Photo-degradation of
bisphenol-A diglycidyl ether cured with ethylene diamine. Polym. Degrad. Stab. 1986, 14, 209–216. [CrossRef]
10. Zhang, Z.; Wang, S.; Zhang, J. Large stabilizing effect of titanium dioxide on photodegradation of
PVC/α-methylstyrene-acrylonitrile copolymer/impact modifier-matrix composites. Polym. Compos. 2014,
35, 2365–2375. [CrossRef]
11. Yousif, E.; Haddad, R. Photodegradation and photostabilization of polymers, especially polystyrene: Review.
SpringerPlus 2013. [CrossRef] [PubMed]
12. Asmatulu, R.; Claus, R.O.; Mecham, J.B.; Corcoran, S.G. Nanotechnology-associated coatings for aircrafts.
Mater. Sci. 2007, 43, 415–422. [CrossRef]
13. Asmatulu, R.; Mahmud, G.A.; Zhang, B.; Ahmed, I. Effects of UV light on water contact angles of
nanocomposite coatings. In Proceedings of the SAMPE Fall Technical Conference, Salt Lake City, UT,
USA, 11–14 October 2010.
14. Copinet, A.; Bertrand, C.; Govindin, S.; Coma, V.; Couturier, Y. Effects of ultraviolet light (315 nm),
temperature and relative humidity on the degradation of polylactic acid plastic films. Chemosphere 2004, 55,
763–773. [CrossRef] [PubMed]
15. Rabek, J.F. Polymer Photodegradation Mechanisms and Experimental Methods; Chapman & Hall: London, UK,
1995.
16. Massey, L.K. The Effects of UV Light and Weather on Plastics and Elastomers, 2nd ed.; William Andrew: Norwich,
NY, USA, 2007.
17. Forsthuber, B.; Schaller, C.; Grüll, G. Evaluation of the photo stabilising efficiency of clear coatings comprising
organic UV absorbers and mineral UV screeners on wood surfaces. Wood Sci. Technol. 2013, 47, 281–297.
[CrossRef]
18. Devi, R.R.; Maji, T.K. Effect of nano-zno on thermal, mechanical, UV stability, and other physical properties
of wood polymer composites. Ind. Eng. Chem. Res. 2012, 51, 3870–3880. [CrossRef]
19. Aloui, F.; Ahajji, A.; Irmouli, Y.; George, B.; Charrier, B.; Merlin, A. Inorganic UV absorbers for the
photostabilisation of wood-clearcoating systems: Comparison with organic UV absorbers. Appl. Surf. Sci.
2007, 253, 3737–3745. [CrossRef]
20. Crawford, J.C. 2(2-hydroxyphenyl)2H-benzotriazole ultraviolet stabilizers. Prog. Polym. Sci. 1999, 24, 7–43.
[CrossRef]
21. Allen, N.S.; Edge, M.; Ortega, A.; Sandoval, G.; Liauw, C.M.; Verran, J.; Stratton, J.; McIntyre, R.B. Degradation
and stabilisation of polymers and coatings: Nano versus pigmentary titania particles. Polym. Degrad. Stab.
2004, 85, 927–946. [CrossRef]
22. Bail, R.; Hong, J.Y.; Chin, B.D. Effect of a red-shifted benzotriazole UV absorber on curing depth and kinetics
in visible light initiated photopolymer resins for 3D printing. J. Ind. Eng. Chem. 2016, 38, 141–145. [CrossRef]
23. Parejo, P.G.; Zayat, M.; Levy, D. Highly efficient UV-absorbing thin-film coatings for protection of organic
materials against photodegradation. J. Mater. Chem. 2006, 16, 2165–2169. [CrossRef]
24. Manaia, E.B.; Kaminski, R.C.K.; Corrêa, M.A.; Chiavacci, L.A. Inorganic UV filters. Braz. J. Pharm. Sci. 2013,
49, 201–209. [CrossRef]
Materials 2017, 10, 180 17 of 18

25. Asmatulu, R.; Mahmud, G.A.; Hille, C.; Misak, H.E. Effects of UV degradation on surface hydrophobicity,
crack, and thickness of MWCNT-based nanocomposite coatings. Prog. Org. Coat. 2011, 72, 553–561.
[CrossRef]
26. Gesner, B.D.; Kelleher, P.G. Oxidation of bisphenol a polymers. J. Appl. Polym. Sci. 1969, 13, 2183–2191.
[CrossRef]
27. Hayyan, M.; Hashim, M.A.; AlNashef, I.M. Superoxide ion: Generation and chemical implications. Chem. Rev.
2016, 116, 3029–3085. [CrossRef] [PubMed]
28. Step, E.; Turro, N.; Gande, M.; Klemchuk, P. Mechanism of polymer stabilization by hindered-amine
light stabilizers (HALS). Model investigations of the interaction of peroxy radicals with hals amines and
amino ethers. Macromolecules 1994, 27, 2529–2539. [CrossRef]
29. Kockler, J.; Oelgemöller, M.; Robertson, S.; Glass, B.D. Photostability of sunscreens. J. Photochem. Photobiol. C
Photochem. Rev. 2012, 13, 91–110. [CrossRef]
30. Fechine, G.J.M.; Rabello, M.S.; Souto Maior, R.M.; Catalani, L.H. Surface characterization of photodegraded
poly(ethylene terephthalate). The effect of ultraviolet absorbers. Polymer 2004, 45, 2303–2308. [CrossRef]
31. Jia, H.; Wang, H.; Chen, W. The combination effect of hindered amine light stabilizers with UV absorbers on
the radiation resistance of polypropylene. Radiat. Phys. Chem. 2007, 76, 1179–1188. [CrossRef]
32. Lee, B.-H.; Kim, H.-J. Influence of isocyanate type of acrylated urethane oligomer and of additives on
weathering of UV-cured films. Polym. Degrad. Stab. 2006, 91, 1025–1035. [CrossRef]
33. Liu, Z.; Chen, S.; Zhang, J. Effect of UV absorbers and hindered amine light stabilizers on the
photodegradation of ethylene-octene copolymer. J. Appl. Polym. Sci. 2013, 127, 1135–1147. [CrossRef]
34. Diepens, M. Photodegradation and Stability of Bisphenol a Polycarbonate in Weathering Conditions; Eindhoven
University of Technology: Eindhoven, The Netherlands, 2009.
35. Irmouli, Y.; George, B.; Merlin, A. Artificial ageing of wood finishes monitored by IR analysis and
color measurements. J. Appl. Polym. Sci. 2012, 124, 1938–1946. [CrossRef]
36. Petersen, E.J.; Lam, T.; Gorham, J.M.; Scott, K.C.; Long, C.J.; Stanley, D.; Sharma, R.; Alexander Liddle, J.;
Pellegrin, B.; Nguyen, T. Methods to assess the impact of UV irradiation on the surface chemistry and
structure of multiwall carbon nanotube epoxy nanocomposites. Carbon 2014, 69, 194–205. [CrossRef]
37. Kowalonek, J. Surface studies of UV-irradiated poly(vinyl chloride)/poly(methyl methacrylate) blends.
Polym. Degrad. Stab. 2016, 133, 367–377. [CrossRef]
38. Zhang, X.; Pi, H.; Guo, S.; Fu, J. Influence of ultraviolet absorbers on the ultraviolet-irradiation behaviour of
rigid poly vinyl chloride. Plast. Rubber Compos. 2016, 45, 352–361. [CrossRef]
39. Mailhot, B.; Morlat-Thérias, S.; Ouahioune, M.; Gardette, J.-L. Study of the degradation of an epoxy/amine
resin, 1. Macromol. Chem. Phys. 2005, 206, 575–584. [CrossRef]
40. Pavia, D.; Lampman, G.; Kriz, G.; Vyvyan, J. Introduction to Spectroscopy; Cengage Learning: Boston, MA,
USA, 2008.
41. Torikai, A.; Hasegawa, H. Accelerated photodegradation of poly(vinyl chloride). Polym. Degrad. Stab. 1999,
63, 441–445. [CrossRef]
42. Muasher, M.; Sain, M. The efficacy of photostabilizers on the color change of wood filled plastic composites.
Polym. Degrad. Stab. 2006, 91, 1156–1165. [CrossRef]
43. Salla, J.; Pandey, K.K.; Srinivas, K. Improvement of UV resistance of wood surfaces by using zno nanoparticles.
Polym. Degrad. Stab. 2012, 97, 592–596. [CrossRef]
44. Zabihi, O. Preparation and characterization of toughened composites of epoxy/poly(3,4-ethylenedioxythiophene)
nanotube: Thermal, mechanical and electrical properties. Compos. Part B Eng. 2013, 45, 1480–1485. [CrossRef]
45. Carbas, R.; Marques, E.; Da Silva, L.; Lopes, A. Effect of cure temperature on the glass transition temperature
and mechanical properties of epoxy adhesives. J. Adhes. 2014, 90, 104–119. [CrossRef]
46. Zabihi, O. Modeling of phenomenological mechanisms during thermal formation and degradation of
an epoxy-based nanocomposite. Thermochim. Acta 2012, 543, 239–245. [CrossRef]
47. Zabihi, O.; Ahmadi, M.; Akhlaghi bagherjeri, M.; Naebe, M. One-pot synthesis of aminated multi-walled
carbon nanotube using thiol-ene click chemistry for improvement of epoxy nanocomposites properties.
RSC Adv. 2015, 5, 98692–98699. [CrossRef]
48. Hill, L.W.; Korzeniowski, H.M.; Ojunga-Andrew, M.; Wilson, R.C. Accelerated clearcoat weathering studied
by dynamic mechanical analysis. Prog. Org. Coat. 1994, 24, 147–173. [CrossRef]
Materials 2017, 10, 180 18 of 18

49. Tcherbi-Narteh, A.; Hosur, M.; Triggs, E.; Jeelani, S. Thermal stability and degradation of diglycidyl ether of
bisphenol a epoxy modified with different nanoclays exposed to UV radiation. Polym. Degrad. Stab. 2013, 98,
759–770. [CrossRef]
50. Chaochanchaikul, K.; Sombatsompop, N. Stabilizations of molecular structures and mechanical properties
of PVC and wood/PVC composites by tinuvin and TiO2 stabilizers. Polym. Eng. Sci. 2011, 51, 1354–1365.
[CrossRef]
51. Basfar, A.A.; Abdel-Aziz, M.M.; Mofti, S. Accelerated aging and stabilization of radiation-vulcanized
EPDM rubber. Radiat. Phys. Chem. 2000, 57, 405–409. [CrossRef]
52. Attwood, J.; Philip, M.; Hulme, A.; Williams, G.; Shipton, P. The effects of ageing by ultraviolet degradation
of recycled polyolefin blends. Polym. Degrad. Stab. 2006, 91, 3407–3415. [CrossRef]
53. Petchwattana, N.; Covavisaruch, S.; Chanakul, S. Mechanical properties, thermal degradation and natural
weathering of high density polyethylene/rice hull composites compatibilized with maleic anhydride
grafted polyethylene. J. Polym. Res. 2012, 19, 9921. [CrossRef]
54. Petrie, E. Epoxy Adhesive Formulations; McGraw-Hill Education: New York, NY, USA, 2005.
55. Kielmann, B.C.; Mai, C. Application and artificial weathering performance of translucent coatings on
resin-treated and dye-stained beech-wood. Prog. Org. Coat. 2016, 95, 54–63. [CrossRef]

© 2017 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).