polymers

Article
Preparation of Polyethylene and Ethylene/Methacrylic
Acid Copolymer Blend Films with Tunable Surface
Properties through Manipulating Processing
Parameters during Film Blowing
Sarmad Ali 1,† , Youxin Ji 1,2,† , Qianlei Zhang 1 , Haoyuan Zhao 1 , Wei Chen 1, * ,
Daoliang Wang 1 , Lingpu Meng 1 and Liangbin Li 1
1 National Synchrotron Radiation Laboratory, Anhui Provincial Engineering Laboratory of Advanced
Functional Polymer Film, CAS Key Laboratory of Soft Matter Chemistry,
University of Science and Technology of China, Hefei 230026, China
2 School of Materials Science and Engineering, The Key Laboratory of Materials Processing and Mold,
Ministry of Education, Henan Key Laboratory of Advanced Nylon Materials and Application,
Zhengzhou University, Zhengzhou 450001, China
* Correspondence: wc003@ustc.edu.cn
† These authors contributed equally to this work.




Received: 10 September 2019; Accepted: 24 September 2019; Published: 26 September 2019


Abstract: Polymer films based on polyethylene (PE) and ionomer ethylene/methacrylic acid (EMAA)
copolymer blend were prepared by film blowing, whose surface properties were tuned by varying
processing parameters, i.e., take up ratio (TUR). Blends of PE/EMAA copolymer were firstly prepared
by the melt-mixing method, before being further blown to films. The wettability of the film was
investigated by measuring the contact angle/water-film encounter time, and optical properties,
i.e., the haze and transmittance. The wettability was found to be enhanced with the increase of TUR.
So too was the haze, while the transmittance was found to be almost independent of TUR. The XPS
and AFM results directly show the increasing polar functional groups (–COO− ) on the surface and
roughness with increasing TUR. Further analysis of the 2D SAXS and WAXS unveiled the origin of the
invariant transmittance, which resulted from the minor change of the crystallinity and the monotonic
increase of the haze, with TUR resulting from the evolution of crystal orientation. In addition to other
post-modification methods, the current study provides an alternative route to prepare large-scale
PE films as the template for the advanced potential applications, i.e., covering in the layer of roof,
the privacy of protective windows, and multitudes of packaging.

Keywords: PE; EMAA; blown films; haze; wettability

1. Introduction
Polyethylene (PE) film is one of the most widely used polymeric materials, which is attributed to
its numerous advantages, i.e., abundant supply, good chemical resistance, low cost, and versatility [1–4].
However, its lack of reactivity, dyeability, poor wettability, and matting limit its potential applications
to some extent. PE films are widely used in multi-product packaging, where optical properties are of
paramount importance [5–12]. Films with low haze and high transparency are preferred for packaging
and agriculture, since it allows the customers to see inside clearly. However, another type of film with
extremely high haze, named matte film, has attracted great interest in the packaging industry in recent
years, especially for the commercial enterprise of superior quality stuff [13]. This is due to the fact that
the matte surface reduces glare for easy viewing and increases the appeal of the products. Moreover,

Polymers 2019, 11, 1565; doi:10.3390/polym11101565 www.mdpi.com/journal/polymers

Polymers 2019, 11, 1565 2 of 13

some of the PE films used in packaging applications are in the form of laminate with other materials,
i.e., paper and aluminum, where the adhesion property or the high wettability is the key issue in the
applications [14,15] The adhesion property mainly depends on the surface free energy and surface
morphology. However, PE films have disadvantages in it owing to its nonpolar nature. Modification of
the PE surface is necessary to enhance the interaction between PE and other metal foil layers [11–13].
Besides packaging, another major usage of PE film is in the field of agriculture as greenhouse
covers, which provide a favorable environment to increase plant yield [16]. In general, greenhouse
films need to be have as high transmittance as possible for the solar spectrum. Thus, films with low
haze and high transparency are favored. However, in peculiar cases, like in the areas where there is
perennial sunshine with no cloud, the direct incident of natural light (high transmittance) may harm
crops and burn their leaves. Under this condition, films with high haze are required. As a result,
the application of PE films as greenhouse covers require tuning the optical properties depending
on local conditions. Besides the optical properties, the fogging phenomenon is also crucial in the
applications of PE films [17]. Drop-like condensation of water on the film leads to the serious lens effect
and falls onto the plants, creating an appropriate environment for the multiplication of disease [2].
The so-called antifogging films with a hydrophilic surface are demanded in order to change the
condensation shape from drop-like to a water layer, which does not reflect the light and can flow
down gradually [2,18]. However, PE films exhibit limitations for greenhouse coverings because of
their hydrophobic behavior [17,19].
Based on the above descriptions, for the major demands, the modification of optical properties,
adhesion properties, and wettability of PE films is necessary to adapt to the highly increasing
requirements of applications. For the film products, transmittance and haze are the key parameters
used to describe the optical properties. The former (transmittance) is defined as the ratio of total
transmitted light to the incident light, while the latter (haze) is the percentage of transmitted light
that deviates from the directly transmitted beam by more than 2.5◦ [20]. Both the internal structure
and surface roughness can influence the haze, which are referred to as bulk (internal) and surface
haze, respectively [5,21]. Bulk scattering is caused by the fluctuation of the refractive index on the
scale of the light wavelength, which usually results from the formation of the superstructure [5].
The scattering intensity is roughly proportional to the sixth power of the radius, supposing that
spherulitic superstructure is generated [22]. Thus, the haze can be tuned though altering the
superstructures, including adding nucleating agents, changing temperature, and flow field. The other
general way of influencing the optical properties is to reduce the thickness of the film. The thick film
attributes the larger spherulite size, which scatters the light at the large angle and results in the higher
haze value [23]. Lots of studies on the quantified relation between superstructure effect and light
scattering have been carried out [5,6,10,18,24–26] Surface haze arises on account of the existence of
surface asperities on the scale of light wavelength (several hundred of nanometers), which induces the
occurrence of diffuse reflection and refraction. Studies on the blown film surface morphology show that
melt flow behavior and crystallization are two main causes to give rise to the surface roughness [5,6,21].
It has been recognized that the major cause of the high haze is surface haze, which comes from the
surface roughness, while the effects of bulk haze are relatively minor, in the case of single-component
polymer films [5,27].
Various attempts have been made to improve the adhesion properties of PE, such as flame
treatment [28], corona treatment [29], plasma treatment [30], and chemical etching [31], which mainly
focus on the post-modification of PE films [32]. However, many of these techniques are subject to
certain limitations, such as severe conditions, tedious fabrication, expensive reagents, and special
equipment. As to the wettability, hydrophilic additives, such as nonionic surfactants (esters of fatty
acids and glycerine or sorbitan) are used to obtain the antifog films [18]. However, the antifog effect
decays rapidly during the lifetime of the film, as the surfactants are extracted by the condensed water
and usually disappear within two years. New formulations with improved antifog effect quality and
duration are needed.
Polymers 2019, 11, x FOR PEER REVIEW 3 of 13
Polymers 2019, 11, x FOR PEER REVIEW 3 of 13
acids and glycerine or sorbitan) are used to obtain the antifog films [18]. However, the antifog effect
acids rapidly
decays and glycerine
duringor sorbitan)
the lifetime are used
of the to as
film, obtain the antifogare
the surfactants films [18]. However,
extracted the antifog
by the condensed effect
water
decays rapidly during the lifetime of the film, as the surfactants are extracted
and usually disappear within two years. New formulations with improved antifog effect quality and by the condensed water
Polymers 2019, 11, 1565 3 of 13
and usually
duration disappear within two years. New formulations with improved antifog effect quality
are needed. and
duration are needed.
An alternative approach to solving the above concerns is polymer blending, which is a practical
way An An alternative
of making
alternative approach
newapproach
materials toto solving
with
solving the
outstanding
the above
above concerns
properties
concerns is polymer
is[5,6,15].
polymer The blending, which
final properties
blending, which is is a practical
aof blends
practical
way
depend
way of making new
on the individual
of making new materialsmaterials
component with outstanding
properties, as
with outstanding properties [5,6,15].
well as the[5,6,15].
properties composition, The
The final final properties
morphology, ofofblends
propertiesinterphase, blends
depend
and ononthe
processing
depend theindividual
individualcomponent
conditions. component
In the present properties,
work, as
properties, aswell
one well
asasof
kind the
the composition,
ionomer
composition, morphology,
resin morphology,
with interphase,
oxygen-containing
interphase,
and
and processing
polarprocessing
groups, partiallyconditions.
conditions. In
neutralized the present
with the
In the present work,
Na ions
work, + one kind of
was added
one kind ionomer
of ionomerto theresinresin
PE and with oxygen-containing
withfabricate of films by
oxygen-containing
polar
blown
polar groups,
film
groups, partially
extrusion.
partially neutralized
Results
neutralizedshowwith withthe
that theNa
the Na
surface ions
+ +ions wasadded
added
properties
was totothe
heavily the PEand
depend
PE andfabricate
onfabricate ofoffilms
the take-up films byby
ratio
blown
(TUR). film
blown film extrusion.
Withextrusion.
the increase Results
of TUR,
Results show
show that
thethat the
hazethe surface
increases properties
surface monotonically, heavily
properties heavily while depend on the
the transmittance
depend take-up
on the take-up remainsratio
ratio
(TUR).
about
(TUR). the With
Withsame
thethe
at aincrease
large of
increase of
value.
TUR,TUR,
Athethe haze increases
transformation
haze increases from monotonically,
hydrophobicwhile
monotonically, while
to the
hydrophilic
the transmittance
takes place
transmittance remains
with
remains
about
increasingthe same
TUR. at
By a large
blending value.
and A transformation
altering the from
processing hydrophobic
parameters,
about the same at a large value. A transformation from hydrophobic to hydrophilic takes place with to hydrophilic
films with takes
desirable place with
surface
increasing
properties are
increasing TUR.
TUR. By
obtained, blending
By blending whichand and altering
is expected
altering to the processing
theprovide a new
processing parameters,
methodology
parameters, films
films with
forwith desirable
the manufacturing
desirable surfacesurface
of
propertiesare
high-performance
properties are obtained, whichis is
films. which
obtained, expectedtoto
expected provide
provide a new
a new methodology
methodology forfor
thethe manufacturingofof
manufacturing
high-performance
high-performance films.
films.
2. Experimental Section
2.2.Experimental
ExperimentalSection
Section
The whole experimental process is shown in Figure 1.
Thewhole
The wholeexperimental
experimentalprocess
processisisshown
shownininFigure
Figure1.1.

Figure 1.
Figure 1. Schematic
Schematic illustration
illustration ofof the
the preparation
preparation of large-scale polyethylene
of large-scale polyethylene (PE) and ionomer
(PE) and ionomer
Figure 1. Schematicacid
ethylene/methacrylic illustration
(EMAA) of the preparation
copolymer films of tunable
with large-scale polyethylene
surface (PE)
properties: (a) and ionomer
preparation
ethylene/methacrylic acid (EMAA) copolymer films with tunable surface properties: (a) preparation
ofethylene/methacrylic
of PE/EMAA granules
PE/EMAA
acidfilm
granules for
for (EMAA) copolymer
blowing;
film blowing; filmfilms
(b) film
(b)
withapparatus;
blowing
blowing
tunable surface properties:performances,
(c) macroscopic
apparatus; (c) macroscopic (a) preparation
performances,
of PE/EMAA
including surfacegranules for
surface wettability film
wettability and blowing;
and optical (b) film
optical properties.
properties. blowing apparatus; (c) macroscopic performances,
including
including surface wettability and optical properties.
2.1. Materials
2.1. Materials
Polyethylene
Polyethylene (PE) (PE) used
used in this study is a mixture of three different kinds of PE: linear low density
Polyethylene
polyethylenes (PE) used
(LLDPE1, in this study copolymer,
ethylene-octene is a mixture of three different
XUS61530, DOW; kinds of PE: ethylene-butene
LLDPE2,
LLDPE2, linear low density
ethylene-butene
polyethylenes
copolymer,
copolymer, 1001AV, (LLDPE1,
1001AV, ethylene-octene
ExxonMobil)
ExxonMobil) andand
low low copolymer,
density XUS61530,
polyethylene
density (LDPE,DOW;
polyethylene 0725N,LLDPE2,
(LDPE, TASNEE) ethylene-butene
with blending
0725N, TASNEE) with
copolymer,
blending
ratio ratio
of 2:1:1 1001AV,
of The
[33]. ExxonMobil) and
2:1:1ethylene/methacrylic low density
[33]. The ethylene/methacrylic
acid (EMAA) polyethylene
acid (LDPE,
(EMAA)iscopolymer
copolymer 0725N, TASNEE)
is ionomer
ionomer resin with
resin
(Surlyn 1601,
blending
(Surlyn 1601,
DuPont) ratio
withDuPont)of
54% MAA 2:1:1 [33].
with The
54% MAAby
neutralized neutralized+
ethylene/methacrylic
the Na ions.by the
The acid (EMAA)
Nachemical
+ ions. The copolymer
chemical
structure is
ofstructureionomer
of EMAA
EMAA copolymer resin
is (Surlyn
copolymer 1601,
illustratedis in DuPont)
illustrated
Scheme in with 54%
1. Scheme MAA
The basic1. Theneutralized by
basicproperties
physical the Na
physical properties
+ ions. The chemical structure of EMAA
of all these of all these polymers
polymers are listedarein listed
Table in
1.
copolymer
Table
PE/EMAA is illustrated
1. PE/EMAA
blend blend
was in Scheme
was
obtained obtained1. The basic physical
by melt-mixing
by melt-mixing through properties
through
corotating of all these
corotating
twin-screw polymers
twin-screw
extruders arecutting
extruders
and listed
andin
Table
cutting
into 1. PE/EMAA
into
granules. granules. blend was
The PE/EMAA
The PE/EMAA obtained
(90/10, bysample
(90/10,
wt/wt) melt-mixing
wt/wt) was
samplethrough
was in
chosen corotating
chosen twin-screw
in this
this study. study. extruders and
cutting into granules. The PE/EMAA (90/10, wt/wt) sample was chosen in this study.
CH3
CH3
CH2 CH2 C CH2
CH2 CH2 C CH2
C O
- C O
O
-
NaO+
Na+
Scheme 1.
Scheme Chemical structure
1. Chemical structure of
of ethylene/methacrylic
ethylene/methacrylic acid
acid (EMAA)
(EMAA) copolymer
copolymer (Surlyn).
(Surlyn).
Scheme 1. Chemical structure of ethylene/methacrylic acid (EMAA) copolymer (Surlyn).
Polymers 2019, 11, 1565 4 of 13

Table 1. Typical molecular characteristics and rheological properties of polymers.

Formula Density (g/cm3 ) Melt Flow Index (g/10 min) M w (kg/mol) PDI
LLDPE1 0.917 0.8 133 4.2
LLDPE2 0.919 1.0 151 4.9
LDPE 0.923 0.75 109 5.1
EMAA 0.940 1.3 — —

2.2. Film Production

PE/EMAA films with different surface properties were produced by a custom-built film blowing
machine. It was equipped with a screw diameter of 25 mm (L/D = 25) and a die having a diameter of
30 mm with a gap of 1 mm. For the detailed setup of this instrument, refer to our previously reported
literature [33–36]. In this study, a wide range of TUR (from 5 to 30) was adopted, during which,
other processing parameters were kept constant with die temperature (220 ◦ C), blow-up ratio (defined
as the ratio of the bubble diameter to the die diameter, BUR 2), extrusion speed (2.37 mm/s), and air
flux for cooling (as shown in Table 2).

Table 2. The processing parameters of blown films (vt is the taking up speed).

TUR-5 TUR-10 TUR-15 TUR-20 TUR-25 TUR-30

vt (mm/s) 11.9 23.9 35.4 47.3 59.3 71.1
TUR 5 10 15 20 25 30

2.3. Characterization

2.3.1. Contact Angle Measurement

Static water contact angle measurement was carried out by Contact Angle Meter SL200B (Solon Tech.
Co., Ltd.). A drop of ultra-pure water (2 µL) was placed on the prepared film surface using microsyringe
appurtenance and images were captured. The water contact angle was calculated by software CAST
2.0. All measurements were repeated three times.

2.3.2. Haze and Transmittance Measurement

Haze and transmittance were measured with the spherical haze and transmittance meter (SGW-820
Haze-meter, Shanghai INESA Physico-Optical Instrument Co.,Ltd.). All measurements were repeated
three times. During the measurements, the thickness of the films was kept same as the actual film
obtained after the blown film processing at various TURs. The experimental thickness information,
including the theoretical thickness at various TURs, is given at Table S1 and Figure S2.

2.3.3. Atomic Force Microscopy (AFM)

The film surface morphology was characterized by the AFM (Veeco Dimension 3100) with contact
mode. The AFM scan size for surface morphology was 2 × 2 µm2 . All samples were tested directly
without further treatment.

2.3.4. SAXS and WAXS Measurements

SAXS measurements were carried out at an in-house small-angle X-ray scattering system with a
vertical layout. A micro-focus X-ray source (Genix3D Cu, wavelength λ = 1.54 Å) equipped with a
PILATUS 300k detector (487 × 407 pixels with a pixel size of 172 × 172 µm2 ) was employed to collect
the 2D SAXS data. WAXS measurements were performed by an in-house set up with the help of an
image plate detector (Mar 345, 3072 × 3072 pixels with a pixel size of 150 × 150 µm2 ) attached to a
micro Cu Kα X-ray source (Incoatec, GmbH, λ = 1.54 Å). All SAXS and WAXS patterns were collected
within 15 min with a sample-to-detector of 2250 mm and 352 mm, respectively [37,38].
Polymers 2019, 11, 1565 5 of 13

Fit2D software from the European Synchrotron Radiation Facility was used to analyze the
data [39,40]. The 2D SAXS and WAXS patterns were integrated to obtain 1D scattering profiles as a
function of the scattering vector
q = 4π(sin θ)/ λ (1)

where q is the module of scattering vector, 2θ the scattering angle, and λ is the X-ray wavelength.
The crystallinity χc is calculated as follows:
P
Ac
χc = P P × 100% (2)
Ac + Aa

where Ac and Aa are the integrated areas of crystalline and amorphous components, respectively,
which are obtained through the multipeak deconvolution of 1D integrated WAXS curve.
The long period L was calculated from the qmax of the 1D SAXS curves:

2π
L= . (3)
qmax

The orientation parameter of the lamellar stack (f ) was estimated from the full width at half
maximum (FWHM) of the azimuthal-integrated intensity distribution of the 2D SAXS patterns,
according to the following equation:
180 − FWHM
f = (4)
180
where f equals to 1 when all lamellae are perpendicular to the flow direction, while 0 for no preferred
orientation situation.

3. Results and Discussion

Blown films wettability: Figure 2a shows the representative photographs of the water droplets on
different film surfaces at the time of 0 min and 12 min for the all TURs. It could be observed that the
contact area of the droplet increased with the increase of both TUR and time, which reflects increasing
of surface wettability. Figure 2b summarizes the quantitative analysis of the time dependence of the
contact angle θ. The contact angle θ showed a similar tendency, i.e., the monotonic reduction in the
contact angle θ with time and the decreasing rate increasing with the TURs. Within the detection
window (<12 min), PE/EMMA films obtained under TUR < 20 had a final contact angle θ > 90◦ ,
while those obtained under TUR > 20 showed θ < 90◦ . Such a phenomenon should be attributed
to the surface modification introduced by varying TURs. Increasing TUR can significantly increase
the number of the polar functional groups of EMAA on the film surface, since only EMAA contains
hydrophilic carboxylic groups, while PE is strongly hydrophobic. Such a conclusion holds for longer
measurement time, as shown in Figure 2c, where the contact angles of different films were obtained
after 12 min. In all, the surface wettability of PE/EMAA film from moderate hydrophobic to strongly
hydrophilic can be manipulated through varying external processing parameters (TUR).
Polymers 2019, 11, 1565 6 of 13
Polymers 2019, 11, x FOR PEER REVIEW 6 of 13

Figure 2. (a) Photographs of the water droplet on different PE/EMAA film surfaces; (b) contact angle as
Figure 2.of
a function (a)time
Photographs
at variousof theup
take water droplet
ratios on (c)
(TURs); different PE/EMAA
static contact film
angle surfaces;
after 12 min.(b) contact angle
as a function of time at various take up ratios (TURs); (c) static contact angle after 12 min.
Optical property: The optical property of blown film is crucial in agriculture, where haze and
Optical property:
transmittance are two key Themeasurable
optical property of blown
parameters, film is crucial
as mentioned in agriculture,
above [5,6]. The total wherehaze hazeandand
transmittance are two key measurable parameters, as mentioned
transmittance of PE/EMAA blown film at various TURs are shown in Figure 3. The transmittance above [5,6]. The total haze and
transmittance
slightly increased of from
PE/EMAA88% toblown89% with filmthe at various
increase TURsof TUR. areSuch
shown in Figure
a minor change 3. The transmittance
of transmittance
slightly the
suggests increased
TUR does fromnot 88%significantly
to 89% withchange the increase of TUR. Such of
the transmittance a minor
film. change
Considering of transmittance
the haze,
no apparent change was observed for a film with TUR < 15. It increased dramatically with thehaze,
suggests the TUR does not significantly change the transmittance of film. Considering the TURsno
apparent
from 39.53% change
(TUR = was15)observed
to 68.05%for (TURa film with
= 30). ToTURunveil< 15.
theItorigin
increasedof thedramatically with the TURs
different performances of
haze and transmittance as a function of TUR, it is desirable to find key factors determining these twoof
from 39.53% (TUR = 15) to 68.05% (TUR = 30). To unveil the origin of the different performances
haze and transmittance
properties. Huck et al. found as athat
function
the haze of TUR, it is originates
actually desirable to find key
mainly from factors determining
the surface these two
irregularities of
properties.
the films, whereasHuck the et al. found that the
transmittance haze actually
is mainly originates
the function of themainly from the surface
inner crystallinity [21]. irregularities
The almost
of the films,
invariable whereas the suggests
transmittance transmittance is mainly
the inner the function
structure of the innerfilm,
of the PE/EMAA crystallinity [21]. The almost
i.e., crystallinity, may
invariable transmittance suggests the inner structure of the PE/EMAA
remain almost unchanged with variable TURs, which will be further elucidated later. For the haze, film, i.e., crystallinity, may
remain
the dramatic almost unchanged
increase with variable
was closely related toTURs, whichproperties
the surface will be further elucidated
of PE/EMAA, later. Forthe
indicating thelarge
haze,
the dramatic increase was closely related to the surface properties
variation of surface properties, i.e., roughness, induced by variable TURs. There are two possible of PE/EMAA, indicating the large
variation offor
mechanisms surface properties,
the change of haze:i.e., one
roughness, induced by
is the extrusion hazevariable
and the TURs.
otherThere
is theare two possible
crystallization
mechanisms for the change of haze: one is the extrusion haze and the
haze [5]. The former is related to the polymer melt and just exists in relation to the die, whereas the other is the crystallization haze
[5]. The former is related to the polymer melt and just exists in relation
latter is related to the flow-induced crystallization close to the surface. Since only TUR was changed to the die, whereas the latter
is related
during the to the flow-induced
whole crystallization
preparation process, close to the surface.
the crystallization Since be
haze should onlytheTUR was changed
dominant during
mechanism
for the change of haze. Increasing TUR could lead to the strengthening of the flow field, andfor
the whole preparation process, the crystallization haze should be the dominant mechanism the
this
change of haze. Increasing TUR could lead to the strengthening of
could cause different anisotropy of crystal. Besides polymer structure, another important concern is the flow field, and this could cause
different
related anisotropy
to the of crystal.
film thickness. Besides
The polymer structure,
film thickness decreases another
with theimportant
increase of concern
the TUR, is related to the
as shown
film thickness. The film thickness decreases with the increase
in Table S1 and Figure S2. The nonmonotonic dependence of film thickness on TUR suggests the of the TUR, as shown in Table S1 and
Figure S2. The nonmonotonic dependence of film thickness on
complicated nature of PE/EMAA blend film, especially at higher TUR regions (TUR > 20). However, TUR suggests the complicated nature
of PE/EMAA
direct experimental blendevidence
film, especially
tracking at the
higher TUR regions
structural evolution(TUR > 20). film
during However,
blowing direct experimental
is necessary to
clarify such a phenomenon and its relation with the haze, which will be published elsewhere. such a
evidence tracking the structural evolution during film blowing is necessary to clarify
phenomenon and its relation with the haze, which will be published elsewhere.
Polymers 2019, 11, x FOR PEER REVIEW 7 of 13
Polymers 2019, 11, 1565 7 of 13

94 75
Transmittance (%)
70
Haze (%)
92 65
60
90
55
50
88
45

86 40
35
84 30
5 10 15 20 25 30
TUR

Figure 3. Haze and transmittance of PE/EMAA films at various TURs.

Figure 3. Haze and transmittance of PE/EMAA films at various TURs.
From the film wettability and optical properties, it was concluded that: at the lower TURs (5 to
20),From
the filmthesurface
film wettability
properties andareoptical
slightly properties,
changed, it was with
while concluded that: atofthe
the increase TUR lower
up to TURs
25 and(5 to30,
20), the film surface properties are slightly changed, while with the increase
the rapid decrease in the contact angle and sharp increase in the haze are exhibited by the films. Both of of TUR up to 25 and 30,
the rapid
these decreaseare
properties in closely
the contact angle
related andsurface
to the sharp increase
properties, in the
i.e.,haze areroughness
surface exhibited by andthe films. Bothof
distribution
ofpolar
these properties
functional are and
groups, closelyinnerrelated to the i.e.,
film structure, surface properties,
crystallinity i.e., surface
and crystal orientation.roughness and
The detailed
distribution of polar functional groups, and inner film structure,
characterization of the surface properties was accomplished based on the XPS and AFM, and that of i.e., crystallinity and crystal
orientation. The detailed
the inner structure was by characterization
WAXS and SAXS. of the surface properties was accomplished based on the
XPS and AFM, and
Chemical that of the
composition ofinner
blownstructure
film surface:was by X-rayWAXS and SAXS.spectroscopy (XPS) is one of the
photoelectron
most Chemical
suitable composition
techniques for ofthe
blown
filmfilm surface:
surface X-ray photoelectron analysis,
composition/enrichment spectroscopy
which(XPS) is one ofin
is quantified
the most
terms suitable
of peak techniques
position and peakfor the film
intensity. The surface
peak positioncomposition/enrichment
contains characteristicanalysis,features of which is
different
quantified in terms of peak position and peak intensity. The peak position
atoms in different states, and corresponding peak intensities are proportional to their quantities. As a contains characteristic
features
result, XPSof different atomsthe
can quantify in different
elemental states, and corresponding
composition of the film peaksurface.intensities
Figure are proportional
4a presents the XPSto
their
whole quantities. As a result,
survey results, XPS can
including the quantify
enlarged the O1selemental
lineshapecomposition
of PE/EMAAoffilms the film
obtainedsurface. Figure
at different
4aTURs.
presents Two thesharp
XPS whole
peaks weresurvey results, including
observed at the binding the enlarged
energiesOof 1s lineshape
289–290 eV of andPE/EMAA531.5–533 films eV,
obtained
which were at different
assignedTURs.to C1sTwo sharp
lattice andpeaks were observed
O1s , respectively [41].atNo theapparent
binding peak energiesshiftofwas 289–290
observedeV
and
for531.5–533
C1s (289–290 eV, which were S3).
eV, Figure assigned
For O to1sC(531.5–533
1s lattice and O1sincreasing
ev), , respectively TUR [41]. Notoapparent
led the transitionpeak shift
from
was observed
singlet to doublet for C1s
peak,(289–290
whereaseV, Figure
further S3). ForTUR
increasing O1s resulted
(531.5–533 ev),emergence
in the increasing of TUR led to peak.
the doublet the
transition
As mentioned from above,
singlet only
to doublet
EMAApeak, containswhereas further
the polar increasing
functional TUR resulted ingroup.
group—carboxylic the emergence
The binding of
the doublet peak. As mentioned above, only EMAA contains the polar
energy of O1s for a single C–O bond falls in the binding energy of 531.5–532 eV, whereas that of the functional group—carboxylic
group.
doubleThe binding
carbonyl energy
organic of OC=O
bond 1s for lies
a single
in theC–Orange bond falls in eV.
of 532–533 the [42].
binding energysuch
Therefore, of 531.5–532
doublet peak eV,
whereas
could bethat of the double
attributed to the carbonyl
coexistence organic bond
of single andC=O lies inbonds
double the range
on the of 532–533 eV. [42].
film surface. The Therefore,
intensity of
such
O1s isdoublet peak could
proportional to thebe attributed to
concentration of the
EMAAcoexistence of single
on the surface. Theand double
counts bonds oncarboxylic
of functional the film
surface.
groupsThe were intensity
calculated of Ofrom
1s is proportional
the area under to the
the peak
concentration
O1s . Figure of EMAA
4b shows onthe
the atomic
surface.concentration
The counts
ofoffunctional
O1s contents. carboxylic
It shows groupsthat were
the Ocalculated
1s count from
remained the area
almost under the
constant peak O
within .
1slow Figure
TURs 4b(5shows
to 20),
the
butatomic
increasedconcentration
dramatically of O 1s contents.
for film obtained It shows
at TURthat=the 30.OThis
1s count remained
suggests morealmost
functional constant
polarwithin
groups
low
(–COOTURs − ) appear
(5 to 20), onbutthe increased
surface at dramatically
the high flowfor film obtained at TUR = 30. This suggests more
condition.
functional polar groups (–COO−) appear on the surface at the high flow condition.
 Polymers
Polymers 2019,
2019, 11,
11, 11, x FOR
x FOR PEER
PEER REVIEW
REVIEW 8 of 13 88 of 13
Polymers 2019, 1565 of 13

Figure
Figure (a) Surface
4. Surface
4. (a) composition
composition survey
survey by scans
by XPS XPS scans at various
at various TURs;
TURs;TURs; (b) calculation
(b) calculation of percentage
of percentage
Figure
atomic 4. (a) Surface
concentration composition
of functionalsurvey
group by
by XPS
O scans
peaks.at various (b) calculation of percentage
1s
atomic concentration of functional group by O1s peaks.
atomic concentration of functional group by O1s peaks.
Surface
Surface roughness
roughness of blown
of blown film:film:
The The atomic
atomic forceforce microscopy
microscopy (AFM) (AFM) was used
was used to analyze
to analyze
Surface
surface film roughness
texture and of blown film:
roughness of The
the atomic force
PE/EMAA blown microscopy
films. Figure(AFM) 5 was used
shows the to analyze
topographic
surface film texture and roughness of the PE/EMAA blown films. Figure 5 shows the topographic
surface
images film
of texture and
PE/EMAA films roughness
obtained of the different
under PE/EMAA blown
TURs. films. Figure
Generally, all AFM 5 shows the topographic
images of PE/EMAA films obtained under different TURs. Generally, all AFM heightheight
imagesimages
showed showed
images
irregular of PE/EMAA
surface films
morphology, obtained
and under
with different
increasing TURs.
TUR, Generally,
more irregular all AFM
stackedheight images
domains showed
appeared
irregular surface morphology, and with increasing TUR, more irregular stacked domains appeared
irregular
above surface morphology, and difference
with increasing the TUR, more irregular stacked domains appeared
above thethe surface.
surface. TheThe orientation
orientation difference of the oflamellaelamellae
on the onsurface
the surface
obtainedobtained
underunder different
different
above
TURs the
could surface.
also The orientation difference of the lamellae on the surface obtained under different
TURs could also be be observed
observed in the
in the AFM AFM phasephase images
images (Figure
(Figure S1). quantitative
S1). The The quantitative analysis
analysis of the of the
AFMTURs
AFM couldresulted
images
images also bein
resulted observed
in the
the in the
surface
surface AFM phase
roughness
roughness (Ra),(Rimages
asa ),
(Figure
as shown
shown inS1).
in Figure 6.The
Figure The quantitative
6. analysis
The roughness
roughness of the
increased
increased
AFM imageswith
monotonically
monotonically resulted
with
thethe in TUR,
TUR,theand
surface
and roughness
changed
changed (Rat
abruptly
abruptly a), as shown in Figure 6. The roughness increased
= 30=(R30
at TUR
TUR a =(R43a = 43 nm).
nm). The almost
The almost doubledouble
monotonically
increase
increase in in
surface with
surface the TUR,
roughness
roughness and changed
indicates
indicates abruptly
the significant
the significant at TUR =
modification
modification 30 (R a = 43 nm). The almost double
of surface
of surface inducedinduced
by TUR.by The
TUR. The
increase
film texture,
film ini.e.,
texture, surface roughness
crystal
i.e., crystalmorphology indicates
morphology andand thelamellar
significant
lamellar orientation,modification ofclearly
is notisclearly
orientation, not surface induced
characterized byby
characterized TUR.
AFM, The
by AFM,
film is
which
which texture,
later i.e., crystal morphology
characterized
is later characterized by X-ray
by X-ray and lamellar orientation, is not clearly characterized by AFM,
scattering.
scattering.
which is later characterized by X-ray scattering.

Figure 5. AFM height images of PE/EMAA films obtained at various TURs.

Figure 5. AFM height images of PE/EMAA films obtained at various TURs.

Figure 5. AFM height images of PE/EMAA films obtained at various TURs.

 Polymers 2019, 11, x FOR PEER REVIEW 9 of 13
Polymers 2019, 11, 1565 9 of 13

Figure 6. The surface roughness Ra of different PE/EMAA films as characterized by AFM.

Figure 6. The surface roughness Ra of different PE/EMAA films as characterized by AFM.
Above crystal surface characterization results have shown that increasing TUR can increase
the quantity
Above of polarsurface
crystal functional groups and results
characterization surfacehave roughness.
shown that The increasing
decreasingTUR contact
can angle
increasewas the
well consistent
quantity of polarwithfunctional
the increase of carboxylic
groups and surface groups on theThe
roughness. surface. With respect
decreasing contact to the was
angle optical
well
properties,
consistentthe withhazethewas initially
increase thought togroups
of carboxylic result from
on thethe coupling
surface. With influence
respect of surface
to the composition
optical properties,
and texture morphology. Since the haze increases continuously
the haze was initially thought to result from the coupling influence of surface compositionwith the increase of TUR, whereas bothand
the concentration of carboxylic groups and surface roughness remains
texture morphology. Since the haze increases continuously with the increase of TUR, whereas both almost constant with TUR < 25,
it the
suggests that the haze
concentration of final polymer
of carboxylic groups films
andare not solely
surface determined
roughness remains by the surface
almost composition
constant with TUR and <
surface
25, it roughness.
suggests that Another
the hazepossible of origin is the orientation
final polymer films are of the
notcrystal
solelylamellae,
determined as discussed
by the below.
surface
Internal hierarchical structure: The internal structure of the
composition and surface roughness. Another possible origin is the orientation of the crystalPE/EMAA films at various TURs were
lamellae,
characterized by
as discussed below. ex situ WAXS and SAXS, as shown in Figure 7. The PE/EMAA films exhibited two
sharp peaks at 2θ
Internal = 21.6 andstructure:
hierarchical
◦ ◦
24.08 , corresponding
The internal to (110) and
structure of(200) crystal planes
the PE/EMAA films of polyethylene
at various TURs in
orthorhombic structure, respectively (Figure 7a). The WAXS scattering
were characterized by ex situ WAXS and SAXS, as shown in Figure 7. The PE/EMAA films exhibited ring first appeared for film
obtained
two sharp at TURpeaks= 5,at which
2θ =indicates
21.6° and the 24.08°,
randomly distributed lamellae.
corresponding to (110) Further
and (200) increase
crystalof TUR
planes ledof
topolyethylene
the four-spotin patterns along the machine direction (MD). This suggests
orthorhombic structure, respectively (Figure 7a). The WAXS scattering ring first highly oriented crystal is
formed under the strong flow field [43–45]. Such transition from low
appeared for film obtained at TUR = 5, which indicates the randomly distributed lamellae. Further anisotropy to high orientation
was further
increase of confirmed
TUR led to by thethe 2D SAXS
four-spot patterns,
patterns along asthe
shown
machine in Figure
direction7b. (MD).
Quantitative analysis
This suggests of
highly
the WAXS and SAXS patterns was accomplished based on the 1D integrated
oriented crystal is formed under the strong flow field [43,44,45]. Such transition from low anisotropy curves, as shown in
Figure
to high 7c,d. The lamellar
orientation wasthicknesses L and crystal
further confirmed by orientations
the 2D SAXS f ofpatterns,
differentas films
showncan be incalculated
Figure 7b.
based on the q max and anisotropy calculation in 1D SAXS curves
Quantitative analysis of the WAXS and SAXS patterns was accomplished based on the 1D integrated (eq. 2–3), while the crystallinity χc
can be obtained through the multi-peak deconvolution of 1D WAXS curves
curves, as shown in Figure 7c and 7d. The lamellar thicknesses L and crystal orientations f of different (eq. 1). As summarized in
Figure
films 7e,
canthe
becrystallinity
calculated based (χc ) increased
on the qnegligibly from 32.8% to 33.9%, so too did the long period L
max and anisotropy calculation in 1D SAXS curves (eq. 2–3),
slightly decrease from 19 to 18 nm. However,
while the crystallinity χc can be obtained through the multi-peak the crystal orientationdeconvolution
(f ) increased monotonically
of 1D WAXS curves with
increasing TUR from 0.58 to 0.75. Such moderate increase of the crystallinity
(eq. 1). As summarized in Figure 7e, the crystallinity (χc) increased negligibly from 32.8% to 33.9%, should be attributed to the
coupling
so too didinfluence
the long of both
period external flowdecrease
L slightly field andfrom the temperature
19 to 18 nm.gradient.
However, Although
the crystalstrong flow field(f)
orientation
favors
increased monotonically with increasing TUR from 0.58 to 0.75. Such moderate increasedown
the formation of oriented crystals, the faster cooling rate will also happen, which slows of the
the crystallization rate. Considering the minor change of the transmittance
crystallinity should be attributed to the coupling influence of both external flow field and the and the significant increase
oftemperature
the haze withgradient.
increasing TUR, it can
Although be concluded
strong flow field that favorsthethe
transmittance
formation of is oriented
mainly determined
crystals, the byfaster
the
crystallinity and crystal orientation, whereas the haze is significantly
cooling rate will also happen, which slows down the crystallization rate. Considering the minor influenced by crystal orientation.
change of the transmittance and the significant increase of the haze with increasing TUR, it can be
concluded that the transmittance is mainly determined by the crystallinity and crystal orientation,
whereas the haze is significantly influenced by crystal orientation.
Polymers 2019, 11, x FOR PEER REVIEW 10 of 13
Polymers 2019, 11, 1565 10 of 13

Figure 7. (a)
Figure (a)Ex
Exsitu
situ2D2DWAXS
WAXSdiffraction
diffractionimages;
images;(b)(b)
2D-SAXS
2D-SAXS scattering patterns,
scattering the machine
patterns, the machine
direction (MD) is horizontal;
direction horizontal; (c)
(c) the
the 1D
1D integrated
integratedSAXS
SAXScurves;
curves;(d)
(d)1D
1Dintegrated
integratedWAXS
WAXScurves;
curves;(e)
(e) the
crystallinity χc (%), orientation factor f, and long period L (nm) calculated from the WAXS and SAXS
the crystallinity χ c (%), orientation factor f, and long period L (nm) calculated from the WAXS and
SAXS
1D 1D curves,
curves, respectively,
respectively, at various
at various TURs. TURs.

4.
4. Conclusions
Conclusions
In this article,
article, the
the PE/EMAA
PE/EMAAfilms filmswithwithtunable
tunable surface
surface properties
properties were were prepared
prepared through
through
manipulating the
manipulating the processing
processingparameter
parameter(TUR) (TUR) during
during film
filmblowing.
blowing.TheThe
filmfilm
surface exhibited
surface strong
exhibited strong
hydrophilic behavior (contact angle = ca. 45 ) and higher optical haze (60%) at the higher taking up
hydrophilic behavior (contact angle = ca. 45°) ◦
and higher optical haze (60%) at the higher taking up
ratios. The
ratios. The inner
innerstructure
structureofoffilm
filminfluenced
influenced slightly onon
slightly thethe
total haze
total (supporting
haze (supporting previous studies).
previous studies).
The super-spherulitic
The super-spheruliticstructure
structurenear
neartotothethe film
film surface
surface waswas the major
the major contributor
contributor to thetolarge
the scattering
large
scattering
from from
the film the film
surface surface roughness,
roughness, which further whichincreased
further increased
total hazetotal haze at TURs.
at higher higher The
TURs. The
roughness
roughness was caused by the EMAA enrichment on the surface, which helped
was caused by the EMAA enrichment on the surface, which helped to increase the film hydrophilicity to increase the film
hydrophilicity
effectively. Theeffectively.
current study Theprovides
current study provides method
an alternative an alternative method
to one-step to one-step
prepare prepare
large-scale PE film
large-scale PE film with polar functional groups and can be used as a template for advanced film
with polar functional groups and can be used as a template for advanced film capable of application in
capable of application in various fields, i.e., agriculture and private stuff packaging.
various fields, i.e., agriculture and private stuff packaging.
Supplementary Materials: The following are available online at www.mdpi.com/xxx/s1, Figure S1: AFM phase
Supplementary
images of PE-EMAA Materials: The following
film obtained areTURs,
at different available online
Figure at http://www.mdpi.com/2073-4360/11/10/1565/s1,
S2: Film thickness vs. the inverse of TUR, Figure S3
Figure S1: AFM phase images of PE-EMAA film obtained at different TURs, Figure S2: Film thickness vs.
XPS C1s lineshape at various TURs. Table S1. Film Thickness of PE-EMAA films obtained under different TURs.
the inverse of TUR, Figure S3 XPS C1s lineshape at various TURs. Table S1. Film Thickness of PE-EMAA films
obtained under different
Acknowledgments: TURs.is supported by the National Key R&D program of China (2016YFB0302500), the
This work
Fundamental
Author Research Funds
Contributions: for the Central
Data curation, S.A. andUniversities (Grants WK2310000079),
Y.J.; formal analysis, Q.Z., H.Z., D.W.,and
andthe National
L.M.; fundingNatural
acquisition,
Science
L.L.; Foundation of China
writing—original draft,(51703217). We are very grateful
S.A.; writing—review to Mr.
and editing, Lihui Wu from NSRL (Hefei) for providing
W.C.
a facility for the XPS measurements. We are thankful to CAS-TWAS for their contribution to the outstanding
Funding: The Fundamental Research Funds for the Central Universities: WK2310000079, the National Key R&D
students of underdeveloped countries.
program of China: 2016YFB0302500, the National Natural Science Foundation of China: 51703217.
Author Contributions:
Acknowledgments: Data
This curation,
work Sarmad Ali
is supported byand
theYouxin Ji; formal
National analysis,
Key R&D QianleiofZhang,
program ChinaHaoyuan Zhao,
(2016YFB0302500),
Daoliang
the Wang, and
Fundamental Lingpu
Research Meng;
Funds for funding acquisition,
the Central Liangbin
Universities (Grants Li;WK2310000079),
writing—originaland draft, Sarmad Ali;
the National Natural
writing—review
Science Foundationand of
editing,
ChinaWei Chen.
(51703217). We are very grateful to Lihui Wu from NSRL (Hefei) for providing
a facility for the XPS measurements. We are thankful to CAS-TWAS for their contribution to the outstanding
Funding:of
students the Fundamental Research
underdeveloped Funds for the Central Universities : WK2310000079, the National Key R&D
countries.
program of China : 2016YFB0302500, the National Natural Science Foundation of China: 51703217.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2019, 11, 1565 11 of 13

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