PES-24-0290.R2 - Proof - Hi - Accepted Paper - 19-10-2024

Polymer Engineering & Science
Pattern of surface energy (tension) change after coating /

printing on a pretreated (LD/LLDPE) co-extruded plastic
film surface and its consequences on lamination and
overprinting
Journal: Polymer Engineering & Science
Manuscript ID PES-24-0290.R2
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Wiley - Manuscript type: Research Article
Date Submitted by the

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10-Oct-2024
Author:
Complete List of Authors: Das, Bidhan; Indian Institute of Packaging, Training and Education
Department, Kolkata Centre
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Chakrabarty, Debabrata; University of Calcutta - Rajabazar Science

College Campus
Mukherjee, Avik; Jadavpur University
Guha, Chandan; Jadavpur University
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Bose, Saswata; Jadavpur University
Keywords: surfaces, adhesion, coatings

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Copyright: Yes
Keywords:
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Page 1 of 39 Polymer Engineering & Science
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Polymer Engineering & Science Page 2 of 39
Pattern of surface energy (tension) change after coating / printing on a pretreated

(LD/LLDPE) co-extruded plastic film surface and its consequences on lamination and
overprinting
Bidhan Das 1, Debabrata Chakrabarty2, Avik Mukherjee3, Chandan Guha3, Saswata Bose3 *
1 Training and Education Department, Kolkata Centre, Indian Institute of Packaging, Kolkata, India
2 Department of Polymer Science and Technology, University of Calcutta, Kolkata, India
3 Chemical Engineering Department, Jadavpur University, Kolkata, India
Correspondence Author: Dr. Saswata Bose, Chemical Engineering Department, Jadavpur University,
188, Raja SC Mullick Road, Kolkata 700032, India.
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Corresponding Author:
Dr. Saswata Bose
Email: saswata.bose@jadavpuruniversity.in, saswataboseiit@gmail.com
Phone: +913324572311
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Abstract: This study embodies the characterization of corona-treated co-extruded transparent

polyethylene films at different voltages after printing with five different colors in order to inspect
whether variations in surface polarities have any influence on the behavior of the ink coatings. The
variation in the coating weights of the differently colored inks’ were studied as a function of
surface energies of the films and found to lie within the range of 0.925–2.7 g/m2 (GSM),
irrespective of surface energies of the films. The surface energies of the respective ink coatings
were also determined separately, which were then compared with the surface energies of the
corona treated co-extruded plastic films under study. Additionally, the force of adhesion of the ink
films over the treated film, at any particular wattage was determined, which varied as white
>magenta>cyan>yellow>black. Other surface characteristics of the ink coatings, such as contact
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angle, coefficient of friction, scuff resistance, were also investigated. The barrier properties,
mechanical and ageing characteristics of the ink coated treated plastics films were found not to get
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impacted upon much by the influence of coating on their surfaces.

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Highlights:
� Subsequent Processing like lamination and overprinting
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� Corona Pre-treatment LD/LLDPE co-extruded film

� Scuffing characteristics of the printed (with different coloured inks) pre-treated (corona)
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LD/LLDPE films
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� Interlocking through its chemisorptive/ adsorptive forces

� For all colored films, the kinetic C.OF. suffered a small increase with surface treatment
level.
Keywords: Rotogravure printing; anilox; printability; coating weight; surface energy; scotch
adhesion; ink bond strength.
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1. Introduction:
Substrates, most commonly used in manufacturing flexible packaging materials include
polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) and polyethylene terephthalate
(PET). All these are characterized by their chemical structures and surface energies.[1,2] All these
substrates suffer from the problem of low wettability properties.[3]Wetting and adhesion of inks,
coatings etc. on any film surface are associated with the nature of the substrates and the
phenomenon of surface energy or surface tension.[4] Polyethylene (PE), Polypropylene (PP),
Polyester (PET), Polyvinyl chloride (PVC) are the most versatile and most commonly used in
manufacturing different flexible packaging specifications to meet the properties required thereof.
Each film is characterized by their surface energies besides their unique chemical structures.[5,6]
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Polyethylene (LDPE/LLDPE) as a substrate remains the most widely used plastic by volume
accounting for about 67% of overall flexible packaging material, now available in the market;
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followed by biaxially oriented polypropylene (BOPP) along with biaxially oriented polyethylene
terephthalate (BOPET) as shown in figure-1. Moreover, LD/LLDPE coextruded film which
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happens to be the most common structural fabrication employed in various flexible packaging
industries.
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Figure-1: Percentages of different plastics used in flexible packaging.
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The widespread versatility of LDPE/LLDPE film lies in the fact that it is non-polar, inert to most
of the packed item, can be readily sealed at a relatively lower temperature compared to other
majority film, has good barrier properties, low C.O.F. and can be used both as a mono layer and
in a composite multilayered structure both as a sealant layer and has a tie-layer.
The most common as well as the greatest drawback of these substrates is their low wettability
properties. Interactions between the surface of the solid plastic film surface, the liquid elements
(i.e. inks, overprint varnishes, adhesives) and the resultant of surface treatments are dictated by the
surface energy of the substrates and the surface tension of the liquids.[7] Printability is the main
factor that controls high quality colour reproduction, increase ink gloss, uniform appearance
without exhibiting any print defects.[8] In order to ensure good printability, the surface energy of
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the substrate and surface tension of the ink, varnish or lacquer should be at compatible levels. The
surface tension of the inks must be lower than (by at least 10 mJ/m2) the wetting tension of the
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substrates to attain good printability, adhesion or ink lay down.[8,9,10]

The Gravure process of printing/lacquering/varnishing is most commonly used in flexible
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packaging industries and the liquid gravure inks used for this purpose are formulated in such a
manner that the inks getting released from the gravure cells properly wet the substrate, release the
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solvent very fast and on drying gives a very good scotch adhesion. The most important and critical
parameters controlling the print quality include ink chemistry, nature of the substrate, surface
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treatment and ink transfer method.[11,12,13]

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The conventional gravure printing inks suitable for a particular substrate mostly consist of a
suitable binder (that binds the dried ink film on the surface), solvent or vehicle (that carries the
solid constituents including binding resin) and colorant (the pigment that gives the desired colour)
and other special additives (if required at all). The types of resin and solvent mostly control the
surface tension of the liquid medium and the pigments are considered to have very little influence
on it.
In the present work, pre-treated LD/LLDPE coextruded film, which happens to be the most
common structural fabrication employed in various flexible packaging industries, (the treatment
levels being varied by applying different voltages) have been coated with liquid gravure inks of
different colours (different pigment being used, the other formulation remaining the same) with
gravure cylinder having a screen size of 150 lines/cm in a commercial gravure printing machine
and thoroughly dried by passing the coated film through a drying tunnel. The film thickness was
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75µm and consisted of three layers. The structure of the film and the blend compositions present
in the individual layers along with the characteristics of polyolefin granules used in this experiment
are furnished in Table-1.
Table-1: Details of composition of the co-extruded film.

Composition
Layer Nature of Mixing MFI Density Slip
Grade Supplier
Polyethylene Ratio
Octane Reliance
LLDPE 0.90 0.918 √
O21010 (India)
Exxon
Exceed 1018 Metallocene
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Mobil 1.00 0.918 √
JA LLDPE 25:25:8
(Singapore)
1st Layer =3:3:1
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SABIC
(Sealant Layer) Sabic
(Saudi LDPE 0.30 0.923 √
HP 0323N
Arab)
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Octane Reliance
LLDPE 0.90 0.918 ×
O19010 (India)
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2nd Layer Butene Reliance

LLDPE 25:25:8 0.90 0.918 ×
(Middle Layer) F19010 (India)
=3:3:1
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Relene Reliance
LDPE 0.50 0.920 ×
1005FY20 (India)
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Exxon
Exceed 1018 Mobil
3rd Layer LLDPE 1.00 0.918 ×
KA (Singapore)
(Corona Treated 25:25
Layer) =3:3
Relene Reliance
LDPE 0.50 0.920 ×
1005FY20 (India)
The film was exposed to corona treatment in line with the co-extruder during its fabrication. The
wattage applied in the corona treater was varied to have different levels of surface treatment and
all these films with different surface polarities were characterized in one of our earlier works.[11]
In an endeavour to find how the inks of different colours interact with the polyolefinic surfaces
with different surface charges and how the polarity of the new surfaces (the inked surfaces) thus
created behave in turn during its subsequent processing as required and demanded by the
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necessities of suitable packaging specification, the present study has been undertaken. The
different packaging films now in commercial use consist of monolayer and multilayers. In case of
monolayer the single plastic film must have the dual characteristics of good integrated pilfer proof
sealing and at the same time good printability. After packing the product, the printed (inked)
surface should have reasonably good surface polarity so as to provide the necessary anchorage
towards the batch printing ink.
In case of multilayer specification, the printed or inked surface must have the necessary charges
or polarity so that there becomes no problem during application of adhesive (proper wetting and
spreading are required here again) and subsequent lamination to the other substrates.
All these are being carried out in the concerned industries in a haphazard manner and in a non-
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scientific manner such that they face various types of problem very frequently and tackle the issues
by “Hit and Miss” policy for the moment itself. Here we have tried to articulate a scientific
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document, the main purpose of which would enable the concerned industries to analyze the issues
quite meticulously in a scientific manner. From the survey of literature, it has been observed that
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no such works have yet been initiated till date. Our aim is thus to provide the flexible packaging
and laminating industries a hassle free, easy and smooth day to day operation.
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2. Experimentation and measurements:

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75µm co-extruded transparent polyethylene film consisting of three layers of identical thicknesses
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was fabricated from a blend of low density polyethylene (LDPE) and linear low density
polyethylene (LLDPE). Both polymers contained EURECAMIDE (an amide compound) slip
additive specifically in the first layer (the layer in direct contact with food or contents). The sealant
layer or the first layer should be the inside layer of the bubble during the fabrication by the
extrusion blown film technique. The outermost layer of the bubble is absolutely devoid of any slip
additive, an essential requirement for the treatment process. The films were blown in a co-extruder
with a blow–up ratio of 2.78:1, the die size of 300 mm and nip gap of 2.2 mm. The line speed of
the extruder was 13.1 m / min and screw rotation were maintained at 80 rpm. All the three screws
had O.D. of 55mm.
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2.1 Corona treatment:

It has been discussed in great detail the necessity of corona treatment on the Polyolefinic
hydrocarbonaceous plastic films like LDPE, LLDPE and PP in particular in our earlier works.[11,12]
In this non-thermal plasma process[14,15] the plastic film is allowed to pass through the corona
discharge unit consisting of a high frequency generator, a high voltage source, a fixed electrode
that produces high voltage electricity and a cylindrical insulator roller opposite, the electrode being
connected to electric supply having high voltage and high frequency.[15] Electric discharge in the
form of blue sparks is emitted by this electrode accompanied by an ozone emission. During this
process energy is released to the film surface via the electrode system as the film passes over the
roller under the fixed electrode where it is subjected to electron bombardment. Oxygen atoms in
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the air gap between the film and the electrode are activated under high voltage and produces polar
groups on the plastic surface. Polar groups in the form of hydroxyl, carboxylic acid, ketone, epoxy,
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ester, peroxide etc. groups are formed on the surface.[8,14] It would be worth mentioning here that
higher corona intensity than needed is much more trouble as lower corona intensity than required.
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The excessive corona application can damage the film surface or surface coating.
In the present study different levels of polarity (surface energies) have been imparted to the plastic
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films by varying the applied voltages in order to find the optimum level of treatment necessary for
anchorage of the conventional printing inks. The wattages consumed (kW) and the corresponding
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surface energies available on the surfaces of the LD/LLDPE film are shown in Table-2. The
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determination of surface energies of the treated films was carried out by following procedures
outlined in our previous work.[11]
Table-2: Study the effect of applied Voltage on Surface Energy/Corona Treatment level for different
colors of ink coated Polyethylene films
Applied Load on PE film (kW) Colour of Ink Surface energy after printing
(dynes/cm)
Yellow 34
Magenta 32
36 Cyan 32
Black 32
White 32
Yellow 34
Magenta 32
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38 Cyan 32
Black 32
White 32
Yellow 34
Magenta 32
40 Cyan 32
Black 32
White 32
Yellow 34
Magenta 32
42 Cyan 32
Black 32
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White 32
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2.2 Printing inks and the process of printing:

Liquid gravure inks (details of which have been listed in Table-3) exclusively suitable for printing
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on the surface of corona treated co-extruded Polyethylene films (LD/LLDPE) were procured from
M/S. Sakata Inx (India) Private Limited. Three primary colour of inks (namely Yellow, Magenta
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and Cyan) and two secondary ink (black and white) were selected in order to investigate the
influence of pigments (if any) on the adhesion characteristics of the dried ink film after getting
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suitably printed. The inks were of low viscosity (15-18sec) such that it can enter and fill the cells
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of the gravure cylinder very fast and at the same time possessing the unique characteristic of being
released very quickly while in contact with the web of film under nip pressure and leave behind a
thoroughly dried uniform ink film over the plastic surface after passing through the drying tunnel
maintained at a temperature of 80-95 ºC by blowing hot air current through the tunnel. The inks
were all identical excepting the colour (pigment) having the same medium and other additives.
The solvents play a great role in preparing the inks and in diluting the inks to achieve the required
low viscosity, an essential parameter of gravure inks. However, it is an added advantage that the
organic solvents employed for the purpose of gravure inks have very low surface tension which
help in wetting and spreading of the ink over the plastic surface.
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Table-3: Details of Printing inks* used:

*All inks used were procured from Sakata Inx (India) Private Limited
Sl. Name of Ink Batch No Manufacturing Code Solid Content (%)

No. Date Tolerances (±2%)
01 Magenta 0001174394 13.05.2023 Geranium – 350, PR-1 26.7
(Red)
02 Cyan (Blue) 0001152667 27-02-2023 ARSR Blue 800 27.7
03 Yellow 0001183594 04-06-2023 ARSR Yellow 238 26.6
04 Black 0001145335 08-02-2023 ARSR 231000 33.9
05 White 0001176309 17.05.2023 ARSR White 102 - II- 48.9

P022
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2.3. Characterization of the printed surface:

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2.3.1 Measurement of coating weight:

Three samples, two from edges and one at the centre were collected from each inked (mother) film
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sample with the help of a template of specified dimension (10cm x 5cm). The sample was weighed
in a digital balance which can weigh up to four decimal places. The ink film was then removed
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from the surface of the plastic film with the help of a cotton flock soaked in suitable solvent and
rubbing it over the inked surface. Once the ink is completely removed, the sample is thoroughly
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dried in an oven maintained at a temperature of 105 0C and weighed further after cooling the
sample to the room temperature. The difference between the two weights gives the coating weight
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of the ink film over the area of the template used for cutting the sample. This was then expressed
in GSM or grams per square meter which is the conventional practice in industries. A gravure
cylinder or annilox is etched in a manner so as to maintain the uniformity of coating throughout
the entire web. The variation of coating weights available with different inks (same annilox or
cylinder, same printing machine under identical physical conditions) as a function of applied load
has been presented later under the section 3.1.
2.3.2 Determination of surface energy of the bare corona treated LDPE/LLDPE film after
printing with inks of different colours:
The surface energies of the corona treated (at different voltages or applied loads) films after
printing with different colors have been determined by following the standard procedure as
outlined in ASTM D 2578–67 [16] using dyne solutions prepared by mixing ethyl cellosolve and
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formamide in different proportions. The same has been described in our earlier works.[11,12] The
results are given in Table-4.
Table-4: Details of characteristics of Printing inks used:
Avg.
Treatment Level Surface
Contact Images Obtained
Film Details before printing Energy Color of Ink
Angle From Goniometer
(kW) (Dyne/cm)
(°)
Yellow 43.7
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Magenta 42.4
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Cyan 42.8
3.0 kW 36
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Black 44
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Transparent PE
film
White 41.4
Yellow 38.4
4.0 kW 40
Magenta 35.6
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Cyan 36.6
Black 43.6
White 32.4
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Yellow 40.2
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Magenta 38.4
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4.5 kW 42
Cyan 38.8
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Black 47.2
2.3.3. Ink bond strength by scotch adhesion test:

A scotch tape, 15mm in width from M/S. 3M India Limited was pressed strongly by the thumb
over the surface of the ink film so that it adheres properly with the ink film. Now the force required
(gmf/15mm) necessary to separate the tape (peel adhesion) is measured in an UTM (universal
tensile testing machine). This gives a measure of the work of adhesion of the ink film on the surface
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of corona treated film. The greater the force required to peel the tape the greater is the force with
which the treated surface pulls the ink film towards it.
2.3.4. Contact angle measurement over the ink surface:
The contact angle with deionized water on the inked surface of the LDPE/LLDPE co-extruded
film was measured and compared to the same parameters on the surface of bare film before printing
with the help of a goniometer. In this connection the values available on a printing surface of a
Nitrogen Plasma treated film was also compared to that of an unprinted plasma treated film sample.
2.3.5. Roughness (coefficient of friction):
The procedure outlined in ASTM D 1894–14[17] was followed for the determination of coefficient
of friction. Both static and kinetic coefficient of friction were evaluated on the ink surface of the
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printed films and compared to those of unprinted film samples.

2.3.6. Mechanical properties:
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ASTM D 882 was followed for the determination of elastic modulus, yield stress, % elongation at
break (%EB), peak stress and tensile energy absorption (TEA) of the printed (overall inked or
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printed) LDPE/ LLDPE co extruded films. The Tear resistance (Greaves Tear) and the Dart impact
of the printed samples were investigated following ASTM D 1004 and ASTM D 1709
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respectively.[18,19]
2.3.7. Barrier properties of the printed film:
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Water vapor transmission rate (WVTR) and Oxygen transmission rate (OTR) of the printed films
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were investigated so as to determine whether the ink film over the plastic film has any influence
on the barrier characteristics of the virgin film. For conducting the testing, the ASTM F 1249 and
ASTM D 1434 were followed.[20,21] An automatic instrument from Systech Illinois (model 7001)
was employed for WVTR test and Gas and Steam Permeability tester from Atsfaar, Italy for the
OTR test respectively.
2.3.8. Scuffing characteristics of the printed surfaces with different colours:
The scuff proofness testing on the printed surface is carried out in two ways: 1) between the print
surface and the unprinted surface and 2) between the two printed surfaces. This has been done as
per ASTM F 2497 [22]with the PIRA Rub resistance tester.
2.3.9. Effect of aging on the surface energy of the ink coated LD/LLDPE co-extruded film:
In order to observe the effect of ageing, small LDPE/LLDPE co-extruded film printed with the
different coloured ink at different wattages were kept in a humidity cabinet (Walk-in Humidity
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Chamber by NewTronics India Ltd.) at a temperature of 40 +/- 2 0 C and 90 +/- 2% relative

humidity under tight winding conditions. At specified time intervals, the spools were taken out
and samples collected for inspection of treatment levels (surface energy). The spools were further
placed in the cabinet and samples collected at stipulated intervals. This process of ageing was
continued for about 120 hundred days.
3. Results and discussions:
3.1 Coating weights:
In an earlier work[11] the variation in the development of surface energies on the non-polar surface
of LDPE /LLDPE co extruded film treated at different voltages and developing different surface
energy has been investigated as a function of the applied kW or in turn voltages and the necessary
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explanations have been provided for that. The transparent films with different treatment levels
were coated or inked with different colours of printing ink and the surface energies over the inked
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films (different colours) were investigated to inspect whether the surface energies underwent any
changes (from the original values) or not. These changes are given in details in Table- 2.
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Surprisingly it was noted that the surface energies were reduced remarkably in all the cases of
coloured inks irrespective of the original surface energies of the transparent films. Another striking
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feature observed was that all coloured ink surfaces now possessed uniform surface tension of 32
dynes/cm in all the cases except the yellow one which showed a value of 34 dynes/cm irrespective
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of different original values of treatment.

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The contact angles were now measured over these inked surfaces which possessed surface tension
level of 34dynes/cm ( for yellow ) and 32 dynes/cm for all other coloured ink surfaces and have
been recorded in table 4. The solidified and hardened ink surfaces showed somewhat irregular
contact angle values. The same yellow coloured surface ( 34 dynes/cm being the surface energy)
exhibited different contact angle values for different surface energies of the original transparent
films. So is the case with other inked surfaces. In an earlier study [11] it was observed that though
the same transparent LD/LLDPE coextruded film treated in one case by conventional corona
treatment technique and in another case by plasma treatment exhibited identical surface tension
levels but differed widely in their contact angle values (the identical surface energy being 56 and
contact angles being 50± 2 for the corona treated film and 42±1 respectively.) The two films
differed only in the development of polarity on their respective surfaces.
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In the present work an attempt has been made to inspect whether such variations in surface
polarities have any influence on the solid deposition from printing inks or coatings. Five suitable
inks (recommended for the PE films) only differing in their colours) were selected and coated over
the entire surface across its width in a particular gravure printing machine with a given anilox. The
inks had identical solids content (except the white) and viscosities within close ranges. The coating
was accomplished with films having different surface energies. The respective coating weights
achieved with five different coloured printing inks on film surfaces treated under different kilo
Wattages are depicted in Figure-2.
As expected, the coating weights obtained with different colours varied within the range 0.925–
2.7 g/m2 (GSM) irrespective of surface energies of the films the yellow showing the least and
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white, the highest ink coating (GSM),in each case of surface energy of the ink film. Thus, it is
quite apparent that coating weight available with a given anilox is independent of surface charges.
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Hence, with each ink the coating weight obtained on films treated at 3.0kW (corresponding surface
tension being 36 dynes/cm remains the same as available on films treated at 4.5 kW (corresponding
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surface tension being 42 dynes/cm).

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Figure-2: Variation of Coating weight of different inks with Applied Load of Corona Treatment
over PE films
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It should be pointed out here that the increase in surface energies of the treated LD/LLDPE co-
extruded film only helps in wetting and spreading of the liquid gravure ink (which gets facilitated
with increase in surface energy) and has little or no influence on the amount of solid deposition.
This is why the coating weights for any particular ink remain the same irrespective of the surface
charges within the range under the study. It might be expected that at the interface of the ink films,
the oxidized film surface and the corresponding ink film surfaces were involved in some
interlocking through its chemisorptive/ adsorptive forces. The polar asperities of the film surface
were interlocked with the polar ink surface. The solid deposit of ink consists mostly of ground
pigment particles and the medium or binder. The overall polarity and hence the resulting solubility
parameter of the two surfaces appear to match closely and hence the deposition becomes stable
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and gets anchored over there. In respect of the minor variations in coating weights as was observed
amongst the inks of different colours it can be argued that the weight ratios of the Pigment:Binder
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varied within the range of color under study. Under identical consistencies (viscosities), the binder
remaining the same the pigment content underwent variations while interacting with the binder.
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The changes in PVC (pigment volume concentration) in respective inks might be the reason for
such minor variation. There is no established fact in this regard so far as our knowledge goes as
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per literature we have surveyed, which accounts for the novelty and uniqueness of this work.
However, it may possibly be assumed that all the different coloured inks only differ in the nature
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of pigment while the other additive including the binder remain the same. The black (an inorganic
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pigment consists of c-black) the particles of which are relatively coarser and assume different
irregular structure and high absorptive and adsorptive characteristics as well. All these factors may
possibly deter the spreadability and wettability.
3.2 Surface energies over the printed surfaces on the LDPE/LLDPE films with corona
treatment at different wattages:
LDPE/LLDPE coextruded films were fabricated and Corona treated at different applied Voltages
so as to get films with different surface polarities or energies. The surface energies were
determined as per ASTM D 2578–67 using dyne solutions prepared by mixing Ethyl cellosolve
and formamide in different proportions so as to get a wide range of such dyne solutions. A detailed
discussion has been made on the level of treatment achieved at different wattages in earlier works
by the same authors.[11,12] These films were printed with different colored inks and surface
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energies/tension over the printed surfaces were measured. The results are tabulated in Table-2 and
4. It is quite apparent that the pattern of changes in surface energy with different colours remained
almost unaltered irrespective of the magnitude of surface energy on the plastic coextruded film
substrates. A few interesting phenomena may be observed here. In all the cases of inks the resulting
surface energy values are always lower than the original surface energy (treatment level) of the
treated films. This is quite expected as only a film of lower surface tension can be wetted and
spread over a surface having higher surface energy. Within the printed surfaces of different colours
the yellow one possessed relatively higher surface charges (34 dynes/cm) while the ink films of
other colours exhibited exactly identical surface behavior (32 dynes/cm) irrespective of highest
surface energy levels of the coextruded film. All the other colours give ink films which are
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absolutely inert to the nature of the pigment and also to the type of initial pretreatment over the
original substrate film as the surface energy over the ink surface remains the same irrespective of
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color. It will be worth mentioning here that the determination of surface energy on a printed (inked)
surface is quite relevant for those cases where reverse printing on the web/ substrate is done and
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some further processing like any adhesive or some special lacquer or coating application on the
printed surface is needed. Thus for multicoloured jobs all the different inks behaving almost
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identical fashion when the job demands a secondary processing or superimposition of colours on
ink coated surface is required to get a definite design.
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Moreover the knowledge of surface energy on an ink coated surface is also important in making
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an ink/ coating formulation as the surface tension of the formulated ink / coating must have to be
less (by about at least 10 dynes/cm or mJ/m2) than the surface energy of the printed surface over
which it is to the applied.[10] The selection of the ingredients and solvents for the coating should
be made accordingly.
3.3 Scotch adhesion of the ink films:
The bond strength achieved with different coloured surfaces of the LDPE/LLDPE coextruded
films undergoing corona treatment at different applied Wattages (thus generating different levels
of treatment) are shown in Figure-3. It is worthwhile mentioning here that after printing or ink
coating, the printed surfaces developed quite different treatment levels as shown earlier in Table-
3. It was observed that the yellow inked surface attained relatively higher treatment level while all
the other inked surfaces displayed quite uniform treatment level which is lower than the ink one.
The yellow inked surface, although exhibited a surface treatment level of 34 dynes /cm on the
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inked surface (over which the tape was pasted) throughout the entire range of treatment level under
study now shows a gradual and steady increase in bond strength with increasing pretreatment level
on the original PE film and achieves the highest bond strength when the original substrate, i.e.
LD/LLDPE film was treated at the highest load (4.5 kW) under study. A careful observation
indicates that the lighter colour shades (in spite of having almost identical coating deposits) like
Cyan, Magenta etc. provides relatively higher adhesion values compared to the darker ones like
black. From the Figure-3, it can be readily observed that the bond strength for every individual-
coloured ink film steadily increases with increase in applied load employed for corona treatment
of the original LD/LLDPE film. This is quite expected as the surface energy of the film undergoes
a steady increase with it. It is also interesting to note that for any given load of treatment within
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the range under investigation the bond strength decreases in the order white
>magenta>cyan>yellow>black of all the five colours under discussion.
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White has always the highest force of scotch adhesion and black, the lowest one. The white ink in
spite of having the highest solid deposition (2.7 GSM) and hence providing a thick film appears to
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anchor quite tenaciously to the substrate (treated PE film) with respect to other inks. As all the
other constituents of every ink remain the same except the pigment, it may possibly be inferred
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that the rutile titanium dioxide (mostly used as white pigment in ink and coatings) present in the
dried film of ink might get involved in some sort of interaction with the polar functional groups
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(i.e. – OH, > C=O, -COOH, -O-O-etc.) on the corona treated film surface. In case carbon black
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(used for pigmentation in black ink) although there are functional groups capable of undergoing
such interaction a lowering of bond strength is observed as the tendency to from agglomerates and
attaining a chain like structure, non-uniformity in structure size shape and pH of black particles
might stand in the way of such interaction and hence resulting in such poor peel bond strength. It
is interesting to note that, on an average, the force of adhesion of the ink films over the treated film
lie the order, white >magenta>cyan>yellow>black for any particular wattage or load within the
range of our study.
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Fo
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Figure-3: Bond Strength of different inks vs. Treatment Level of Corona Treatment over PE films.
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3.4. Contact angle of the ink films over LD/LLDPE coextruded films corona treated at
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different wattages.
Table-4 gives a tabular representation of the variation in contact angle of the different (colour) ink
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films deposited on corona treated co-extruded LD/LLDPE films. The film surface develops
different surface energies due to the differences in applied loads. The variation in surface energies
over the film surface helps to pull the ink film surfaces at different forces over it. The greater the
pulling force the ink spreads over the film surface quite readily leading to an intimate contact
between the ink film and the substrate film. The resultant of the three forces exerted by the surface
energy of the substrate corona treated PE film, the surface tension of the fluid ink and the interfacial
tension between these two leads to bring the ink film at equilibrium after spreading at a definite
contact angle. A smaller value of this contact angle gives an indication of the intimacy of the ink
film with the substrate, can be readily understood that a greater intimacy leads to development of
more and more van der Waals forces and in turn the forces of adhesion. The Figure-3 can be
considered as a replica of observations made earlier with the forces of adhesion with different inks
and thus normally corroborate the findings.
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The contact angle values are found to undergo systematic changes for each colour with the
variation in surfaces energies of the substrate films. Thus all the coloured ink films exhibit gradual
decrease in contact angle with a concomitant increase in applied loads for treatment or in turn with
an increase in surface energy of the film. Secondly for any given applied load the white ink shows
the minimum value of contact angle and the black ink highest one. The order of increases in the
contact angle lies in the order white<magenta<cyan<yellow<black which is as expected the
reserve of the order for forces of adhesion. The highest wattage considered in the present study
(4.5 kW) always develops the highest surface energy, on the substrate and hence the least contact
angles for all the inks under study. The changes in contact angle are within very close ranges.
However, all the inks have reasonably good spreadability at the surface energies available within
Fo
the range of treatment considered as all the contact angle are for less than right angle.
3.5. Coefficient of friction over the printed surface as a function of applied voltage
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The two types of friction as reported in the present investigation differ only in their mode of
observation but not in its execution. The static COF refers to the sudden jerk or force required to
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start the operation i.e. when the first layer of film at the top of a big spool or roll is pulled to slide
over the remaining part of the spool. When a big spool of film is allowed to be stored, the large
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number of layers are in intimate contact with each other. The roughness of the film layers helps
the peaks and crests to protrude the crevices or troughs of the adjacent layer. Thus the force
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required to pull out the layers at the beginning of operations is referred to as static COF. As the
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roll sets in operation the force required to separate the individual layer is referred to as the kinetic
COF.
This study (both static and kinetic coefficient of friction) with the printed LD/LLDPE film
(printing being carried out with different colours of conventional PE inks) is quite important and
relevant to the Packaging industries particularly when the printed film is subjected to any further
secondary operation like over printing (super imposition of colour), over coating or any adhesive
application. In such cases, the printed surface is to pass over a large member of metallic (steel
rolls) and if a smooth sailing is not there, development of scratch marks, lines etc. may take place.
Thus there should be minimum friction between the printed surface and any metallic part it may
come in contact.
Figure-4 displays the mode of changes in coefficient of friction (both static and kinetic) of the
colour films as a function of surface energy developed on the subjected substrate at different
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applied loads (kW). The static coefficients of friction undergo a steady increase for all the coloured
(different pigmented) inks over the entire range of surface treatment under study. The Static COF
attains its maximum values at the highest level of surface energy of the substrate irrespective of
the colour of the inks. It may possibly be argued that the higher level of surface treatment at high
applied wattages may develop lot more of micro etching or indentations on the surface. The liquid
inks by virtue of its flow ability conform to the contours of the substrate surface and its
morphology. Thus, the COF increases with increase in applied load for treatment.
The Kinetic coefficients of friction as noted in all the cases of colours are substantially lower
than its static coefficient of friction values when compared at the same treatment level (applied
load). In each case of coloured film the kinetic coefficient of friction undergoes very little
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increment with increase in surface treatment level. The increase in micro-etching with increase
in surface energy level hardly influence the kinetic co-efficient of friction. It has already been
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mentioned and explained earlier (Section 3.2) that the surface energy over yellow pigmented
ink is the lowest ( minimum contact angle) in all the cases of LD/LLDPE co-extruded film
ee
irrespective of different surface energies of the original co-extruded film achieved due to
treatment at different voltages. Thus the yellow colored surfaces behave as inert layer and the
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inductive influence of surface charge (diffusion) through inert yellow layer appears to exert
predominating influence over the surface characteristics particularly when the surfaces are
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subjected to the test of friction ( or roughening). Once this behavior is brought into play the
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surfaces get roughened or eroded more and more at higher voltages and hence the observation
becomes inconsistent.
a b
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Figure-4: C.O.F.(a-kinetic, b- static) of different inks vs. Applied Load of Corona Treatment over
PE films.
3.6. Scuffing characteristics of the printed (with different coloured inks) pre-
treated (corona) LD/LLDPE films.
Scuff Proofness or measure of resistance on scuffing over the printed surface of any film
(LD/LLDPE co-extruded film in the present case) is an important and essential characteristic of
any printed surface. Considering the possibilities of the printed surface of the film (particularly the
exposed printed one) to undergo friction during subsequent processing (if any) when the inked
surface undergoes friction over a large member of static or rotating rollers, the coating is subjected
Fo
to scuffing. If the coating is loosely held to the surface or the coating itself develops rough surface
due to off gauge or wide distribution of pigment particles within, it undergoes scuffing or abrasion
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and a consequent loss in coating material, a phenomenon which is manifested by a loss in weight.
The coated/ printed material may undergo scuffing also during transportation of the same when it
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remains in tightly wound condition in a reel as the coated surface undergoes fractioning over the
uncoated surface. In order to inspect this quality of scuff proofness, samples of dimensions as
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specified in ASTM F 2497[23] are cut with the help of a template and are put into the frame of scuff
proof tester with the printed surface exposed outwards. Now another circular sample of diameter
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(50mm) is punched out from the same specimen and wrapped around a circular device which is
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capable of undergoing to and fro movement over the framed sample such that the printed surface
of this interfaces with the printed surface of the other. The framed sample is to the weighed before
subjecting the same to the test. The rotating circular device may be exposed with different loads,
e.g. 50 gms, 100 gms, 200 gms and 400 gms. In the present work experiment was carried out with
200 gms and it was subjected to undergo 250 revolutions over the other printed specimen. After
the stipulated no. of revolutions, the sample was weighed again. This procedure was followed for
all the colours under study.
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(a) (c)
(b)
(d) (e)
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Figure-5: Scuff resistance of differently colored inks coated over PE at various applied loads-(a,b,c,d,e-yellow,
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magenta, cyan, black, white)

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The performance was also investigated for all the voltages, normally 3.0 kW, 3.5 kW, 4.0 kW and
4.5 kW at which the substrate films were exposed for corona treatment for each individual coloured
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ink. The results have been shown in bar diagram (Figure-5) as a function of wattages employed
for treatment where two blocks for each colour (one representing for untested and the other for
tested sample) have been shown adjacent to each other). It is interesting to note that irrespective
of colour or wattages employed for treatment within the range under study, no change in weight
was observed. It means that the abrasion resistances developed even at a voltage as low as 3.0 kW
are sufficient enough to resist frictional losses under stipulated conditions. The inference of this
investigation is quite inconclusive and scuffing at higher revolutions and higher load might have
led to some conclusion.
3.7. Barrier properties of printed/coated LD/LLDPE co-extruded films pre-treated at
different wattages.
The barrier properties in terms of water vapour transmission rate (WVTR) and oxygen
transmission rate (OTR) of the colored LD/LLDPE co-extruded films as are commonly required
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for packaging films have being measured as per its corresponding ASTM standards (ASTM F1249
and ASTM F 1434)[20,21] respectively and their graphical representations have been manifested in
fig.-6. Undoubtedly, the ink coating forms a very thin film (may be microlayer or less than that)
over the LDPE films being corona treated at a given (4.0kW) wattage. In an earlier study, the same
barrier properties were investigated [11] with transparent LD/ LLDPE films being treated at
different wattages. In that case it was observed that these two barrier parameter namely WVTR
and OTR were independent of the applied voltage. From Figure-6, it can be observed that
irrespective of colour both the WVTR and OTR remains unaltered and hence almost the same
values. This is as expected, provided the thickness of substrate film and its composition remains
the same, the coating ink film hardly affects the barrier characteristics under a suitable physical
Fo
condition. Both the WVTR and OTR properties refer to the transmission (diffusion characteristics)
of moisture vapor and oxygen through the bulk of the film and have got no associated relationship
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to the surface characteristics. Printing/coloring merely changes the surface behavior. Although
the thickness of the film increases marginally (thickness of a film has influence over diffusivity of
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any gas or vapour), it affects very little the two said parameters.
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Figure-6: OTR and WVTR values for the differently coloured films
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3.8 Mechanical properties of ink coated pre-treated (corona treatment being done before ink
coating LD/LDPE co-extruded films.
In order to investigate the influence (if any) of ink coating on the mechanical properties of
LD/LLDPE co-extruded film already corona treated at 4.5 kW a representative film sample of
75μm thickness was coated with white ink (coating grammage - 2.7GSM) and subjected to testing
for mechanical properties in an in universal testing machine following the procedure as outlined
in ASTM D 882[24]. The results obtained from mechanical testing are shown in Table-5.
Table-5: Mechanical data of the 75µm LDPE/LLDPE Transparent Film before and after Corona
Treatment on the film.[11]
Dart Dart
Fo
Impact Impact
Elastic
Tensile Tear Test Test
Modulu Yield Peak Brea
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Energy Resistanc (gm) (gm)

s Stress Stress k
Direction Absorptio e (gf) ASTM D as per
(N/mm2) (MPa (MPa Extn
ee
n (TEA, J) ASTM D 1709 ASTM D

ASTM ) ) (%)
1004 before 1709 after
D 882
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Treatmen Treatmen
t t
Machine
ev
Direction
(MD) and
iew
108.57 12.11 24.22 628.6 8.55 1072.25

Before
Treatmen
t
Machine
Direction
(MD) and
109.45 12.5 23.85 627.5 8.50 1073.00
after
Treatmen
t 419.50 419.00
Cross
Direction 156.23 11.20 23.50 683.8 8.33 1236.75
(CD) and
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Before
Treatmen
t
Cross
Direction
(CD) and
155.75 11.50 22.85 684.0 8.35 1235.50
after
Treatmen
t
Fo
The mechanical parameters namely elastic modulus, yield stress, peak stress, elongation at break,
tensile energy absorption, tear resistance and impact energy of the said film were compared before
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coating and after coating. The same study was undertaken with samples in both the machine
direction (MD) and cross directions (CD). Each of the mechanical properties as mentioned above
ee
was found to be almost identical when the values before printing and after printing were compared.
Thus coating layer of white ink film over the corona treated substrate of LD/LLDPE film has little
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or no influence on the mechanical properties of the film. This is as per our expectations, since
mechanical properties are considered to be bulk properties whereas coating on any surface merely
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changes or modifies the surface properties of the substrate. In a manner similar to the explanation
iew
offered under section 3.7, we reiterate that the testing parameters mentioned here, relate to the bulk
or load bearing properties of any material ( here film) under different conditions of stress like
static, sudden etc. It also relates to flexibility (elongation) property. However, our works like
surface treatment (Corona discharge), printing, colouring etc modify the surface
properties[11,12]. As this modification involves only the surface, it does not affect the mechanical
properties as mentioned here.
3.9. Ageing characteristics of printed surface of corona treated LD/LLDPE co-extruded film
In packaging industries, printed films are sometimes used as monolayers/unsupported or as
multilayers laminated structures as the specification demands. However in both cases the printed
film remains in tightly wound condition in a large spool form over some iron/plastic/paper core.
In such cases, as the printed surface of film remains in intimate contact with the unprinted one,
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(the surface away from the corona treated one and having much lower surface energy) it becomes
necessary to inspect whether such intimacy has led to any deterioration in the surface quality and
made it unsuitable for sequent processing operations like batch printing in case of monolayer
(unsupported) application or for adhesive application in case of lamination particularly for reverse
printed laminated jobs.
The problem becomes much more aggravated when the printed spool remains in WIP (work-in-
progress) for a long period of time. In India the environmental conditions such as temperature,
relative humidity (%) are sometimes found to have profound influence on the surface
characteristics of such stored printed or coated film spools. In order to investigate such influences
(if any) the LD/LLDPE co-extruded films coated with white lacquer (being previously corona
Fo
treated at 4.5kW) tightly wound in large no. of layers over a core were kept in a humidity chamber
maintained at 90 % ± 2% RH and temperature of 40° ± 2 ºC for a period of four months. Samples
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of films were used to be collected at regular intervals and the printed surface was subjected to
surface energy testing as per ASTM D 2578 Standards[16] with freshly prepared dyne solution each
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time. The results have been shown in Figure-7. It is quite evident that no change in surface
behaviour or surface energy occurs over the period understudy. Thus it can be predicted that
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printed or lacquered LD/LLDPE co-extruded films can be stored WIP (work in progress) without
any change in surface energy for at least a period of four months. The basic purpose of this study
ev
was to investigate the influence of time over the static charge developed on the film surface during
iew
its fabrication. It is imperative to mention here that surface treatment (in this case printing/coating)
greatly reduces the original surface treatment level, i.e. developed on the bare film itself. The
resulting static charge on the printed surface however does not undergo any decay with time, if
properly stored (being kept in suspended condition in a room where physical conditions like
temperature, RH etc are properly controlled). This is of great technological importance in industry
where further processing like lamination or overprinting are to be carried out.
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(b) (c)
(a)
(d) (e)
Fo
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Figure-7: Surface Energy vs no. of days for differently coloured inks (a,b,c,d,e- yellow, magenta, cyan, white
black)
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4. Conclusion
The experimental findings discussed above indicate a few important attributes. Attempts have been
ev
made to determine the state of the surface energy of the treated surface of the substrate
iew
(LD/LLDPE) film when covered with coating/printing ink. It was noted that the surface energy
over the coating surface did not vary or varied over a narrow range irrespective of colour, coating
weight, and variation in the surface energies over the substrates (LD/LLDPE films) which were
corona treated at different electrical power. It is worth while mentioning here that the inks of
different colours as used in this study contain two constituents in common, resin and solvent. The
third constituent i.e. the pigments (different for different ink) are quite inert in attributing any
specific spreading/wetting characteristics to the ink. Thus the surface energies over the inked
surfaces appear to remain the same. In all the coloured films, there was a drop in the level of
surface energies concerning the initial levels achieved over the LD/LLDPE film surfaces primarily
by treating at different wattages. It is worth mentioning here that for obvious reasons, during
subsequent processing like lacquering or application of adhesive, the surface energy of the coating
solution is required to be less than that of the coated surface at least by 10 dynes on which it would
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be applied for proper wetting, spreading, and necessary adhesion[11,12]. The other surface features
like roughness/coefficient of friction etc. and even the bulk mechanical properties did not undergo
any changes when compared as a function of the original surface energies of the LD/LLDPE film.
The minor variations in contact angle hardly have any impact on respective surface properties.
5. Acknowledgment
We acknowledge the intense guidance of M/S. A.B. Polypacks Pvt. Ltd. in fabricating the co-
extruded, treated films and carrying out the other conversion processes. We also acknowledge the
assistance and support from Indian Institute of Packaging, Kolkata and M/S DIC India Pvt. Ltd.
And Chemical Engineering Department, Jadavpur University particularly in carrying out
instrumental analysis.
Fo
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References:
[1] Jin M, Thomsen F, Skrivanek T,Willers T. Advances in contact angle, wettability and adhesion.
ee
In : Mittal KL, ed. Chapter 17: Why Test Inks cannot Tell the Whole Truth about Surface Free
Energy of Solids. Hoboken, NJ, USA: John Wiley and Son. 2015;2:419-438.
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[2] Lindner M, Rodler N, Jesdinszki M, Schmid M, Sangerlaub S. Surface energy of corona treated
PP, PE and PET films, its alteration as function of storage time and the effect of various corona
ev
dosages on their bond strength after lamination. J Appl polym Sci.2017; 135(11):1-9.
[3] Shaw DR, Gyuk PM, West AT, Momoh M, Wageners E. Surface modification of polymer
iew
films using an atmospheric plasma jet.In Proc 22nd ISPC. York. Paper presented at: 22nd
International symposium on Plasma chemistry: Antwerp, Belgium.2015.
[4] Aydemir C, Altay BN, Akyol M. Surface analysis of polymer films for wettability and ink
adhesion. Color Res Appl. 2020;1–11.
[5] Altay BN, Bloembergen S, Aydemir C, Karademir A, Fleming PD. Use of nanoparticle binders
for paper coatings: a review. J. Graph. Eng. Des.2017; 8(1), 39.
[6] Ramirez JCC,Tumolva TP. Analysis and optimization of water-based printing ink formulations
for polyethylene films. Appl Adhes Sci. 2018; 6:1.
[7] Żołek-Tryznowska Z. Additives for Ink Manufacture. In: Izdebska-Podsiadły J, Thomas S, eds.
Printing on Polymers: Fundamentals and Applications. Elsevier. 2016;57-66.
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[8] Rentzhog M, Fogden A. Print quality and resistance for water-based flexography on polymer-
coated boards: Dependence on ink formulation and substrate pretreatment. Prog. Org. Coat..2006;
57(3): 183–194.
[9] Nemani SK, Annavarapu RK, Mohammadian B,et al.Surface Modification of Polymers:
Methods and Applications. Adv. Mater. Interfaces.2018; 1801247.
[10]Pascual M, Sanchis R, Sánchez L, García D, Balart R. Surface Modification of Low Density
Polyethylene (LDPE) Film Using Corona Discharge Plasma for Technological Applications. J.
Adhes. Sci. Technol. 2008; 22(13): 1425–1442.
[11] Das B, Chakrabarty D, Guha C, Bose S. Effects of corona treatment on surface properties of
co‐extruded transparent polyethylene film. Polym Eng Sci.2021; 61(5): 1449–1462.
Fo
[12] Das B, Chakrabarty D, Mukherjee A, Guha C, Bose S. Mechanical and surface properties of
corona-treated titanium dioxide-embedded opaque white low-density/ Linear low-density
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polyethylene film. Polym Eng Sci. 2023; 63(2): 546+.

[13] Abourayan HM, Dowling DP. In: Aliofkhazraei M, ed. Plasma processing for Tailoring the
ee
Surface Properties of Polymers, Surf. Eng., IntechOpen.2015.

[14] Lahti J, Tuominen M. The effects of corona and flame treatment: part 1. PE-LD coated
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packaging board. In Proceedings of the 11th TAPPI Europlace Conference. 2007;

https://www.researchgate.net/publication/267305163
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[15] Electro Tech Industries. Theory of corona Treatment and Static Electricity. Ahmedabad,
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Gujarat, India: Electro Tech, Inc. 2019. https://www.etind.com/corona-treatment.pdf. Accessed

December 27, 2019.
[16] ASTM International. Standard Test Method For Wetting Tension Of Polyethylene And
Polypropylene Films.(D2578-08).2022.
[17] ASTM International. Standard Test Method for Static and Kinetic Coefficients of Friction of
Plastic Film and Sheeting.(D1894-14).2014.
[18] ASTM International. Standard Test Method for Tear Resistance (Graves Tear) of Plastic Film
and Sheeting. (D1004).2021.
[19] ASTM International. Standard Test Methods for Impact Resistance of Plastic Film by the
Free-Falling Dart Method.(D1709).2022.
[20] ASTM International. Standard Test Method for Water Vapor Transmission Rate Through
Plastic Film and Sheeting Using a Modulated Infrared Sensor. (F1249).2020.
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[21]ASTM International.Standard Test Method for Determining Gas Permeability Characteristics

of Plastic Film and Sheeting. (D1434-82).1998.
[22] ASTM International. Standard Practice for Abrasion and Scuff Resistance of Inkjet Media by
the Sutherland Rub Tester.( F2497).2005.
[23] ASTM International. Standard Practice for Abrasion and Scuff Resistance of Inkjet Media by
the Sutherland Rub Tester. (F2497).2005.
[24] ASTM International. Standard Test Method for Seal Strength of Flexible Barrier Materials.
(F88/F88M).2021.
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Response to the Specific comments made by Reviewer-2:
2.1“The wattages consumed (kW) and the corresponding surface energies available on the
surfaces of the LD/LLDPE film are shown in Table-2”
→
However, Table shows the term named “surface energy of PE film” not “applied voltage”. Is this
error? Also, unit of surface energy should be dyne/cm as author explained, but here kW is shown.
Response: It has been rightly pointed out by the reviewer, the error has been addressed and
rectified in the edited manuscript.
2.3“The results are given in Table-3”

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→
Is it in Table-4?
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Response: Yes it is in Table -4. The error as indicated by the reviewer has been addressed and
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3.1 It should be pointed out here that the increase in surface energies of the treated
LD/LLDPE co-extruded film only helps in wetting and spreading of the liquid gravure ink
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(which gets facilitated with increase in surface energy) and has little or no influence on the
amount of solid deposition.
→
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(1) From Table-4, the case of “42 dyne/cm” of “Surface Energy” seems not low in contact angle.
That is, even when surface energy increases as 36 dyne/cm→40 dyne/cm→42 dyne/cm, 42
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dyne/cm is not good in reducing contact angle. In this case, could you say that the increase in
surface energies helps in wetting and spreading of the liquid gravure ink?
Response: It is an established fact that a higher surface energy always facilitates surface
wettability and spreadability. In this regard our previously published papers could be referred to
as well. It is well explained in the papers under reference nos- [11],[12].
Reviewer: Again, Table-4 shows that when surface energy increases from 40 dyne/cm to 42
dyne/cm, the contact angle for yellow changes from 38.4 to 40.2, rather increasing at 42 dyne/cm
and decreasing in wettability. The contact angle for magenta also increases from 35.6 to 38.4,
while those for cyan also increase from 36.6 to 38.8. In other words, wettability decreases at
higher surface energy (at 42 dyne/cm).
The description by the author seems to disagree with Table 4.
Response:
We apprehend some confusion in understanding.

Please note that the surface energies as have been considered by the reviewer are the original
values achieved on surfaces of transparent (no colour or ink on the surface) LD /LLDPE
coextruded films being achieved immediately when
John Wiley corona treatment was applied at different
& Sons
electrical loads, in line with extrusion and the corresponding contact angles were described in detail
in our earlier communication (Reference [11] Das B, Chakrabarty D, Guha C, Bose S. Effects of
corona treatment on surface properties of co‐extruded transparent polyethylene film. Polym Eng
Sci.2021; 61(5): 1449–1462). These transparent films with different treatment levels were coated or
inked with different colours of printing ink and the surface energies over the inked films (different
colours) were investigated to inspect whether the surface energies underwent any changes (from
the original values) or not. These changes are given in details in Table- 2. Surprisingly it was noted
that the surface energies were reduced remarkably in all the cases of coloured inks irrespective of
the original surface energies of the transparent films. Another striking feature observed was that all
coloured ink surfaces now possessed uniform surface tension of 32 dynes/cm in all the cases except
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the yellow one which showed a value of 34 dynes/cm irrespective of different original values of
treatment.
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The contact angles were now measured over these inked surfaces which possessed surface tension
level of 34dynes/cm ( for yellow ) and 32 dynes/cm for all other coloured ink surfaces and have
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been recorded in table 4. The solidified and hardened ink surfaces showed somewhat irregular
contact angle values. The same yellow coloured surface ( 34 dynes/cm being the surface energy)
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exhibited different contact angle values for different surface energies of the original transparent
films. So is the case with other inked surfaces. In an earlier study (Ref. [11] Das B, Chakrabarty D,
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Guha C, Bose S. Effects of corona treatment on surface properties of co‐extruded transparent

polyethylene film. Polym Eng Sci.2021; 61(5): 1449–1462.) it was observed that though the same
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transparent LD/LLDPE coextruded film treated in one case by conventional corona treatment
technique and in another case by plasma treatment exhibited identical surface tension levels but
differed widely in their contact angle values (the identical surface energy being 56 and contact
angles being 50± 2 for the corona treated film and 42±1 respectively.) The two films differed only
in the development of polarity on their respective surfaces. In the present case the presence of
pigment particles ( having different structure , polarity and chemical composition) embedded in a
different resin matrix and laid over the original treated plain transparent film might have caused in
the observed variation in contact angles. Surface energy /tension gives a relative idea of spreading
characteristics on a plain smooth and blemish free surface but the contact angle appears to be
affected by the polarity, surface irregularities and also the pigment particle size distribution besides
the important parameter of surface energy.
It is worthwhile to draw the attention of the reviewer that though the yellow inked surfaces
demonstrated identical surface tension values of 34 dynes/cm incases of original plain films treated
John Wiley & Sons
at different electrical loads, the contact angles still varied within the range of 40±4. Such variation
in contact angle is quite common in actual practice. Such variation in case of magenta was 38±4
and for cyan it was 39±4.
(2) Also, only for black ink, the trend is quite different among them. Author should denote
it and provide scientific discussion.
Response: We feel thankful to the reviewer as he has kindly pointed out the deficiency. There is no
established fact in this regard so far as our knowledge goes as per literature we have surveyed,
However, it may possibly be assumed that all the different coloured inks only differ in the nature
of pigments while the other additives including the binder remain the same. The black (an
inorganic pigment consists of c-black) the particles of which are relatively coarser and assume
different irregular structure and high absorptive and adsorptive characteristics as well. All these
factors may possibly deter the spreadability and wettability.
Fo
Reviewer: As there appears to be only speculation and a lacking of evidence, preferably with
experimental data to support above. For instance, the roughness of the film surface, microscopic
image, and absorption properties, etc.
rP
Response: Determination of Coefficient of friction (a measure of roughness) over the black inked
surface of LD/LLDPE coextruded films (having different surface energies) was done and has been
ee
shown in fig. 4 a and 4 b. It was observed that though the original surface energy values of the
rR
transparent film differed, the surface energy over the black ink in all cases came down to only 32
dynes/cm. The coefficient of friction varied over a narrow range on the black inked surfacebecause
ev
of the course C-black particles (pigment), its irregular structure, surface PH values and absorption
characteristics. The range in the values of contact angle over the black surface has been found to be
iew
laying 42 ± 5. Thus the coefficient values were in the range of 0.23 ± 0.06. It corroborates our
earlier findings (Reference 11) on surface energy vs contact angle.
3.2 The results are tabulated in Table-3.

→
Is this Table-2?
rectified in the edited manuscript. It is in the table 2 and 4.
Why is the surface energy of only yellow large as 34 dyne? Author should provide scientific
consideration for that.
Response: In this case also appropriate explanation cannot be provided because of lack of
information. However, in the light of explanation as provided for c-black it is worth while
mentioning here that the yellow pigment consists mostly of either arylamide or benzamide which
is organic in nature, smooth and consistent in its structure without any pores in its structure. This
does not allow any absorption allowing easy wetting and spreading which accounts for lowering
in surface energy. John Wiley & Sons
Reviewer: The reviewer is asking for discussion of why surface energies are higher, not lower.
Response: The yellow shade is lighter and translucent one. While all other shades are heavier and
opaque in nature. There is every possibility of charge transfer from the surface of plain transparent
LD/LLDPE film through the translucent yellow ink film while the other shades lack this
characteristics. This might have caused a restricted amount of charge transfer through the ink film
causing the surface lower surface energies.
3.4 Thus all the coloured ink films exhibit gradual decrease in contact angle with a
concomitant increase in applied loads for treatment or in turn with an increase in surface
energy of the film.
Fo
→
Same as 3.1
rP
From Table-4, the case of “42 dyne/cm” of “Surface Energy” seems not low in contact angle.
That is, even when surface energy increases as 36 dyne/cm→40 dyne/cm→42dyne/cm, 42
ee
dyne/cm is not good in reducing contact angle. In this case, could you say that all the coloured
ink films exhibit gradual decrease in contact angle with a concomitant increase in applied loads?
rR
Response: Yes, quite obviously. The higher surface energy (over the surface of which coating is
spread) assists in more and more improved spreading and wetting of the liquid coating resulting
in lesser values of contact angle.
ev
Reviewer: Again, in Table 4, when surface energy increases from 40 dyne/cm to 42 dyne/cm, the
contact angle for yellow changes from 38.4 to 40.2, rather increasing at 42 dyne/cm. The same is
iew
also in the case of magenta and cyan.
Response: The reply to this quarry is same as explained in the point 3.1 (1) above.
3.5 It may possibly be argued that the higher level of surface treatment at high applied
wattages may develop lot more of micro etching or indentations on the surface.
→
This is critically important discussion, and it is necessary for more evidence to scientifically
discuss for explanation of the phenomenon.
Response: Yes, it is agreed that we cannot cite any reference for such conclusion. The increases
in the values of COF with increases in applied voltage may be considered as a direct evidence
for increases in roughness which can only arise due to the impingement of radiation over the film
surface which as such is smooth and devoid of any roughness.
Reviewer: Preferably with experimental data to support above. For instance, the roughness of
the film surface and microscopic image.
John Wiley & Sons

Response: We regret to inform you tht presently we have no infrastructure for determining the
roughness of the surface, That is why we have considered the coefficient of friction values as the
indirect evidence of surface roughness.
In each case of coloured film the kinetic coefficient of friction undergoes very little
increment with increase in surface treatment level.
→
For yellow ink, the trend is not consistent. Author should provide scientific discussion for that.
Response: It has already been mentioned and explained earlier (Section 3.2) that the surface
energy over yellow pigmented ink is the lowest ( minimum contact angle) in all the cases of
Fo
LD/LLDPE co-extruded film irrespective of different surface energies of the original co-
extruded film achieved due to treatment at different voltages. Thus the yellow colored surfaces
behave as inert layer and the inductive influence of surface charge (diffusion) through inert
rP
yellow layer appears to exert predominating influence over the surface characteristics
particularly when the surfaces are subjected to the test of friction ( or roughening). Once this
behavior is brought into play the surfaces get roughened or eroded more and more at higher
ee
voltages and hence the observation becomes inconsistent.
Reviewer: Again, in Section 3.2, in Table 4, yellow pigment ink exhibits the high contact angle;
rR
43.7, 38.4, 40.2 respectively for 36 dyne/cm, 40 dyne/cm, 42 dyne/cm of surface energies, not
minimum contact angle.
ev
Response: Yes, we agree that we have made some mistakes in commenting that the yellow pigment
shows the minimum contact angle. In each case of the inked surfaces the contact angle varies over
iew
a range i.e. it is not a single value as has been shown in the table 4.
The increase in micro-etching with increase in surface energy hardly influence the kinetic
co-efficient of friction.
→
Since the results are only described, the discussion on the reasons for the results and their assumed
scientific behaviors including the difference between static and kinetic friction should be given
here.
Response: The two types of friction as reported in the present investigation differ only in their
mode of observation but not in its execution. The static COF refers to the sudden jerk or force
required to start the operation i.e. when the first layer of film at the top of a big spool or roll is
pulled to slide over the remaining part of the spool. When a big spool of film is allowed to be
stored, the large number of layers are in intimate contact with each other. The roughness of the
film layers helps the peaks and crests to protrude the crevices or troughs of the adjacent
layer. Thus the force required to pull out the layers at the beginning of operations is referred to
as static COF. As the roll sets in operation the force required to separate the individual layer is
referred to as the kinetic COF.
John Wiley & Sons

Reviewer: This is a statement of static and dynamic friction. The reviewer asks why increased
micro-etching does not affect dynamic friction, not static friction.
Response: Once the static friction is overcome and the spool of roll sets in motion the momentum
of the web is sufficient enough to overcome the effect of micro etching. That is why the kinetic /
dynamic friction is not much affected.
3.7 Respectively and their graphical representations have been manifested in fig.-8.
→
There is no fig.-8.
Fo
From Figure-5, it can be observed that irrespective of colour both the WVTR and OTR
rP
remains unaltered and hence almost the same values.

→
ee
It is understood that there is no significant change in WVTR and OTR, however, it is necessary
for discussion to consider the more scientific explanation and industrial significance of each value
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itself.
Response: Both the WVTR and OTR properties refer to the transmission (diffusion characteristics)
ev
of moisture vapor and oxygen through the bulk of the film and have got no associated relationship
to the surface characteristics. Printing/coloring merely changes the surface behavior. Although
the thickness of the film increases marginally (thickness of a film has influence over diffusivity of
iew
any gas or vapour), it affects very little the two said parameters.
3.8 The mechanical parameters namely elastic modulus, yield stress, peak stress, elongation
at break, tensile energy absorption, tear resistance and impact energy of the said film were
compared before coating and after coating.
→
Same as 3.7.
It is understood that there is no significant change, however, it is necessary for discussion to
consider the more scientific explanation and industrial significance of each value itself.
Response: In a manner similar to the explanation offered under section 3.7, we reiterate that the
testing parameters mentioned here, relate to the bulk or load bearing properties of any material
( here film) under different conditions of stress like static, sudden etc. It also relates to flexibility
(elongation) property. However, our works like surface treatment (Corona discharge), printing,
colouring etc modify the surface properties. As this modification involves only the surface, it does
not affect the mechanical properties as mentioned here.
3.9. It is quite evident that no change in surface behavior or surface energy occurs over the
period under study.
John Wiley & Sons
→
Same as 3.7.
It is understood that there is no significant change, however, it is necessary for discussion to
consider the more scientific explanation and industrial significance of each value itself.
Response: The basic purpose of this study was to investigate the influence of time over the static charge
developed on the film surface during its fabrication. It is imperative to mention here that surface treatment
(in this case printing/coating) greatly reduces the original surface treatment level, i.e. developed on the
bare film itself. The resulting static charge on the printed surface however does not undergo any decay
with time, if properly stored (being kept in suspended condition in a room where physical conditions like
temperature, RH etc are properly controlled). This is of great technological importance in industry where
further processing like lamination or overprinting are to be carri
Fo
Other points:
rP
Figure 2 shows the data as lines, but are they not the values when Applied Load is 3.0 kW, 4.0 kW,
ee
or 4.5 kW? In other words, isn't it a plot, not a straight line?
Response: It is quite apparent from the fig. 2 that the coating weight of the individual colour
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remain constant over the entire range of electric load applied.

The coating weights are given in the ordinate of the plot and the exact coating weight of each
ev
colour can be obtained by extrapolating the individual line of colour to the ordinate.
iew
3.1 “This is why the coating～and gets anchored over there.”

→
Here the author discusses adhesion issues. However, a discussion should be given on the
experimental results where the weight of the coating is independent of the load.
Response : The coating weight achieved on a given surface is a function of the solid content and
the corresponding viscosity of the liquid ink medium. The electrical loads as given in the plot
given an indication of a surface energy achieved on the surface due to the application of electrical
load and consequently gives a relative idea of the spread ability of the liquid ink over the surface.
Thus the surface energy has not got any relationship with the coating weight.
3.2 “Within the printed surfaces of different colours the yellow one possessed relatively higher
surface charges (34 dynes/cm) while the ink films of other colours exhibited exactly identical
surface behavior (32 dynes/cm) irrespective of highest surface energy levels of the coextruded
film.”
→
A discussion on why the surface energy for the yellow ink is significantly higher at 34 dynes
John Wiley & Sons
compared to the other colors would enhance the manuscript.
Response: The reason has already been explained in the sec. 3.2 in the response of the
reviewer’s quarries.
3.3:
There are similar expressions such as "peeling force" and "bond strength" in the manuscript and
figure. It should be better to standardize them to one term.
Response: Necessary action has been taken and the manuscript is modified as such.
3.3 “at the highest load (4.5 kg) under study.”

→
Is 4.5 kg an error for 4.5 kW?
Response : 4.5 kW. Yes it was typographical error and necessary action has been taken.
Fo
“A careful observation indicates that the lighter colour shades (in spite of having almost identical
rP
coating deposits) like Cyan, Magenta etc. provides relatively higher adhesion values compared to
the darker ones like black, green etc. From the Figure-3,”
→
ee
There is no green in Figure-3.
Response: Yes, we appreciate the reviewer’s observation. We regret to inform that no work has
rR
been done on green ink.

ev
iew
John Wiley & Sons

PES-24-0290.R2 - Proof - Hi - Accepted Paper - 19-10-2024

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Polymer Engineering & Science

Pattern of surface energy (tension) change after coating /

Journal: Polymer Engineering & Science

Wiley - Manuscript type: Research Article

Date Submitted by the

Chakrabarty, Debabrata; University of Calcutta - Rajabazar Science

Bose, Saswata; Jadavpur University

Keywords: surfaces, adhesion, coatings

John Wiley & Sons

338x190mm (200 x 200 DPI)

John Wiley & Sons

Pattern of surface energy (tension) change after coating / printing on a pretreated

Abstract: This study embodies the characterization of corona-treated co-extruded transparent

impacted upon much by the influence of coating on their surfaces.

� Corona Pre-treatment LD/LLDPE co-extruded film

� Interlocking through its chemisorptive/ adsorptive forces

Figure-1: Percentages of different plastics used in flexible packaging.

substrates to attain good printability, adhesion or ink lay down.[8,9,10]

treatment and ink transfer method.[11,12,13]

Table-1: Details of composition of the co-extruded film.

2nd Layer Butene Reliance

2. Experimentation and measurements:

2.1 Corona treatment:

2.2 Printing inks and the process of printing:

Table-3: Details of Printing inks* used:

Sl. Name of Ink Batch No Manufacturing Code Solid Content (%)

03 Yellow 0001183594 04-06-2023 ARSR Yellow 238 26.6

04 Black 0001145335 08-02-2023 ARSR 231000 33.9

05 White 0001176309 17.05.2023 ARSR White 102 - II- 48.9

2.3. Characterization of the printed surface:

2.3.1 Measurement of coating weight:

2.3.3. Ink bond strength by scotch adhesion test:

printed films and compared to those of unprinted film samples.

Chamber by NewTronics India Ltd.) at a temperature of 40 +/- 2 0 C and 90 +/- 2% relative

of different original values of treatment.

surface tension being 42 dynes/cm).

magenta, cyan, black, white)

Energy Resistanc (gm) (gm)

n (TEA, J) ASTM D 1709 ASTM D

108.57 12.11 24.22 628.6 8.55 1072.25

polyethylene film. Polym Eng Sci. 2023; 63(2): 546+.

Surface Properties of Polymers, Surf. Eng., IntechOpen.2015.

packaging board. In Proceedings of the 11th TAPPI Europlace Conference. 2007;

Gujarat, India: Electro Tech, Inc. 2019. https://www.etind.com/corona-treatment.pdf. Accessed

[21]ASTM International.Standard Test Method for Determining Gas Permeability Characteristics

Response to the Specific comments made by Reviewer-2:

2.3“The results are given in Table-3”

We apprehend some confusion in understanding.

Guha C, Bose S. Effects of corona treatment on surface properties of co‐extruded transparent

3.2 The results are tabulated in Table-3.

also in the case of magenta and cyan.

John Wiley & Sons

voltages and hence the observation becomes inconsistent.

John Wiley & Sons

remains unaltered and hence almost the same values.

or 4.5 kW? In other words, isn't it a plot, not a straight line?

remain constant over the entire range of electric load applied.

3.1 “This is why the coating～and gets anchored over there.”

3.3 “at the highest load (4.5 kg) under study.”