coatings
Article
The Influence of the Roll-Laminating Process on the Bonding
Quality of Polymer-Coated Steel Interface
Jiyang Liu, Qingdong Zhang *, Boyang Zhang * and Mingyang Yu






Citation: Liu, J.; Zhang, Q.; Zhang,
B.; Yu, M. The Influence of the
Roll-Laminating Process on the
Bonding Quality of Polymer-Coated
Steel Interface. Coatings 2021, 11, 472.
https://doi.org/10.3390/
coatings11040472
Academic Editor: Nicolas Delorme
Received: 21 March 2021
Accepted: 14 April 2021
Published: 17 April 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2021, 11, 472. https://doi.org/10.3390/coatings11040472
School of Mechanical Engineering, University of Science and Technology, Beijing 100083, China;
b20170270@xs.ustb.edu.cn (J.L.); b20190253@xs.ustb.edu.cn (M.Y.)
* Correspondence: zhang_qd@me.ustb.edu.cn (Q.Z.); asdfaa01@foxmail.com (B.Z.)
Abstract: Polymer-coated steel (PCS) is a new type of metal packaging material under development,
which has better performance in saving resources, energy, and environmental protection. The
lamination process has an important influence on the bonding quality of the PCS interface. PCS
samples under different lamination temperatures and lamination speeds were prepared through
experiments. A binding rate is defined to represent the real bonding area of the PCS interface.
The micro-scratch tester and scanner are used to study the influence of the lamination process on
the bonding rate and bonding strength of the PCS interface. It is proposed that the bonding rate
and bonding strength of the PCS interface increases with the increase of lamination temperature
and increases with the decrease of lamination speed. The PCS interface bonding rate and bonding
strength are positively correlated. SEM and DSC experiments revealed the cause of bubbles on the
PCS surface. It is proposed that controlling the uniformity of the TFS surface temperature can reduce
the quality defects of PCS surface bubbles. Relevant research results bring guiding significance for
the formation of enterprises.
Keywords: polymer-coated steel; lamination process; interface defect; lamination quality; binding
rate; bonding strength
1. Introduction
With the gradual development of the metal packaging industry in the direction of
green, energy saving, and environmental protection, more and more attention has been
paid to the surface-coating technology of metal products. Polymer-coated steel (PCS), a
new type of metal and non-metal layered composite strip, is mainly used in the metal
packaging industry. It can replace tin plate to reduce the consumption of tin resources and
increase the corrosion resistance and aesthetics of the product. At present, PCS products
have been widely used in Japan, Europe and the United States. The mass popularization of
PCS products is bound to be the future development trend [1–4].
PCS is prepared by roll-pressing and the hot-fusion coating process. Through a series
of physical and chemical reactions such as continuous contact temperature rise, surface
melting, roll bonding, hydrogen bonding, cooling and solidification, etc., the two different
materials of steel and plastic are firmly bonded at the interface. The material distribution
of PCS along the thickness direction is plastic, hydrated chromium oxide layer, metallic
chromium layer and ordinary steel plate [5–8].
Since the PCS material was born in Japan in the 1990s, it has a development history of
about 30 years. At present, the research on PCS materials in the world mainly focuses on the
PCS coating process [9–11], coating quality characterization [12–14], heat transfer during
the coating process [15], PCS heat treatment [16,17], PCS application [18,19], film surface
modification [20–22] and so on. Komai [23] used cathodic electrolysis to prepare tin-free
steel (TFS) with water and oxidation layers on the surface. The peeling experiment indicates
that the presence of a hydrated chromium oxide layer on the substrate surface can increase
the adhesion of the PCS interface. Suzuki [24] studied the wet adhesion characteristics of
https://www.mdpi.com/journal/coatings
 Coatings 2021, 11, 472 2 of 15

polymer films through cooking experiments on PCS samples and proposed two effective
methods to improve interfacial adhesion: chrome-plating the steel plate and increasing the
film temperature, thereby increasing the thickness of the amorphous polymer film layer.
This supplements the previous results. Cho [10,11] studied the influence of the coating
temperature on the thickness of the polymer crystalline layer and pointed out that as the
coating temperature increases, the thickness of the amorphous layer of the polymer film
increases, which improves the interface bonding strength. It can be seen that the thickness
of the melting layer of the polymer film during the pretreatment of the substrate surface
and the coating process is an effective method to improve the bonding strength of the PCS
interface. Regarding the surface treatment of substrates, most studies in the world are
related to the interaction between the hydrated chromium oxide layer on the surface of TFS
and the interface bonding, and the effect of the surface micro-morphology of TFS on the
interface bonding is rarely mentioned. At the same time, to propose a set of indicators to
accurately evaluate the quality of PCS coatings is a unified goal that has not been reached
by various experts in the world.
In addition, there is still a lot of research on the mechanism that restricts the high-
speed coating of metal plates in the field of PCS manufacturing process. Increasing the
speed of PCS coating can increase the production efficiency of enterprises and reduce the
production cost of PCS to a certain extent. In addition, experimental and theoretical studies
are required for the influence of the surface morphology of the substrate chrome plate
on the bonding quality of the PCS interface and the experimental basis for the hydrogen
bonding of the PCS micro-interface.
From the perspective of the bonding quality of the PCS interface, this paper proposes
an index that characterizes the true bonding area of the PCS interface—the bonding rate.
Through the preparation of coated iron samples, the detection of the interfacial bonding
rate and interfacial bonding strength as well as the influence of the rolling coating process
parameters on the quality of PCS interfacial bonding were studied. The interface bonding
rate index is defined to characterize the bonding quality of the PCS interface. The scratch
experiment explained the failure mechanism of the coated iron interface. Through the
differential scanning calorimetry test, the reason for the bubbles on the surface of the PCS
sample was studied because the surface temperature of the chrome-plated plate of the
base material was not uniformly controlled, and the melting thickness of the polymer film
was not uniform during the coating process. It solves the problem of film quality in PCS
production and brings certain production benefits to the production of enterprises.

2. Experiment
2.1. Materials
In the lamination experiment, tin-free steel (TFS) and polyethylene terephthalate (PET)
film were selected as raw materials. The laminated substrate TFS came from Shanghai
Yigang Storage Co., Ltd (Yigang Storage Co., Ltd, Shanghai, China). The cladding PET
film came from Shanghai Baowu Steel Co., Ltd (Shanghai Baowu Steel Co., Ltd, Shanghai,
China). The TFS material has a three-layer structure in the thickness direction, which are
Coatings 2021, 11, x FOR PEER REVIEW strip steel, a metallic chromium layer, and a hydrated chromium oxide layer [6,7,25],
3 of 15 as
shown in Figure 1. The thickness of the hydrated chromium oxide is 135 mg/m2 . The
total thickness of the TFS is approximately 0.18 mm. The total thickness of the PET film is
25 um [26].

Figure 1. The surface structure of tin-free steel (TFS).

Figure 1. The surface structure of tin-free steel (TFS).

2.2. Laminating Experiment

2.2.1. Laminating Equipment
The PCS laminating equipment, as shown in Figure 2, came from Shanghai Lianjing
Coatings 2021, 11, 472 3 of 15

Figure 1. The surface structure of tin-free steel (TFS).

2.2.Laminating
2.2. LaminatingExperiment
Experiment
2.2.1.
2.2.1.Laminating
LaminatingEquipment
Equipment
The
ThePCS
PCSlaminating
laminatingequipment,
equipment,as asshown
shownin inFigure
Figure2,2,came
camefromfromShanghai
ShanghaiLianjing
Lianjing
Electronic
ElectronicTechnology
Technology Co., LtdLtd
Co., (Lianjing Electronic
(Lianjing Technology
Electronic Co., Ltd,
Technology Shanghai,
Co., China).
Ltd, Shanghai,
This laminating equipment can perform single-sided laminating tests
China). This laminating equipment can perform single-sided laminating tests of TFS sam- of TFS samples.
The
ples.whole laminating
The whole laminatingequipment
equipment is mainly composed
is mainly composed of three
of threeparts:
parts:console,
console,heating
heating
part
partand
andpressing
pressingdevice.
device.The Theheating
heatingpart
partisisaapair
pairofofelectromagnetic
electromagneticinduction
inductionheatingheating
rollers
rollersplaced
placedupupand
anddown.
down.The Themain
mainfunction
functionisisto toheat
heatthe
thesample.
sample.The Theelectromagnetic
electromagnetic
induction
inductionheating
heatingroller
rollerhas
hasaadiameter
diameterof of200
200mm,mm,aalength
lengthof of1.2
1.2m,m,and
andaatemperature
temperature
control accuracy of ± 1 K. The pressing device uses a set of electromagnetic
control accuracy of ±1 K. The pressing device uses a set of electromagnetic induction induction
heat-
heating rollers and silicone rubber rollers. The pressing control method
ing rollers and silicone rubber rollers. The pressing control method is a displacement con-is a displacement
control.
trol. TheThe displacement
displacement ofof thesilicone
the siliconeroller
rollercan
canbe be manually
manually controlled
controlled by by rotating
rotatingthethe
handrail.
handrail. The electromagnetic induction heating roller and the heating roller the
The electromagnetic induction heating roller and the heating roller of heating
of the heat-
part are the
ing part are same. It isItprepared
the same. is prepared by bycovering
covering a layer
a layerofof
silicone
siliconerubber
rubberwithwithaasteel
steelcore.
core.
The
The diameter of the steel core is 180 mm, the thickness of the silicone layer is 20 mm,and
diameter of the steel core is 180 mm, the thickness of the silicone layer is 20 mm, and
the
thelength
lengthofofthe
thesilicone
siliconeroller
rollerisis1.2
1.2m.m.The
Theoperation
operationof ofthe
theheating
heatingpart
partandandthethepressing
pressing
device
deviceare
arecontrolled
controlledby byaaconsole,
console,whichwhichsends
sendsinstructions
instructionsthrough
throughaahuman–computer
human–computer
interaction
interaction panel to control the rotation speed and temperature of
panel to control the rotation speed and temperature of the
the rollers,
rollers, respectively.
respectively.

Figure2.2.Lamination
Figure Laminationexperimental
experimentalequipment.
equipment.

Theprinciple
The principleof
oflamination
laminationexperiment
experimentisisshown
shownin inFigure
Figure3.3.TheThelaminating
laminatingequip-
equip-
mentconsists
ment consistsofofthree
threeparts:
parts:heating
heatingroller,
roller,laminating
laminatingroller,
roller,and
andworktable.
worktable.TheTheheating
heating
roller
roller isisused
usedtotoprovide
providethe
thetemperature
temperaturerequired
requiredduring
duringthethelamination
laminationprocess.
process.The
The
worktable
worktablecan cancontrol
controlthe
theheating
heatingtemperature
temperatureofofthe theheating
heatingroller
rollerand
andthe
therotation
rotationspeed
speed
of
ofthe
thelaminating
laminatingroller.
roller.The
ThePET
PETfilm
filmisisfirst
firstfixed
fixedononthe
thesurface
surfaceof ofthe
theTFS
TFSwith
withaahigh-
high-
temperature
temperature adhesive tape, and then placed in the laminating device horizontally.The
adhesive tape, and then placed in the laminating device horizontally. The
PET film and TFS substrate are laminated under the double pressure of heating roller and
silicone roller.
 cooling roller. Therefore, under the dual effects of TFS heating and silicon resin roll cool-
ing, a temperature gradient appears inside the PET along the thickness direction, forming
a partial melting. The PET film melts completely on the side near the TFS but does not
melt on the side near the silicone roller. After the PET film and TFS leave the heating roller
and the silicone roller, the PET film is quickly cooled with a coolant to quickly solidify the
Coatings 2021, 11, 472 4 of 15
molten part of the PET, thereby avoiding recrystallization of the PET. Finally, the prepa-
ration of PCS material is completed.

Laminating roller
Polymer
Silicone layer
Laminating roll

TFS

Running direction
Running direction

Heating roller

Figure 3. Schematic
Figure 3. Schematic diagram
diagram of
of laminating
laminating process.
process.

2.2.2.During the laminating

Experimental Schemeprocess, the heating roller acts as a heat source to continuously
provide heat to the TFS, and the TFS transfers the heat to the PET film and then to the
The size of the TFS sample plate is 150 mm × 10 mm × 0.18 mm, and the size of the
silicone roller. The silicone roller maintains a constant temperature under the action of
PET film is roller.
the cooling 130 mm × 8 mm. under
Therefore, As thethe
sample size is relatively
dual effects small,and
of TFS heating thesilicon
electromagnetic
resin roll
induction heating roller in the pressing device can provide enough
cooling, a temperature gradient appears inside the PET along the thickness heat for the TFS, so
direction,
this experiment only uses the pressing device for lamination. By controlling
forming a partial melting. The PET film melts completely on the side near the TFS but the rotation
speednot
does andmelt
temperature
on the sideof the
nearelectromagnetic induction
the silicone roller. After heating
the PETroller, the lamination
film and test
TFS leave the
under different temperature and speed conditions was carried out. The lamination
heating roller and the silicone roller, the PET film is quickly cooled with a coolant to quickly test
under different pressure conditions can be carried out by controlling the displacement
solidify the molten part of the PET, thereby avoiding recrystallization of the PET. Finally, of
the silicone rubber roller. The experimental
the preparation of PCS material is completed. scheme is shown in Table 1.

Table Experimental
2.2.2. 1. PCS experimental
Schemeprotocol.
The size ofNumber
Sample is 150 mm ×(K)
the TFS sample plateTemperature 10 mm × 0.18 mm, andSpeed(m/min)
Laminating the size of the
PET film is 1301 mm × 8 mm. As the sample size is relatively small, the electromagnetic
528 3
induction heating
2 roller in the pressing device
528 can provide enough heat 6for the TFS, so
this experiment 3 only uses the pressing device
528 for lamination. By controlling 9 the rotation
speed and temperature
4
of the electromagnetic
533
induction heating roller, the lamination test
3
under different temperature and speed conditions was carried out. The lamination test
5 533 6
under different pressure conditions can be carried out by controlling the displacement of
6 533 9
the silicone rubber roller. The experimental scheme is shown in Table 1.
7 538 3
8 538 6
Table 1. PCS experimental protocol.
9 538 9
Sample Number Temperature (K) Laminating Speed(m/min)
1 528 3
2 528 6
3 528 9
4 533 3
5 533 6
6 533 9
7 538 3
8 538 6
9 538 9

2.3. Scanning Electron Microscope Experiment (SEM)

The PCS cross-section observation experiment was carried out on a scanning electron
microscope (ZEISS GeminiSEM 500, Aalen, Germany). The PCS cross-section was analyzed
by line scan using the matching EDS spectrometer to obtain the Fe, C, O, and Cr element
content on the cross-section.
Coatings 2021, 11, x FOR PEER REVIEW 5 of 15

2.3. Scanning Electron Microscope Experiment (SEM)

Coatings 2021, 11, 472 5 of 15
The PCS cross-section observation experiment was carried out on a scanning electron
microscope (ZEISS GeminiSEM 500, Aalen, Germany). The PCS cross-section was ana-
lyzed by line scan using the matching EDS spectrometer to obtain the Fe, C, O, and Cr
elementThecontent
sampleon thewas
size cross-section.
10mm × 10mm × 0.18mm. Alcohol was used to clean the surface
The
of the sampleand
sample, sizethen
wasthe
10mm × 10mm
sample × 0.18mm.
was placed in anAlcohol wascleaning
ultrasonic used to clean the for
machine surface
deep
ofcleaning
the sample,
for 5and
min.thenA the
fan sample wastoplaced
was used in an
dry the ultrasonic
sample cleaning
surface. It wasmachine forwhere
observed deep
cleaning
bubbles for 5 min. A
appeared at fan
the was
crossused to dry the sample surface. It was observed where bub-
section.
bles appeared at the cross section.
2.4. Differential Scanning Calorimetry (DSC)
2.4. Differential
The thermal Scanning Calorimetry
performance (DSC)
of the PET film was performed on a differential scanning
calorimeter
The thermal performance of the PET film wasNitrogen
(DSC 214 Polyma, Selb, Germany). performedwasonused as a protective
a differential gas.
scanning
calorimeter (DSC 214 Polyma, Selb, Germany). Nitrogen was used as a protective gas. Theis
The material required for the experiment was 3 to 5 mg. The implementation scheme
shown in
material Figure for
required 4. First, the temperature
the experiment was 3 towas raised
5 mg. The to 573.15 K at a rate
implementation of 50
scheme K/min,
is shown
and the temperature was kept for five minutes to eliminate the thermal
in Figure 4. First, the temperature was raised to 573.15 K at a rate of 50 K/min, and history ofthe
the
temperature was kept for five minutes to eliminate the thermal history of the material.K
material. Then it was cooled to 298.15 K at a rate of 10 K/min, and then heated to 573.15
at 10 itK/min
Then [27,28].to The
was cooled experimental
298.15 K at a rate results use theand
of 10 K/min, curve
thenduring
heatedtheto second
573.15 K heating
at 10
process.
K/min [27,28]. The experimental results use the curve during the second heating process.

Constant temperature 5min

300
Temperature (K)

10 K/min
10 K/min

50 K/min

50 K/min
25

Time (s)
Differentialscanning
Figure4.4.Differential
Figure scanningcalorimetry
calorimetryexperiment
experimentprocess.
process.

2.5. Micro-Scratch Tester

2.5. Micro-Scratch Tester
The PCS interface bonding performance was performed on a micro-scratch tester
The PCS interface
(CSM—MCT, bonding performance
Peseux, Switzerland). The load was settingperformed
value was on15aN.micro-scratch tester
The scratch length
(CSM—MCT, Peseux , Switzerland). The load setting value was
was 5 mm. The test temperature was 293.15 K, and the air humidity was 60%. A round 15 N. The scratch length
was 5 mm.indenter
diamond The testwith
temperature
a radius of was100293.15
um was K, and
used,the
andairthe
humidity
experiment was was
60%.carried
A round out
diamond
perpendicular to the sample surface in a progressive loading manner. Through online out
indenter with a radius of 100 um was used, and the experiment was carried real-
perpendicular
time observation to the sample
of the contact surface
pressurein at
a progressive
the indenter, loading
acoustic manner. Through
signals, friction, online
reduction
real-time observation of the contact pressure at the indenter, acoustic
depth, residual depth and other information, the interface bonding strength of different signals, friction, re-
duction depth, residual depth and other information, the interface
samples and the failure mechanism of the sample surface lamination were compared and bonding strength of
different
analyzed. samples and themethod
The drawing failure is mechanism of the
a straight-line sampleatsurface
drawing a constantlamination weresample
speed. The com-
pared
size wasand10analyzed.
mm × 10The mm. drawing method iswas
The experiment a straight-line
repeated three drawing
times forat aeach
constant speed.
sample. The
The sample size was 10 mm × 10 mm.
average value was taken as the experimental result. The experiment was repeated three times for each
sample. AnThe average
acoustic value was
emission (AE)taken
sensoras was
the experimental
installed on the result.
scratch meter to monitor the
An acoustic emission (AE) sensor was installed
sound signal generated during the scratching process. Before on the scratch meter to monitor
the experiment, alcohol the
and
sound
an air signal generated
gun were used toduring
clean the the sample,
scratching process.
using Before the
an MH-008S experiment,
ultrasonic alcohol
cleaning and
machine
anto air gun were
perform used to
ultrasonic clean the
cleaning onsample,
the sampleusing
foran MH-008S
3 min, ultrasonic
and alcohol cleaning
as the machine
cleaning solvent.
toDuring
performthe ultrasonic
experiment,cleaning
an optical onmicroscope
the sample was forused
3 min, and alcohol
to observe as the
the scratch cleaning
morphology
of the sample surface. Then, a scratch test was performed on each sample. During the
experiment, the stroke speed was 5 mm/min, the loading pressure range was 0.01 to 15 N,
and the load was gradually loaded. The load increase rate was 15 N/min, the acoustic
sensor sensitivity was set to 9, and the acoustic signal acquisition frequency was 30 Hz.
 solvent. During the experiment, an optical microscope was used to observe the scratch
morphology of the sample surface. Then, a scratch test was performed on each sample.
During the experiment, the stroke speed was 5 mm/min, the loading pressure range was
Coatings 2021, 11, 472 0.01 to 15 N, and the load was gradually loaded. The load increase rate was 15 N/min, 6 ofthe
15
acoustic sensor sensitivity was set to 9, and the acoustic signal acquisition frequency was
30 Hz.

3.3.Results
Resultsand
andDiscussion
Discussion
3.1.
3.1. CharacterizationofofInterface
Characterization InterfaceBinding
BindingRate
Rate
The
ThePCS
PCSsample
sampleprepared
prepared bybythethe
roll-pressing
roll-pressinghot-melt coating
hot-melt process
coating has irregularly
process has irregu-
shaped
larly shaped white spots on the surface of the coated sample, as shown in The
white spots on the surface of the coated sample, as shown in Figure 5. existence
Figure 5. The
of white spots greatly affects the aesthetics of PCS samples, and there may
existence of white spots greatly affects the aesthetics of PCS samples, and there may bebe problems
with the quality
problems of the
with the film.ofInthe
quality order
film.toIn
explore
order totheexplore
formation factors of this
the formation typeofof
factors defect
this type
and the influence of the process parameters on the area, the number and shape of white
of defect and the influence of the process parameters on the area, the number and shape
spots, cross-sectional observation experiments and surface image recognition of white
of white spots, cross-sectional observation experiments and surface image recognition of
spots were carried out using scanning electron microscopes and scanners.
white spots were carried out using scanning electron microscopes and scanners.

Figure5.5.Polymer-coated
Figure Polymer-coatedsteel
steelsample.
sample.

Takingthe
Taking thePCSPCSsample
sampleprepared
preparedwith withthe
theheating
heatingroller
rollertemperature
temperatureof of528
528KKandand
the film speed of 9 m/min as the object, the white spots on the surface
the film speed of 9 m/min as the object, the white spots on the surface of the sample of the sample were
randomly
were selected
randomly for SEM
selected forcross-sectional observation.
SEM cross-sectional As shown
observation. in Figure
As shown in6,Figure
the polymer
6, the
film was film
polymer separated from the chrome-plated
was separated steel strip. steel
from the chrome-plated Usingstrip.
an EDS energy
Using an spectrometer
EDS energy
to perform a to
spectrometer line scan analysis
perform in the
a line scan direction
analysis perpendicular
in the to the interface,
direction perpendicular it was
to the found
interface,
itthat
wasthere is athat
found gapthere
of about 40-um
is a gap of thickness
about 40-um between the polymer
thickness betweenand the the chrome-plated
polymer and the
steel strip. Thesteel
chrome-plated content ofThe
strip. C, O, and Feofelements
content C, O, andinFethe gap hadina the
elements significant
gap haddrop, indicat-
a significant
ing that
drop, there were
indicating that bubbles
there were between
bubblesthebetween
polymer film
the and the
polymer filmchrome-plated steel strip.
and the chrome-plated
Therefore,
steel strip. the white spots
Therefore, observed
the white onobserved
spots the PCS surface
on the are
PCSdue to bubbles
surface are dueformed by the
to bubbles
separation
formed of the
by the film/iron
separation ofinterface.
the film/iron interface.
The reason for the bubble generation should be a surface defect formed by the fast
coating speed during the roll-coating process, and the gas between the chrome-plated
 is no common interface between the substrate and PET. The uneven temperature distri-
bution on the TFS surface during the coating process can cause bubbles to appear on the
PCS surface. The melting thickness of PET is mainly determined by the heating tempera-
ture of the TFS surface. When the temperature is lower than the melting point of PET, PET
does not melt. Unmelted PET cannot be combined with TFS due to its inactive molecular
Coatings 2021, 11, 472 7 of 15
segment structure, and bubbles are formed. So, the non-wetting behavior of the steel by
molten PET is the cause of the bubble formation.

Figure 6. Scanning electron

Figure micrograph
6. Scanning of PCS interface.
electron micrograph of PCS interface.

An interface bonding rate is

The reason fordefined
the bubbleto characterize
generationthe area be
should of the “bubble”
a surface surface
defect formed by the fast
defect. As shown in Equation (1), Stotal is the total area of the selected area, Sbubble is
coating speed during the roll-coating process, and the gas between the chrome-plated steel
strip and the polymer film cannot escape in time. Bubble formation is because there is no
the bubble area, and r is the binding rate. The test was repeated three times for each sam-
common interface between the substrate and PET. The uneven temperature distribution
ple, and the average value was taken as the final result.
on the TFS surface during the coating process can cause bubbles to appear on the PCS
surface. The melting S − Sbubble of PET is mainly determined by the heating temperature
r = totalthickness × 100% (1)
of the TFS surface. When Stotalthe temperature is lower than the melting point of PET, PET
does not melt. Unmelted PET cannot be combined with TFS due to its inactive molecular
In order tosegment
study thestructure,
thermal properties
and bubbles of the
are PET at theSo,
formed. bubble, the DSC experiment
the non-wetting behavior of the steel by
was performedmolten
on the PET film at the bubble on the PCS
PET is the cause of the bubble formation.surface and the non-bubbled PET
film, and the DSC curve of the original
An interface bonding PET before
rate lamination
is defined was used the
to characterize as aarea
comparative
of the “bubble” surface
analysis. defect. As shown in Equation (1), Stotal is the total area of the selected area, Sbubble is the
During thebubble
lamination process,
area, and thebinding
r is the PET film is partially
rate. melted
The test was in the three
repeated thickness
timesdi-for each sample,
rection under the heating action of TFS and the cooling action
and the average value was taken as the final result. of the laminating roll. Then,
under the action of the cooling liquid, the molten part is cooled and solidified and trans-
formed into an amorphous layer. During the heating S − Sbubble of the DSC experiment,
process
r = total × 100% (1)
when the temperature of the laminated PET film is between Stotal 310 K and 350 K, the part of
the amorphous layer in the PET recrystallizes and absorbs heat to produce an endothermic
In order
peak. The ideal original PETtofilm
study is the thermal properties
a crystalline polymer,ofand
the its
PETDSCat the bubble,
curve doesthe DSC experiment
not
was performed on the PET film at the bubble on the PCS surface and the non-bubbled PET
produce an endothermic peak. As shown in Figure 7, by comparing the size of the PET
film, and the DSC curve of the original PET before lamination was used as a comparative
analysis.
During the lamination process, the PET film is partially melted in the thickness
direction under the heating action of TFS and the cooling action of the laminating roll.
Then, under the action of the cooling liquid, the molten part is cooled and solidified and
transformed into an amorphous layer. During the heating process of the DSC experiment,
when the temperature of the laminated PET film is between 310 K and 350 K, the part of
the amorphous layer in the PET recrystallizes and absorbs heat to produce an endothermic
peak. The ideal original PET film is a crystalline polymer, and its DSC curve does not
 Coatings 2021, 11, x FOR PEER REVIEW 8 of 15
Coatings 2021, 11,
Coatings x FOR
2021, PEER REVIEW
11, 472 8 of 158 of 15

endothermic
endothermic peak inpeak
the in theexperimental
DSC DSC experimentalcurve,curve,
it can it
becan be determined
determined whetherwhether the PET
the PET
produce an
film melts. endothermic peak. As shown in Figure 7, by comparing the size of the PET
film melts. It can It
becan be found
found that
that the thecurves
DSC DSC curves
of PETofatPETthe at the bubble
bubble and PET andbefore
PET before
lam- lam-
endothermic
ination peak in the
basically overlap. DSC experimental
It shows that curve,
thefilm
PETdoes it can
filmnot
does be determined
notatmelt at whether
the bubble. the PET
ination
filmbasically
melts. overlap.
It can beItfound
shows that the
that the PET
DSC curves of PET melt
at thethe bubble.
bubble and PET before
lamination basically overlap. It shows that the PET film does not melt at the bubble.

Figure
7. DSC7.7.curves
FigureFigure DSCcurves
DSC curves of
of PETof PETbefore
PET
before before lamination,
lamination,
lamination, atatbubble,
at bubble, bubble, andlamination.
and
and after afterlamination.
after lamination.

AAscanner
scanner was
wasusedused to scan the
thesurface images of thethe
samples prepared under different
A scanner was used to scantothe
scansurface surface
images images
of the of samples samples
prepared prepared
underunder
differ-differ-
process
ent conditions.
process Use Use
conditions. image recognition
image recognition software
softwareto perform
to performsecondary processing
secondary processingon
ent process conditions. Use image recognition software to perform secondary processing
scanned
on scanned images.images. Use Python
Use Python language
language to write
to write a picture
a picture color recognition
color recognition program,
program,
on scanned images. Use Python language to write a picture color recognition program,
calculate the area of the white part and the area ofofthe gray part ininthe picture. The white
calculate the area of the white part and the area of the gray part in the picture. The white white
calculate the area of the white part and the area the gray part the picture. The
part is the bubble. Calculate the interface binding rate according to formula (1). As shown
part ispart is the bubble.
the bubble. Calculate
Calculate the interface
the interface binding binding rate according
rate according to formula
to formula (1). As(1).
shown As shown
in
inFigure
Figure 8,8,the
the picture
picture on
on the
the left
left isisaafilm-coating
film-coating test,
test,using
using image
image software
software totoidentify
identify
in Figure 8, the picture on the left is a film-coating test, using image software to identify
the surface of the sample. The blue part in the picture on the right isisthe part with a good
the surface of the sample. The blue part in the picture on the right is the part with a gooda good
the surface of the sample. The blue part in the picture on the right the part with
combination,
combination, and the
andwhite white
the white part is the bubble. It was calculated that the area ofofwhite
combination, and the part ispartthe isbubble.
the bubble.
It wasItcalculated
was calculated
that the thatarea
theof
area
white white
bubbles accounts for 37.9% of the total area. Therefore, the interface binding rate of the
bubbles accounts for 37.9% of the total area. Therefore, the interface binding rate of the the
bubbles accounts for 37.9% of the total area. Therefore, the interface binding rate of
sample
sample is 62.1%.
is 62.1%.
sample is 62.1%.

Figure
8. PCS8.8.
FigureFigure PCSinterface
PCS interface
interface binding
binding
binding rate.
rate. rate.
Coatings 2021, 11, x FOR PEER REVIEW 9 of 15

Coatings 2021, 11, 472 9 of 15

3.2. Effect of Process Parameters on the Binding Rate

As shown in the test plan in Table 1, the gap between the roll gaps is 5 um, and the
3.2. Effect of Process Parameters on the Binding Rate
surface roughness of the chrome-plated steel strip is 0.2 um. Taking the heating roller
As shown
temperature in the test
and filming planasinindependent
speed Table 1, the variables,
gap betweenandthe
theroll gaps isbonding
interfacial 5 um, and the
rate
surface roughness of the chrome-plated steel strip is 0.2 um. Taking the heating
as dependent variables, the influence of the heating roller temperature and filming speed roller
ontemperature and filming
the PCS interface bondingspeed as independent
rate was variables, and
studied. The temperature of the interfacial
the heating bonding
roller was
rate as dependent variables, the influence of the heating roller temperature
528 K, 533 K, and 538 K; the film speed was 3 m/min, 6 m/min, and 9 m/min. Surface and filming
speed on the PCS interface bonding rate was studied. The temperature of the heating
scanning and image recognition processing were performed on the coated PCS samples
roller was 528 K, 533 K, and 538 K; the film speed was 3 m/min, 6 m/min, and 9 m/min.
to characterize the binding rate. Each sample was randomly selected from three different
Surface scanning and image recognition processing were performed on the coated PCS
locations for testing, and finally, the average value was calculated. The size of each in-
samples to characterize the binding rate. Each sample was randomly selected from three
spection image is 30 mm × 30 mm. The interface bonding ratio of sample 1 to sample 9 is
different locations for testing, and finally, the average value was calculated. The size of
shown in Figure 9, and the corresponding test parameters are shown in Table 1 test
each inspection image is 30 mm × 30 mm. The interface bonding ratio of sample 1 to
scheme.
sample 9 is shown in Figure 9, and the corresponding test parameters are shown in Table 1
test scheme.

Figure 9. PCS interface binding rate (r) under different heating temperature (T) and speed (v) conditions.
Figure 9. PCS interface binding rate (r) under different heating temperature (T) and speed (v) con-
ditions.Samples 1 to 3 are coated samples with a heating roller temperature of 528 K and a
coating speed of 3 m/min, 6 m/min, and 9 m/min. Comparing sample 1, sample 2 and
sample 3, it can be found that the bubbles on the surface of sample 3 are obvious, while
Coatings 2021, 11, 472 10 of 15

the bubbles on the surface of samples 1 and 2 are relatively few. Comparing samples 4 to
6 and samples 7 to 9, the same pattern can be found. Under the same heating roll degree
and reduction conditions, as the coating speed increases, the PCS surface bonding rate
gradually decreases. This is because the lower coating speed increases the PCS coating time.
The increase in the coating time leads to an increase in the heat transfer time of the film iron,
which increases the internal temperature of the polymer film and increases the melting of
the polymer film. Thickness improves the interface bonding rate. At the same time, the
reduction of the coating speed also increases the heat transfer time between the heating
roller and the chrome-plated steel, making the surface temperature of the chrome-plating
steel more uniform, so that the high polymer films are melted. The cause of bubbles on the
surface of the coated sample may be the low melting thickness of the polymer film, and the
faster coating speed reduces the heat transfer time at the film/iron interface and increases
the instability of the surface temperature of the chrome-plated steel strip. On the contrary,
when the coating speed is low, the increase of heat transfer time at the film/iron interface
makes PET easier to melt, the number of bubbles on the surface of PCS decreases and the
binding rate increases. Therefore, in order to ensure the bonding rate of the PCS coating
interface and ensure an effective coating quality, the coating speed should be reduced.
Comparing sample 1, sample 4, and sample 7, it can be found that as the temperature
of the heating roller increases, the bubbles on the surface of the PCS gradually decrease,
and the interface bonding rate gradually increases. Under the same laminating speed, the
laminating time is the same, but as the temperature of the heating roller increases, the
internal temperature of the PET film increases. Comparing the law of the influence of the
coating speed on the bonding rate of the PCS interface, it can be found that the bonding
rate of the PCS interface has a great relationship with the internal temperature of the PET
film. The increase in the temperature of the heating roller directly leads to an increase in the
internal temperature of the PET and improves the bonding rate of the PCS interface. Table
2 shows the experimental results of each binding rate test and the standard deviation of the
binding rate. Figure 10 shows the interface bonding rate of the coated samples prepared
under the conditions of different heating roller temperatures and filming speeds. It can be
found that the influence of the heating roller temperature on the interface bonding rate is
much smaller than that of the filming speed. The effect of heat transfer time on the bonding
rate is much greater than the initial heating temperature of the polymer film.

Table 2. PCS interface bonding rate under different temperature and speed conditions.

Binding Rate
Sample Temperature Laminating Speed
Number (K) (m/min) Average Standard
1 2 3
Value (%) Deviation (%)
1 528 3 98.91 99.58 99.14 99.21 0.28
2 528 6 73.2 84.36 71.94 76.5 5.58
3 528 9 37.4 33.11 40.19 36.9 2.91
4 533 3 99.85 99.89 99.66 99.8 0.1
5 533 6 94.25 97.63 97.11 96.33 1.49
6 533 9 56.33 48.33 49.24 51.3 3.57
7 538 3 99.89 99.93 99.88 99.9 0.02
8 538 6 99.3 99.67 96.83 98.6 1.26
9 538 9 59.31 66.43 60.53 62.09 3.11
 Coatings2021,
Coatings 11,x 472
2021,11, FOR PEER REVIEW 11 11
of of1515

3 m/min
6 m/min
99.21 99.8 99.9 98.6 9 m/min
100 96.33

Binding rate (%)

80 76.5

62.09
60
51.3

40 36.9

20

0
528 533 538
Temperature (k)
Figure10.
Figure PCS
10.PCS interface
interface bondingrate
bonding rate(r)(r)under
underdifferent
differenttemperature
temperature(T)
(T)and
andspeed
speed(v)
(v)conditions.
conditions.

The bonding rate between the chrome-plated steel strip and the polymer film interface
The bonding rate between the chrome-plated steel strip and the polymer film inter-
is intended to indicate the problem of bubble defects on the surface of the finished PCS.
face is intended to indicate the problem of bubble defects on the surface of the finished
Through the coating test and the bonding rate detection test under different test parameters,
PCS. Through the coating test and the bonding rate detection test under different test pa-
it is found that the main factor affecting the area and number of bubbles at the film/iron
rameters, it is found that the main factor affecting the area and number of bubbles at the
bonding interface is the coating speed. This is because the decrease in the coating speed
film/iron bonding interface is the coating speed. This is because the decrease in the coating
increases the film/heat transfer time at the iron interface and the heating time of the
speed increases the film/heat transfer time at the iron interface and the heating time of the
chrome-plated steel strip. The increase in the heating time of the chrome-plated steel strip
chrome-plated steel strip. The increase in the heating time of the chrome-plated steel strip
makes the surface temperature of the steel strip more uniform and consistent, thereby
makes the surface temperature of the steel strip more uniform and consistent, thereby
reducing the interface bonding rate.
reducing the interface bonding rate.
3.3. Interfacial Damage and Failure Mechanisms
3.3. Interfacial Damage and Failure Mechanisms
The micron scratch test was performed on samples 1, 2, 3, 6, and 9. Holmberg [29]
The micron
studied scratch test
the deformation was performed
behavior of the diamondon samples
spherical 1, 2, 3, 6, and
indenter 9. Holmberg
sliding [29]
on the surface
studied the deformation behavior of the diamond spherical indenter
of TiN coated steel through the scratch experiment and used a finite element to simulate the sliding on the surface
ofstress
TiN coated
and cracksteel through during
formation the scratch experimentprocess.
the scratching and used It isa pointed
finite element
out that tothe
simulate
contact
the
and stress and crack
deformation formationbetween
mechanism duringthe theindenter
scratching andprocess.
the coating It is
can pointed
be divided out into
that three
the
contact
types: and deformation
ploughing, mechanism
interface sliding and between the indenter
fracture. and thestage,
In the plowing coating thecan be divided
indenter slides
into three
on the types:ofploughing,
surface the coating,interface sliding material
and the coating and fracture.
undergoesIn theelastoplastic
plowing stage, the in-
deformation
denter
to form slides on the
grooves surface
on the of the
surface. Thecoating,
interface and the coating
sliding stage is material
during the undergoes
movement elasto-
of the
plastic deformation to form
spherical indenter, the front surface ofgrooves on the surface. The interface sliding
indenter rubs against the upper surface of thestage is during
the movement
coating, and the of the spherical
bending indenter,ofthe
or stretching thefront
coatingsurface of the indenter
is accompanied by the rubs against the
generation and
upper
release surface of the
of stress. coating,
Fracture is and the bending
the separation ofor
thestretching
coating from of thethecoating is accompanied
base material.
by theThe scratch morphology
generation and release of in stress.
Figure Fracture
11 showsisthat theinseparation
the initial ofstage
theofcoating
pressure fromapplica-
the
tion,material.
base no obvious scratches are left on the surface of the sample, and the polymer film mainly
undergoes
The scratchelastic deformation.
morphology As the 11
in Figure pressure
showsof theinindenter
that the initialincreases,
stage ofthe surfaceappli-
pressure of the
polymer film has dents and plastic deformation occurs. This
cation, no obvious scratches are left on the surface of the sample, and the polymer film stage is the plowing stage, and
the polymer
mainly undergoesfilm elastic
has undergone
deformation. elastoplastic deformation.
As the pressure of theAs the pressure
indenter increases,increases,
the sur- the
indenter
face of the and the film
polymer filmslide relatively,
has dents and and thedeformation
plastic film deformsoccurs. to release
Thisthe stress.
stage is theThen,
plow- the
film
ing breaks
stage, andtotherelease
polymer the stress
film has again. It can beelastoplastic
undergone seen from the scratch morphology
deformation. As the pressure map in
increases, the indenter and the film slide relatively, and the film deforms to releasebefore
Figure 11 that there is no crack or film/iron separation on the surface of the sample the
and after
stress. Then, thethe
scratch
film experiment,
breaks to release only athe dent formed
stress by the
again. scratch
It can track.from
be seen It shows that the
the scratch
stress caused
morphology mapby inploughing,
Figure 11interface
that theresliding, and fracture
is no crack or film/iron during the experiment
separation did not
on the surface
affect the area outside the scratch track. It indirectly indicates
of the sample before and after the scratch experiment, only a dent formed by the scratch that the bonding strength
between
track. the polymer
It shows that the filmstressand the chrome-plated
caused by ploughing,steel sheet sliding,
interface is greater andthan the sum
fracture of the
during
pressure required to cause the film to undergo plastic deformation,
the experiment did not affect the area outside the scratch track. It indirectly indicates that bending and stretching.
the bonding strength between the polymer film and the chrome-plated steel sheet is
 As shown in Figure 11, when the scratch length is 0.9 mm, the slope of the penetration
depth and the residual depth has abrupt changes, and the acoustic signal and friction have
also changed significantly. Combining with the scratch topography, it can be concluded
that the polymer film has been completely broken. Due to the large difference between
Coatings 2021, 11, 472 the elastic modulus of PET and TFS, the sudden gradual penetration depth indicates 12 that
of 15
the indenter has touched TFS, resulting in a decrease in penetration depth as the pressure
of the indenter increases. The sudden change in friction is also caused by the difference in
the coefficient of dynamic friction between the indenter and PET and TFS. The head pres-
Fromcorresponding
sure the perspective of PCS
to 0.9 mm product application,
is approximately scratches
2.5 N. onconcluded
It can be the PCS surface
that thewill not
critical
cause cracks near the scratches and film/iron
load of this coated sample is about 2.5 N. separation.

Figure 11. Schematic diagram of scratch morphology.

Figure 11. Schematic diagram of scratch morphology.
The penetration depth is the depth at which the indenter penetrates into the sample
during the experiment, the residual depth is the depth after the material rebounds, and
the difference between the penetration depth and the residual depth is the elastic recovery
of the film. The difference between the penetration depth and the elastic recovery is the
plastic deformation of the film.
As shown in Figure 11, when the scratch length is 0.9 mm, the slope of the penetration
depth and the residual depth has abrupt changes, and the acoustic signal and friction have
also changed significantly. Combining with the scratch topography, it can be concluded
that the polymer film has been completely broken. Due to the large difference between the
elastic modulus of PET and TFS, the sudden gradual penetration depth indicates that the
indenter has touched TFS, resulting in a decrease in penetration depth as the pressure of
the indenter increases. The sudden change in friction is also caused by the difference in the
coefficient of dynamic friction between the indenter and PET and TFS. The head pressure
corresponding to 0.9 mm is approximately 2.5 N. It can be concluded that the critical load
of this coated sample is about 2.5 N.

3.4. Effect of Process Parameters on the Bonding Strength

As shown in the experimental program in 2.2.2, the micro-scratch test was performed
on samples 1-3, 6, and 9. Figure 12 (a–c) are graphs of micron scratches when the heating
2021, 11, x FOR PEER REVIEW 13 of 15

Coatings 2021, 11,3.4.

472 Effect of Process Parameters on the Bonding Strength 13 of 15

As shown in the experimental program in 2.2.2, the micro-scratch test was performed
on samples 1-3, 6, and 9. Figure 12 (a–c) are graphs of micron scratches when the heating
roller temperature is 528
roller K and theis film
temperature speed
528 K is 3film
and the m/min,
speed6 m/min and 96m/min.
is 3 m/min, m/minThe
and 9 m/min. The
critical loads corresponding
critical loadsto a-c are 3.15 N,to2.88
corresponding a-c N,
areand
3.152.65 N, respectively.
N, 2.88 N, and 2.65 N, respectively.

2.5
3.15N 2.0
2.88
（a）T = 255
（a）T=528 K, ℃, v = 3m / min
v=3 m/min （b）T = 255
（b）T=528 K, ℃, v = 6m / min
v=6 m/min
0

Penetration depth (um)

Penetration depth (um)

0
2.0
1.5 -3
-3

Friction (N)
Friction (N)

1.5
-6
-6 1.0
1.0 Friction Friction -9
Penetration depth -9 Penetration depth
0.5
0.5 -12
-12
-15
0.0 0.0
-15
-18
0 1 2 3 4 0 1 2 3 4
Pressure (N) Pressure (N)

2.65N 2.76N
（c）T = 255
（c）T=528 K, ℃, v = 9m / min
v=9 m/min （d）T = 260
（d）T=533 K, ℃, v = 9m / min
v=9 m/min
Penetration depth (um)

2.0

Penetration depth (um)

0 1.5 0

-3 -3
1.5
Friction (N)
Friction (N)

1.0
-6 -6
1.0 Friction
Friction
Penetration depth -9
Penetration depth -9 0.5
0.5
-12
-12

0.0 0.0 -15

-15
0 1 2 3 4 0 1 2 3 4
Pressure (N) Pressure (N)

2.0
2.86N 3
（e）T = 265
（e）T=538 K, ℃, v = 9m / min
v=9 m/min
Penetration depth (um)

0
1.5
Friction (N)

-3

1.0 -6
Friction
Penetration depth -9
0.5

-12
0.0
-15
0 1 2 3 4
Pressure (N)

Figure 12. Critical load of sample under different process parameters ((a–c) correspond to lamination speed 3 m/min, 6
m/min, 9 Figure
m/min,12. (d,e) correspond
Critical load of to heating
sample temperature
under different 533 K, 538
process K).
parameters ((a-c) correspond to lamina-
tion speed 3 m/min, 6 m/min, 9 m/min, (d,e) correspond to heating temperature 533 K, 538 K).
As the lamination speed increases, the critical load of the sample gradually decreases,
and the bonding
As the lamination speed strength
increases, of the PCS
the critical load interface gradually
of the sample graduallydecreases. This is because as
decreases,
and the bondingthe lamination
strength of thespeed increases,gradually
PCS interface the contact time of the
decreases. Thislamination
is becausezone
as thedecreases during
lamination speed increases, the contact time of the lamination zone decreases during the at the contact
the lamination process, which leads to a decrease in the heat transfer time
interface
lamination process, whichofleads
PETtoand TFS, which
a decrease in theinheat
turntransfer
causestime
the melt
at thethickness of PET to decrease.
contact inter-
According to the principle of the PCS roll hot melt lamination
face of PET and TFS, which in turn causes the melt thickness of PET to decrease. According process, the high polymer
to the principle of the PCS roll hot melt lamination process, the high polymer film is par- chrome-plated
film is partially melted in the thickness direction under the heating of the
steel
tially melted in the during direction
thickness the lamination
underprocess. Theofmolten
the heating part of the substance
the chrome-plated quickly transforms
steel during
the lamination process. The molten part of the substance quickly transforms into an amor- polymer during
into an amorphous substance to reduce the recrystallization of the molten
phous substancethe coolingthe
to reduce process. Therefore,ofthe
recrystallization thekey to improving
molten the bonding
polymer during strength of the PCS
the cooling
interface is to increase the thickness of the polymer amorphous layer. The increase in the
process. Therefore, the key to improving the bonding strength of the PCS interface is to
filming speed reduces the melting thickness of the polymer film, resulting in a decrease in
the interface bonding strength.
Coatings 2021, 11, 472 14 of 15

Figure 12c–e are the samples under different heating temperatures and the same
laminating speed. The critical loads of the coated samples correspond to the heating
temperatures of 528 K, 533 K and 538 K are 2.65 N, 2.76 N, and 2.86 N, respectively. As
the heating temperature increases, the bonding strength of the PCS interface increases.
Under the same lamination speed, the heat transfer time in the laminating area is the same,
but an increase of the heating temperature can directly lead to an increase of the melting
thickness of the polymer film. Therefore, increasing the heating temperature can increase
the bonding strength of the PCS interface.

4. Conclusions
The lamination temperature and lamination speed during the lamination process
have an important influence on the interface bonding quality of PCS materials. As the
lamination temperature increases, the PCS interface bonding rate gradually increases, and
the interface bonding strength gradually increases. As the lamination speed increases,
the PCS interface bonding rate gradually decreases, and the interface bonding strength
gradually decreases. The PCS interface bonding rate and interface bonding strength are
positively correlated. Increasing the lamination temperature and reducing the lamination
speed are effective measures to improve the bonding rate and bonding strength of the PCS
interface. SEM and DSC experiments revealed that the non-wetting behavior of the steel by
molten PET is the cause of the bubble formation. It is speculated that the main reason is
that the surface temperature of TFS is uneven during the filming process, which leads to
the formation of bubbles in some areas of the polymer film not melting. Relevant research
results provide guidance for enterprise production.

Author Contributions: Conceptualization, J.L., Q.Z.; methodology, B.Z.; software, J.L., and M.Y.;
validation, J.L.; formal analysis, J.L.; investigation, J.L.; resources, J.L.; data curation, M.Y.; writing—
original draft preparation, J.L., M.Y.; writing—review and editing, J.L., B.Z.; visualization, J.L., B.Z.;
supervision, Q.Z.; project administration, Q.Z., J.L., and B.Z.; funding acquisition, Q.Z. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (No.
U1760106).
Institutional Review Board Statement: Not applicable
Informed Consent Statement: Not applicable
Data Availability Statement: All data in this work are available on request by contacting the corre-
sponding author.
Acknowledgments: The authors are grateful for the support of the State Key Laboratory for Ad-
vanced Metals and Materials, University of Science and Technology, Beijing.
Conflicts of Interest: The authors declare no conflict of interest.

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