Wear 486-487 (2021) 204069

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Wear
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Scratch behavior and mechanical properties of alternating multi-layered

PMMA/PC materials
Yang Xu a, Jingxian Qin a, Jiabin Shen a, *, Shaoyun Guo a, **, Khalid Lamnawar b
a
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Sichuan Provincial Engineering Laboratory of Plastic/Rubber
Complex Processing Technology, Chengdu, 610065, China
b
Université de Lyon, INSA Lyon, CNRS, UMR 5223, Ingénierie des Matériaux Polymères, F-69621, Villeurbanne, France

A R T I C L E I N F O A B S T R A C T

Keywords: Poly (methyl methacrylate) (PMMA)/polycarbonate (PC) laminates have been widely used as backboards for 5G
Scratch resistance cellphones where surface aesthetics are required. For this reason, the scratch behavior of the material is of
Multilayer structure particular interest. In the present work, the scratch behavior of alternating multi-layered PMMA/PC materials
Polymethyl methacrylate
was studied by progressive normal load scratch tests and finite element modeling (FEM). The experimental re­
Polycarbonate
Interfacial delamination
sults showed that interfacial delamination between the PMMA and PC layers occurred after the onset of scratch
damage. The detailed delamination process and related mechanisms were revealed by FEM. It was found that
interfacial delamination during scratching can be divided into three successive stages: delamination initiation,
delamination expansion, and delamination propagation. All stages were revealed to be dominated by shearing
mode (Mode II & III) crack propagation, while opening mode (Mode I) crack propagation was not involved.
Furthermore, the mechanical results demonstrated a dramatic enhancement of ductility and toughness when the
number of layers was increased.

1. Introduction provides toughness, while the rigid and brittle PMMA acts as a surface
layer to provide better scratch resistance.
The rapid development of communication technology has brought On the one hand, as aforementioned, scratch resistance of the
human society into the 5G era. The data transmission speed is over ten PMMA/PC laminate is vital for its usage. Despite the superior scratch
times faster in this network as opposed to its 4G counterpart. However, resistance of PMMA among thermoplastics, the surface PMMA layer of a
the 5G signal attenuates rapidly while transmitting in metals and as far PMMA/PC laminate is still susceptible to damage by scratching when in
as metal penetration is concerned, it is only barely possible [1]. sliding contact with objects possessing higher hardness, such as metal
Consequently, metals have been abandoned on backboards of 5G cell­ keys and zippers. Therefore, a PMMA/PC laminate with improved
phones to avoid signal shielding, and instead materials with much lower scratch resistance is always in demand. Efforts have been devoted to
electrical conductivity, including plastics, glass and ceramics, are explore scratch behaviors of PMMA [3,4], and strategies to enhance
preferred by 5G cellphone producers [2]. Among these alternatives, scratch resistance of PMMA have been proposed, such as reinforcement
plastics earn their market share due to advantages such as being cheap by nano-particles [5], in-situ forming of an Interpenetrating Polymer
and light-weight, with excellent processability, and easy color Network (IPN) with a thermoset polymer [6], or coating the surface with
modulation. a protective layer [7].
To meet the requirements of cellphone usage scenarios, such as being However, when it comes to PMMA in a laminated structure, research
dropped on the ground and scratched by hard asperities, a plastic should not be restricted to improving scratch resistance of PMMA simply
backboard should possess both good toughness and high surface hard­ by increasing its rigidity through the introduction of a second compo­
ness. Bi-layered PMMA/PC (Fig. S1) is a particular plastic that meets nent as a modifier. A polymer laminate is a unique structure consisting
these requirements and that has been developed and widely used as a 5G of at least two components which differ greatly in constitutive behav­
cellphone backboard. In this kind of laminate, the soft and ductile PC iors. The mismatched constitutive behaviors between layers generate

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (J. Shen), [email protected] (S. Guo).

https://doi.org/10.1016/j.wear.2021.204069
Received 22 March 2021; Received in revised form 6 August 2021; Accepted 12 August 2021
Available online 13 August 2021
0043-1648/© 2021 Elsevier B.V. All rights reserved.
Y. Xu et al. Wear 486-487 (2021) 204069

abrupt transitions of elasticity and plasticity at the interface, resulting in

a redistribution of stress and strain during scratching. Therefore, the
scratch behavior of a laminate is noticeably different as compared with
the bulk material of the top layer, which has been proved by our pre­
vious works [8,9] and many other studies [10–21]. It is revealed by this
research that the layer thickness and stacking sequence play decisive
roles in determining the scratch behavior and properties of laminates.
As a matter of fact, since most polymer laminates are composed of
partially compatible layers, they are also characterized by relatively
weak interfacial bonding which can potentially lead to delamination
during scratching. Such is also the case for the PMMA/PC laminate since
it is a partially compatible system [22–26].
Several studies have focused on the scratch behavior of layered
polymers consisting of partially compatible polymers, such as PP/PA Fig. 1. Delamination between PMMA and PC in a bilayer PMMA/PC sheet.
[19], PET/PA [20], and PET/PE [13]. Interfacial delamination has been
observed in these studies, indicating that this phenomenon is universal system made it possible to discover the effect of changing the constitu­
for partially compatible layered polymers during scratching. Therefore, tive behavior of the soft layer and the interfacial bonding on the scratch
apart from the aforementioned influences of layer thickness and stack­ behavior of PMMA-based laminates.
ing sequence, interfacial bonding strength might also significantly affect The second reason for choosing this material pair was that the
the scratch behavior and consequently the scratch resistance of polymer scratch behavior of a PMMA/PC laminate has yet to be studied. Such
laminates. Nevertheless, to the best of our knowledge, the detailed research will not only contribute to a more thorough understanding of
delamination process during scratching and related mechanisms has yet the relationship between scratch behavior and structure, but also pro­
to be revealed, and is thus one of the focal points of the present work. vide useful guidelines for designing a PMMA/PC laminate with
On the other hand, the current bi-layered PMMA/PC material also enhanced scratch resistance.
has several drawbacks compared with glass and ceramics. Its lack of Emphasis of the present research was on the scratch damage
stiffness is one of them, since the content of relatively soft PC is usually behavior of the prepared alternating multi-layered PMMA/PC sheets,
more than 90 wt%. A reasonable and effective solution to this disad­ especially the interfacial delamination process and related mechanisms
vantage is to simply increase the content of the relatively rigid PMMA occurring during scratching, which were studied by both progressive
component from less than 10 wt% to for instance 50 wt%. However, this normal load scratch tests according to ASTM/ISO standards and by FEM.
will lead to a dramatic decrease of toughness of the entire bi-layered In addition to this, the mechanical properties of the prepared materials,
material and is not feasible in a traditional bi-layered structure. Fortu­ including the tensile strength, CHARPY unnotched impact strength and
nately, a unique layered structure, i.e., an alternating multi-layered flexural property were studied.
structure, which is fabricated by a novel and advanced extrusion tech­
nology called layer-multiplying co-extrusion technology, has shown 2. Experimental section
promise as a means to overcome this problem. Many studies have shown
that for alternating multilayered materials comprising a brittle and a 2.1. Materials
ductile polymer, the overall toughness and ductility increased with an
increasing number of layers [27–34]. For instance, Li et al. [27] studied PMMA resin (HR 1000L), with a melt flow rate of 2.0 g/10 min
the impact behavior of alternating multilayered polypropylene (230 ◦ C/3.8 kg), was supplied by Kuraray (Japan). PC resin (IV 2200R),
(PP)/poly (ethylene-co-octene) (POE) materials and found that this with a melt flow rate of 12 g/10 min (300 ◦ C/1.2 kg), was supplied by
unique structure made it possible to toughen PP. The notable improve­ Idemitsu Kosan (Japan).
ment of the toughness of the alternating multi-layered blends was
ascribed to the synergetic effects of interface delaminations, craze 2.2. Specimen preparation
deflection, and a larger stress whitening zone during the fracture
process. Before melt processing, PMMA and PC resins were dried in an air
In the present work, alternating multi-layered PMMA/PC sheets with drying oven at 100 ◦ C for 12 h. Alternating multi-layered PMMA/PC
50 wt% PMMA and a maximum number of layers of up to 256 were materials with varying numbers of layers were fabricated by a
prepared and employed as model systems. The scratch behavior and laboratory-built layer-multiplying co-extrusion system, as illustrated in
mechanical properties, including the tensile strength, CHARPY Fig. 2. In simple terms, PMMA and PC granules were added into two
unnotched impact strength and flexural property, were studied on the single-screw extruders, and their melts combined and formed a 2-layer
prepared alternating multi-layered PMMA/PC. melt in a co-extrusion block. Then the 2-layer melt was flowed
Herein, the PMMA/PC laminate was chosen as a model system for through a number of layer-multiplying elements (LMEs). In the first
two reasons. The first was that when comparing the current PMMA/PC LME, the 2-layer melt was divided into a left and right part at the
system with our previous work focused on scratch behavior of a multi- entrance, whereafter the two parts recombined vertically at the exit to
layered PMMA/PVDF system [8,9], the differences lay in the constitu­ form a 4-layer melt. Duplication of this dividing-recombining process as
tive behavior of the soft layer and interfacial bonding strength between the PMMA/PC melt flowed through the LMEs resulted in a multiplica­
layers. During compression, PC demonstrated a noteworthy strain tion of the number of layers. A multi-layered PMMA/PC material with a
hardening after yielding, while such a behavior was absent for PVDF layer number of 2(n+1) was achieved by assembling n LMEs. The
(Fig. S2). Meanwhile, the interfacial interaction between PMMA and maximum number of LMEs employed in this study was seven, so that the
PVDF was perfect since PMMA was fully compatible with PVDF [35]. maximum number of layers of the prepared multi-layered PMMA/PC
However, this was not the case for the current partially compatible material was 27+1 = 256.
PMMA/PC system. During extrusion, the temperature of both extruders from hopper to
As shown in Fig. 1, delamination occurred in the bilayer PMMA/PC die was maintained at 220 ◦ C, 240 ◦ C and 260 ◦ C, and the temperature of
material by the PMMA layer being peeled off the PC layer, and this was all LMEs was set to 250 ◦ C. In this work, extrudates with a width of 3.3
attributed to the relatively weak interfacial bonding strength between mm and a thickness of 1.6 mm were prepared, and PMMA:PC thickness
PMMA and PC. Therefore, employing a PMMA/PC laminate as a model ratio was kept around 1:1. To eliminate the thermal history, all

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 2. Schematic of the layer-multiplying co-extrusion technology.

extrudates were sandwiched between two glass plates and annealed at carried out along the extrusion direction at a crosshead speed of 5 mm/
160 ◦ C under a pressure of 10 KPa for 1 h before scratch and mechanical min. At least five parallel specimens were tested for each material.
tests.
2.6. Impact test
2.3. Scratch test
The CHARPY unnotched impact strength was measured using an ST-
Scratch tests were conducted on a Scratch 3.5 Machine (Surface 5.5D impact tester (Qijiang, China) according to ISO 179. The prepa­
Machine Systems, USA) according to ASTM D7027-20. A stainless-steel ration process of specimens for impact tests is illustrated in Fig. 3. Seven
spherical tip with a diameter of 1 mm was used for all tests. The scratch PMMA/PC multi-layered sheets with dimension of 100 mm (length) ×
length and velocity were set to 100 mm and 25 mm/s, respectively. 33 mm (width) × 1.6 mm (thickness) were stacked and placed in a mold
During scratching, the normal load imposed by the scratch tip on the chamber, where they were hot pressed at 200 ◦ C under 5 MPa pressure
specimen increased linearly from 1 N at the start to 130 N at the end. As to form a brick with a dimension of 100 mm (length) × 37 mm (width)
the normal load increased, the scratch formed on the specimen became × 10 mm (thickness). Subsequently, the brick was cut into parts with
larger in size and at some point, material removal caused by the dimensions of 100 mm (length) × 4 mm (width) × 10 mm (thickness)
scratching occurred. The normal load corresponding to the onset loca­ using an automatic cutting machine. At least ten parallel specimens were
tion of material removal was termed the critical normal load of material tested for each material.
removal, Fcr. An example of how Fcr was determined has been demon­
strated in our previous work [9]. Eight scratch tests were conducted on
2.7. Flexural test
each specimen and the average value of Fcr was calculated. It should be
noted that there were two sides for alternating multi-layered PMMA/PC
Flexural properties were determined on a CMT-4104 universal
materials: one PMMA side and one PC side. Scratch tests were carried
testing machine (MTS systems, USA) according to ISO 178. Specimens
out on both sides of all alternating multi-layered PMMA/PC materials,
with a dimension of 80 mm (length) × 25 mm (width) × 1.6 mm
termed the PMMA side and PC side, respectively.
(thickness) were cut from the center of the extrudates using an auto­
matic cutting machine. During tests, the gap (?) between supports was
2.4. Optical microscopy 25.6 mm (16 × thickness) and the test speed was set to 1 mm/min. At
least three parallel specimens were tested for each material.
An Olympus BX51 polarizing microscope equipped with a camera
was used as an optical microscopy (OM). In order to observe the layered 3. FEM modeling
structure and scratch deformation at the subsurface of PMMA/PC multi-
layered materials, specimens were cut along the center line of the Simulations of scratch deformation of alternating multi-layered
scratch groove by using a microtome, after which the side faces of the PMMA/PC materials were carried out using a commercial finite
dissected specimens were observed in the microscope and micrographs element package, ABAQUS/Explicit. Dimensions, meshing and bound­
were recorded (?). ary conditions of multi-layered models were the same as in our previous
work [8,9], in which the basic principles of determining constitutive
2.5. Tensile test behaviors and the coefficient of friction for scratch modeling of poly­
mers have been described in detail. The parameters for scratch modeling
Tensile tests were performed using an Instron5567 tension machine of PMMA have also been established. In this work, the same parameters
(Canton, MA, USA) according to ISO 527-2. Standard dumbbell-shaped for PMMA as in our previous work were employed, and those used for
specimens with a gauge length of 25 mm were cut directly from the the scratch modeling of PC can be found in the supporting information
center of the extrudates for tensile tests. All specimens were placed at (Fig. S3).
25 ◦ C and 50% relative humidity for at least 24 h, after which tests were Fig. 4 displays the simulation results of the scratch deformation of PC

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 3. Schematic of specimen preparation process for impact test.

Fig. 4. Comparisons between experimental and simulation results of scratch deformation of the pure PC material. (a) Size of scratch groove at a normal load of 110
N; (b) Scratch coefficient of friction (SCOF) as a function of the normal load.

and compares them with experimental results. Overall, apart from the 4. Results and discussion
shoulder height, the simulation results obtained for PC matched the
experimental results in terms of both scratch size at large plastic 4.1. Scratch behaviors of pure PC
deformation and SCOF curve over a wide range of normal load. There­
fore, scratch modeling on PC in this work can be regarded as The emphasis of this study was on the scratch behavior of alternating
quantitative. multi-layered PMMA/PC materials. In order to better understand the
In terms of multi-layered models, the interfacial interaction between scratch behavior of PMMA/PC laminates, it is necessary to first intro­
layers was treated as perfect bonding in our previous work of multi- duce that of pure PMMA and pure PC. The scratch behavior of pure
layered PMMA/PVDF system [8,9], since PMMA was fully compatible PMMA has been described in detail in our previous work [9]. Briefly
with PVDF. However, this was not the case for the current partially speaking, as the normal load is increased, the scratch deformation of
compatible PMMA/PC system as mentioned above. Consequently, for pure PMMA can be divided into three stages. Stage I, termed as smooth
multi-layered PMMA/PC systems, the interfacial interaction between ironing, was the initial deformation stage caused by compressive
layers can no longer be regarded as perfect bonding. To address this yielding of PMMA. Stage III was material removal, which occurred at a
issue, cohesive layers consisting of COH3D8 elements were inserted normal load of ca. 100 N at which severe damage took place. Stage II was
between the PMMA and the PC layer to act as interfaces as shown in the transition region between smooth ironing and material removal
Fig. 5. This special type of element vanished once the delamination featured by periodic micro-cracks.
criterion was met, which made it possible to study the delamination The scratch behavior of pure PC is demonstrated herein. Fig. 6 shows
process between PMMA and PC during scratching and to analyze the a typical scratch of PC as well as its scratch-induced deformation and
related mechanisms. Since the thickness of the interface between PMMA damage features. The width of the scratch became larger as the normal
and PC was measured to be ultra small (ca. 3 nm [36]), the thickness of load increased, and finally material removal occurred at ca. 110 N as
the cohesive layers in the multi-layered PMMA/PC models was set to be shown in Fig. 6(a). The OM photos taken at different positions of the
zero. scratch path clearly demonstrate that the scratch deformation of pure PC

Fig. 5. Illustration of alternating multi-layered PMMA/PC model containing zero-thickness cohesive elements as interfacial layers.

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 6. Scratch-induced deformation and damage features on a pure PC sheet (top view). (a) Photograph of a scratch taken by a digital camera; (b) OM photograph of
the smooth ironing region; (c) OM photograph at the onset of material removal; (d) Magnified photo at the onset of material removal; (e) OM photograph of the
material removal region.

can be divided into two regions as shown in Fig. 6(b–e). In stage I (Fig. 6 side of alternating multi-layered PMMA/PC materials. Results of the 2L
(b)), termed smooth ironing, the scratch groove was formed due to and 4L samples were omitted since they were quite similar to their 8L
compressive plastic deformation of PC without material damage counterpart. At the onset of material removal (Fig. 8(b1 to g1)), damage
[37–39]. Stage II (Fig. 6(e)) was the material removal region where the features of all multi-layered samples were analogous to that of pure PC
fracture of PC occurred. Focusing on the characteristics at the onset of ((Fig. 8(a1)), where crescent-shaped cracks were observed. However,
material removal shown in Fig. 6(d), a crescent-shaped crack can be within the material removal region (Fig. 8(b2)-(g2)), only the 8L sample
observed, which was clearly caused by the PC material being torn from (Fig. 8(b2)) showed similar damage features to that of pure PC (Fig. 8
the substrate and dragged forward. It was proved by FEM that the (a2)). The scratches of the 8L sample in the material removal region
maximum tensile stress behind the scratch tip caused material removal were dark and coarse due to the formation of a rough surface (Fig. 8(a3)
of PC during scratching (discussed in Fig. S4). & (b3)), whereas scratches of samples with more than eight layers were
much brighter and smoother (Fig. 8(c2 to g2)). It is revealed in Fig. 8(c3
to g3) that for samples with a number of layers above eight, material
4.2. Scratch behavior of alternating multi-layered PMMA/PC materials
removal occurred without significantly changing the roughness of the
scratches, which was due to delamination between the PC and PMMA
4.2.1. Structure of alternating multi-layered PMMA/PC materials
layers as clearly displayed by Fig. 8(c4 to g4). Similar phenomena and
Fig. 7 shows a photograph of the cross-section of the 256L sample,
trends were observed when testing the PMMA side of multi-layered
demonstrating the structure of the prepared alternating multi-layered
PMMA/PC materials, as shown in Fig. S6.
PMMA/PC materials. Fig. 7 clearly displays the well-defined layer
As mentioned earlier, interfacial delamination was also observed by
structure of the sample, in which the bright layer is PMMA and the dark
several former studies on scratch behaviors of layered polymers con­
layer is PC. It should be noted that UV-absorbent was added to the PC
sisting of partially compatible components [11,17,18]. Nevertheless, the
resin by the manufacturer, wherefore the PC layer appeared darker than
detailed delamination process during scratching and related mecha­
PMMA when observed by optical microscope under transmission mode.
nisms has not been revealed, and will be discussed in the next section.

4.2.2. Experimental results of scratch tests

4.3. FEM study on the delamination between PC and PMMA layers
The scratch behavior of a polymeric laminate mainly consists of two
aspects: a critical normal load of material removal (Fcr) and a scratch
In this part, the PC side of the 16L model was employed as a typical
damage feature after material removal. Fig. S5 shows the effect of the
example to elucidate the delamination process during scratching. As
numbers of layers in the multi-layered PMMA/PC materials on Fcr for the
emphasis of this work, the present section addresses several issues
two sides. Fcr was between 100 N and 120 N for the PC side, whereas it
regarding delamination between the PC and PMMA layers during
was between 98 N and 115 N for PMMA. Overall, as the number of layers
scratching, including:
of multi-layered PMMA/PC materials changed, the variation range of Fcr
was relatively small for both sides.
Fig. 8 demonstrates the scratch-induced damage features on the PC

Fig. 7. Photograph of cross-section of 256L sample obtained by optical microscope.

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 8. Scratch-induced damage features on the PC side of alternating multi-layered PC/PMMA materials. (a1-g1): OM photographs at the onset of material removal
(top view); (a2-g2): OM photographs of the material removal region (top view); (a3-g3): OM photographs of the material removal region (side view); (b4-f4): OM
photographs at the end of a scratch (side view). (a) to (g) denote pure PC and samples with 8, 16, 32, 64, 128 and 256 layers. (1) to (4) denotes the onset of material
removal (top view), within the material removal region (top view), within the material removal region (side view), and the end of the scratch (side view).

(i) whether material removal caused delamination, or the other way

around;
(ii) the detailed delamination process;
(iii) mechanisms related to delamination during scratching.

4.3.1. Sequence of material removal and interfacial delamination

In ABAQUS, the constitutive response of zero-thickness cohesive el­
ements is primarily described directly in terms of the ‘traction-separa­
tion’ law as shown in Fig. 9 [40]. Traction, t, representing the nominal
stress vector, consists of three components in three-dimensional prob­
lems: tn, ts, and tt, which correspond to the normal and the two shear
tractions, respectively. The corresponding separations, δ, which repre­
sent the relative displacement between the top and bottom of the
cohesive layer, are denoted by δn, δs, and δt, respectively. tno, tso, and tto Fig. 9. Typical traction-separation response of zero-thickness cohe­
sive elements.
represent the peak values of the nominal stress, δn0, δs0, and δt0 repre­
sent the effective displacement at the initiation of damage, and δnt, δst,
and δtt represent the effective displacement at complete failure. GIC, GIIC release rate) corresponding to the normal and the two shear tractions,
and GIIIC, for which the values are equal to the area below the respectively. K is the interfacial elastic stiffness, the value of which is
traction-separation curve, are the fracture energies (critical energy equal to the slope of traction-separation curve before damage initiation:

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Y. Xu et al. Wear 486-487 (2021) 204069

K = t0/δ0. increased. When δt was above 16%*Lelement, interfacial delamination

In this work, a quadratic nominal stress criterion (QUADSCRT) was occurred as indicated by the white area in Fig. 10(a). The critical normal
adopted as the damage criterion for cohesive layers. QUADSCRT is the load of delamination decreased from 130 N to 25 N as δt increased from
parameter denoting the evolution of the delamination progress. The 20%*Lelement to 100%*Lelement. Therefore, a larger δt resulted in a softer
maximum value of QUADSCRT is 1, at which point δ reaches δo, rep­ and more deformable interface, and ultimately led to more significant
resenting the initiation of interfacial delamination. Damage of interfa­ delamination. Fig. 10(a) also manifests that 9%*Lelement was an appro­
cial cohesive layers is assumed to initiate when a quadratic interaction priate δt value, neither too small to cause convergence problem, nor too
function involving the nominal stress ratios reaches a value of one. This large for the FEM results to become excessively inaccurate. Hence, δt
criterion can be represented as expression (1): was determined to be 9%*Lelement in the following part.
In order to further investigate whether material removal caused
tn 2 ts 2 tt 2
{ 0 } + { 0} + { 0} = 1 (1) delamination, or the other way round, it was necessary to determine the
tn ts tt
critical Gc value above which interfacial delamination between PC and
To model the delamination between PMMA and PC through cohesive PMMA during scratching will be prevented. Fig. 10(b) illustrates the
elements following a traction-separation response, five groups of pa­ effect of the Gc value on delamination of the 16L model. As can be seen,
rameters are required: to (tno, tso, tto), δo (δno, δso, δto), δt (δnt, δst QUADSCRT became smaller as Gc increased. When Gc increased from
, δtt), GC (GIC, GIIC, GIIIC), and K (Kn, Ks, Kt). However, only one (?) 0.05 N/mm to 0.25 N/mm, the critical normal load of delamination also
group of parameters, namely GC (GIC, GIIC, GIIIC), can be determined increased from 5 N to 108 N. Upon further increasing Gc to 0.3 N/mm
through experimental tests. The others are unmeasurable and adjust­ and above, interfacial delamination no longer took place. Therefore, the
able, and were determined circumstantially. critical value of Gc, above which interfacial delamination between PC
In this part, it was assumed that GC = GIC = GIIC = GIIIC, δo = δt/2, and PMMA during scratching will be prevented, lies between 0.25 N/
therefore to = 2GC/δt, K = to/δo = 4GC/(δt)2. GIC between PC and PMMA mm to 0.3 N/mm for the PC side of the 16L model. As a result, the Gc
was tested to be ca. 0.5 N/mm through a T-peel test [32], leaving the between PC and PMMA (0.5 N/mm) is significantly larger than the
only remaining unknown parameter to be δt. As the thickness of the determined critical value of the 16L model. Meanwhile, this model also
interface layer tended toward zero, so did δt, and the interfacial elastic showed the highest possibility of delamination (possessing the lowest
stiffness, K, tended toward infinity. However, a very large stiffness may critical normal load of delamination) during scratching as shown in
result in a convergence problem in FEM, thus a finite δt value is required Fig. S7. Thus, it can now be concluded that during scratch testing of
to fulfill the modeling process. alternating multi-layered PMMA/PC materials, interfacial delamination
To determine a proper δt value, the length of the cohesive element will not be triggered simply by scratch-induced plastic deformation.
along the thickness direction (Lelement) was adopted as a reference. The Consequently, the delamination phenomena observed in Fig. 8 and
size and meshing method of the FEM model used in this study were the Fig. S6 were induced by material removal, which provoked interference
same as in our previous work [8,9]. The length of the FEM model was 14 on the interface and subsequent interfacial delamination.
mm, which was divided into 512 meshes. Therefore, Lelement = 14
mm/512 = 27.34 μm. What must be pointed out was that although this 4.3.2. Detailed delamination process
element size was found to be the most appropriate by our previous It has been proved that interfacial delamination between PMMA and
parametric study where interfacial delamination was not considered, it PC during scratching was induced by material removal. Thus, in order
may not still be the most appropriate value in this work involving for FEM to represent the delamination process more accurately, material
interfacial delamination, and the FEM results might not be fully removal of PC and PMMA must be allowed during scratch modeling. We
converged. Nevertheless, using the same element size over the different have made attempts to include material removal of PC and PMMA
runs still allowed making comparative analysis, even though the abso­ during scratch modeling of multi-layered models. However, the FEM
lute element size value might not be perfectly accurate. Different pro­ process would be terminated immediately at the onset of material
portions of Lelement from 2% to 100% were used as δt to further removal due to excessive distortion of the elements. To address this
determine a proper δt value. For example, a proportion of 2% meant δt = issue, a small value of GC (0.20 N/mm) was employed in FEM without
Lelement * 2% = 0.547 μm, and a proportion of 100% meant δt = Lelement * considering material removal of PC and PMMA. This allowed interfacial
100% = 27.34 μm. delamination during scratching to take place without convergence
The effect of the δt value on the delamination is shown in Fig. 10(a), problems.
which clearly revealed that as δt became larger, QUADSCRT also FEM results of interfacial delamination induced by scratch

Fig. 10. FEM study on the effect of (a) the δt value, and (b) the GC value on delamination between PC and PMMA of 16L model.

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Y. Xu et al. Wear 486-487 (2021) 204069

deformation are shown in Fig. 11(b-1 to b-3). Some typical field-test

results of interfacial delamination were also given in Fig. 11(a-1 to a-
3) to make comparisons. Although excluding material removal is not the
actual situation, the obtained delamination features through FEM
(Fig. 11(b-1 to b-3)) were still in good agreement with experimental
results (Fig. 11(a-1 to a-3)). The main difference between delamination
in FEM and delamination in scratch tests was that the former was
induced by plastic deformation, whereas the latter was triggered by
material removal. Fig. 11 revealed that after delamination occurred, the
subsequent delamination process would follow a similar procedure
regardless of the cause of delamination. Consequently, it was reasonable
and feasible to describe the detailed delamination process in a qualita­
tive manner by adopting a small value of GC without considering ma­
terial removal.
The simulated delamination process between PMMA and PC during
scratching is presented in Fig. 12(a–i). It was revealed via FEM that
delamination can be divided into three successive stages. Stage I was
delamination initiation (Fig. 12(c–e)), which was induced at the center
of the scratch. Stage II was delamination expansion (Fig. 12(f–h)), in
which the delamination zone fanned out symmetrically and rapidly to­
wards the two edges of the scratch as the normal load increased.
Eventually the delamination process involved into stage III, delamina­
tion propagation, during which the delamination zone developed stably
along the scratch direction without the width increasing (Fig. 12(i)).
It must be pointed out that stage I did not exist in the field test, since Fig. 12. Delamination process between PMMA and PC during scratching (top
the GC value (0.2 N/mm) used in Fig. 12 was much smaller than the view). (a–e) Evolution of the delamination zone as the normal load increased;
actual value (0.5 N/mm). Meanwhile, delamination was not observed (f) OM photograph of the PC side of the 32L sample at the onset of material
before material removal as shown in Fig. S8. It was clearly observed removal; (g) OM photograph of the PMMA side of the 16L sample in the ma­
from experimental results (Fig. 12(j and k)) that a large area of delam­ terial removal region.
ination immediately appeared right after the onset of material removal.
Therefore, during the actual scratch test, the delamination process Mode III (tearing) cracks, as illustrated in Fig. 13(a). A Mode I crack is
developed into stage II and III directly after onset of material removal caused by normal stress, while Mode II & III cracks are induced by shear
without going through stage I. The high degree of agreement between stress. The difference between Mode II and Mode III cracks is that for the
the FEM result (Fig. 12(i)) and experimental results (Fig. 12(j and k)) former the shear stress is parallel to the crack propagation direction,
also further confirmed the reliability of the delamination process while for the latter the shear stress is perpendicular to the crack prop­
revealed by FEM. agation direction. This section aims at determining the dominant type of
crack during delamination between PMMA and PC evoked by scratch­
4.3.3. Mechanism related to delamination during scratching ing. The basic idea to fulfill this purpose is to study the variation ten­
As shown in Fig. 11, delamination during scratching is virtually a dency of three parameters, namely QUADSCRT, critical normal load
process of crack development and propagation. According to the theory (Fcr) of the delamination initiation, and Fcr of delamination expansion,
of fracture mechanics [41], cracks can be divided into three major cat­ by varying GC of one type of crack from 0.10 N/mm to 0.50 N/mm,
egories, namely Mode I (opening) cracks, Mode II (sliding) cracks, and while fixing GC of the other two types of cracks at 0.25 N/mm. The

Fig. 11. Typical delamination features of PMMA/PC multi-layered materials at the end of a scratch (side view). (a-1) OM photograph of the PMMA side of the 16L
sample; (a-2) OM photograph of the PC side of the 256L sample; (a-3) OM photograph of the PMMA side of the 256L sample; (b-1), (b-2) and (b-3): FEM results of the
PC side of the 16L model with an increasing normal load.

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 13. Effects of GC of three types of cracks on delamination parameters during scratching. (a) Illustration of three crack types; Effect of GC of (b) Mode I, (c) Mode
II, and (d) Mode III cracks on QUADSCRT as a function of the normal load; Effect of GC of three types of cracks on Fcr of (e) delamination initiation, and (f)
delamination expansion.

results are summarized in Fig. 13(b–f) and Fig 14. to the characteristics of scratch deformation, involving an indentation in
It was revealed by Fig. 13(b,e,f) and Fig. 14(a) that Mode I cracks the normal direction and a tangential movement along the direction
made no contribution to the delamination process, since QUADSCRT parallel to the interfaces. Only the tangential movement could possibly
and the two Fcr of delamination remained nearly unchanged as GC of lead to delamination, which would undoubtedly be a shear-dominated
Mode I cracks increased. In terms of Mode II and III cracks, QUADSCRT process. To be more specific, Mode II cracks contributed more to the
decreased and two Fcr of delamination both increased as GC of both types delamination initiation stage (Stage I in Fig. 12) than Mode III cracks,
of cracks became larger, as shown in Fig. 13(c–f) and Fig. 14(b and c). while Mode III cracks accounted for a greater proportion in the delam­
No delamination occurred while GC of Mode II cracks was above 0.35 N/ ination expansion stage (Stage II in Fig. 12) than Mode II cracks.
mm (Fig. 14(b)), or GC of Mode III cracks was larger than 0.40 N/mm
(Fig. 14(c)). Therefore, both Mode II and Mode III cracks were involved 4.4. Mechanical properties of alternating multi-layered PMMA/PC
in the delamination process. Nevertheless, significant differences be­ materials
tween the effects of Mode II and Mode III cracks on the delamination
process were still observed. QUADSCRT and Fcr of delamination initia­ Mechanical tests, including tensile tests, flexural tests and impact
tion were more sensitive to the GC of Mode II cracks (Fig. 13(c,e)) than tests were conducted to study the effect of the number of layers on the
that of Mode III cracks (Fig. 13(d)), whereas the Fcr of delamination overall performances of the prepared alternating multi-layered PMMA/
expansion was more sensitive to the GC of Mode III cracks than that of PC materials. The results are summarized in Fig. 15. According to tensile
Mode II cracks (Fig. 13(f)). tests (Fig. 15(a and b)), as the number of layers increased, the tensile
Based on the above results, it could be concluded that the interfacial behavior of multi-layered PMMA/PC materials gradually transformed
delamination between PMMA and PC during scratching was dominated from brittle fracture without yielding, resembling PMMA, into ductile
by shearing (Mode II & III) crack propagation, whereas opening (Mode I) fracture with necking, resembling PC. Compared with the 2L material,
cracks were not involved in the process. This discovery is closely related the elongation at break of the 256L material increased by 243% from

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Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 14. Effects of GC of three types of cracks on delamination contours during scratching. (a) varying GC of Mode I cracks from 0.10 N/mm to 0.50 N/mm while
fixing GC of the other two types of cracks at 0.25 N/mm; (b) varying GC of Mode II cracks from 0.10 N/mm to 0.50 N/mm while fixing GC of the other two types of
cracks at 0.25 N/mm; (c) varying GC of Mode III cracks from 0.10 N/mm to 0.50 N/mm while fixing GC of the other two types of cracks at 0.25 N/mm.

12.0% to 41.2% (Fig. 15(c)). A similar tendency was observed in flexural 2. A deformation zone forming in the ductile layer in response to the
tests (Fig. 15(d and e)): the 2L material broke at merely 3.8% flexural stress concentration at the craze tip, while adhesion produces
strain, while the 256L material could endure a fold-over test without yielding of brittle layers, which leads to cooperative yielding of both
breaking (Fig. 15(e)). Meanwhile, it was also discovered by impact components. Shear deformation of the brittle layers is attributed to
testing that the transition from brittle to ductile occurred as the layer the local shear stress concentration at the interface created by
number increased to 128 (Fig. 15(f)). Compared with the 2L material, impingement of a ductile shear band. Therefore, crazing or cracking
the unnotched impact strength of 256L material increased by 447% from of the brittle layer was suppressed and shear bands that extended
11.5 kJ/m2 to 62.8 kJ/m2. through several layers produced shear yielding of both components.
As indicated in Fig. 15, the number of layers, or the individual layer
thickness, played a decisive role in determining the toughness of the The above results clearly demonstrate prominent enhancements of
alternating multi-layered PMMA/PC materials. The brittle-ductile the overall ductility of the alternating multi-layered PMMA/PC material
transition occurred once the average layer thickness of the brittle as its number of layers increased to 256, endowing the 256L material
PMMA phase was reduced to below a critical value, ca. 10 μm in this with the potential to serve as a backboard for 5G cellphones. It should
work. Many other studies have focused on the mechanical behavior of however be pointed out that due to the limitation of the current alter­
alternating-multilayered polymeric systems consisting of one relatively nating multilayered coextrusion technology, a well-defined layer
brittle component and another relatively ductile component, such as structure could no longer be maintained in alternating multilayered PC/
PC/SAN [32,33,42–47], PP/POE [27–29], PVDF/PMMA [48–50], and PMMA materials when the number of layers was above 256, which led to
also PC/PMMA [32–34]. All these studies have come to a general decreased toughness. For example, it was found that the unnotched
conclusion that in such alternating-multilayered polymeric materials, impact strength of the 512 L material was smaller than that of its 256 L
increasing the number of layers led to an improvement of the overall counterpart. If a perfect layer structure can be achieved in materials
toughness. This notable toughness enhancement can be ascribed to the with a higher layer number, further increasing the number of layers
following reasons: would definitely contribute to better toughness.

1. Synergetic effects of the interfaces’ delaminations, craze deflection, 5. Conclusions

larger subcritical damage zone (stress whitening zone) and a com­
bination of voids and deformation during the fracture process. PMMA/PC laminates are extensively used as backboards for 5G

10
Y. Xu et al. Wear 486-487 (2021) 204069

Fig. 15. The mechanical behavior of alternating multi-layered PMMA/PC materials. (a) Tensile stress-strain curves; (b) Photographs of specimens after tensile tests;
(c) Elongation at break obtained from tensile tests; (d) Flexural stress-strain curves; (e) Photographs of specimens after being folded in half; (f) CHARPY unnotched
impact strength; (g) Photographs of specimens after impact tests.

cellphones. Their scratch behavior is of particular interest but has not the work reported in this paper.
been studied before. This work mainly aimed at exploring the scratch
behavior and related mechanisms of this partially compatible polymeric Acknowledgements
laminate system via progressive normal load scratch tests and FEM.
In this study, alternating multi-layered PMMA/PC materials with a The authors appreciate the financial support of National Natural
maximum number of layers up to 256 and a PMMA content of 50 wt% Science Foundation of China (51420105004) for this work. The authors
were employed as model systems. Firstly, the scratch behavior of the would also like to thank Prof. Hung-Jue Sue (Polymer Technology
prepared alternating multi-layered PMMA/PC sheets were studied. Center, Department of Materials Science and Engineering, Texas A&M
Interfacial delamination between the PMMA and PC layers was observed University, USA) for his great help in revising this paper.
after material removal for multi-layered materials with a layer number
of 16 and above. Then, the detailed delamination process during
Appendix A. Supplementary data
scratching and related mechanisms was studied by FEM. This explora­
tion revealed that the delamination process during scratching could be
Supplementary data to this article can be found online at https://doi.
divided into three successive stages: delamination initiation, delami­
org/10.1016/j.wear.2021.204069.
nation expansion and delamination propagation. Interfacial delamina­
tion between PMMA and PC during scratching was found to be
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