Surface & Coatings Technology 332 (2017) 474–483

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Enhanced replication ratio of injection molded plastic parts by using an T

innovative combination of laser-structuring and PVD coating
K. Bobzina, C.H. Hopmannb, A. Gillnerc, T. Brögelmanna, N.C. Kruppea, M. Orthb, M. Stegerc,
M. Naderia,⁎
a
Surface Engineering Institute, RWTH Aachen University, Kackertstr. 15, 52072 Aachen, Germany
b
Institute of Plastics Processing, RWTH Aachen University, Seffenter Weg 201, 52074 Aachen, Germany
c
Chair for Laser Technology, RWTH Aachen University, Steinbachstr. 15, 52074 Aachen, Germany

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

Keywords: The properties of plastic products can be optimized by a suitable design of the component surface. One pro-
PVD mising method for plastics processing by injection molding is the use of molding tools structured in the micro-
(Cr,Al)N meter range. Within the scope of this paper, laser micro-structuring was carried out on two injection molds. A
mfMS chromium-based nitride coating was deposited on one of the micro-structured mold by means of middle fre-
Tribology
quency magnetron sputtering (mfMS). Commercial plastics polycarbonate (PC2245) and polymethyl methacrylate
Shear energy
Laser structured mold
(PMMA 7 N) were considered for all investigations. The coating contained xCr = 51 at.−% chromium,
Replication ratio xAl = 30 at.−% aluminum and xN = 19 at.−% nitrogen exhibited a fine and dense columnar structure. It was
experimentally seen that the coefficient of friction measured using a pin on disc tribometer reduces about 11% in
case of PMMA 7 N, and about 17% for PC2245, using PVD. By comparing coated and uncoated surfaces, a lower
wettability in contact with the plastics melt of PC2245 and PMMA 7 N analyzed by means of high temperature
contact angle (CA) measurements was achieved for coated surfaces. This corresponds to the low amount of shear
energy required for the separation of the solidified PC2245 and PMMA from the samples surfaces after the CA
measurements. The influence of the temperature on coating property, roughness, after the CA measurements was
observed as well. It was shown that the replication ratio of optical micro-structures can be increased significantly
up to 20–30% by using a PVD coated in comparison to an uncoated mold.

1. Introduction requirements for the production of optical structures [7]. Moreover,

A prerequisite for the innovation of many products and technologies
in sectors such as automotive, healthcare, aerospace, electronics,
packaging or textile is the plastics industry [1]. The properties of plastic
products are influenced not only by the choice of main plastic material,
but also considerably by the design of the surface. Over the past years,
surfaces featuring functional structures have become more and more
attractive for many applications [2–4].
Among the decisive steps for the production of functional structured
plastic components is the structure design as well as the highly precise
structuring of the mold surface. A suitable technique for manufacturing
structured injection molds presents itself in laser ablation, which offers
a high level of accuracy and precision [5]. Laser surface structuring is
an innovative manufacturing technology for a wide range of machin-
able materials and with a high level of flexibility [6]. On the other
hand, high process accuracy and low tolerances are process
structures in the order of a few micro-meters can significantly change
surface properties such as topography, roughness as well as the adhe-
sion of plastic melts on the mold surface [8]. Due to a significant in-
crease in the contact area caused by the micro-structuring of mold in-
serts, large release forces can be imposed during the production, which
cause a breaking of the structures and a clogging of the mold [9]. An
additional increase in surface area occurs with a nano-scaled roughness
induced by the ablation process through ultra-short pulse laser. This
nano-scale roughness superimposes the intended micro-structure [10].
Further, a crucial procedure for the production of structured optical
plastic components is a specified injection molding process. This is
needed to achieve a high geometrical replication accuracy of the plastic
components as well as a reproducible replication molding [11]. Using a
specific modification of the surface properties of molding tools, the
interactions between the plastics melt and mold surface can be influ-
enced.

⁎
Corresponding author.
E-mail address: naderi@iot.rwth-aachen.de (M. Naderi).

http://dx.doi.org/10.1016/j.surfcoat.2017.09.068
Received 20 April 2017; Received in revised form 28 August 2017; Accepted 1 September 2017
Available online 28 September 2017
0257-8972/ © 2017 Elsevier B.V. All rights reserved.
K. Bobzin et al.
The above-mentioned aspects are dependent on various factors. A
point criticizing the process side is, among other things, the thermal
state of the mold during the injection molding of structured optical
plastic components. This has a decisive influence on the melt viscosity,
the flowability as well as on the quality of the structured plastic com-
ponents. In the conventional injection molding process the temperature
difference between the mold surface and the oncoming melt leads to
solidification of plastics melt and formation of a layer on a surface
cavity [11–14]. This temperature difference can influence the optical
and mechanical properties of plastics components. Michaeli et al. [11]
described the effect of the surface temperature on the molding accuracy
of micro-structures. Micro-structures used for optical applications are
frequently molded from amorphous thermoplastics such as poly-
carbonate (PC) and polymethyl methacrylate (PMMA) [12]. In order to
prevent premature solidification of PC and PMMA, the surface tem-
perature of the mold should be increased during injection [13,14]. For
such plastics a contact temperature of mold and plastics melt above the
glass transition temperature is sufficient to prevent premature solidifi-
cation [14,17]. Nevertheless, the demolding of such brittle plastic
materials is still a challenge in the replication of structured plastic
components. Moreover, tool wear should not compromise the integrity
of the tool and consequently the quality of the molded optical part,
especially on the micro-structured level [15]. One approach to improve
the quality of plastic components can be achieved by controlling mold
and material temperatures by means of laser-based variothermal in-
jection molding [16–18]. On the one hand, the tribological system plays
an important role in the molding and demolding of structured plastic
components. Specifically, the adhesive and abrasive wear of the mold
surface are important failure mechanisms in plastics processing. This
problem originates in the prolonged contact with (i) the molten plastics
during molding as well as (ii) the solidified plastics melt during the
demolding of plastic. On the other hand, the corrosion of mold surfaces
due to exhaust gases or decomposition products from the plastics play
an important role in plastics processing [19].
The key to overcome the above-mentioned challenges is to modify
the surface of the tool using innovative surface engineering. One pro-
mising approach is to coat micro-structured molds via physical vapor
deposition (PVD) [20–22]. This approach results in a high durability
and cost-effectiveness of the tools. Additionally, compared to an un-
coated mold PVD coatings reduce release forces, maximize demolding
precision and results in decreased surface roughness after structuring.
Furthermore, PVD coatings have improved wear protection due to the
contact between the coating and the plastics melt during the molding
process [23–25].
Titanium and chromium-based nitride hard coatings deposited by
PVD technology are the most widely used protective coatings in plastics
processing [26–28]. One of the first chromium-containing hard coatings
developed by PVD technology was the binary CrN coating. Similar to
TiN, CrN has been successfully applied to molding dies, wear compo-
nents, and cutting tools. CrN is known to be superior to TiN in aspects
such as corrosion and wear resistance towards plastics [26–29]. For the
deposition of ternary (Cr,Al)N hard coatings, the coating properties of
CrN can be improved by adding aluminum. The hardness of (Cr,Al)N
can be adjusted by controlling the chromium/aluminum ratio [23,30].
In addition to abrasion resistance and corrosion protection in aggressive
environments, (Cr,Al)N furthermore offers a high adhesion resistance
[30–34]. PVD processes feature numerous variants, for instance middle
frequency (mf) magnetron sputtering [23,34]. During reactive magne-
tron sputtering, certain regions on the target become poisoned with an
insulating layer of the reactive product. The problem of target poi-
soning was overcome through the introduction of pulsed magnetron
sputtering processes such as the asymmetric bipolar middle frequency
magnetron sputtering (mfMS) [23]. Dual magnetron technology was
developed to deposit insulating materials such as oxides [23,34].
Within the scope of this paper, the suitability of a (Cr,Al)N coating
deposited on a micro-structured mold via mfMS was evaluated in terms
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Surface & Coatings Technology 332 (2017) 474–483
of the replication ratio of the injection molded plastic components in
comparison to an uncoated reference. On the one hand, specific coating
properties such as morphology and chemical composition, as well as the
mechanical properties universal hardness HU and indentation modulus
EIT were analyzed. On the other hand, specific properties with re-
levance to the demolding behavior such as surface roughness Ra and Rz
and coating thickness and its influence on the structure height of the
micro-structured mold and replication ratio were analyzed as well.
In order to gain a better understanding of the influence of the
coating on the replication of micro-structured plastics components, the
coating was analyzed with regard to its properties in contact with the
investigated plastics. To do so, application-oriented system tests were
used. This included the friction behavior of coated samples in contact
with solidified plastic melts, measured by using an application-oriented
tribological model test in a pin on disc tribometer. The motivation of
the latter study was to determine possible friction behavior of the
structured mold, which can occur upon contact with solidified plastics
melt during the demolding of plastic components. Furthermore, ana-
lyses of the wetting behavior of plastics melts on coated and uncoated
surfaces were investigated by means of high temperature contact angle
measurements as well as the shear energy while shearing the solidified
plastics from the surface. The influence of the temperature after high
temperature contact angle measurements on the surface roughness Ra
and Rz were observed.
2. Experimental procedures
The micro-structuring of the samples was performed by the chair for
Laser Technology (LLT) at RWTH Aachen University. The micro-struc-
tured samples were coated by the Surface Engineering Institute (IOT) at
RWTH Aachen University. The replications of micro-structured and
coated molds were carried out at the Institute of Plastics Processing
(IKV) at RWTH Aachen University. For all tests, two different brittle
plastics polycarbonate Makrolon® LED 2245 (hereafter called PC2245)
and polymethyl methacrylate PMMA 7 N were used.
2.1. Structuring of the mold
Within the scope of this paper, two molds made of the hardened
cold work steel H11 (X37CrMoV5, 1.2343) were used. This steel is a
widely-used material for mold inserts. The dimensions of the molds
were 80 mm × 80 mm × 5 mm with a hardness of (57 ± 1) HRC and
an arithmetic average surface roughness of Ra = 0.01 μm. The micro-
structuring was carried out by means of ultra-short pulse laser ablation,
TruMicro 5050 type from TRUMPF GmbH & Co. KG, Ditzingen,
Germany, with an amplification wavelength of λ = 1030 nm. The laser
operated at a repetition rate of up to f = 400 kHz and at a pulse
duration of τ = 12 ps. Within the scope of this paper, various micro-
structures with a field size of 10 mm × 10 mm (Fig. 1a)) and heights of
h = 50 μm and h = 100 μm were ablated from the molds (Fig. 1b)).
These related to the so-called “line structures”, which are aligned par-
allel to the melting direction, as well as the “cross structures”, in which
a crossed orientation of the structure is formed. One of the two micro-
structured molds served as a reference; the second one was coated in
order to observe the influence of the coating on the replication of micro-
structures.
2.2. Coating of micro-structured mold
In order to investigate the influence of the coating on the structure
height as well as on the replication of micro-structured mold, a ternary
chromium-based nitride (Cr,Al)N hard coating was deposited onto the
micro-structured cold work steel H11 (X37CrMoV5, 1.2343) by means
of mfMS. Moreover, accompanying substrate materials made of H11
with a diameter of Ø = 25 mm, a thickness of d = 8 mm and a hard-
ness of (57 ± 1) HRC without laser pretreatment were coated. For the
K. Bobzin et al. Surface & Coatings Technology 332 (2017) 474–483

Fig. 1. Schematic of micro-structured mold a) and in-

vestigated micro-structures with structure heights of
h = 50 and h = 100 μm b).

Fig. 2. Configuration of industrial coating unit CC800/9

Sinox a), pulse profile b) and CrAl20- and AlCr20-target (c)
for deposition of nitride and oxynitride hard coatings.

characterization analyses, please refer to chapter 2.3, 2.4, 2.5 and 2.6.
The coating was deposited in the industrial coating unit CC800/9,
CemeCon AG, Würselen, Germany, equipped with four bipolar-pulsed
middle frequency cathodes, using a rectangular pulse shape (Fig. 2a)
and b)).
For the deposition of the nitride hard coating, two cathodes were
used; cathode 1 (C 1) and cathode 3 (C 3). The average distance be-
tween substrate and target was approximately d = 40 mm (Fig. 2b)).
CrAl20 targets consisting of a Cr target with 20 Al plugs of a diameter of
Ø = 15 mm (purity: Cr 99.9% and Al 99.5%) and AlCr20 targets con-
sisting of a Al target with 20 Cr plugs of a diameter of Ø = 15 mm
(purity: Al 99.9% and Cr 99.5%) were used (Fig. 2c)). The substrates
were cleaned in-situ, using an Ar+ ion bombardment for t = 60 min
with a frequency of f = 250 kHz and an argon pressure of
p = 200 mPa. The coating parameters are listed in Table 1.
Micrographs of fractured cross-section were taken using a secondary
electron (SE) detector. Moreover, a glow discharge optical emission
spectroscopy (GDOES) was applied to quantify the chemical composi-
tion of the coating with Y 5000 RF, HORIBA Jobin Yvon GmbH,
Bensheim, Germany. Furthermore, universal hardness HU and in-
dentation modulus EIT were measured by means of nanoindention XP,
MTS Systems Corporation, Oak Ridge, Tennessee, USA, by applying a
Berkovich tip with a nominal edge radius of approximately r = 20 nm
following the method proposed by Oliver and Pharr [35]. 20 indents
were carried out on each coating and the average of determined values
for HU and EIT of the coatings was considered. Moreover, by using
confocal laser scanning microscopy (CLSM) Keyence VK X210, Tokio,
Japan, the arithmetic average surface roughness Ra and the mean
roughness height Rz of the PVD hard coating were determined ac-
cording to ISO 4287.

2.4. Analyses of injection molded micro-structured plastic components

2.3. Analyses of coating properties

For the molding of micro-structured plastic components, amorphous

Analyses of the surface morphology and the topography of nitride
optical materials such as polycarbonate (PC) and polymethyl metha-
hard coating was performed by means of a scanning electron micro-
crylate (PMMA) are used. Makrolon LED2245 from Covestro AG,
scope (SEM) ZEISS DSM 982 Gemini, Jena, Germany, at the Central
Leverkusen, Germany, which is used in applications such as optical fi-
Facility for Electron Microscopy (GfE) of RWTH Aachen University.
bers and light guides, is used as PC type. The material provides easy
releasability, particularly for the use in injection molding. The glass
Table 1
Process parameters for deposition of (Cr,Al)N coating using CC800/9 Sinox. transition temperature is T = 145 °C, the recommended processing
temperature is T = 280 °C, and the recommended mold temperature
Process parameter Abbreviation Unit Value between T = 80 °C and T = 120 °C [36]. In addition, PMMA Plexiglas
7 N produced by Evonik Röhm GmbH, Darmstadt, Germany, is used.
Target mfMS cathode 1 C1 – CrAl20
Power density mfMS ρC1 W cm− 2 4.55 PMMA 7 N has a generally very high transparency and is therefore used
cathode1 in various optical applications such as lenses, displays or automotive
Target mfMS cathode 3 C3 – AlCr20 headlights. The glass transition temperature is T = 110 °C, the pro-
Power density mfMS cathode ρC3 W cm− 2 4.55 cessing window ranges from T = 220 °C to T = 260 °C [37]. For the
3
Pressure p mPa 2 × 10− 4
molding of plastic components, a fully hydraulic injection molding
Argon gas flow j(Ar) sccm 120 machine CX 160-1000 by KraussMaffei Technologies GmbH, Munich,
Nitrogen gas flow j(N2) sccm 80 (pressure Germany, was used at IKV. An external set-up with a robot-guided laser
controlled) scanner was chosen. As a laser source, a fibre-coupled high power diode
Bias voltage VBias V − 40
laser unit type LDF 1500-2700 by Laserline GmbH, Mülheim-Kärlich,
Pulse mode – – Bipolar
Frequency f kHz 18.50 Germany, with a maximum beam output power of P = 2.7 kW was
used. Both uncoated and coated micro-structured molds were used for

476
K. Bobzin et al. Surface & Coatings Technology 332 (2017) 474–483

Fig. 3. Calculation of replication ratio of micro-structured

mold a) and micro-structured plastics component b).

the molding of structured plastic components by means of conventional Table 2

injection molding at P = 0 W and laser-based variothermal injection Process parameters for PoD tribometer measurements.
molding at laser power of P = 319 W. T ≈ 80 °C and T ≈ 145 °C were
Process parameter Unit Value
used to investigate the influence of the surface temperature on the re-
plication ratio for P = 0 W and P = 319 W respectively. For amorphous Substrate – H11 (X37CrMoV5, 1.2343)
thermoplastics a contact temperature of cavity steel and plastics melt Coating – (Cr,Al)N
above the glass transition temperature is sufficient to prevent pre- Counterpart – PC2245 and PMMA 7 N pins (Ø = 6 mm)
Temperature TPC2245 °C 150 ± 5
mature solidification [14,17]. Therefore, a laser power of P = 319 W Temperature T PMMA °C 110 ± 5
was considered for the molding of structured plastic components. Load F N 2
After the replication of the micro-structured plastic components, the Rel. humidity % 30 ± 5
replication ratio was calculated. For this purpose, the real height of the Rel. velocity ν cm s− 1 10
Distance s m 100
micro-structured mold hm was measured using CLSM, since this method
Radius r mm 5
allows a real three-dimensional resolution and therefore a quantitative
analyzation of the surface topography (Fig. 3a)). In addition, the height
of the demolded structured plastics component hp was also determined investigations were carried out in order to determine the adhesion
by means of CLSM (Fig. 3b)). The replication ratio R was calculated strength between the solidified PC2245 and PMMA 7 N pellet and the
from R = (hp/hm) 100%. PVD-coated as well as the uncoated samples. Shear tests were applied
by means of a shear testing machine by walter + bai AG, Löhningen,
2.5. Analyses of friction behavior of surfaces in contact with plastics Switzerland, referring to DIN EN 15340. Fig. 5a) and b) illustrate the
diagram of the shear test and a resulting load-displacement curve read
In order to analyze the friction behavior of a mold surface during after a measurement. During the shear test, an indexable insert made
demolding, an application-oriented tribological model test was carried from cemented carbide is used to apply a force parallel and close to the
out in a pin on disc tribometer PoD. This was realized by analyzing the interface substrate/solidified PC2245 and PMMA 7 N pellet. Di is the
coefficient of friction CoF between the nitride hard coating and the result of the displacement at this location; the displacement is in di-
uncoated substrate against PC2245 and PMMA 7 N as counterparts rection of the force Fi. If F is increased by Fi and the corresponding
(Fig. 4 a)). All investigations were performed according to DIN increase in the displacement is Di, the incremental work, done by the
50324:1992-07 by using pin on disc tribometer, CSM Instruments, Pe- load Fi passing through the displacement Di, is approximately FiΔDi
seux, Switzerland. The PC2245 and PMMA 7 N pins feature diameters of [38]. The load-displacement curves were used for the calculation of the
∅ = 6 mm. The parameters of the PoD measurements are presented in shear energy E, which is needed for the separation of the solidified
Table 2. PC2245 and PMMA 7 N from the samples surfaces.
The sample surfaces were further analyzed via high temperature
2.6. Analyses of wetting behavior and adhesion of surfaces in contact with contact angle measurements after the heat treatment. The investiga-
plastics tions to observe Ra and Rz were carried out using CLSM according to
ISO 4287. The surface roughnesses were observed before and after the
Due to the contact of structured molds with the plastics melt during heat treatments and, in the area under the solidified PC2245 and PMMA
the molding of plastic components, application-oriented system tests 7 N pellet, also after the shear test.
were used in order to analyze the wetting behavior of molten PC2245
and PMMA 7 N in contact with the PVD hard coating. The investiga- 3. Results and discussion
tions were carried out by using high temperature contact angle CA
measurements according to DIN EN 828:1998-01 using the device DSA 3.1. Characterization of the (Cr,Al)N coating
10, Kruess GmbH, Hamburg, Germany, (Fig. 4b)). Hardened tool steel
H11 served as a reference. The results from the analyses of the chemical composition by means
After the high temperature contact angle measurements, further of GDOES show that the chromium-based nitride coating contains

Fig. 4. Pin-on-disc-tribometer wear test a) and

High temperature contact angle b) [23].

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K. Bobzin et al.
xCr = 51 at.−% chromium, xAl = 30 at.−% aluminum and
xN = 19 at.−% nitrogen. Aluminum has been successfully incorporated
into the binary cubic CrN, which results in an increase of hardness and
influences the coating's micro-structure [39]. This corresponds to the
(Cr,Al)N coating's universal hardness of HU = (9.0 ± 0.75) GPa and
indentation modulus of EIT = (180.42 ± 21) GPa. For comparison, the
uncoated H11 features HU = (3.11 ± 0.38) GPa and EIT =
(201.19 ± 16.28) GPa. According to the results, the (Cr,Al)N coating
shows high potential as protective coating for injection mold against
abrasive and adhesive wear during the processing of PC2245 and PMMA
7 N [23].
Fig. 6 illustrates the SEM cross-section fracture investigated for the
analyses of the morphology and the topography of the (Cr,Al)N coating.
The coating exhibited a fine and dense columnar structure. Measure-
ments revealed the thickness of the coating to be d = 1.5 μm. This low
thickness promises a good replication of the micro-structures without
influencing the results of the replication process. The roughness para-
meters of the coating surface, determined by CLSM, are Ra =
(0.023 ± 0.001) μm and Rz = (0.265 ± 0.03) μm. Interestingly, the
Ra value of the obtained coating is similar to that of the uncoated mold.
This shows that this approach does not change the roughness of the
substrate.
3.2. Replication property of the coated and uncoated micro-structured
molds
Fig. 7 illustrates the three-dimensional (3-D) CLSM images of the
micro-structured molds with line and cross-structures for two different
structure heights. Fig. 7a) shows the image prior to, Fig. 7b) after the
coating process. Due to variation in laser ablation processing, the in-
tended structure sizes are different from the measured structure height
in the mold. It can be observed that the coating process does not in-
fluence the contour of the structures; only the structural height is af-
fected by change.
The replication ratios are determined by measuring the heights of
the replicated structures from both coated and uncoated mold. Due to a
significant increase in the contact area caused by the micro-structuring
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Surface & Coatings Technology 332 (2017) 474–483
Fig. 5. Schematic of shear test a) and the resulting force-
displacement curve after shear test b).
of the mold inserts, large release forces are imposed during the de-
molding of PMMA 7 N. An increase in surface area occurs for nano-
scaled roughness. It is induced by an ablation process carried out with
ultra-short pulse laser (Fig. 8a)). This nano-scale roughness super-
imposes the intended micro-structure. By using PMMA 7 N, the struc-
tures break from the uncoated mold during demolding and, in contrast
to the coated mold, the PMMA 7 N sticks to the structures (Fig. 8b)). For
this purpose, a determination of the replication ratio of micro-structure
plastics component replicated from uncoated mold is not possible.
Fig. 9a) illustrates 3-D CLSM images of the micro-structured plastics
component made from PMMA 7 N, exemplarily for h = 50 μm. The
images show line and cross structures using coated mold. Fig. 9b) il-
lustrates the replication ratio of the micro-structured PMMA 7 N cal-
culated from two different laser powers, PLaser = 0 W and
PLaser = 319 W. Using a (Cr,Al)N coating to modify the surface topo-
graphy leads to an improvement of the surface wettability, compared
with PMMA 7 N. This results in an improvement of the replication ratio
of micro-structured plastic components. Due to a significantly higher
surface temperature for the higher laser power PLaser = 319 W, the
replication ratio increases for line structures as well as for cross struc-
tures.
In contrast to PMMA 7 N, PC2245 could be demolded from coated
and uncoated molds (Fig. 10). The influence of the laser power as well
as the (Cr,Al)N coating were observed. Generally, the replication ratio
of cross structures is lower than the replication of line structures. With
increasing laser power from PLaser = 0 W to PLaser = 319 W, the re-
plication ratio increases from R = 54% to R = 84% for line structures,
and from R = 44% to R = 65% for cross structures. The influence of
the coating is significantly higher than the laser power. The replication
ratio is R = 94% for line structures, and R = 89% for cross structures.
It could be observed that the replication ratio of micro-structures
using an (Cr,Al)N coating is up to 30% higher compared to replications
without a coating. Similar results can be observed for different structure
geometries and structure heights. In order to gain a better under-
standing of the positive influence of the coating on the replication ra-
tios, an application-oriented tribological model test in a pin on disc
tribometer was carried out to analyze the friction behavior of the
Fig. 6. Schematic of micro-structured and PVD-coated
mold and SEM cross section of (Cr,Al)N coating.
K. Bobzin et al. Surface & Coatings Technology 332 (2017) 474–483

Fig. 7. 3-D imaging in CLSM of micro-structured

mold with line and cross structures prior to
coating a) and after coating b).

Fig. 8. Roughness after laser-structuring of mold a) and

Failure of PMMA 7 N during demolding of uncoated mold
b).

coatings against the plastics. Moreover, the coating was analyzed by reference against counterparts made of PC2245 and PMMA 7 N (Fig. 11).
means of application-oriented system tests on the wetting and adhesion Generally, the CoF of PMMA 7 N is higher than the CoF of PC2245 for
behavior towards the investigated plastics. both coated and uncoated samples. A particularly positive character-
istic is that the (Cr,Al)N coating exhibits a lower CoF in comparison to
uncoated substrates, both with PC2245 and PMMA 7 N. The CoF of ni-
3.3. Friction behavior of the coated and uncoated H11 steel
tride hard coatings against PC2245 is CoF = (0.64 ± 0.06); against
PMMA 7 N, it is CoF = (0.78 ± 0.07). After the PoD test, the CoF for
In addition to the research objective, improvement of the replication
the uncoated substrate H11 against PC2245 is CoF = (0.81 ± 0.03);
ratio of micro-structured plastic components using (Cr,Al)N coating,
against PMMA 7 N, it is CoF = (0.89 ± 0.04). It can be concluded that
PVD coating should also fulfill other requirements. These are related to
in the case of PMMA 7 N, the use of PVD decreases the coefficient of
the friction behavior of the mold surface in contact with PC2245 and
friction about 11% and for PC2245 about 17%.
PMMA 7 N. Application-oriented tribological model tests in a pin on
disc tribometer were performed to observe the coefficient of friction
CoF of the substrate H11 coated with (Cr,Al)N as well as of an uncoated

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K. Bobzin et al. Surface & Coatings Technology 332 (2017) 474–483

Fig. 9. 3-D imaging in CLSM of micro-structured

PMMA 7 N exemplary for h = 50 μm line and cross
structures a) and calculated replication ratio of micro-
structured PMMA 7 N using coated mold.

3.4. Wettability, adhesion and roughness of the coated and uncoated H11
steel

Time-dependent high temperature contact angle (CA) measure-

ments were conducted to analyze the wetting behavior of molten PC2245
and PMMA 7 N on the (Cr,Al)N coating. Processing temperatures were
TPC2245 = 300 °C and TPMMA 7N = 220 °C; measurements were taken
for t = 50 min (Fig. 12). Generally, the contact angles of PMMA 7 N are
higher than those of PC2245 for coated and uncoated samples. Fig. 12
reveals that a lower adhesion affinity, i.e. a higher contact angle, of
PC2245 and PMMA 7 N on coated surfaces in comparison to uncoated
substrates H11 is achieved. This can be traced exemplarily in Fig. 12,
which presents photographs of the wetting behavior of PMMA 7 N on
(Cr,Al)N and H11.
Furthermore, investigations were carried out in order to determine
the energy, which is required for the separation of the solidified PC2245
and PMMA 7 N from the sample surfaces after the high temperature
contact angle measurements. Fig. 13 shows the results of the shear tests.
Generally, it can be observed that the energy needed to separate the Fig. 11. Tribological investigations between (Cr,Al)N coating as well as uncoated H11
solidified PMMA 7 N pellets from the uncoated H11 is lower than for against PC2245 and PMMA 7 N.
PC2245. As PMMA is much more brittle than PC2245, it cannot withstand
the forces [40]. From Fig. 13, it can be concluded that the shear energy
coated substrate, which is E(Cr,Al)N = (0.75 ± 0.08) kN mm. With re-
required to separate the solidified PC2245 from the uncoated H11 is
gard to the tests for PMMA 7 N, the shear energy for uncoated H11 is
EH11 = (1.00 ± 0.15) kN mm, which is higher than the energy for the
EH11 = (0.05 ± 0.01) kN mm and for the coated substrate, it is

Fig. 10. 3-D imaging in CLSM of micro-structured

PMMA 7 N exemplary for h = 50 μm line and cross
structures using coated mold a) and calculated re-
plication ratio of micro-structured plastics component
from PC2245 using uncoated and coated mold.

480
K. Bobzin et al.
E(Cr,Al)N = (0.01 ± 0.002) kN mm. These results are in accordance
with the results from the contact angle measurements in Fig. 12. A
lower wettability of PC2245 and PMMA 7 N on coated surfaces is
achieved in comparison to the uncoated substrate H11.
Since the contact angle measurements were performed at high
temperatures, the coating properties were remeasured afterwards.
Fig. 14 shows a comparison between the Ra and Rz values of H11 and
(Cr,Al)N prior to and after the CA measurements at TPMMA 7N = 220 °C
and TPC2245 = 300 °C. Moreover, the areas under the solidified PMMA
7 N and PC2245 were also measured after the shear tests. It should be
noted that the temperature has a stronger influence on the surface
roughness of substrate H11 than of (Cr,Al)N. Particularly positive is
that for (Cr,Al)N, the arithmetic average surface roughness only
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Surface & Coatings Technology 332 (2017) 474–483
Fig. 12. Time dependent development of high temperature
contact angles of molten PC2245 and PMMA 7 N against
(Cr,Al)N and uncoated H11.
increases from Ra = 0.023 μm to Ra = 0.026 μm at TPMMA 7N = 220 °C
and to Ra = 0.029 μm at TPC2245 = 300 °C. After the shear test, the
arithmetic average surface roughness increases to Ra = 0.025 at TPMMA
7 N = 220 °C and to Ra = 0.058 μm at TPC2245 = 300 °C. For H11, the
following increases of the Ra value can be observed: from
Ra = 0.019 μm to Ra = 0.068 at TPMMA 7 N = 220 °C and to
Ra = 0.037 μm at TPC2245 = 300 °C. After the shear test, the arithmetic
average surface roughness increases to Ra = 0.078 at TPMMA
7 N = 220 °C and to Ra = 0.089 μm at TPC2245 = 300 °C. This can serve
as another benefit the (Cr,Al)N coating has to offer for the replication of
micro-structures with PC2245 and PMMA 7 N, as the coating is less af-
fected by the processing temperatures TPMMA 7 N and TPC2245 than the
uncoated H11. This can be attributed to the enormous effect
Fig. 13. Shear energies after high temperature contact angle
of solidified PC2245 and PMMA 7 N against uncoated H11 and
(Cr,Al)N coating.
K. Bobzin et al.
temperature has on uncoated surfaces. An assumption is that the
chromium from the coating forms a chemical compound with the
carbon from plastics, which could lead to increase the surface rough-
ness after high temperature contact angle measurements. Another
reason of increasing the roughness could be due to a high oxidation of
uncoated surface in comparison to coated surface. However, this effect
is not yet completely understood and will be further investigated in
more details in future work.
It can be concluded that the (Cr,Al)N coating can decrease both the
CoF of mold surfaces in contact with solidified plastics melt during the
demolding of plastic components as well as the optical quality of re-
plicated micro-structured plastic components. Moreover, by comparing
the results of the high temperature contact angle measurements and the
PoD test, a correlation can be derived.
The weak affinity of nitride coating to plastic melt may also con-
tribute to the lower wettability of the coated surface, which stems
partially from the lower surface roughness of the coating. This corre-
sponds to the low adhesion strength and the low coefficient of friction
between the coated surfaces and the solidified plastics. These contribute
to a decrease of deforming forces for the replication of micro-structured
mold and therefore to the quality of optical plastic components.
4. Conclusion
Within the scope of this work, the combination of an innovative
technologies such as laser structuring, PVD coating and laser-based
variothermal injection molding were contemplated to enhance the re-
plication ratio of injection molded plastic components. It was observed
that an increase in laser power during the molding results in an increase
of the replication ratio. Though better replication can be achieved using
laser-based variothermal injection molding, the physical adhesion of
the plastics melt on the surface of the micro-structured can influence
the product quality negatively. In the case of PMMA 7 N, micro-struc-
tures break during the demolding of the uncoated mold. In order to
improve the demolding of brittle polymers, to increase the durability of
micro-structures and to enhance the quality of plastics component, a
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Surface & Coatings Technology 332 (2017) 474–483
Fig. 14. Surface roughness of uncoated H11 and nitride
coating after high temperature contact angle measurements.
(Cr,Al)N coating was deposited on the micro-structured mold by means
of mfMS. Compared to the uncoated micro-structured mold, an increase
in the replication ratio up to 30% can be achieved by using the (Cr,Al)N
coating. The tribological investigations performed in a pin on disc test
show a significant decrease of the coefficient of friction by using the
(Cr,Al)N coating. Time-dependent high temperature contact angle (CA)
measurements reveal that a lower wettability of coated tools results in a
low shear energy. This is of especially great importance for the se-
paration of solidified PC2245 and PMMA 7 N from the sample surfaces
after high temperature contact angle measurements and could be
proved for the first time. The low surface roughness of the (Cr,Al)N
coating even at higher temperatures can result in an enhanced flow-
ability of polymer melts in the mold cavity, compared to the uncoated
mold. It can moreover result in an improvement of the demolding of
optical functional plastics components.
Acknowledgment
The authors gratefully acknowledge the financial support of the
German Research Foundation, Deutsche Forschungsgemeinschaft (DFG
EXC 128), within the Cluster of Excellence “Integrative Production
Technology for High-Wage Countries” and the research area “Multi-
Technology Products”.
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