polymers

Article
Calculation of the Contact Angle of Polymer Melts on
Tool Surfaces from Viscosity Parameters
Gernot Zitzenbacher 1, * ID
, Hannes Dirnberger 1 , Manuel Längauer 1 and Clemens Holzer 2
1 Department of Materials Technology, School of Engineering, University of Applied Sciences Upper Austria,
4600 Wels, Austria; [email protected] (H.D.); [email protected] (M.L.)
2 Department Polymer Engineering and Science, Chair of Polymer Processing, Montanuniversitaet Leoben,
8700 Leoben, Austria; [email protected]
* Correspondence: [email protected]; Tel.: +43-(0)50804-44520

Received: 18 October 2017; Accepted: 22 December 2017; Published: 30 December 2017

Abstract: It is of great importance for polymer processing whether and how viscosity influences
the wettability of tool surfaces. We demonstrate the existence of a distinct relationship between the
contact angle of molten polymers and zero shear viscosity in this paper. The contact angle of molten
polypropylene and polymethylmethacrylate on polished steel was studied in a high temperature
chamber using the sessile drop method. A high pressure capillary rheometer with a slit die was
employed to determine the shear viscosity curves in a low shear rate range. A linear relation between
the contact angle and zero shear viscosity was obtained. Furthermore, the contact angle and the zero
shear viscosity values of the different polymers were combined to one function. It is revealed that,
for the wetting of tool surfaces by molten polymers, a lower viscosity is advantageous. Furthermore,
a model based on the temperature shift concept is proposed which allows the calculation of the
contact angle of molten polymers on steel for different temperatures directly from shear viscosity data.

Keywords: polypropylene; polymethylmethacrylate; contact angle; viscosity; tool surface; wetting;

injection molding; extrusion

1. Introduction
Many phenomena in polymer processing are influenced by the wettability of solid surfaces by
polymer melts. The wettability of solid surfaces in tools and molds affects the replication of surface
structures and remolding forces in injection molding. As an example, in micro injection molding the
wettability of the mold surface and the temperature dependence of viscosity near the glass transition
temperature are important for the replication of surface structures [1]. Ejection forces decrease linearly
with the contact angle of the polymer melt on the mold coating [2]. Rytka et al. [3] reported that the
dewetting potential correlates well with the replicated height of different mold structures. A lower
dewetting potential of a polymer leads to a better replication accuracy.
Wettability also affects the polymer melt flow in flow channels and dies. Fluoropolymers on
die surfaces influence wall slip and shark skin in polymer melt rheology. Hatzikiriakos et al. [4]
investigated the effect of fluoropolymer coatings on high density polyethylene (HDPE). Seidel et al. [5]
found that polyetheretherketone (PEEK) and polytetrafluoroethylene (PTFE) induce wall slip of the
polymer melt and cause a smooth extrudate surface. Agassant et al. [6] reported that coatings such as
PTFE, which enhance slip at the wall, reduce or even eliminate sharkskin.
Hard coatings, which are often applied to screws and tools by physical vapor deposition (PVD)
or plasma assisted chemical vapor deposition (PACVD), and metals can also influence the polymer
melt flow and the extrudate appearance. Ramamurthy [7] studied the effect of different metals on
wall slip and on the extrudate appearance of polyethylene. He observed that beryllium copper as

Polymers 2018, 10, 38; doi:10.3390/polym10010038 www.mdpi.com/journal/polymers

Polymers 2018, 10, 38 2 of 12

a die material causes a lower critical wall shear stress for the onset of wall slip compared to steel.
Rauwendaal [8] reported that the reduction of the pressure loss in a spiral mandrel extrusion die with
a Lunac coating can be obtained. Zitzenbacher et al. [9,10] investigated the effect of diamond-like
carbon (DLC), titanium nitride (TiN), titanium aluminum nitride (TiAlN), and steel on wall slip of
a polypropylene copolymer and polymethylmethacrylate (PMMA). It was observed that a higher
polarity as exhibited by TiN reduces wall slip of PP, especially at higher temperatures. PMMA slips
only on polished steel, but no slip was found on DLC.
Young’s equation [11] is needed to describe the wetting of a solid surface by a liquid

σSL = σS − σL cosθ (1)

It is obtained from a balance of the surface energy between the liquid and the solid σSL , the surface
energy of the solid σS and the surface tension of the liquid σL including the contact angle θ at the
three phase points of liquid, solid, and surrounding atmosphere. According to Kumar [12] a complete
wetting (θ = 0◦ ), a partial wetting (0◦ < θ < 90◦ ), a partial non-wetting (90◦ < θ < 180◦ ) and a total
non-wetting (θ = 180◦ ) can be distinguished.
Although the wettability of solid substrates is often determined at room temperature, the contact
angle in the polymer melt state is needed for the explanation of phenomena which are related to
the interface between polymers and tool or screw materials. Schonhorn et al. [13] investigated the
wetting of aluminum, mica, and Teflon by an ethylene-vinyl acetate copolymer and polyethylene melts.
Silberzan et al. [14] studied the spreading behavior of poly(dimethylsiloxane) (PDMS) liquids on silica
surfaces at room temperature through optical microscopy and ellipsometry. Anastasiadis et al. [15]
investigated the wetting of molten linear low density and high density polyethylene on steel and
fluoropolymer coatings. Wulf et al. [16] studied the surface tension of a polystyrene melt dependent
on temperature in a sessile drop experiment. Wouters et al. [17] determined the surface tension of
epoxy resins, polyesters, and additives. Kopczynska [18] and Yang et al. [19] investigated the surface
tension of molten polycarbonate (PC), polystyrene (PS), styrene acrylonitrile (SAN), polyethylene (PE),
and polyamide 6 (PA 6). Zitzenbacher et al. [20] studied the contact angle of molten polypropylene (PP),
HDPE, PMMA, and Polyamid 6.6 (PA 6.6) on steel and different coatings such as titanium aluminum
nitride (TiAlN), titanium nitride (TiN), chromium nitride (CrN), silicone doped diamond-like carbon
(DLC), and polytetrafluoroethylene (PTFE). They observed a decrease in the contact angle of the molten
polymers with a rising surface energy of the coating. Vera et al. [21] investigated the contact angle of
molten PP, acrylonitrile butadiene styrene (ABS), and PC on steel, different titanium nitride coatings
(TiNOx , TiNOy , and TiNOz ), CrN, and DLC. Furthermore, they measured the surface tension of the
molten polymers and evaluated work of adhesion on the solid substrates.
It is of great importance for polymer melt flow and surface structure replication whether and
how viscosity influences the wettability of tool surfaces, especially in processes such as injection
molding and extrusion technology. Furthermore, shear viscosity curves are often more easily available,
but the contact angle of polymer melts on solid surfaces can only be determined in time consuming
experiments. The goal of this paper was to study the influence of shear viscosity on the contact angle of
molten polymers on tool steel. The contact angle was determined employing the sessile drop method
in a high temperature chamber and the shear viscosity curves were measured in a low shear rate range
using a high pressure capillary rheometer with a slit die. Furthermore, the contact angle and the shear
viscosity curves were determined at elevated temperatures. It is demonstrated that the contact angle
of the molten polymers is a function of zero shear viscosity. The data of the two different polymeric
materials, PP and PMMA, are combined to one function. As a final result, a model is proposed to calculate
the contact angle of polymer melts on steel for different temperatures directly from zero shear viscosity.
Polymers 2018, 10, 38 3 of 12

2. Materials and Methods

A polypropylene homopolymer (PP) HD 120 MO, produced by Borealis, Linz, Austria,
and a polymethylmethacrylate (PMMA) PLEXIGLAS 7M from Evonik, Darmstadt, Germany,
were investigated in this study in order to gain a better understanding about their processing behavior.
PP HD 120 MO has a melt flow rate (MFR) of 8 g (10 min)−1 at 230 C/2.16 kg and is used for injection
molding applications. PMMA PLEXIGLAS 7M has a MFR of 3.45 g (10 min)−1 at 230 ◦ C/3.80 kg and is
employed for extruded profiles and panels. The MFR values mentioned were taken from the material
datasheets. The testing temperature range of the polymeric materials was chosen according to the
material suppliers’ recommended melt temperature range. PP was studied at a temperature of 185,
200, 210, and 220 ◦ C. The testing temperature of PMMA was 230, 240, 250, and 260 ◦ C, respectively.
PMMA was predried before the experiments.
The viscosity curves of these polymeric materials were determined using a high pressure capillary
rheometer Rheograph 6000, produced by Goettfert, Buchen, Germany, with a slit die. The slit die
concept was employed because it allows the measurement of viscosity data in a low shear rate range,
which was chosen between 0.1 and 350 s−1 . Furthermore, directly measured pressure data is obtained
which leads to true wall shear stresses, without having to use Bagley correction. First, the polymeric
material was filled into the reservoir channel, melted, and heated up to the defined temperature.
The slit die was heated to the same temperature. When extruding the melt, the piston velocity was
increased stepwise in order to obtain rheological data at different apparent wall shear rate values.
The wall shear stress τw was evaluated according to Walters [22]

HW ∆p
τw = (2)
2( H + W ) ∆L

where H is the height of the flow channel, W is the width of the flow channel, ∆L is the distance
between the pressure transducers, and ∆p is the measured pressure loss.
The apparent wall shear stress is
. 6Q
γap = (3)
W H2
where Q is the volume flow rate.
The Weissenberg–Rabinowitsch equation [23,24] was used to obtain the true shear rate at the wall

.
  
.
. γap d logγap
γw = 3 +  (4)
4 d(logτw )

Shear viscosity η can then be evaluated by introducing Equations (2) and (4) in Equation (5)
τw
η= . (5)
γw

The measurement and evaluation of the viscosity dependent on shear rate was conducted at
least four times at each temperature. A mean value was calculated from these data at each shear
rate value to obtain the final viscosity curve. The shear viscosity curve was approximated with the
Bird-Carreau-Yasuda model [24] using the least squares method

.

h i n −1
.
a a
η γ = η0 1 + λγ (6)

where η0 is zero shear viscosity, λ is a time constant, n is the Power Law index, and a accounts for the
width of the transition region between zero shear viscosity and the Power Law region.
A Drop Shape Analyzer DSA 30S, produced by Kruess, Hamburg, Germany, with a high
temperature chamber TC 21 was employed to measure the contact angle of the molten PP and PMMA
Polymers 2018, 10, 38 4 of 12

on steel with the sessile drop method. The experiments were carried out under nitrogen atmosphere
with a gas flow rate of 20 NL·h−1 to avoid thermooxidative degradation of the polymeric materials.
A schematic diagram of the test setup is shown in [20].
The X38CrMoV5 1 steel discs with a diameter of 40 mm and a thickness of 10 mm were heat
treated and polished to an area-weighted surface roughness Sa of 15.1 ± 5.7 nm. The surface roughness
of the steel samples was determined by means of a confocal microscope DCM3D, Leica Microsystems,
Wetzlar, Germany at three positions on the sample, one in the center, and two 10 mm from the
center, once in x- and once in y-direction. Before the contact angle measurements the steel discs
were cleaned carefully with isopropanol using a tissue and dried with an air stream. Afterwards,
Polymers
the 2017, 9, 38was placed in the high temperature chamber and preheated 15 min to obtain a uniform
steel sample 4 of 12
temperature distribution.
Microsystems,
In the next Wetzlar,
step, the Germany at three was
polymer sample positions
placed ononthethe
sample,
solid one in the
surface withcenter, and
a pair oftwo 10 mm
tweezers.
from
The the center,of
positioning once x- and once
theinpolymer samplein y-direction.
was conducted Beforeas thefast
contact angle measurements
as possible the steel
to avoid substantial
discs were decrease
temperature cleaned andcarefully with isopropanol
high nitrogen loss in theusing a tissue andchamber.
high temperature dried with Afteranmelting
air stream.
the
Afterwards,
polymer sample,the the
steel sample
drop shapewaswasplaced in the
recorded high temperature
dependent chamber
on time with a CCD and preheated
camera with 15 min to
a frame
obtain
rate of 1afps.
uniform temperature
The contact distribution.
angle was evaluated using the recorded video data. The drop contour was
In the next step, the polymer
approximated with a polynomial function sample nearwas
theplaced on the
base line. Thesolid
slopesurface with a pair of function
of the approximation tweezers.
inThe
the positioning
contact pointofofthe the polymer
three phasessample was conducted
was used to evaluate as thefast as possible
contact angle. Each to avoid
test wassubstantial
carried
temperature decrease and high nitrogen loss in the high temperature
out at least three times in order to verify its reproducibility and a mean value was calculated. chamber. After melting the
polymer sample, the drop shape was recorded dependent on time with a CCD camera with a frame
3.rate of 1 fps. The contact angle was evaluated using the recorded video data. The drop contour was
Results
approximated with a polynomial function near the base line. The slope of the approximation
3.1. Shear Viscosity Curves
function in the contact point of the three phases was used to evaluate the contact angle. Each test was
carried
The out at least
shear three of
viscosity times
PP inandorder
PMMA to verify its reproducibility
dependent on shear rate andata mean value
different was calculated.
temperatures is
represented as the approximated curves in Figures 1 and 2. Table 1 shows the Bird-Carreau-Yasuda
3. Results at different temperatures T, including the zero shear viscosity η0 , the time constant λ,
parameters
the Power Law index n, the width of the transition region a and the coefficient of determination R2 .
3.1.good
The Shearreproducibility
Viscosity Curvesof the tests is indicated by the standard deviation of the measured shear
Thevalues
viscosity shearwhich
viscosity of PP andonPMMA
is dependent dependent
shear rate on shearbetween
and temperature rate at different
0.5% and temperatures
4.8%. is
represented as the approximated curves in Figures 1 and 2. Table 1 shows the Bird–Carreau–Yasuda
Both polymer melts exhibit shear thinning behavior, which means that shear viscosity decreases
parameters
with at different
rising shear temperaturesshear
rate. Furthermore, T, including
viscosity thedecreases
zero shear viscosity
with 0, the time constant
risingηtemperature. λ, the
The shear
Power Law index n, the width of the transition region a and the coefficient of determination R². The
viscosity curve of PP reveals a negative slope even at low shear rates. The width of the Newtonian
good reproducibility
tableau of PMMA decreases of thewithtests is temperature.
rising indicated byThe thegood
standard deviationof of
approximation thethe measured
measured shear
viscosity
2.
viscosity values which is dependent on shear rate and temperature between 0.5% and 4.8%.
data with the Bird-Carreau-Yasuda model is indicated by the coefficient of determination, R

10000
T = 185 °C
T = 200 °C
T = 210 °C
T = 220 °C
Shear viscosity η (Pa s)

1000

100

10
0.1
0 1 10 100 1000
.
Shear rate γ (s-1)

Figure 1. Shear
Figure viscosity
1. Shear of of
viscosity polypropylene dependent
polypropylene onon
dependent shear rate
shear at at
rate different temperatures.
different temperatures.

10000
T = 230 °C
T = 240 °C
T = 250 °C
T = 260 °C
ear viscosity η (Pa s)

1000

100
 100

She
10
0.1
0 1 10 100 1000
.
Shear rate γ (s-1)
Polymers 2018, 10, 38 5 of 12
Figure 1. Shear viscosity of polypropylene dependent on shear rate at different temperatures.

10000
T = 230 °C
T = 240 °C
T = 250 °C
T = 260 °C

Shear viscosity η (Pa s)

1000

Polymers 2017, 9, 38 5 of 12
100

Both polymer melts exhibit shear thinning behavior, which means that shear viscosity decreases
with rising shear rate. Furthermore, shear viscosity decreases with rising temperature. The shear
viscosity curve of PP reveals 10a negative slope even at low shear rates. The width of the Newtonian
0.1
0 1 10 100 1000
tableau of PMMA decreases with rising temperature. Shear rate γ (sThe
.
) good approximation of the measured -1

viscosity data with the Bird–Carreau–Yasuda model is indicated by the coefficient

Figure
2. Shear2.viscosity
of determination,
Figure Shear
R². viscosity of polymethylmethacrylate
of polymethylmethacrylate dependent dependent
on shearon
rateshear rate attemperatures.
at different different
temperatures.
1. Bird-Carreau-Yasuda
TableTable 1. Bird–Carreau–Yasuda parameters
parametersofofthe thepolymers PPand
polymers PP andPMMA
PMMA at different
at different temperatures
temperatures
T including
T including the zero
the zero shear
shear viscosityη0η,0,the
viscosity thetime constant λλ,
time constant , the
thePower
PowerLaw index
Law n, the
index width
n, the of theof the
width
transition
transition region
region a, and
a, and thethe determination R².
coefficientofofdetermination
coefficient R2 .

Polymer T (°C) η0 (Pa·s) λ (s) n (-) a (-) R²

Polymer T (◦ C) η0 (Pa·s) λ (s) n (-) a (-) R2
PP 185 3777.92 0.1059 0.27 0.68 1.00
PP 185 3777.92 0.1059 0.27 0.68 1.00
PP PP 200 200 2628.462628.46 0.0368
0.0368 0.15
0.15 0.640.64 1.00 1.00
PP PP 210 210 2210.412210.41 0.0472
0.0472 0.23
0.23 0.610.61 1.00 1.00
PP PP 220 220 1719.04 0.0358 0.21 0.65 1.00
1719.04 0.0358 0.21 0.65 1.00
PMMA 230 5993.19 0.0574 0.35 1.62 1.00
PMMA PMMA230 240 5993.193585.80 0.0574
0.0141 0.35
0.08 0.851.62 1.00 1.00
PMMA PMMA240 250 3585.802213.47 0.0141
0.0054 0.08
0.00 0.630.85 1.00 1.00
PMMA 260 1553.75 0.0041 0.00 0.60 1.00
PMMA 250 2213.47 0.0054 0.00 0.63 1.00
PMMA 260 1553.75 0.0041 0.00 0.60 1.00
3.2. Contact Angle of the Molten Polymers
3.2. Contact
The Angle
contact of the of
angle Molten
the Polymers
molten polymers on polished steel depends on temperature.
Figures 3 The
andcontact
4 showangle of the molten
the mean values polymers on polished
of the measured steel depends
contact angle dataon temperature. Figures 3
at different temperatures,
and 4 show the mean values of the measured contact angle data at different temperatures,
including their positive and negative deviations. The contact angle values were taken at the end of including
their
the test positive
runs and negative
to ensure stable deviations.
conditions.The PPcontact angle values
and PMMA revealwere taken at the
a decrease endcontact
in the of the test runs with
angle
to ensure stable conditions. PP and PMMA reveal a decrease in the contact angle
rising temperature. The contact angle of molten PP on polished steel is 85.0 , 77.1 , 72.6 , and 67.1◦
◦ ◦ with◦ rising
temperature. The contact angle of molten PP on polished steel is 85.0°, 77.1°, 72.6°, and 67.1° at
at temperatures of 185, 200, 210, and 220 ◦ C, respectively. The low positive and negative deviations
temperatures of 185, 200, 210, and 220 °C, respectively. The low positive and negative deviations
indicate the high reproducibility of the tests.
indicate the high reproducibility of the tests. ◦ at a
The The
contact angle
contact angleof of
molten
moltenPMMA
PMMA on on polished steelisis101.8,
polished steel 101.8,80.0,
80.0, 71.3,
71.3, andand
68.0 68.0
°C at C a
temperature of 230, 240, ◦ 260 ◦ C,
temperature of 230, 240,250,
250,and
and 260
260 °C,C,respectively.
respectively. At temperatures
At the the temperatures of 230 of
and230260and
°C, the
positiveand
the positive and negative
negative deviations
deviations areare
higher.
higher.

120

100

80
Contact angle (°)

60

40

20

0
185 200 210 220
Temperature (°C)

Figure
Figure 3. Contact
3. Contact angle
angle ofofmolten
moltenpolypropylene
polypropylene on
onsteel
steelatat
different temperatures.
different temperatures.
 Polymers2018,
Polymers 9, 38
2017,10, 38 66of
of12
12
Polymers 2017, 9, 38 6 of 12
120
120

100
100

80

(°) (°)
80

Contact angle
angle
60
60
Contact

40
40

20
20

0
0 230 240 250 260
230 240 Temperature (°C)
250 260
Temperature (°C)
Figure 4. Contact angle of molten polymethylmethacrylate on steel at different temperatures.
Figure
Figure4.
4.Contact
Contactangle
angleof
ofmolten
moltenpolymethylmethacrylate
polymethylmethacrylateon
on steel
steel at
at different
different temperatures.
temperatures.
3.3. Relation Between the Contact Angle and Zero Shear Viscosity
3.3.
3.3. Relation
Relation Between
Between thethe Contact
Contact Angle
Angle andand Zero
Zero Shear
Shear Viscosity
Viscosity
Zero shear viscosity depends on material and process parameters. The consideration that the
Zero
contact
Zero shear
angle
shearofviscosity
polymer depends
viscosity melts
depends on
on material
on tool surfaces and
material could
and process parameters.
be influenced
process parameters. The
The consideration
in a similar that
manner compared
consideration that the
theto
contact angle of polymer melts on tool surfaces could be influenced in a similar
viscosity was the motivation to study the relation between the contact angle and zero shear viscosity.
contact angle of polymer melts on tool surfaces could be influenced in a similar manner
manner compared
compared to
to
viscosity
The mean
viscosity was
was the
the motivation
values to
tostudy
of the measured
motivation the
therelation
studycontact between
angle
relation data were
between the
thecontact
plottedangle
contact and
andzero
zeroshear
in dependence
angle viscosity.
of zero
shear shear
viscosity.
The
The mean
viscosity
mean (seevalues
valuesTableof the measured
1).measured
of the The dependence contact angle
of thedata
contact angle data
contact were
wereangle plotted
of molten
plotted in dependence
PP and of
in dependence PMMA of zero
on zero
zero shear shear
shear
viscosity
viscosity
(see Table(see
viscosity 1). Table
is presented
The 1). Thein dependence
dependence Figures of the
of the 5contact
and contact
6.angle
The angle PP
ofmeasured
molten ofdata
molten were
and PMMA PP andon PMMA
approximated on with
zero shear zero shear
linear
viscosity is
viscosity
presented is
functions in presented
using in
the 5least
Figures Figures
and 6.squares 5 and 6.
method.data
The measured The measured
Thewere
approximation data
approximated were
functions approximated
andfunctions
with linear with linear
the coefficients
using the of
functions using the least squares method.
determination R² are given in Equations (7) and (8)
least squares method. The approximation The
functions approximation
and the functions
coefficients of and the
determinationcoefficients
R 2 are givenof
determination
in Equations (7) R²and
are (8)
given in Equations (7) and (8)
PP: 𝜃𝜃 = 0.0086𝜂𝜂0 + 53.34, 𝑅𝑅 2
2 = 0.98 (7)
PPPP:: θ𝜃𝜃==0.0086η
0.0086𝜂𝜂0 0++53.34,
53.34,R𝑅𝑅2= = 0.98
0.98 (7)
(7)
PMMA:
PMMA : θ 𝜃𝜃==0.0077η
0.0077𝜂𝜂
0+0+ 54.52,
54.52, 2 2 = 0.99
R𝑅𝑅 = 0.99 (8)
(8)
PMMA: 𝜃𝜃 = 0.0077𝜂𝜂0 + 54.52, 𝑅𝑅2 = 0.99 (8)
The The
values of the
values ofcoefficient of determination
the coefficient of determination R2 areR2slightly belowbelow
are slightly 1, which indicates
1, which a gooda linear
indicates good
The values
correlation
linear
of the
correlation
coefficient
between of
the contact
between
determination
angle angle
the contact and zero R 2 are slightly below 1, which indicates a good linear
andshear viscosity.
zero shear viscosity.
correlation between
The slopes
slopes the contact angle
of Equations andare zero shear viscosity. (Pa∙s)−1,−respectively.
The of Equations (7)(7) and
and(8) (8) are0.0086
0.0086and
and0.0077
0.0077 (Pa·s) 1 , respectively.Furthermore, the
Furthermore,
The
differenceslopes of
between Equations
thethe (7)
distancesand (8)
onon are
thethe0.0086
contact and 0.0077 (Pa∙s) −1, respectively. Furthermore, the
the difference between distances contactangle
anglecoordinate
coordinateaxis axisofofEquations
Equations (7)
(7) and (8) is
and (8) is
difference
low.between
rather low. the distances
Thesevalues
values are53.34
53.34° ◦onforthePPcontact
and54.42 angle
54.42° forcoordinate
◦ for PMMA. axis of Equations (7) and (8) is
rather These are for PP and PMMA.
rather low. These values are 53.34° for PP and 54.42° for PMMA.
120
120

100
100

80
Contact angle θ (°)

80
Contact angle θ (°)

60
60

40
40

20
20

0
0 0 1000 2000 3000 4000 5000 6000 7000
0 1000 2000 Zero shear 4000η0 (Pa·s)
3000 viscosity 5000 6000 7000
Zero shear viscosity η0 (Pa·s)
Figure 5. Contact angle of the molten polypropylene on steel dependent on zero shear viscosity and
Figure 5. Contact angle of the molten polypropylene on steel dependent on zero shear viscosity and
Figure 5. Contact
approximated angle
with of thefunction.
a linear molten polypropylene on steel dependent on zero shear viscosity and
approximated with a linear function.
approximated with a linear function.
Polymers 2018, 10, 38 7 of 12
Polymers 2017, 9, 38 7 of 12

Polymers 2017, 9, 38 120 7 of 12

120
100

100

(°) θ (°)
80

angle θangle
80
60
ContactContact

60
40

40
20

20
0
0 1000 2000 3000 4000 5000 6000 7000
Zero shear viscosity η0 (Pa·s)
0
0 1000 2000 3000 4000 5000 6000 7000
Figure 6. Contact angle of molten polymethylmethacrylate
Zero shear viscosity η0on
(Pa·s) on steel dependent on zero shear
Figure 6. Contact angle of molten polymethylmethacrylate steel dependent on zero shear viscosity
viscosity and approximated with a linear function.
and approximated
Figure 6. Contactwith a linear
angle function.
of molten polymethylmethacrylate on steel dependent on zero shear
Ifviscosity and approximated
the contact angle can bewith a linear function.
calculated directly from zero shear viscosity for one polymer, this
If the contact angle can be calculated
equation could be the same for other polymers. directly from zero
The contact shear
angle viscosity
values for one
of PP and PMMApolymer,
were
this If the contact angle can be calculated directly from zero shearangle
viscosity forofone polymer, this
plotted dependent on zero shear viscosity in one diagram and approximated with onePMMA
equation could be the same for other polymers. The contact values PP and linear
equation
were plottedcould be the same
dependent on for shear
zero other viscosity
polymers.inThe one contact
diagramangle
and values of PP and
approximated PMMA
with one were
linear
function to prove this hypothesis (see Figure 7)
plotted to
function dependent
prove thison zero shear
hypothesis (seeviscosity
Figure 7)in one diagram and approximated with one linear
function to prove this hypothesis (see Figure𝜃𝜃 = 0.0077𝜂𝜂7) 0 + 54.92, 𝑅𝑅2 = 0.98 (9)
2
θ = 0.0077η0 + 54.92, R = 0.98 (9)
Although PP and PMMA are completely different
𝜃𝜃 = 0.0077𝜂𝜂 polymeric2 materials, the relation between contact
0 + 54.92, 𝑅𝑅 = 0.98 (9)
angle and zero shear viscosity follows one function, which is supported by the coefficient of
Although
Although PP and
PP PMMA
and PMMA are completely
are completely different polymeric
different materials,
polymeric the relation
materials, between
the relation contact
between
determination R² of 0.98. Now, the contact angle of a polymer melt on polished steel can directly be
angle and zero shear viscosity follows one function, which is supported by the coefficient of
contact angle and zero shear viscosity follows one function, which is supported by the coefficient of
calculated from 2zero shear viscosity of this material using Equation (9), but for a generalization of
determinationRR² of
determination of 0.98.
0.98. Now,
Now,the thecontact
contactangle
angleof ofaapolymer
polymermelt
meltononpolished
polishedsteel
steelcan
candirectly
directlybebe
this finding, further experiments with other polymers are required.
calculatedfrom
calculated fromzero
zeroshear
shear viscosity
viscosity of of this
this material
material using
using Equation
Equation (9), (9),
but but
for afor a generalization
generalization of thisof
this finding,
finding, further
further experiments
experiments
120
with with
otherother polymers
polymers are required.
are required.

120
100

100 PP
(°) θ (°)

80
PMMA
angle θangle

80 PP
60 PMMA
Contact

60
40
Contact

40
20

20
0
0 1000 2000 3000 4000 5000 6000 7000
0 Zero shear viscosity η0(Pa·s)
0 1000 2000 3000 4000 5000 6000 7000
Figure 7. Material invariant master curveZero
of the contact
shear angle
viscosity of molten polymers on steel dependent
η0(Pa·s)

on zero shear viscosity and approximated with a linear function.

Figure7.7.Material
Figure Materialinvariant
invariantmaster
mastercurve
curveof
ofthe
thecontact
contactangle
angleof ofmolten
moltenpolymers
polymerson
onsteel
steeldependent
dependent
on zero shear viscosity and approximated with a linear function.
3.4. Implementation of a Temperature Shift Factor for the Contact Angle
on zero shear viscosity and approximated with a linear function.

Zero shear viscosity

3.4. Implementation η0 at different
of a Temperature Shifttemperatures T can beAngle
Factor for the Contact calculated from zero shear viscosity at
a reference temperature T0 employing the temperature shift concept
Zero shear viscosity η0 at different temperatures T can be calculated from zero shear viscosity at
a reference temperature T0 employing the (𝑇𝑇) = 𝜂𝜂0 (𝑇𝑇0 )𝑎𝑎shift
𝜂𝜂0temperature 𝑇𝑇,η (𝑇𝑇)
concept (10)
where aT,η is the temperature shift factor for shear
𝜂𝜂0 (𝑇𝑇) = 𝜂𝜂viscosity.
0 (𝑇𝑇0 )𝑎𝑎 𝑇𝑇,η (𝑇𝑇) (10)
The temperature shift factor of viscosity can be expressed at temperatures, T, well above the
where aT,η is the temperature shift factor for shear viscosity.
glass transition temperature Tg (T > Tg + 100 °C) using Arrhenius’ law [25]
The temperature shift factor of viscosity can be expressed at temperatures, T, well above the
glass transition temperature Tg (T > Tg + 100 °C) using Arrhenius’ law [25]
Polymers 2018, 10, 38 8 of 12

3.4. Implementation of a Temperature Shift Factor for the Contact Angle

Zero shear viscosity η0 at different temperatures T can be calculated from zero shear viscosity at a
reference temperature T0 employing the temperature shift concept

η0 ( T ) = η0 ( T0 ) a T,η ( T ) (10)

where aT,η is the temperature shift factor for shear viscosity.

The temperature shift factor of viscosity can be expressed at temperatures, T, well above the glass
transition temperature Tg (T > Tg + 100 ◦ C) using Arrhenius’ law [25]
  
E0 1 1
aT,η ( T ) = − (11)
R T T0

where E0 is the activation energy and R is the gas constant. The glass transition temperature is 108 ◦ C
for PMMA and 0 ◦ C for PP, respectively.
It is assumed that the contact angle θ(T) at a certain temperature can be calculated from the
contact angle at a reference temperature θ(T0 ) using a temperature shift factor aT,θ

θ( T ) = θ( T0 ) aT,θ ( T ) (12)

Because of the linear relation between contact angle and zero shear viscosity and under
consideration of Equation (9) the slope k can be expressed as

θ( T ) − θ( T0 )
k= = 0.0077 (13)
η0 ( T ) − η0 ( T0 )

Introducing Equations (10) and (12) in Equation (13) yields

θ( T0 )[ aT,θ ( T ) − 1]
k= (14)
η0 ( T0 )[ aT,η ( T ) − 1]

Then, the temperature shift factor aT,θ for the contact angle can be expressed from Equation (14)

η0 ( T0 )
aT,θ ( T ) = k· ·[ aT,η ( T ) − 1] + 1 (15)
θ( T0 )

After introducing Equation (15) in Equation (12), the contact angle θ can be calculated at different
temperatures T from zero shear viscosity at reference temperature η0 (T0 ) and from the temperature
shift factor of viscosity aT,η

θ( T ) = 0.0077η0 ( T0 )[ aT,η ( T ) − 1] + θ( T0 ) (16)

In the next step, this model was applied to the studied polymers. The temperature shift factor of
viscosity aT,η of the polymer melts was calculated by employing Equations (10) and (11). The zero
shear viscosity values η0 , which were determined at different temperatures (see Table 1), were shifted
to the lowest temperature to obtain the activation energy, E0 . A mean value for the activation energy
was calculated from these data. The evaluated parameters for the calculation of the contact angle θ of
PP and PMMA according to Equation (16) are given in Table 2. A comparison of the calculated
contact angle from viscosity parameters to the experimental determined values is presented in
the Figures 8 and 9. The negligible deviations between the calculated contact angle curve and the
experimentally determined values confirm the validity of the proposed model. It has to be considered
that errors in the calculated values can occur below and above the studied temperature range.
Polymers 2018, 10, 38 9 of 12

Table 2. Reference temperature T0 , activation energy E0 , zero shear viscosity at reference temperature
η0 (T0 ), and contact angle at reference temperature θ(T0 ) for the calculation of the temperature
dependent contact angle from viscosity parameters of the polymers polypropylene (PP) and
polymethylmethacrylate (PMMA) on steel.

Polymer T 0 (◦ C) E0 (kJ·mol−1 ) η(T 0 ) (Pa·s) θ(T 0 ) (◦ )

PP 185 42.92 3777.92 85.0
PMMA 230 109.62 5993.19 101.8
Polymers 2017, 9, 38 9 of 12
Polymers 2017, 9, 38 9 of 12
120
120
Calculated
100 Experimental
Calculated
100 Experimental
θ (°)θ (°)

80
80
angle
angle

60
Contact

60
Contact

40
40

20
20

0
0170 180 190 200 210 220 230 240
170 180 190 Temperature
200 T (°C)
210 220 230 240
Temperature T (°C)
Figure 8. Comparison of the contact angle calculated from viscosity parameters to experimental
Figure 8.8. Comparison
Figure
determined Comparison
values of
of
of the contact
contact angle
thepolypropylene
of molten
molten
calculated
angle on
calculated from
from viscosity
steeldependent
dependentviscosity parameters
parameters to
ontemperature.
temperature. to experimental
experimental
determined values polypropylene on steel on
determined values of molten polypropylene on steel dependent on temperature.
120
120
Calculated
100 Calculated
Experimental
100 Experimental
θ (°)

80
θ (°)

80
angle
angle

60
Contact

60
Contact

40
40

20
20

0
0220 230 240 250 260 270
220 230 Temperature
240 T (°C)
250 260 270
Temperature T (°C)
Figure 9. Comparison of the contact angle calculated from viscosity parameters to experimental
Figure 9.9. Comparison
determined
Figure Comparison of the
thepolymethylmethacrylate
values of molten
of contact angle
contact angle calculated
calculatedonfrom
from viscosity
steelviscosity
dependent parameters to experimental
experimental
on temperature.
parameters to
determined values of molten polymethylmethacrylate on steel dependent on temperature.
determined values of molten polymethylmethacrylate on steel dependent on temperature.
4. Discussion
4. Discussion
4. Discussion
According to Young [11], the contact angle θ of a liquid on a solid is influenced by the surface
energy According
of the solid,to Young [11], tension
the surface the contact angle
of the liquidθ of a liquid on a solid is between
influenced by the and
surface
According to Young [11], the contact angle θ ofand the surface
a liquid energy
on a solid is influenced thebysolid
the surfacethe
energy We
liquid. of the solid, the
observed surface tension
a decrease in the ofof the liquid
contact and
angleand the surface
of polymer energy
melts between steel.
on polished the solid and
Theand the
reason
energy of the solid, the surface tension the liquid the surface energy between the solid the
liquid.
for thisWe We observed
dependency a decrease in the contact angle of polymer melts on polished steel. The reason
liquid. observed aoriginates
decrease ininthe thecontact
decreaseangleof of
thepolymer
surface melts
tension onof liquidssteel.
polished and polymer
The reason melts
for
for this dependency
withdependency
rising temperature. originates in the decrease of the surface tension of liquids and polymer melts
this originatesSeveral authorsofreported
in the decrease the surfacethetension
decrease of surface
of liquids tension with
and polymer meltsrising
with
with rising temperature.
temperature. EötvösSeveral Several authors
[26] proposed reported
an equation whichthe decrease
predicts of surface
a linear dependencetension with rising
rising temperature. authors reported the decrease of surface tension with risingoftemperature.
the surface
temperature.
tension [26] Eötvös
of a proposed
liquid on an[26] proposed
temperature. an equation
Other predicts which
authors [16–19] predicts a linear dependence of the surface
Eötvös equation which a linearobserved
dependence a decrease
of the in surface
surface tension
tension of of
a
tension
epoxy on of a
resins, liquid on
polyesters, temperature.
PE, authors Other
PC, PS, [16–19] authors
PMMA,observed [16–19]
and PA melts observed
with in a
risingdecrease in
temperature.surface tension of
liquid temperature. Other a decrease surface tension of Furthermore,
epoxy resins,
epoxy
the resins,inpolyesters,
decrease the PS,
contact PE, PC,ofPS,
angle PMMA, and PA melts with rising temperature. Furthermore,
polyesters, PE, PC, PMMA, and the
PA molten
melts withpolymers on polished
rising temperature. steel is influenced
Furthermore, the by a change
decrease in
the decrease in the contact angle of the molten polymers on
of the surface energy between steel and the polymer melts with rising temperature. polished steel is influenced by a change
of theWesurface
obtainedenergy between
a linear steelbetween
relation and the the
polymer
contact melts with
angle rising
of the temperature.
molten polymers and zero shear
We obtained a linear relation between the contact
viscosity. This means that the contact angle increases with rising zero shear angle of the molten polymers andItzero
viscosity. has shear
to be
viscosity. This means that the contact angle increases with rising zero
considered that zero shear viscosity can be influenced by temperature, pressure, and the average shear viscosity. It has to be
considered that zero shear viscosity can be influenced by temperature,
molecular weight. The used zero shear viscosity values were obtained from the rheological pressure, and the average
Polymers 2018, 10, 38 10 of 12

the contact angle of the molten polymers on polished steel is influenced by a change of the surface
energy between steel and the polymer melts with rising temperature.
We obtained a linear relation between the contact angle of the molten polymers and zero
shear viscosity. This means that the contact angle increases with rising zero shear viscosity. It has
to be considered that zero shear viscosity can be influenced by temperature, pressure, and the
average molecular weight. The used zero shear viscosity values were obtained from the rheological
measurement of shear viscosity curves at different temperatures and fit the well-known concept of
temperature shift of viscosity. This temperature shift can be calculated using the Arrhenius Equation
(see Equation (11)) or the Williams-Landel-Ferry Equation [27]

−C1 ( T − T0 )
logaT,η ( T ) = (17)
C2 + T − T0

which both depend exponentially on temperature. Herein, C1 and C2 are material specific parameters
and T0 is the reference temperature.
In this study, we found that based on the linear correlation between the contact angle of molten
polymers and zero shear viscosity the temperature shift concept can also be applied to the contact
angle of dependence of zero shear viscosity also determine temperature dependence of the contact
angle polymer melts on steel surfaces. The Arrhenius Equation is based on the thermally activated
overcoming of energy barriers in rotational potentials of molecule segments. When considering a melt
drop on a steel surface, temperature change will lead to a rearrangement of the polymer chains so
that the equilibrium of forces in the three-phase point between melt, atmosphere, and solid substrate
remains fulfilled. We state that the same mechanisms which determine temperature of polymer melts
on steel.
It was also shown that the obtained relation between the contact angle and zero shear viscosity
is a linear function, independent of the polymer used. This relation was verified for PP and PMMA.
Other polymers have to be studied to enable a generalization of this relation between the contact angle
and zero shear viscosity.
Furthermore, zero shear viscosity depends on the average molecular weight. The average
molecular weight and the width of the molecular weight distribution influence shear viscosity curves.
When polymer grades with the same distribution width but different average molecular weight are
compared, the viscosity curve with the higher average molecular weight is shifted to higher zero shear
viscosity values. The reason can be found in zero shear viscosity η0 , which exhibits a dependence on
the average molecular weight Mw [28]
a
η0 ∼ M w (18)

where a is approximately 3.4. This means that zero shear viscosity of the same polymer increases with
rising average molecular weight according to a power law. This study does not yet include grades with
different average molecular weight, but there are plans to study in future work if molecular weight
influences the contact angle in a similar way to temperature.

5. Conclusions
Currently, the contact angle of molten polymers on solid substrates can only be determined in time
consuming experiments at different high temperatures, but shear viscosity curves are often more easily
available for polymeric materials. We demonstrate in this paper that viscosity influences the wetting of
steel by molten polymers. The contact angle of molten polypropylene and polymethylmethacrylate on
polished steel was directly calculated from zero shear viscosity. The obtained linear equation is valid
for both polymers and allows the assignment of a certain zero shear viscosity to a contact angle value.
Furthermore, for the wetting of solid surfaces by molten polymers as it takes place in injection molding,
a lower viscosity is advantageous because the contact angle decreases with falling zero shear viscosity.
The zero shear viscosity depends strongly on temperature and can be assigned with a shift factor to a
Polymers 2018, 10, 38 11 of 12

certain temperature. Since temperature dependence of the wettability is of great interest, we proposed
a model to calculate the contact angle at different temperatures directly from the temperature shift
factor of viscosity, zero shear viscosity, and the contact angle at a reference temperature. The validity
of our model is confirmed by the good agreement with the experimentally determined contact angle
values. As a prospect for future work, other polymers and tool materials have to be studied to enable a
generalization of the relation between the contact angle and zero shear viscosity.

Acknowledgments: Financial support for vital parts of this project was provided by the State Government of
Upper Austria and the European Union in the measure IWB 2020: ProFVK.
Author Contributions: Gernot Zitzenbacher conceived and designed the experiments; Hannes Dirnberger and
Manuel Längauer performed the experiments; Gernot Zitzenbacher, Hannes Dirnberger, Manuel Längauer,
and Clemens Holzer analyzed the data; Gernot Zitzenbacher wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the
decision to publish the results.

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