Polymer Testing 128 (2023) 108188

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Investigation of a Finite-Difference-Method based real-time viscous heating

compensation in a nozzle viscometer for inline viscosity measurement of
phenol resins
Peter Wappler, M.Sc. a, *, Romit Kulkarni a, Thomas Guenther a, b, Serhat Sahakalkan a,
Karl-Peter Fritz a, André Zimmermann a, b
a
Hahn-Schickard, 70569, Stuttgart, Germany
b
Institute for Micro Integration (IFM), University of Stuttgart, 70569, Stuttgart, Germany

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

Keywords: This work is motivated by the rarely available material data for thermosets and a missing inline viscosity
Thermoset injection molding measurement method to monitor melt property deviations. A nozzle viscometer is designed for inline viscosity
Phenolic resins measurement of phenol-formaldehyde compounds. The nozzle viscometer is mounted at the plasticizing unit of
Inline rheometer
an injection molding machine. A fluid coolant circuit allows a dynamic tempering to pause the transient
Nozzle viscometer
crosslinking reaction. A 2D FDM model is implemented, to calculate the viscous heating within an injection cycle
Slit die
FDM model and to compensate the temperature rising effect in the viscosity measurement. The FDM model processes the
Wall slip inline sensor signals in a closed loop correction in real time to determine a corrected reactive viscosity model.
Viscous heating The signal-to-noise-ratio quantifies the reliability of the inline viscosity measurement method.
Reactive viscosity
Master curve

1. Introduction uncommon in thermoset injection molding. This work is motivated to

Plastic injection molding is the most widely used manufacturing
process for producing complex components. The processing of thermo­
sets is a demanding special process in this context. Unlike thermoplas­
tics, thermosets undergo a chemical reaction during the molding
process, resulting in a permanent and irreversibly crosslinked structure.
Besides unsaturated polyesters, phenolic resins are the most impor­
tant thermosets in terms of volume in the injection molding process [[1],
p. 432]. Fiber-reinforced phenol-formaldehyde molding compounds
have high molding precision, excellent strength and rigidity, resistance
to heat and chemicals, and good electrical insulation properties while
being inexpensive. They are increasingly being used to manufacture
functional parts that were previously made from aluminum die casting
[[2], p. 73].
Filling simulations are used to design the plastic injection molds in
order to ensure a correct cavity filling and a wide process window.
Inaccurate material data can cause an unstable process or even an
unfillable mold cavity, resulting in a mold design correction. Mold
design correction loops are very expensive and time-consuming and not
access melt viscosity information during the injection molding process.
This enables a material characterization, predicting part quality and
compensating fluctuating material properties.
The material data for thermosets in commercial software programs
are rarely available, incomplete or deviate strongly from the real ma­
terial properties. The reason for the lack of material data are the
expensive laboratory measurements and the limited comparability of
the material pretreatment conditions in the laboratory to the injection
molding process.
Capillary rheometers and rotational rheometers are usually used in
the laboratory to determine a reactive viscosity model. However, rota­
tional rheometers do not always cover the shear rate range relevant for
the injection molding process.
The pretreatment process and plasticization have a significant in­
fluence on the material properties. Höer [[3], p. 62] investigated the
influence of moisture on the flow behavior of phenolic resins (PF) with a
rotational rheometer. He proved that the complex viscosity can differ
due to several factors. The influence of material preconditioning is sig­
nificant and can differ with each plastic manufacturer. Furthermore the

* Corresponding author.
E-mail address: Peter.Wappler@Hahn-Schickard.de (P. Wappler).

https://doi.org/10.1016/j.polymertesting.2023.108188
Received 18 June 2023; Received in revised form 22 August 2023; Accepted 31 August 2023
Available online 10 September 2023
0142-9418/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
P. Wappler et al. Polymer Testing 128 (2023) 108188

plasticization in an injection molding process is based not only on 2. Theory/calculation

convection, but also on shearing and distributing the melt by the plas­
ticizing screw. Consequently, it can be assumed that the melt properties This section deals with the mathematical modeling based on the
in the injection molding process differ from those in the laboratory. Navier-Stokes equations.
The influences due to pretreatment and plasticizing will not be The following boundary conditions are assumed for the determina­
emulated accurately in the laboratory. An inline viscosity measurement tion of fluid flow properties in a slit die with (a) stationary flow condi­
after the plasticizing process would allow a more precise material tion, (b) incompressible fluid, (c) laminar fluid flow, (d) negligible
characterization. Some approaches use a nozzle viscometer mounted inertial and gravitational forces, (e) constant pressure distribution in the
directly on the plasticizing unit or a viscometer located in the mold slit die cross section, (f) constant thermodynamic material parameters
cavity. The measuring principles based on a high-pressure capillary (density, heat capacity and thermal diffusivity), (g) and adiabatic walls
rheometer are already used in the laboratory. In this measurement of the slit die.
method, the plasticized melt in the barrel chamber is injected at a Equation of momentum (1) describes the flow of liquids and gases in
constant pressure or volume flow through a defined flow channel in the a finite volume with cartesian coordinates x, y, z, time t, velocity com­
nozzle viscometer. Prototypes for thermoplastic nozzle viscometers have ponents u, v, w, pressure p, temperature T, density ρ, and dynamic vis­
already been investigated for laboratory applications. Table 1 groups the cosity η.
work published within the last two decades according to their applica­ ⎛ ⎞
tion focus. ⎜ ∂u
The inline viscosity measurement system developed in this work ∂u ∂u ∂u ⎟
ρ⎜
⎜ +u +v + w
⎟
⎟
shares the approach of a nozzle viscometer mounted on the plasticizing ∂t
⎝⏟⏞⏞⏟ ∂x
⏟⏞⏞⏟ ∂y ∂z ⎠
⏟⏞⏞⏟ ⏟̅⏞⏞̅⏟
unit. The following unique features distinguish it from previous appli­ (1) (2)
⎛
(3) (4)
⎞ (1)
cations: (1) Viscosity measurement of thermosets, (2) fluid coolant cir­
cuit, (3) interchangeable slit die channels with different channel ∂p ⎜ ∂2 u ∂2 u ∂2 u ⎟
⎜ ⎟
=− + η⎜ 2 + 2 + 2 ⎟
geometries, (4) adapter function for mounting on other plasticizing ∂x ∂x
⎝⏟⏞⏞⏟ ∂y ∂z ⎠
⏟⏞⏞⏟
units, (5) and a threaded clamp for fast mounting. (5) (6)
The nozzle viscometer measurement is subject to various disturbing
influences, such as viscous heating, wall slip, pressure effects, transient Based on the assumptions, the following terms can be neglected and
reaction kinetic processes and the exothermic crosslinking of thermosets set to zero. Term (1) = 0, since laminar flow is considered to be sta­
[ [19], p. 209]. Wall slip refers to a melt velocity at the wall that is tionary. Term (2) = 0, since flow changes in the x-direction are
greater than 0 because the melt does not adhere to the channel wall. neglected. Term (3) = 0, since flow velocities in y-direction are not
Analytical and numerical methods are used to calculate viscous considered. Term (4) = 0, since flow velocities in z-direction are not
heating, wall slip, and pressure effects based on information such as considered. Term (5) = 0, since flow changes in the x-direction are
volume flow, pressure difference, melt temperature, and various slit die neglected. Term (6) = 0, since flow variables remain constant in the z-
geometries. direction.
Numerical mathematics provide suitable approximation methods to After simplifying the formula from (1) with the specified assump­
solve the systems of equations iteratively. Common approximation tions and boundary conditions, the following formulation remains.
methods are the Finite Difference Method (FDM), Finite Volume Method ∂p ∂2 u ∂τyx
(FVM) and Finite Element Method (FEM). They differ in their numerical =η 2 = (2)
∂x ∂y ∂y
properties in terms of flexibility and accuracy [ [20], pp. 10–14].
The slit die channel represents a simple geometric complexity and is Given equation (2) with τyx as shear stress in x, y plane and the
suitable for a FDM model applying a structured mesh topology with the boundary conditions, the pressure gradient is constant over the co­
advantage of a high numerical accuracy. ordinates y and z. Consequently, equation (2) yields a one-dimensional
In this work, a 2D FDM model is implemented, to calculate the solution domain for the flow velocity in x-direction, illustrated in Fig. 1.
viscous heating within an injection cycle and to compensate the tem­ The slit height h(x) is discretized in n grid points in y-direction. Every
perature rising effect in the viscosity measurement. The FDM model grid point is indexed with j ∈ [1, …, n].
processes the signals in a closed loop correction to determine the cor­ To calculate the numerical flow, equation (2) is converted from
rected viscosity in real time. Further advantages of the implementation analytical to numerical notation as expressed in equation (3). Gx rep­
are the easy definition of the boundary conditions (e.g. slit die geome­ resents the finite pressure gradient.
try) and mesh increments, without need of a proprietary CFD (Compu­
tational Fluid Dynamics) software.

Table 1
Viscosity measurement applications for thermoplastic injection molding.
Polymer Rheometer Cross Autors
processing location section

powder IM nozzle slit die Gornik [4], Sanetrnik [5]

thermoplastic mold cavity slit die Aho et al. [6], Zhang [7], Wu
IM et al. [8]
thermoplastic hot runner capillary Hopmann [9]
IM die
thermoplastic nozzle capillary Gou [10], Wappler [11]
IM die
thermoplastic nozzle slit die Cavic [ [12], p. 67], Fernandez
IM [13], Eben [ [14], p. 54], Kruppa
[ [15], p. 33], Volpe [16], Geyer
Fig. 1. Schematic representation of pressure flow through slit as 1D solu­
[17], Schaible [18]
tion area.

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P. Wappler et al. Polymer Testing 128 (2023) 108188

⎧ ⎫
∂p 1 ( ⎨ ) ( )⎬ With the given function it is possible to set up a linear system of equa­
≈ Gx = ηj+1 uj+1 − uj − ηj− 12 uj − uj− 1 (3) tions in the following form:
∂x (Δy)2 ⎩ 2 ⎭
A⋅x = b
The viscosity is indexed by j ∓ 1/2 in equation (3), since this value is (11)
valid between two velocity grid points uj . Later in the numerical
implementation, these flow quantities, such as shear rate and tempera­ A is the coefficient matrix of dimension n × n, b contains the previously
ture, are linearly interpolated to the grid points using the trapezoidal defined boundary conditions including wall velocity and volume flow.
rule. The solution vector x defines the flow velocities and a pressure gradient.
⎛ ⎞ For every grid point between P2 and Pn− 1 one can set an equation
based on (4). The grid points P1 and Pn are determined by the constraint
ηj− 12 ⋅ uj− 1 − ⎜ ⎟ 2
⎝ηj− 12 ⋅ ηj+12 ⎠⋅uj + ηj+12 ⋅ uj+1 − (Δy) ⋅ Gx = 0 (4) of the wall velocity.
⎛ ⎞

The given material PF is a thermoset compound. Its melt viscosity ⎜ ⎟

P2 : ⇔ η1 12 ⋅u1 − ⎝η1 12 ⋅η2 12 ⎠⋅u2 + η2 12 ⋅u3 − (Δy)2 ⋅Gx = 0
depends on shear rate, temperature and curing degree.
During plasticization of PF in the barrel, the curing degree is low and
the rising temperature starts to melt the polymer granulate. The melt ⎛ ⎞
viscosity of thermoset resins will decrease. By continuing rise of tem­ ⎜ ⎟
P3 : ⇔ η2 12 ⋅u2 − ⎝η2 12 ⋅η3 12 ⎠⋅u3 + η3 12 ⋅u4 − (Δy)2 ⋅Gx = 0
perature the reaction of cure kinetic gets more dominant, resulting in a
rising melt viscosity. The viscosity curve of thermoset materials can be
characterized by a parabolic curve over temperature and time.
……
The mathematical models to describe the rheological and thermal
behavior of thermoset compounds include reactive viscosity and cure ⎛ ⎞
kinetics models. A common reactive viscosity model for PF compounds ⎜ ⎟
Pn− : ⇔ ηn− 32 ⋅un− 2 − ⎝ηn− 32 ⋅ηn− 12 ⎠⋅un + ηn− 12 ⋅un − (Δy)2 ⋅Gx = 0
is the Cross Castro Macosko model (CCM) [21]. The first term in equa­ 1

tion (5) is based on the Cross-WLF model and the second term is related
to the gel model [22]. The solution vector x consists of n-2 velocity vectors and a pressure
( )(c1 +c2 α) gradient Gx , consequently there are n-2 unknowns to solve. By merging
η0 (T) αg
η(γ̇, T, α) = ( )1− n ⋅ (5) n-2 equations based on (4) and the last equation with the volume flow
αg − α
rate (10), the linear equation system has as many equations as unknowns
η0 (T)⋅γ̇
1+ τ∗
and is thus considered as determined.
η0 (T) = B⋅exp(Tb /T) (6) The linear system of equations can now be set up in the following
equation (12).
The reactive viscosity model based on CCM, does not offer a pressure ⎡ ⎤
sensitive coefficient, compared to the Cross-WLF model. The pressure
sensitive model based on Cross-WLF can be easily adapted here for the ⎢ η ⋅η
⎢ 1 1 − η 1 0 ⎥
⎥
⎢ 1 2 ⎥
used implementation. Due to the limited model selection in the com­ ⎢ 2 2 2
2 ⎥
⎢ ⋯ 0 Δy2 ⎥
mercial simulation software, this model could not be used. Later this ⎢ − η η 1 ⋅η 1 − η 1 ⎥
⎢ 1 ⎥
work a comparison to other CCM models is proposed. Due to this, a ⎢
⎢ 2 2 3 3 ⋱ ⋮ ⋮ ⎥
⎥
2 2 2 2
pressure compensation is possible, but omitted in this work. ⎢
⎢ ⋱ 0 Δy2
⎥
⎥
0 − η 1 η 1 ⋅η 1
For the numerical implementation, the shear rate is converted into ⎢
⎢ 3 3 4
⎥
⎥
⎢ ⎥
the differential notation (7). ⎢ 2 2 2 ⎥
⎢ ⎥
⃒ ⃒ ⎢ ⋱ − η 3 Δy2 ⎥
⃒uj − uj+1 ⃒ ⎢ ⎥
γ̇ j+12 = ⃒⃒ ⃒ (7) ⎢
⎢ ⋮ ⋱ ⋱ n− ⎥
⎥
Δy ⃒ ⎢ 2 ⎥
⎢ 0 ⋯ 0 − η 3 η 3 ⋅η 1 Δy2 ⎥
⎢ ⎥
Like mentioned before the shear rate is even valid between two ve­ ⎢ n− n− n− ⎥
⎢ ⎥
locity grid points uj . For this reason the shear rate is also indexed by j∓ ⎢
⎢
4 ⋯ 4 2 2 2 ⎥
⎥
1/2 in equation (7). ⎣ 2 4 0 ⎦
(12)
The volumetric flow rate V̇ can be calculated as the integration of the ⎡ ⎤
fluid velocity u(y) over the gap height h(x) multiplied by the wedge gap
⎢ ⎥
width W, described in equation (8). Based on the assumption, the flow ⎢ η 1 ⋅u1 ⎥
⎢ 1 ⎥
variables are constant in z-direction. Due to the simplification, the fluid u2 ⎢ 2 ⎥
velocity profile is not integrated over the wedge gap width W. ⎡ ⎤ ⎢
⎢
⎥
⎥
u3 ⎢ 0 ⎥
∫0 ⎢ ⎥ ⎢
⎢
⎥
⎥
⎢ u4 ⎥ ⎢ ⋮ ⎥
V̇ = W⋅ u(y)dy (8) ⎢
⋅⎢
⎥ ⎢
⎥=⎢ ⎥
h(x) ⎢ ⋮ ⎥ ⎢ ⎥
⎣ ⎦ ⎢ 0 ⎥
⎥
The fluid velocity in a slit is numerically integrated by applying un− 1
⎢ ⎥
⎢ η 1 ⋅un ⎥
⎢ n− ⎥
Simpson’s rule, due to the parabolic profile of the velocity field, ⎢ ⎥
Gx ⎢ 2 ⎥
described in the following equation (9). ⎢
⎣ a
⎥
⎦
Δy
V̇ ≈ W⋅ {u1 + 4 ⋅ u2 + 2 ⋅ u3 + … + 4 ⋅ un− 1 + un } (9)
3
The volume flow term is substituted with a, due to a better overview.
Transforming equation (9) to
3⋅V̇
3⋅V̇ a= (13)
u1 + 4⋅u2 + 2⋅u3 + … + 4⋅un− 1 + un − =0 (10) W⋅Δy
W⋅Δy

3
P. Wappler et al. Polymer Testing 128 (2023) 108188

The coefficient matrix A contains the variable of the viscosity η. Due

to the short time scale, the curing degree can be assumed to be constant
over the whole slit length. Even the temperature over the slit die height
is assumed to be constant, but not constant over slit length. In the finite
stripe of the slit channel, the viscosity is dependent on the fluid velocity
uj with constant temperature (Tj = const.) and constant curing degree
(αj = const.) in x-direction, calculated by equation (5). In the first iter­
ation zero viscosity η0 is set as initial value for all viscosity values ηj . The
calculated solution vector x with the fluid velocities is used to determine
the updated viscosity according to the viscosity model (5). After k iter­
ation steps, the solution converges to a stationary velocity and viscosity
profile. As an abort criterion for the iteration loops a velocity difference
Fig. 3. Schematic representation of the structured mesh in the slit die channel.
as residuum smaller than a defined error is used. Here e.g. uk − uk− 1 <
10− 7 m/s.
In this implementation, the definition of slit die geometry is modi­
The flowchart in Fig. 2 illustrates the iteration process of the FDM
fiable, concerning different slit die length, heights, or a varying slit die
model.
height in flow direction. This opportunity allows the FDM model to
Only one iteration is required to calculate the flow quantities for a
calculate different viscous heating effects or wall slip effects for different
Newtonian fluid, since the constant viscosity η does not depend on the
slit die geometries and to compare these results with experimental
solution vector x or the fluid velocity u, respectively.
pressure and temperature measurements.
Up to this point, the flow quantities have been calculated for one
The flow velocities uj,i are calculated for each grid point Pj,i indexed
finite stripe on the y-axis.
The slit die channel is now discretized in flow direction (x-direction), with j ∈ [1, n] in y-axis and i ∈ [1, m] in x-axis. The pressure gradient Gi =
to calculate the pressure drop along the slit die. The simplified mesh in dp/dx is calculated on a finite stripe. The total pressure drop in the
the slit die channel is illustrated in Fig. 3. An applied loop in the nu­ channel is determined by integrating the pressure gradient over the slit
merical implementation calculates the flow variables over all finite die length, described in equation (14).
stripe i ∈ [1, m] in flow direction.

Fig. 2. Flow chart of the FDM iteration process for one finite stripe.

4
P. Wappler et al. Polymer Testing 128 (2023) 108188

∫ L
p= Gx dx (14)
0

Transformed in a numerical form, the total pressure drop along the

slit die channel is described in equation (15).
∑i ( )
1 1 1
pi = (Gxk− 1 + Gxk ) ⋅ Δx = Gx1 + Gx2 + … + Gxi− 1 + Gxi ⋅Δx
k=1
2 2 2
(15)
Viscous heating has a significant impact on the melt viscosity, due to
the shear dissipation, especially in case of PF thermoset compounds. The
relative temperature rise is more significant in contrast to thermoplastic
polymer melts with a much higher temperature level.
The energy equation (16) is used to calculate the temperature dis­
tribution in flow direction with cartesian coordinates denoted as x, y, z,
time t, velocity components u, v, w, pressure p, temperature T, density ρ,
shear stress τyx , shear rate γ̇, heat source Q̇, specific heat capacity cp and
thermal conductivity λ.
⎛ ⎞
⎜ ∂T ( 2 )
∂T ∂T ∂T ⎟ ∂ T ∂2 T ∂2 T
ρ⋅cp ⎜
⎜ +u +v +w
⎟
⎟=λ + + + τyx ⋅γ̇ + Q̇
∂t
⎝⏟⏞⏞⏟ ∂x ∂y ∂z ⎠ ∂x2 ∂y2 ∂z2 ⏟⏞⏞⏟
⏟⏞⏞⏟ ⏟̅⏞⏞̅⏟ ⏟̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅⏞⏞̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅⏟ (5)
(1) (2) (3) (4)

(16)
Based on the assumption of steady-state flow, the local temperature
change over time can be considered constant, thus term (1) = 0. Since
flow velocities in y and z direction are not considered term (2) and (3) =
0. Due to the short injection time of the melt in the slit die channel, the
heat conduction and heat source can be neglected. Thus the system can
be considered to be adiabatic with term (4) and (5) = 0.
According to these assumptions, the convective and dissipative terms
Fig. 4. Flow chart of the signal processing to determine reactive viscosity
remain in the scalar energy equation and one obtains following equation models based on the Cross Castro Macosko Model.
(17).
dT corrected reactive viscosity over all experimental data. This allows to
ρ⋅cp ⋅u = − τyx ⋅γ̇ (17)
dx generate a viscosity master curve with constant temperature for various
By substituting the right dissipation term in equation (17) with slit die channels.
pressure gradient dp/dx based on equation (2), the following formula For completeness, the model of the reaction kinetics is included in
(18) is obtained. the flow diagram to describe the crosslinking behavior. There are
different inline measurement methods to monitor the reaction kinetic
dT = −
dp
(18) processes in the mold. These approaches based on Raman spectroscopy
ρ⋅cp [24], IR-spectroscopy [25], ultrasonic monitoring [26] or dielectric
analysis (DEA) [24,27–30]. The authors of this paper are not aware of
High shear rates near the wall lead the viscous heating in concen­
any research on the use of this application in a nozzle viscometer in
trated area. In practice, however, It is not necessary to take the tem­
thermoset injection molding. Possible challenges against the use of this
perature distribution over the slit die height into account [23]. Thus
measurement technique could be the high pressure and wear loads in the
viscous heating is not calculated locally for each grid point over dy. As
nozzle viscometer and finally the high financial investment. This
an approximation, an average temperature increase over the slit die
application seems to be very interesting for further investigations, but
height is sufficient to describe the observed effect.
will not discussed in this work.
Based on the FDM model it is possible to calculate velocity profile,
Another possibility is to calculate the theoretical curing degree based
pressure drop and heat dissipation of melt temperature in the nozzle
on a known model of reaction kinetics and processing conditions. The
viscometer for different slit die channel geometries. The FDM model is
nozzle viscometer can only operate in a limited process window, hence
used to compensate the temperature rise and to determine a master
the thermoset melt doesn’t get stuck in the viscometer, due to cross­
curve of the reactive viscosity. Fig. 4 shows the flow chart of the signal
linking. By this circumstance, the viscometer is limited to cover the
processing to determine the reactive viscosity model.
whole crosslinking behavior in order to fit a model of reaction kinetics.
In the first step, experimental data are filtered of invalid cycles. This
Different offline measurement methods are used to fit a reaction kinetics
step will be explained in the following chapter. Based on the uncorrected
model from other authors.
pressure signals, the model parameters of the reactive model will be
Kamal-Sourour [31] developed a method to determine coefficients
fitted in a first iteration. The FDM model calculates with the known
for the reaction kinetic model n-th order based on Differential Scanning
boundary condition and the first iteration of the reactive model the heat
Calorimetry (DSC) measurements. Tran et al. [22] determined co­
dissipation along the slit die channel. The algorithm calculates the dif­
efficients of the reaction kinetic model for PF by using the approach from
ference between the pressure drop with and without temperature rise
Kamal-Sourour. Furthermore he investigated wall slip effects to consider
along the slit die channel. The pressure difference in the slit die is added
these in the simulation by a reverse engineering approach.
to the measured pressure signals, which are effected by shear heating.
Franieck et al. [32] analyzed and compared the curing kinetics of an
The shear heating compensated pressure drop allows to determine a
epoxy phenol molding compound by dynamic off-line DSC and
corrected viscosity. With this iteration it is possible to calculate a

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P. Wappler et al. Polymer Testing 128 (2023) 108188

isothermal inline DEA measurement. Both measurement methods seem
to be interesting for further works to consider reaction kinetics. Ageyeva
et al. [33] summerize further mathematical modeling of reaction ki­
netics for thermoplastic resign.
3. Materials
This chapter shows the technical construction and implementation of
a novel nozzle viscometer approach for inline PF material processing.
The used materials and equipment are listed below:
• Phenol-formaldehyde resins (PF): SUPRAPLAST PK3280 manufac­
tured by Süd-West-Chemie
• Injection molding maschine: ALLROUNDER 370 V by Arburg with a
20 mm Plasticizing unit
• Inline melt sensors: Type 4021B by Kistler
• Data acquisition system: CRONOSflex by IMC
• Software Tools for data processing: Studio 5.2 R9, Python V3.6 by
IMC
• Simulation Software: Sigmasoft
process has to be stopped. A time consuming dismounting and
cleaning of the nozzle viscometer can be avoided.
On the basis of the technical specification, the first prototype of a
nozzle viscometer is designed, shown in Fig. 6. The viscometer di­
mensions consider mechanical simulation results to guarantee reliability
against melt pressure loads up to 2500 bar.
This nozzle viscometer is characterized by some unique features,
which differ from other concepts:
• An adapter to the plasticizing unit enables the use in practice, due to
following features:
o The nozzle viscometer can be assembled quickly without having to
twist the entire nozzle body with the sensor cables and cooling
conduits.
o Disassembly takes less than 3 min.
o Different adapters allow it to use the nozzle viscometer on other
machines.
• Interchangeable slit die channels for different melt viscosities and to
investigate wall slip effects as seen in Fig. 7.

The process window depends strongly on the material and its reac­
tion kinetics. Fig. 5 shows a Differential Scanning Calorimetry (DSC)
measurement of the PF material, which provides information about the
heating rate depending crosslinking behavior. Temperature at which the
crosslinking process starts is determined as Onset temperature. The
measurement results shows that the Onset temperatures are between
121 and 147 ◦ C depending on the heating rate. It can be assumed that no
significant crosslinking processes take place below 120 ◦ C. Tempering
the nozzle viscometer therefore does not require temperatures above
120 ◦ C to avoid solidification in the viscometer channel.
The following technical specifications are defined for the nozzle
viscometer application.

• Relevant process window during injection phase defines a volume

flow rate between 0.5 and 9.0 cm3/s und a melt temperature between
90 and 120 ◦ C.
• Due to the transient reaction kinetics, the process is subject to dwell
time limits depending on temperature and material properties. A
dynamic temperature control is desirable with a proper heating rate
to reach 110 ◦ C and a cooling rate to reach 30 ◦ C within 5 min. This Fig. 6. Nozzle viscometer for inline viscosity measurement of phenol-
allows pausing the curing reaction of the PF material, when the formaldehyde resins.

Fig. 5. Differential Scanning Calorimetry measurements of phenol-formaldehyde resin at different heating rates.

6
P. Wappler et al.
Fig. 7. Left: melt flow channel from screw barrel to nozzle tip – right: interchangeable slit die channels with different channel geometries.
• Different nozzle tips with varying nozzle diameters are mountable.
This enables to set different pressure levels in the slit die channel.
Thus, pressure sensitive viscosity parameters can be determined.
• A fluid coolant circuit for dynamic tempering between 20 ◦ C and
120 ◦ C depicted in Fig. 8.
• FDM tool to define wall slip effects and to calculate temperature-
compensated viscosity models.
• With an overall length of 180 mm, it is possible to install the nozzle
viscometer on the injection molding machine with only minor
modifications. This enables the opportunity to combine the nozzle
viscometer with the molding tool for an inline process control.
Fig. 7 shows the geometry of the melt flow channel from screw barrel
to nozzle tip. The construction regards avoidance of edges to reduce
shear stress spots, the sensor front is planar to the channel wall and the
cross section surface in the flow channel is similar along the flow di­
rection except the inlet and outlet section.
A fluid coolant circuit is designed in the viscometer body under the
terms of installation space between the inline sensors and screws. The
cooling conduits are located close to the slit die channel to enable a
dynamic tempering between 20 ◦ C and 120 ◦ C (Fig. 8).
A thermal simulation quantifies the heating and cooling rate of the
nozzle viscometer in Fig. 9. The position of the calculated temperature is
the channel wall of the second inline sensor. The start conditions of
cooling phase are 110 ◦ C viscometer body temperature and 20 ◦ C at the
coolant circuit wall, whereas the heating phase starts with 20 ◦ C
viscometer body temperature and 110 ◦ C at the coolant circuit wall.
cooling phase heating phase
initial viscometer body temperature 110 ◦ C 20 ◦ C
coolant circuit wall temperature 20 ◦ C 110 ◦ C
initial melt temperature 110 ◦ C no melt
melt volume flow 3 cm3/s until filled no melt
Fig. 8. Coolant circuit in the viscometer body for dynamic tempering between 20 ◦ C and 120 ◦ C.
7
Polymer Testing 128 (2023) 108188
The cooling phase initially shows an overshoot to about 140 ◦ C. This
effect is feasible by the viscous heating of the melt during the injection
phase in the first seconds. After the flow channel is filled the tempera­
ture dropped under 120 ◦ C in a couple of seconds. After 110 s the flow
channel wall temperature dropped under 40 ◦ C.
Whereas the heating phase starts with a cold nozzle viscometer, the
coolant circuit can heat up the slit die channel wall over 90 ◦ C in less
than 100 s. The simulation shows that the coolant circuit enables a dy­
namic temperature control. Based on the DSC measurements in Fig. 5 the
crosslinking effects are not significant below a melt temperature of
120 ◦ C.
In practice, it could be proven, that solidified melt in the nozzle
viscometer could be melted fast enough to purge the slit die channel
bevor the crosslinking solidifying gets dominating. After the purge step
the process can continue as usual. To ensure an accurate viscosity
measurement, the process runs until a thermal equilibrium has been
reached in the machine and the nozzle viscometer. For the following
experiments, it can take up to 30 min to reach a thermal equilibrium.
4. Experimental
This chapter covers the signal processing and analyzing the wall slip
effect as basis for the viscosity measurement.
Fig. 10 shows pressure signals of the three inline sensors and the
screw volume signal over time in a 15 × 3 mm2 slit die channel at
volume flow rate of Q = 3 cm3/s, 110 ◦ C barrel temperature and without
mold cavity. The graph shows at injection start a pressure increase from
all inline sensors until a screw volume of V = 16 cm3 is reached. After a
maximum the pressure signals drop until they reach a static level at V =
10 cm3. The fluid dynamics show time or volume dependent
characteristics.
Various effects like viscous heating, wall slip, reaction kinetics or
viscoelasticity are taken into account for this process, which can influ­
ence the viscosity measurement.
P. Wappler et al. Polymer Testing 128 (2023) 108188

Fig. 9. Simulation result of transient temperature progression at the flow channel wall of nozzle viscometer. Start condition of cooling phase: 110 ◦ C viscometer body
temperature and 20 ◦ C at the coolant circuit wall. Start condition of heating phase: 20 ◦ C viscometer body temperature and 110 ◦ C at the coolant circuit wall.

Fig. 10. Inline pressure signals in the slit die channel and screw volume signal over time at volume flow rate of 3 cm3/s and 110 ◦ C barrel temperature.

For the measurement test series, there are upper limits to the limit at V = 16 cm3 and thus cannot maintain the set volume flow. The
maximum volume flow. Fig. 11 illustrates an injection cycle with a process gets significantly unstable due the nonlinear screw volume
volume flow of 9 cm3/s. The machine reaches the hydraulic pressure characteristic and a sudden pressure drop in the slit die channel. Since

Fig. 11. Unstable injection cycle at volume flow of 9 cm3/s.

8
P. Wappler et al. Polymer Testing 128 (2023) 108188

the severe pressure drop with a sudden viscosity change does not seem can be taken from a graph [36, p. 224]. For the further investigations,
plausible, it can be assumed here that wall slip is present, which falsifies the influence of the sidewall is nevertheless neglected, since the influ­
the viscosity measurement. This wall slip effect, along with other flow ence of wall sliding and the viscous heating is considered to be more
anomalies, has been observed by other authors and will be discussed relevant.
later in this paper.
Δp⋅W⋅H 3
An algorithm calculates a coefficient of determination R2 for the η= (19)
12⋅Q⋅L
linearity of the volume flow. This allows to quantify the process stability
and to filter unstable injection cycles over a critical R2 value. A critical 6⋅Q
R2 value of 0.999 seems to be eligible in this experimental set up. γ̇ = ⋅eslit (20)
W⋅H 2
The pressure drop is determined by the difference of the pressure
signals Δp13 = p1 − p3 . Fig. 12 shows a pressure drop in the slit die In the literature, the Weissenberg-Rabinowitsch correction or
channel over time. The course of the pressure drop reaches its maximum Schümmer’s assumption are used to determine the representative shear
at about t = 1.3 s at a screw volume of about 16 cm3. After the maximum rate of a non-newtonian fluid in the flat gap [19, p. 200]. Both methods
pressure drop peak with Δp13,H = 600 bar the pressure drop decreases have been proven successfully [37]. For the signal processing in this
until t = 3.7 s with a screw volume of V = 10 cm3 and remains in a work, Schümmer’s method was easier to implement with an empirically
stationary phase with a pressure drop Δp13,G = 230 bar until end of determined correction factor eslit in equation (20).
cycle. Based on equations (2), (19) and (20) shear stress at the wall τw can
This pressure drop course can be observed at different volume flows, formulated as follows:
but the maximum pressure difference Δp13 is always at the same volume Δp⋅H
position. This effect is not dependent on time, but on the screw path. τw = η⋅γ = (21)
L⋅2
Depending on the dwell position of the melt in the nozzle viscometer,
For fluids with wall adhesion condition, the wall shear stress in­
this has an influence on the melt properties. Since the melt can exhibit
creases linearly with the shear rate and the flow consists predominantly
different properties locally, it must be assumed that this effect is also
of the shear amount without wall slip. Flow anomalies occur, if the shear
dependent on the screw path. The effect described above can be
rate exceeds a critical wall shear stress τc , illustrated in Fig. 13. In such
explained by a change in the melt property. Another explanation could
instances, the wall shear stress no longer increases proportionally or
be a change in wall slip.
even remains constant with respect to the apparent shear rate. From the
Brockhaus [34] summarized the occurrence and intensity of wall slip
by different factors, such as polymer type, additives, wall surface of
capillary, capillary geometry, wall shear stress, pressure, and tempera­
ture along capillary.
In this experimental set up the mentioned factors like polymer type,
additives, wall surface, and capillary geometry are assumed as constant
while the wall shear stress, pressure and temperature factor can vary
within a cycle. For this reason the wall shear stress is calculated for the
Δp13,H and Δp13,G to evaluate, if a slide effect is obvious. An evidence for
wall slip is a non-linear characteristic of wall shear stress over shear rate.
Equation (19) can be used to calculate the viscosity η of a Newtonian
incompressible fluid through a slit [ [35], p. 225] with the known
pressure drop Δp, volume flow Q, slit die width W, height H, length L,
and the Schümmer correction parameter eslit with 0.772 to determine the
representative shear rate for a non-newtonian fluid [ [36], p. XX].
This equation is only valid if the ratio of slit die width to height is
greater than 10: W/H >10. The 15 × 3 mm2 slit die channel has a W/ H
= 5 and did not fulfill this requirement. For channels with a W/ H <10
the influence of the side walls can be taken into account by a correction Fig. 13. Calculated wall shear stress for polystyrene under the influence of a
factor for the volume flow. A recommended correction factor by Squires wall slip and different capillary diameter [38].

Fig. 12. Pressure drop in the slit die channel over time at volume flow rate of 3 cm3/s and 110 ◦ C barrel temperature.

9
P. Wappler et al.
literature [22,34,39–41], common critical shear stresses τc are given as
0.1 Mpa. The shear and slip amount are present simultaneously above
the critical wall shear stress.
Based on a slip velocity model, Rosenbaum und Hatzikiriakos [38]
calculated wall shear stress under the influence of wall slip for poly­
styrene. The resulting wall shear stress characteristics depends on the
capillary diameter shown in Fig. 13.
Hatzikiriakos and Dealy [ [40], p. 717] established that the critical
wall shear stress τc of HDPE resin can be described as a function of the
average molecular weight and is independent of temperature for the
onset of slip. The slip velocity uG can be described as a nonlinear func­
tion of the wall shear stress, low wall normal stress and is strong affected
by temperature.
Fig. 14 depicts the calculated wall shear stress at maximum pressure
drop difference τH and at the stationary phase τG . The wall shear stress
values in this experiment are between 0.3 and 1.5 MPa. Wall slip seems
likely, since the wall shear stress exceeds common critical shear stresses
about 0.1 MPa. Therefore, wall slip will be considered for further data
evaluation.
It is noticeable that at shear rates γ̇ < 40/s the measurement points
deviate significantly from the trend line γ̇ > 40/s. This phenomenon
appears at both wall shear stress parameters τH and τG . The melt dwell
time is longer at low volume flows. A plausible explanation seems to be,
that there is more time for the reaction kinetic process, which results in a
higher curing degree, a higher melt viscosity and a higher wall shear
stress. Based on this hypothesis there has to be a shear amount in the
fluid flow, this implies that the stationary phase is not entirely governed
by wall slip.
The wall shear stress at the maximum pressure drop difference τH
increases proportionally over the shear rate. In contrast to τH , the
pressure drop difference at the stationary phase τG remains mainly
constant over shear rate. This flow anomalies, described earlier in
Fig. 13, indicates a predominant wall slip at the stationary phase. For the
further determination of viscosity, the wall shear stress at the maximum
pressure drop difference τH will be taken into account.
The wall shear stress over shear rate and different barrel temperature
settings is shown in Fig. 15. Like in the previous figure, the wall shear
stress increases linearly with the shear rate. Likewise, a significant vis­
cosity increase can be seen at low volume flow rates or longer dwell
times, respectively. This can be explained by a higher crosslinking
behavior. This effect seems to be more pronounced at higher tempera­
tures and less pronounced at lower temperatures, which confirms the
hypothesis of temperature dependent crosslinking influence.
There is a significant temperature influence on the wall shear stress
over shear rate. Two explanations seem to be plausible. It is well known
that the temperature affects the melt viscosity. Another reason could be
the temperature dependence on the wall slip amount.
To validate if wall slip is present, different channel geometries are
Fig. 14. Wall shear stress over shear rate with Δp13,H and Δp13,G .
10
Polymer Testing 128 (2023) 108188
Fig. 15. Wall shear stress over shear rate and different barrel tempera­
ture settings.
used based on Mooneys method [42]. For this purpose, the volume flow
rates at the same wall shear stress must be determined for at least two
different capillaries with the same W/H/L (Width/Hight/Length) ratio.
The wall shear stress depends on the volume flow rate, which is limited
due to the process window. In this experimental set up there are two
channel geometries with the same W/H/L ratio available, as requested
by mooneys method. The cross sections of the channels have a dimen­
sion of 10 × 2.5 mm2 and 20 × 5 mm2. Due to the limited process
window, it is not possible to perform the same shear rates. Nevertheless,
effects can be recognized at least qualitatively.
A deviation from the trend line can be seen in Fig. 16 at lower volume
flows, as observed in the previous experiments in Fig. 14. This effect is
very evident with the smaller channel cross-section. The smaller channel
cross-section with 10 × 2.5 mm2 has a larger surface-volume-ratio,
which in turn means faster melt heating. This effect confirms the
assumption of an increased degree of crosslinking, as previously
observed. In the case of the larger channel cross-section with its smaller
surface-volume-ratio, lower melt heating and a lower degree of cross­
linking can therefore be assumed. The other channel sections with 15 ×
4 mm2 and and 20 × 5 mm2 reveal a smaller deviation from the trend
line at lower volume flow and confirm this hypothesis of a crosslinking
effect.
Neglecting the crosslinking effect of the smaller volume flows, a shift
of the trend line of the three channel cross sections 10 × 2.5 mm2, 15 × 4
mm2, and 20 × 5 mm2 can be recognized. In case of a complete wall
adhesion condition, the trend lines should coincide. The shift of the
trend line from smaller cross sections to lower wall shear stresses can be
explained by wall slip effects.
The channel with 15 × 3 mm2 cross sections seems to have a higher
slip rate than the other inserts. An explanation could be the wall
roughness, which is presumably higher for the others, since these inserts
were mounted for the first time for these tests. The 15 × 3 mm2 channel
has been used for previous tests of over 2000 cycles. Different authors
detect a correlation between surface roughness and wall slip velocity.
For example Sanetrnik [5] investigated, that wall slip velocity decreases
with increasing surface roughness by processing powder injection
molding materials. It seems possible that the PF melt smoothens the
channel surface. Consequently, surface roughness should be considered
for prospective investigations.
For the determination of viscosity and signal noise ratio (SNR), wall
adhesion condition is assumed for the following data analysis for
simplification.
5. Results
As the last chapter points out, the determination of the viscosity is
subject to various disturbing influences, such as volume flow instability,
P. Wappler et al.
Fig. 16. Wall shear stress over shear rate with different channel geometries.
signal processing, transient crosslinking, wall slip, and viscous heating.
Compensations for the influencing factors crosslinking and wall slip
have already been investigated in other works. The focus in this work is
the compensation of viscous heating influence on the viscosity
measurement.
Inline sensors were used, which are intended to measure melt pres­
sure based on a piezoresistive effect and temperature based on k-type
thermocouples. The measurement signals showed a temperature in­
crease of about 4 K during the injection phase. This measured temper­
ature rise appears to be low. The theoretical temperature rise can be
determined relative to the pressure drop in the slit die with formula (18).
Using the example in Fig. 12 with a pressure drop of approx. 600 bar, a
temperature rise of 20 K is expected, which differs from the measured
signal by a magnitude of five.
Other authors are using infrared temperature sensors [43,44] to
measure the dynamic melt temperature accurately. Tosello [ [45], p. 35]
compared the signals of an infrared sensor and a k-type thermocouple
and measured a five times higher temperature maximum peak. This
confirms our observation and leads to the conclusion that the temper­
ature responsiveness of the used inline sensors are too slow and not
Fig. 17. Viscosity over shear rate and barrel temperature and the fitted Cross Castro Macosko model.
11
Polymer Testing 128 (2023) 108188
convenient to determine the dynamic viscous heating effect in the in­
jection phase. However, the signal delivers relevant information about
the mean temperature in the slit die channel.
Due to the missing temperature information, the temperature rise is
calculated with a FDM model based on volume flow, mean melt tem­
perature, and an inertial viscosity model. The calculated pressure dif­
ference due to viscous heating can be applied to the sensor signal and a
corrected viscosity model can be generated.
The viscosity is calculated by formula (19) over the representative
shear rate formulated by equation (20). Fig. 17 shows the experimen­
tally measured viscosity and the fitted Cross Castro Macosko model
based on equation (5). The curing degree is assumed to be constant,
since this value could not be determined in this experiment. Thus, an
initial viscosity model is set up without compensation of the viscous
heating, meaning the individual viscosity measurement can’t be regar­
ded as isothermal within an injection cycle.
In the next step, the measured process parameters represent the input
parameters to the FDM model. Based on the dissipation term from
equation (18), the FDM model calculates the theoretical viscous heating
and the resulting pressure deviation between isothermal and non-
P. Wappler et al.
isothermal fluid flow. This pressure deviation is added to the measured
pressure signal and the new viscosity model is corrected.
The experimentally measured pressure drop (blue error bars) over
the slit die channel is shown in Fig. 18. The measured mean melt tem­
perature of 113 ◦ C defines the start temperature at channel position LC
= 0 mm. The FDM calculated temperature rises over the slit die channel
up to 133 ◦ C with a decreasing pressure gradient. This progression seems
plausible, due to the increasing temperature the viscosity decreases
together with the pressure drop and the viscous heating. The tempera­
ture rise of 20 K over 600 bar or 0.033 K/bar corresponds to the liter­
ature of [ [46], p. 363], [ [19], p. 79] and [ [36], p. 213].
The slope of the FDM calculated pressure drop decreases along the
slit die channel and is in a good agreement with the experimentally
measured pressure. The FDM yields the theoretical pressure drop
without viscous heating. The isothermal pressure drop (green line) fol­
lows a straight linear course as expected shown in Fig. 18. A loop
function in the algorithm compensates the viscous heating in every
cycle. Finally, the initial viscosity model is corrected with the isothermal
pressure drop.
The following Table 2 lists all reactive viscosity coefficients of
different materials based on the CCM model, revealed in equation (5):
There are no material data on the reactive viscosity model available
for the PF materials used in the experiments. A series of experiments
with a plate rheometer was set up. Different oscillating and rotating
modes and even pretreatment steps were investigated to measure the
viscosity. However, it was not possible to perform a valid viscosity
measurement because the plates slide on the PF. It seems that the critical
shear stress was exceeded even with different test configurations before
a valid measurement was possible.
For this reason, the PF material is compared with other PF materials
of Sumitomo Bakelite Co. [48] in Fig. 19. These PF materials are com­
parable to the material of SWC and should exhibit similar flow proper­
ties. Tran [47, p. 68] generated the experimental data of X655 based on
a plate rheometer and suitable material pretreatment steps. Sumitomo
Bakelite Co. [48] kindly provided material data of X7500 for this work.
All models shown in Fig. 19 refer to the same melt temperature. The
curing degree of PK3280 could not be determined during the experi­
ment, so this information is not available. The degree of crosslinking of
the PF masses X655 and X7500 was defined in such a way that models
coincide in the relevant volume flow range between 1 cm3/s and 3 cm3/s
and is equivalent to a shear rate range between 30/s and 80/s.
The results of the fitted reactive viscosity coefficients in Table 2
reveal, that the shear thinning properties described by power law index
Fig. 18. Experimentally measured pressure drop (blue error bars), FDM calculated temperature rise (red dotted line) and temperature compensated pressure drop
(green line) in the slit die channel. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
12
Polymer Testing 128 (2023) 108188
are close to each other for all materials and appear to be realistic.
For material characterization, a statement on the accuracy and
repeatability of the measurement is important. The measurement ac­
curacy describes the maximum expected measurement error between
the determined and true measured value. The determination of nozzle
viscometer measurement accuracy cannot be calculated, since no true
measured value is known for the viscosity measurement.
At least the repeatability of the inline viscosity measurement can be
determined. This is dependent on the machine control, sensor mea­
surement accuracy, material fluctuations, signal processing and process
parameters. The repeatability of viscosity measurements across all ma­
chine configurations yielded a mean standard deviation of σ = 418.7
Pa*s. To quantify the reliability and usability of the viscosity measure­
ment, the standard deviation is related with the signal strength using a
signal-to-noise ratio SNR. For further investigations, SNR is introduced
as a normalized quantity of repeatability. The definition is the ratio of
mean value μ to standard deviation σ of a measurement, formulated in
equation (22).
SNR = μ/σ (22)
The subject of further work is to investigate the SNR of the inline
viscosity measurement and its dependencies, especially dependencies
that are controllable, such as flow rate, nozzle diameter or barrel tem­
perature. All other previously mentioned dependencies are kept as
constant as possible.
The dependence of the SNR of the viscosity measurement over vol­
ume flow and nozzle diameter is plotted in Fig. 20. The SNR value
cannot be calculated for the total volume flow range, due to the fact that
with certain process configurations the flow rate stability cannot be
guaranteed and the filter function does not consider invalid cycles in the
evaluation.
The graph shows across all flow rates and nozzle diameters pre­
dominantly a SNR over 50.
A significant dependence of the SNR on the nozzle diameter is not
detected for values of the volume flow. The variation of the nozzle di­
ameters aims at the investigation of a pressure dependence. However,
since this pressure dependence seems not significant for SNR, no further
investigations were taken.
Fig. 21 shows the SNR versus the volume flow rate, but with the
influence of the barrel temperature setting.
Even this plot shows, that there is no significant dependency of SNR
on volume flow or barrel temperature setting. The average SNR over
volume flow and barrel temperature setting is mostly above 50, similar
P. Wappler et al. Polymer Testing 128 (2023) 108188

Table 2
Reactive viscosity coefficients of different materials based on CCM model.
Material parameters Unit PK3280, SWC (initial) PK3280, SWC (Corrected) Vyncolit X655, Sumitomo [ [47], p. 68] Vyncolit X7500, Sumitomo [48]
3
δ: melt density kg/m 1800 1800 1762 1762
cp : specific heat capacity J/kg*K 968 968 968 968
n: power law index - 0.423656 0.477842 0.432 0.450
τ∗ : shear stress at transition Pa 1.18923e-08 1052.24 2.8e-9 1
B: pre-exponential Pa*s 1228.50 3.60111e-09 1.7e+5 2.5e-8
TB : temperature sensitivity of η0 K 1.75424e+4 14047.9 1.49e+4 1.6e+4
c1 : experimental constant - – – 6.22 1.8
c2 : experimental constant - – – − 5.05 27.5
αg : gelation point - – – 0.7 0.4
α: crosslinking density - – – 0.345 0.145

Fig. 19. Comparison of different materials based on the Cross Castro Macosko model.

Fig. 20. Signal-to-noise-ratio of viscosity over volume flow rate and nozzle diameter.

to Fig. 20. 6. Conclusions

The determination of the viscosity is subject to volume flow insta­

bility, signal processing, transient crosslinking, wall slip, and viscous

13
P. Wappler et al.
Fig. 21. Signal-to-noise-ratio of viscosity over volume flow rate and barrel temperature setting.
heating. The focus of this work is to implement a nozzle viscometer for
inline viscosity measurement and to compensate viscous heating effects
in real time.
The experiment revealed an upper limit to the maximum volume
flow, due to a limited machine force capability. At a volume flow beyond
7 cm3/s a constant volume flow cannot be ensured by the machine
control. A nonlinear screw volume characteristic appears and leads to an
unstable volume flow. The coefficient of determination R2 for the line­
arity of the volume flow is used to filter invalid cycles with R2 < 0.999,
which cannot ensure constant volume flow condition.
The pressure drop in the slit die channel shows a dynamic but
repeatable characteristic. The pressure drop rises to a maximum peak Δ
p13,H and after a decrease the pressure drop remains in a stationary
pressure level Δp13,G until the end of the cycle. The dynamic course of
pressure drop correlates with the screw position and indicates a varying
melt property or a wall slip effect.
Based on the defined pressure drop variables the wall shear stress
variables τH and τG can be calculated and investigated. The wall shear
stress τH increases proportionally over the shear rate. In contrast to this
course, the wall shear stress τG remains mainly constant over shear rate.
This indicates a predominant wall slip at the stationary phase. For this
reason, the variables at the maximum pressure drop (Δp13,H and τH ) will
be taken into account for the viscosity determination.
Different channel geometries are applied to verify that wall slip is
present even in the phase of the maximum pressure drop. A quantitative
determination of the wall slip velocity based on Mooney’s method was
omitted, due to the disturbing crosslinking effect at lower volume flow,
which has to be compensated previously.
A significant melt viscosity increase is observed at low volume flow
rates. It seems that a longer dwell time results in a higher curing degree.
This effect seems to be more pronounced at higher temperatures, which
confirms the hypothesis of temperature dependent crosslinking
influence.
The investigation with different channel geometries reveals a dual
interaction between increasing surface-to-volume-ratio and dwell time
effecting a higher wall shear stress. This confirms the hypothesis of a
crosslinking effect and viscosity increase at lower volume flow rates.
With a known reaction kinetic model the curing degree can be
calculated in real time based on the known dwell time and measured
melt temperature. According to the method of Kamal-Sourour [31],
offline measurements with differential scanning calorimetry (DSC) are
necessary to determine the model coefficients of a reaction kinetic
14
Polymer Testing 128 (2023) 108188
model. The crosslinking effect described above could be compensated
and allows a more accurate viscosity determination.
A FDM model is implemented based on Navier-Stokes equations and
the reaction viscosity model by the Cross Castro Macosko to calculate
viscous heating along the slit die for each injection cycle. This applica­
tion aims for an inline compensation of viscous heating influence on the
viscosity measurement in real time.
The experimentally measured viscosity data are fitted to the Cross
Castro Macosko model as an inertial reactive viscosity model without
compensation of viscous heating. The FDM model calculates the tem­
perature rise based on volume flow, mean melt temperature, and the
inertial reactive viscosity model. The calculated pressure difference due
to viscous heating can be applied to the sensor pressure signals. The
result of the FDM calculated pressure drop is in a good agreement with
the experimentally measured pressure. With the corrected pressure drop
values a master curve of the viscosity model can be generated without
viscous heating influence.
The calculated power law index, which describes the shear thinning
properties of the viscosity, is close to similar PF materials measured by a
plate rheometer.
With an average signal-to-noise-ratio over 50 the reliability seems to
be satisfying for a characterization of reactive viscosity models or the
detection of material-related process fluctuations. The disturbance var­
iables due to a material preparation or material pretreatment different
from the laboratory can be measured.
This work aims on the implementation of an assistance system for a
material characterization, predicting part quality and compensating
fluctuating material properties.
Funding
This research work was funded by Bundesministerium für Wirtschaft
und Energie. Project number: ZF4002641WO9.
Ethics approval
All authors confirm that they follow all ethical guidelines. All authors
certify that they have no affiliations with or involvement in any orga­
nization or entity with any financial interest or non-financial interest in
the subject matter or materials discussed in this manuscript.
P. Wappler et al.
Consent for publication
The authors agree with the publication.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The authors do not have permission to share data.
Acknowledgment
The authors acknowledge the project cooperation partners of Süd-
West-Chemie, namely Sebastian Ziller and Elmar Lang. The interesting
correspondence with Gerdy De Ganck of Sumitomo Bakelite Co. about
the rheological deep dive is acknowledged as well. Last but not least,
support by Dennis Stahl and Mehmet Haybat is acknowledged.
References
[1] W. Kaiser, Kunststoffchemie für Ingenieure: von der Synthese bis zur Anwendung, 2,
Aufl. München: Hanser, 2007.
[2] AVK, Industrievereinigung Verstärkte Kunststoffe, Handbuch
Faserverbundkunststoffe: Grundlagen, Verarbeitung, Anwendungen ; mit 46 Tabellen, 3.,
Vollst. überarb. Aufl, in: Praxis., Vieweg + Teubner, Wiesbaden, 2010.
[3] M. Höer, Einfluss der Material- und Verarbeitungseigenschaften von
Phenolharzformmassen auf die Qualität spritzgegossener Bauteile, Univ.-Verl,
Chemnitz, 2014.
[4] C. Gornik, Viscosity measuring methods for feedstocks directly on injection
molding machines, Mater. Sci. Forum 591 (593) (Aug. 2008) 174–178. https://doi.
org/10.4028/www.scientific.net/MSF.591-593.174.
[5] D. Sanetrnik, B. Hausnerova, V. Pata, Online rheometry investigation of flow/slip
behavior of powder injection molding feedstocks, Polymers 11 (3) (Mar. 2019)
432, https://doi.org/10.3390/polym11030432.
[6] J. Aho, S. Syrjälä, Shear viscosity measurements of polymer melts using injection
molding machine with adjustable slit die, Polym. Test. 30 (6) (Sep. 2011) 595–601,
https://doi.org/10.1016/j.polymertesting.2011.04.014.
[7] N. Zhang, M.D. Gilchrist, Characterization of thermo-rheological behavior of
polymer melts during the micro injection moulding process, Polym. Test. 31 (6)
(Sep. 2012) 748–758, https://doi.org/10.1016/j.polymertesting.2012.04.012.
[8] W. Wu, B. Zhao, F. Mo, B. Li, B. Jiang, In-line steady shear flow characteristics of
polymer melt in rectangular slit cavities during thin-wall/micro injection molding,
Mater. Des. 223 (Nov. 2022), 111266, https://doi.org/10.1016/j.
matdes.2022.111266.
[9] C. Hopmann, M. Theunissen, J. Heinisch, ‘Online Analysis of Melt Viscosity during
Injection Moulding with a Hot Runner Rheometer’, Presented at the
PROCEEDINGS of the EUROPE/AFRICA CONFERENCE DRESDEN 2017, POLYMER
PROCESSING SOCIETY PPS, Dresden, Germany, 2019, 070022, https://doi.org/
10.1063/1.5084866.
[10] G. Gou, P. Xie, W. Yang, Y. Ding, Online measurement of rheological properties of
polypropylene based on an injection molding machine to simulate the injection-
molding process, Polym. Test. 30 (8) (Dec. 2011) 826–832, https://doi.org/
10.1016/j.polymertesting.2011.08.005.
[11] P. Wappler, T. Horter, R. Kulkarni, T. Guenther, K.-P. Fritz, A. Zimmermann,
Development of a nozzle capillary viscometer for inline viscosity measurement of
thermoplastics, Int. J. Adv. Manuf. Technol. (Jan. 2022), https://doi.org/10.1007/
s00170-021-08394-4.
[12] M. Cavic, Kontinuierliche Prozeßüberwachung beim Spritzgießen unter
Einbeziehung von Konzepten zur Verbesserung der Schmelzequalität, Shaker,
Aachen, 2005.
[13] A. Fernandez, M. Muniesa, C. Javierre, In-line rheological testing of thermoplastics
and a monitored device for an injection moulding machine: application to raw and
recycled polypropylene, Polym. Test. 33 (Feb. 2014) 107–115, https://doi.org/
10.1016/j.polymertesting.2013.11.008.
[14] J. Eben, Identifikation und Reduzierung realer Schwankungen durch
praxistaugliche Prozessführungsmethoden beim Spritzgießen, Chemnitz: Univ.-
Verl, 2014.
[15] S. Kruppa, Adaptive Prozessführung und alternative Einspritzkonzepte beim
Spritzgießen von Thermoplasten, Universität Duisburg-Essen, Duisburg, 2015.
[16] V. Volpe, R. Pantani, Determination of the effect of pressure on viscosity at high
shear rates by using an injection molding machine, J. Appl. Polym. Sci. 135 (24)
(Jun. 2018), 45277, https://doi.org/10.1002/app.45277.
[17] A. Geyer, C. Bonten, ‘Material Characterization within the Injection Molding
Process’, Presented at the PROCEEDINGS of the EUROPE/AFRICA CONFERENCE
15
Polymer Testing 128 (2023) 108188
DRESDEN 2017, POLYMER PROCESSING SOCIETY PPS, Dresden, Germany, 2019,
120005, https://doi.org/10.1063/1.5084895.
[18] T. Schaible, C. Bonten, In-line measurement and modeling of temperature,
pressure, and blowing agent dependent viscosity of polymer melts, Appl. Rheol. 32
(1) (Aug. 2022) 69–82, https://doi.org/10.1515/arh-2022-0123.
[19] T. Osswald, N. Rudolph, Polymer Rheology. In Fundamentals and Applications,
München [u.a.]: Hanser, 2015 [Online]. Available: http://d-nb.info/1030080
992/04.
[20] E. Laurien, H. Oertel, Numerische Strömungsmechanik: Grundgleichungen und Modelle
- Lösungsmethoden - Qualität und Genauigkeit ; mit über 530 Wiederholungs- und
Verständnisfragen, 5., Überarb. und erw. Aufl, Springer Vieweg, Lehrbuch.
Wiesbaden, 2013.
[21] J.M. Castro, C.W. Macosko, Studies of mold filling and curing in the reaction
injection molding process, AIChE J. 28 (2) (Mar. 1982) 250–260, https://doi.org/
10.1002/aic.690280213.
[22] N.T. Tran, M. Gehde, Creating material data for thermoset injection molding
simulation process, Polym. Test. 73 (Feb. 2019) 284–292, https://doi.org/
10.1016/j.polymertesting.2018.11.042.
[23] H.M. Laun, Pressure dependent viscosity and dissipative heating in capillary
rheometry of polymer melts, Rheol. Acta 42 (4) (Jul. 2003) 295–308, https://doi.
org/10.1007/s00397-002-0291-6.
[24] R. Hardis, J.L.P. Jessop, F.E. Peters, M.R. Kessler, Cure kinetics characterization
and monitoring of an epoxy resin using DSC, Raman spectroscopy, and DEA,
Compos. Appl. Sci. Manuf. 49 (Jun. 2013) 100–108, https://doi.org/10.1016/j.
compositesa.2013.01.021.
[25] S. Weiss, R. Seidl, W. Kessler, R.W. Kessler, E.M. Zikulnig-Rusch, A. Kandelbauer,
Multivariate process trajectories for molecular description of MF thermal curing
and correlation with hydrolytic stability, J. Appl. Polym. Sci. 138 (27) (Jul. 2021),
50635, https://doi.org/10.1002/app.50635.
[26] N. Ghodhbani, P. Maréchal, H. Duflo, Ultrasound monitoring of the cure kinetics of
an epoxy resin: identification, frequency and temperature dependence, Polym.
Test. 56 (Dec. 2016) 156–166, https://doi.org/10.1016/j.
polymertesting.2016.10.009.
[27] A. Chaloupka, T. Pflock, R. Horny, N. Rudolph, S.R. Horn, Dielectric and
rheological study of the molecular dynamics during the cure of an epoxy resin,
J. Polym. Sci., Part B: Polym. Phys. 56 (12) (Jun. 2018) 907–913, https://doi.org/
10.1002/polb.24604.
[28] I. Alig, D. Fischer, D. Lellinger, B. Steinhoff, Combination of NIR, Raman,
ultrasonic and dielectric spectroscopy for in-line monitoring of the extrusion
process, Macromol. Symp. 230 (1) (Dec. 2005) 51–58, https://doi.org/10.1002/
masy.200551141.
[29] B. Kaya, ‘Concept Development and Implementation of Online Monitoring Methods
in the Transfer Molding Process for Electronic Packages’, Fakultät IV-
Elektrotechnik und Informatik, Technische Universität Berlin, Berlin, 2018.
[30] S. Yan, H. Zeizinger, C. Merten, S. Schmauder, In-situ investigation of dielectric
properties and reaction kinetics of a glass-fiber-reinforced epoxy composite
material using dielectric analysis, Polym. Eng. Sci. 61 (6) (Jun. 2021) 1673–1684,
https://doi.org/10.1002/pen.25691.
[31] M.R. Kamal, S. Sourour, Kinetics and thermal characterization of thermoset cure,
Polym. Eng. Sci. 13 (1) (Jan. 1973) 59–64, https://doi.org/10.1002/
pen.760130110.
[32] E. Franieck, M. Fleischmann, O. Hölck, L. Kutuzova, A. Kandelbauer, Cure kinetics
modeling of a high glass transition temperature epoxy molding compound (EMC)
based on inline dielectric analysis, Polymers 13 (11) (May 2021) 1734, https://doi.
org/10.3390/polym13111734.
[33] Sibikin Ageyeva, Kovács, A Review of thermoplastic resin transfer molding: process
modeling and simulation, Polymers 11 (10) (Sep. 2019) 1555, https://doi.org/
10.3390/polym11101555.
[34] S. Brockhaus, B. Klie, V. Schöppner, U. Giese, Grundlegende Studie und alternative
Methode zur Bewertung des Wandgleiteffekts bei hochviskosen
Kautschukmischungen, KGK rubberpoint, Nov. 2014.
[35] T.A. Osswald, J.P. Hernández-Ortiz, Polymer Processing: Modeling and Simulation,
Hanser Publishers, Munich ; Cincinnati, 2006.
[36] T. Schröder, Rheologie der ststoffe: Theorie und Praxis, 2, in: Aktualisierte und
erweiterte Auflage. München, Hanser, 2020.
[37] P. Schümmer, R.H. Worthoff, An elementary method for the evaluation of a flow
curve, Chem. Eng. Sci. 33 (6) (1978) 759–763, https://doi.org/10.1016/0009-
2509(78)80054-2.
[38] E.E. Rosenbaum, S.G. Hatzikiriakos, Wall slip in the capillary flow of molten
polymers subject to viscous heating, AIChE J. 43 (3) (Mar. 1997) 598–608, https://
doi.org/10.1002/aic.690430305.
[39] K. Geiger, RheologieEPDM-Kautschuk.pdf, Kautschuk und Gummi Kunststoffe, Jan.
1989.
[40] S.G. Hatzikiriakos, J.M. Dealy, Wall slip of molten high density polyethylenes. II.
Capillary rheometer studies, J. Rheol. 36 (4) (May 1992) 703–741, https://doi.
org/10.1122/1.550313.
[41] Moldflow Insight, Autodesk Moldflow Simulation 2017 - Wall Slip Parameters
Dialog, Autodesk Knowledge Network, 2017. https://knowledge.autodesk.com/s
upport/moldflow-insight/learn-explore/caas/CloudHelp/cloudhelp/2018/ENU/
MoldflowInsight-Analyses/files/GUID-9A0A156B-631B-4E20-8705-B09FC8C
384BB-htm.html. (Accessed 13 May 2019).
[42] M. Mooney, Explicit formulas for slip and fluidity, J. Rheol. 2 (2) (Apr. 1931)
210–222, https://doi.org/10.1122/1.2116364.
[43] C. Hopmann, J. Heinisch, Process control strategies for injection molding processes
with changing raw material viscosity, J. Polym. Eng. 0 (0) (Jan. 2017), https://doi.
org/10.1515/polyeng-2017-0180.
P. Wappler et al.
[44] S.P. Johnston, G.A. Mendible, R.X. Gao, D.O. Kazmer, Estimation of bulk melt-
temperature from in-mold thermal sensors for injection molding, Part A: method,
Int. Polym. Process. 30 (4) (Aug. 2015) 460–466, https://doi.org/10.3139/
217.3019.
[45] G. Tosello, Micro Injection Molding, 2018, p. 403.
16
Polymer Testing 128 (2023) 108188
[46] K. Kohlgrüber, M. Ullrich, R. Rudolf, T. König (Eds.), Der gleichläufige
Doppelschneckenextruder: Grundlagen, Technologie, Anwendungen, 2., neu Bearbeitete
und erweiterte Auflage, Hanser, München, 2016.
[47] N.T. Tran, Universitätsbibliothek, Creating Material Properties for Thermoset
Injection Molding Simulation Process, 2020.
[48] G. De Ganck, Example Rheological Data, vol. 28, 2021. Jun.