polymers

Article
Creep and Recovery Behaviour of Polyolefin-Rubber
Nanocomposites Developed for
Additive Manufacturing
Fugen Daver 1, *, Mladenko Kajtaz 1 , Milan Brandt 1 and Robert A. Shanks 2
1 School of Engineering, RMIT University, P.O. Box 71, Bundoora, Victoria 3083, Australia;
mladenko.kajtaz@rmit.edu.au (M.K.); milan.brandt@rmit.edu.au (M.B.)
2 School of Science, RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia;
robert.shanks@rmit.edu.au
* Correspondence: fugen.daver@rmit.edu.au

Academic Editor: Lloyd M. Robeson

Received: 17 October 2016; Accepted: 7 December 2016; Published: 15 December 2016

Abstract: Nanocomposite application in automotive engineering materials is subject to continual

stress fields together with recovery periods, under extremes of temperature variations. The aim is to
prepare and characterize polyolefin-rubber nanocomposites developed for additive manufacturing
in terms of their time-dependent deformation behaviour as revealed in creep-recovery experiments.
The composites consisted of linear low density polyethylene and functionalized rubber particles.
Maleic anhydride compatibilizer grafted to polyethylene was used to enhance adhesion between the
polyethylene and rubber; and multi-walled carbon nanotubes were introduced to impart electrical
conductivity. Various compositions of nanocomposites were tested under constant stress in creep
and recovery. A four-element mechanistic Burger model was employed to model the creep phase of
the composites, while a Weibull distribution function was employed to model the recovery phase
of the composites. Finite element analysis using Abaqus enabled numerical modelling of the creep
phase of the composites. Both analytical and numerical solutions were found to be consistent
with the experimental results. Creep and recovery were dependent on: (i) composite composition;
(ii) compatibilizers content; (iii) carbon nanotubes that formed a percolation network.

Keywords: polyethylene; polymer-matrix composite; creep and recovery; modelling; nanocomposite

1. Introduction
Dimensional stability of composites over their expected lifetime is an important aspect for
engineering applications. This is particularly important when the innovative functional polymeric
materials incorporating nanomaterials are used in integrated systems such as automotive applications
and the components are exposed to varying stresses over extended periods at elevated temperatures.
Creep and recovery experiments present a sensitive means of assessing the dimensional stability of
polymeric materials by understanding their viscoelastic deformation behaviour under constant stress
and temperature [1–4].
In creep experiment, a constant stress (σ) is applied instantaneously to a material under isothermal
conditions, and the resulting strain (ε) is measured as a function of time. Total strain consists
of (i) reversible and recoverable elastic strain (εe ); (ii) time-dependent viscoelastic strain (εve );
and (iii) inelastic viscous strain (εv ). The material first experiences an instantaneous, elastic deformation
upon application of the stress. Viscous and viscoelastic flow then occur at a decreasing rate before
the deformation reaches a steady state. An instantaneous, elastic recovery takes place with a sharp
decrease in strain upon removal of the stress. Time dependent viscoelastic recovery proceeds at a

Polymers 2016, 8, 437; doi:10.3390/polym8120437 www.mdpi.com/journal/polymers

Polymers 2016, 8, 437 2 of 13

slower rate. The strain remaining at the end of the test indicates permanent viscous flow that is
irrecoverable and it is referred to as unrecovered creep or the permanent set of the material.
Creep behaviour is a time-temperature dependent phenomenon and various theoretical and
mechanistic models have been used to describe viscoelastic behaviour of polymeric materials [5].
In linear viscoelastic behaviour, at any fixed time (isochronous) following initiation of a loading history,
the strain should be proportional to the stress and the strain generated by a load should be independent
from any previously applied load. Otherwise, the limits of linearity will be reached and the material
can no longer be considered as linear viscoelastic. The degree of non-linearity can be influenced by
factors such as applied stress level, strain rate, and temperature. All linear viscoelastic models to
define creep behaviour are made up of linear springs and linear dashpots [6].
For solids that exhibit only elastic behaviour, the material is represented by an ideal spring
element, where E is the Hookean elastic modulus (Equation (1)). The implication is that the energy
stored is recoverable and this translates to the immediate restoration of the original state upon removal
of the stress.
σ = Eε (1)

A material is represented by a dashpot when it exhibits viscous liquid behaviour, where η is the
Newtonian viscosity (Equation (2)). The viscous deformation resulting from an applied stress is a
time-dependent response. The deformation is linear with time under a constant stress and the imposed
deformation is permanent.
d
σ=η (2)
dt
The Maxwell model combines these two elements in series and assumes an additive contribution
from an elastic spring and viscous dashpot (Equation (3)).
  
d 1 dσ σ
= + (3)
dt E dt η

The Kelvin-Voigt model incorporates the two elements in parallel with the stress apportioned to
both elements. The time dependent response of a dashpot is accompanied by the restorative force of
the spring. A four element Burger model is composed of the Maxwell model and Kelvin-Voigt model
in series [7]. The springs correspond to elastic sections with moduli E1 and E2 while the dashpots
represent the viscosities η1 and η2 . The four element Burger model has been used with varying degree
of success in predicting creep behaviour of reinforced composites [8,9]. The model incorporates the
elastic (εe ), viscous (εv ), and viscoelastic (εve ) components of the strain to describe the mechanical
creep behaviour of polymeric materials (Equation (4)).
  
σ σt σ E2 t
( t ) = + + 1 − exp − (4)
E1 η1 E2 η2

Retardation time, τ is obtainedfrom the

 exponential term of the Equation (4) and it is a measure of
the time required to reach 63.2% or 1 − 1e of the total deformation of the material in the Kelvin-Voigt
unit (Equation (5)).
η
τ= 2 (5)
E2
The recovery behaviour of thermoplastics has been successfully modelled by means of a Weibull
distribution function [10–12]. The Weibull distribution function enables prediction of time dependent
recovery strain (εr ) in the material in terms of viscoelastic strain recovery (εve ) and permanent strain
(ε∞ ) upon removal of the stress as shown in Equation (6).
"  βr #
t − t0

εr (t) = εve exp − + ε∞ (6)
ηr
Polymers 2016, 8, 437 3 of 13

where, the εve is defined by the characteristic life factor (ηr ) and shape parameters (βr ) over recovery
time t and t0 is the time of stress removal.
In an earlier study, we have developed polyolefin-rubber composites by melt mixing linear low
density polyethylene with functionalized (i.e., de-vulcanized and surface activated) rubber particles
through interactions of pre-functionalized polymer in the interface [13]. Increasing the rubber content
of the composite from 30% to 70% in the overall composite composition decreased the elastic modulus
and tensile strength while increasing the percentage elongation at break. Characterization of the
composites in terms of their mechanical properties confirmed that the inclusion of the grafted maleic
anhydride as compatibilizer in the composites enhanced the elongation at break and produced
toughened polyolefin-rubber composites. Incorporation of carbon nanotubes with the help of a
master-batch improved the electrical conductivity of the nanocomposites by selective localization of
carbon nanotubes in the polyethylene phase [13].
Incorporation of rubber particles, which inherently possess elastomeric properties, is expected to
have an adverse effect on the overall creep properties of the composites due to low elastic modulus
of rubber phase. In this study, the creep and recovery behaviour of nanocomposites under different
stresses and temperatures was modelled by means of analytical and numerical methods. The aim was
to elucidate the effect of (i) composite composition; (ii) compatibilizers; and (iii) carbon nanotubes on
the viscoelastic deformation of the material.

2. Materials and Methods

2.1. Materials
Linear low-density polyethylene (LLDPE) was melt mixed with maleic anhydride grafted
polyethylene (MA-g-PE) which is grafted with maleic anhydride 0.90%·w/w. Functionalized
rubber particles (FRP) that were produced according to a patented process were obtained from
Polymeric Powders Company, Melbourne, Australia. Multi-walled carbon nanotubes (MWCNT) were
incorporated into the polyolefin–rubber composites in the form of a masterbatch, Plasticyl LDPE2001
(Nanocyl, Sambreville, Belgium) that is based on low density polyethylene (LDPE) [14].

2.2. Composite Preparation

LLDPE was fed into the pre-heated non-intermeshing, counter rotating internal batch mixer at
180 ◦C and it was mixed at 50 rpm for 1 min to ensure complete melting of polymer prior to the
introduction of the masterbatch Plasticyl LDPE2001, FRP, and MA-g-PE, to improve compatibility
between the rubber and the polyethylene. All four ingredients were mixed for another 5 min at
180 ◦ C before the mixture was removed for further processing. Table 1 shows the compositions of the
LLDPE–FRP nanocomposites. The specimens for all creep and recovery experiments were prepared by
compression moulding at 180 ◦ C for 5 min under a force of 50 kN followed by water-cooling of the
mould to below 50 ◦ C prior to pressure release and ejection from the mould. Compression moulded
plaques were cut into strips of approximately 25 × 4.5 × 0.5 mm dimensions. Details of the specimen
preparation are given elsewhere [13].

Table 1. Composition of the LLDPE–FRP nanocomposites.

Composition (%·w/w)
Composite code
LLDPE FRP MA-g-PE MWCNT
PB1 70 30 - -
PB3 30 70 - -
PB4 65 30 5 -
PB5 25 70 5 -
C-PB4 62 30 5 3
C-PB5 22 70 5 3
Polymers 2016, 8, 437 4 of 13

2.3. Thermomechanical Properties

A Q800 Dynamic Mechanical Analyser (TA Instruments, New Castle, DE, USA) in tensile mode
was used for 2016,
Polymers creep-
8, x recovery (static force thermomechanometry, sf-TM). Sf-TM analysis was performed
FOR PEER REVIEW 4 of 13
by subjecting the test specimens to an applied stress of 1.2 MPa for 30 min followed by a recovery
periodperformed
of 120 min at 25 ◦ C according
by subjecting the test specimens
to ASTM to anstandards
applied stress
[15].of The
1.2 MPa for 30stress
applied min followed by a to
was chosen
recovery
be within period viscoelastic
the linear of 120 min at 25 °Cof
region according to ASTM
all composites standards
tested [15]. The from
as identified applied
thestress was
isochronous
chosen to be within the linear viscoelastic region of all composites tested
stress–strain curves. Tests were conducted at a series of temperatures, from room temperature as identified from the to
◦ isochronous stress–strain curves. Tests were conducted at a series of temperatures, from room
80 C, to obtain long term deformation behaviour of the material by employing time-temperature
temperature to 80 °C, to obtain long term deformation behaviour of the material by employing
superposition principle.
time-temperature superposition principle.

3. Results and Discussion

3. Results and Discussion

3.1. Strain Response of Composites with Creep Stress

3.1. Strain Response of Composites with Creep Stress
The creep and and
The creep recovery
recoverycurves
curvesof of
polyolefin-rubber
polyolefin-rubber composite (PB1)
composite (PB1) areare presented
presented in Figure
in Figure 1. 1.
The creep
The creep stress varied between 1.2 and 6 MPa. In all creep curves, an instantaneous increase in in
stress varied between 1.2 and 6 MPa. In all creep curves, an instantaneous increase
strain strain
occursoccurs
due todueelastic response
to elastic of theofmaterial.
response the material.This This
is followed by aby
is followed viscoelastic response,
a viscoelastic response, which
which
involves involves time-dependent
time-dependent molecularmolecular rearrangement.
rearrangement. Viscous Viscous
flow isflow is observed
observed towards
towards thethe
end endof the
of the load application
load application period. of
period. Removal Removal
the load of results
the loadinresults
a rapidin decrease
a rapid decrease
in strain in response,
strain response,
which is
which
equal to is equal
the initial to the
elastic initial The
response. elastic response.
recovery Theinvolves
period recoverytime-dependent
period involvesmolecular time-dependent
relaxation
molecular relaxation as the polymer attempts to regain original dimensions. Since the polymer
as the polymer attempts to regain original dimensions. Since the polymer experienced viscous flow,
experienced viscous flow, full recovery is not reached resulting in permanent deformation. Higher
full recovery is not reached resulting in permanent deformation. Higher imposed stresses resulted
imposed stresses resulted in creep becoming increasingly irreversible. This permanent strain is of
in creep becoming
significant increasingly
importance irreversible.
in engineering This permanent
applications strain
as it may result in aisloss
of significant
of dimensional importance
stability in
engineering applications
under long term loading. as it may result in a loss of dimensional stability under long term loading.
Isochronous
Isochronouscurves obtained
curves obtainedfrom Figure
from Figure 1 1are
areshown
shown in Figure
Figure2.2.AAlinear
linear relationship
relationship between
between
stress and
stressstrain was observed
and strain was observed to a stress of 3 MPa.
to a stress of 3 MPa.TheThe maximum
maximum creep
creepstress
stresswas waskept
keptbelow
belowthisthislimit
so thatlimit so that the were
the composites composites
tested were
withintested
their within their linear region
linear viscoelastic viscoelastic
during region
creepduring creep
experiments.
experiments.
The creep and recovery curves for the composites PB1, PB3, PB4, and PB5 are shown in Figure 3.
The addition The creep and recovery
of (MA-g-PE) curvesto
proved forenhance
the composites PB1, PB3, between
the bonding PB4, and PB5 theare shownand
phases in Figure
the 3. creep
The addition of (MA-g-PE) proved to enhance the bonding between the phases and the creep
deformation of PB4 and PB5 under the same load was significantly lower than the composites PB1 and
deformation of PB4 and PB5 under the same load was significantly lower than the composites PB1
PB3 which were formed without compatibilizer (MA-g-PE).
and PB3 which were formed without compatibilizer (MA-g-PE).
The creep and and
The creep recovery
recoverycurves
curves forfor
thethecomposites
composites PB4, C-PB4and
PB4, C-PB4 andPB5, PB5, C-PB5
C-PB5 areare shown
shown in in
FigureFigure
4. Incorporation of MWCNT
4. Incorporation of MWCNT into theintocomposites did not did
the composites introduce a constraint
not introduce on deformation
a constraint on
duringdeformation
the creep phase. during Composites
the creep phase. with carbon nanotubes
Composites with carbon demonstrated higher creep
nanotubes demonstrated deformation
higher creep
compared with their
deformation counterpart
compared without
with their the carbon
counterpart nanotubes.
without Thisnanotubes.
the carbon is due to the Thiscarbon
is duenanotubes
to the
carbon nanotubes being introduced via a low viscosity master-batch,
being introduced via a low viscosity master-batch, Plasticyl LDPE2001. This finding confirms Plasticyl LDPE2001. This our
finding confirms our earlier observation in regard to the decrease
earlier observation in regard to the decrease in Young modulus following the addition of carbon in Young modulus following the
addition
nanotubes intoofthecarbon nanotubes
composite into the composite [13].
[13].

12
1.2MPa
10
3MPa
Strain (%)

8 4MPa
6 6MPa
4
2
0
0.00 50.00 100.00 150.00 200.00
Time (min)

Figure 1. Creep-recovery response of composite material (PB1) at different initial stresses.

Figure 1. Creep-recovery response of composite material (PB1) at different initial stresses.
Polymers 2016, 8, x FOR PEER REVIEW 5 of 13

Figure 1. Creep-recovery response of composite material (PB1) at different initial stresses.

Polymers
Polymers 2016,
2016, 8,
8, 437
437 55 of
of 13
13
Polymers 2016, 8, 437 5 of 13
7
7 30 min 50 min
67 10 min
20 min 40 min
30 min
20 min 50 min
6 40 min 60 min
30 min 50 min
10 min 20 min 40 min
56 10 min 60 min
60 min

(MPa)
5
(MPa)
(MPa) 45
4
Stress

34
Stress

3
Stress

23
2
12
1
01
0 0 2 4 6 8 10 12 14
0
0 2 4 6Strain (%)8 10 12 14
0 2 4 6 8 10 12 14
Strain (%)
Strain (%)
Figure 2. Isochronous curves obtained from creep curves as shown in Figure 1.
Figure
Figure2.
2.Isochronous
Isochronouscurves
curvesobtained
obtained from
from creep
creep curves
curves as shown in Figure 1.
Figure 2. Isochronous curves obtained from creep curves as
as shown
shown in
in Figure
Figure 1.
1.
8
8
78 PB1
7 PB1
PB3
67 PB1
PB3
PB4
6 PB3
56 PB4
PB5
(%)(%)

5 PB4
45 PB5
Strain

PB5
(%)

4
Strain

34
Strain

3
23
2
12
1
01
0 0.00 50.00 100.00 150.00
0
0.00 50.00 Time (min) 100.00 150.00
0.00 50.00 100.00 150.00
Time (min)
Time (min)
Figure
Figure 3.
3. The
Theeffect
effect of
of compatibilizer
compatibilizer (MA-g-PE)
(MA-g-PE) on
on creep-recovery
creep-recovery behaviour.
behaviour.
Figure 3. The effect of compatibilizer (MA-g-PE) on creep-recovery behaviour.
Figure 3. The effect of compatibilizer (MA-g-PE) on creep-recovery behaviour.
7
7
67 PB4
6 PB4
PB5
56 PB4
C-PB4
5
(%)(%)

45 PB5
C-PB5
PB5
Strain

4
(%)

34
Strain
Strain

3
23
2
12
1
01
0 0.00 50.00 100.00 150.00
0
0.00 50.00 Time (min) 100.00 150.00
0.00 50.00 100.00 150.00
Time (min)
Time
Figure 4. MWCNT and (min)
creep-recovery behaviour.

Figure 4. MWCNT and creep-recovery behaviour.

Figure 4. MWCNT and creep-recovery behaviour.
Polymers 2016, 8, 437 6 of 13
Polymers 2016, 8, 437 6 of 13

3.2.
3.2. Application
Application of
of Time-Temperature Superposition for
Time-Temperature Superposition for Long
Long Term
TermDeformation
DeformationBehaviour
Behaviour
A
A series
series of
of creep
creep experiments
experiments were
were conducted
conducted at
at different
different temperatures,
temperatures, from
from 30
30 to
to 80
80 °C
◦ C with
with
10
10 C increments for the PB4 and PB5, to enable assessment of the deformation behaviour of
°C
◦ increments for the PB4 and PB5, to enable assessment of the deformation behaviour of the
the
composites under ambient temperatures for long periods of time (Figure
composites under ambient temperatures for long periods of time (Figure 5). 5).

6
a) PB4 80 ⁰C
5
70 ⁰C
4
Strain (%)

60 ⁰C
3
50 ⁰C
2 40 ⁰C
30 ⁰C
1

0
0 10 20 30 40 50 60 70
Time (min)

25 b) PB5 80 ⁰C

20
70 ⁰C
Strain (%)

15 60 ⁰C
50 ⁰C
10 40 ⁰C
30 ⁰C
5

0
0 10 20 30 40 50 60 70
Time (min)

Figure 5. Creep response of (a) PB4; and (b) PB5 at an applied stress of 1.2 MPa.
Figure 5. Creep response of (a) PB4; and (b) PB5 at an applied stress of 1.2 MPa.

Time temperature
Time temperature superposition
superposition principle
principle was was applied
applied to to estimate
estimate creep
creep performance
performance of of the
the
composite at
composite atlonger
longerdurations.
durations.The The relative
relative creep-time
creep-time master
master curvescurves for composite
for composite PB4PB5
PB4 and andwere PB5
were obtained by shifting the creep strain at different temperatures, while keeping 30 ◦ C as the
obtained by shifting the creep strain at different temperatures, while keeping 30 °C as the reference
reference temperature.
temperature.
The time-temperature
The time-temperature shift factor, aaTT,, was
shift factor, was calculated
calculated from
from the the shifting
shifting procedure.
procedure. If
If an
an arbitrary
arbitrary
T s is taken to fix one curve, then if t
reference temperature Ts is taken to fix one curve, then if ts is the time of a value on the curve at
reference temperature s is the time of a value on the curve at T
Tss
with a particular strain and t is the time of a value with the same relative creep on a
with a particular strain and t is the time of a value with the same relative creep on a curve at a differentcurve at a different
temperature, then
temperature, then the
the amount
amountof ofshift
shiftrequired
requiredtotosuperpose
superposethe theaxis
axisisisa adisplacement
displacementofof
(log
(logts t–s –log
logt)
along the log time axis. The shift factor is defined by Equation
t) along the log time axis. The shift factor is defined by Equation (7). (7).

ts
loglog
aT = =
loglogts −−log
logt ==log
log (7)
t
 Polymers 2016, 8, 437 7 of 13
Polymers 2016, 8, 437 7 of 13
Figure 6 shows that creep master curves for PB4 and PB5 demonstrate a similar trend. The PB4
having a low rubber content of 30% exhibits a strain of just over 5%, while PB5 with a higher rubber
Figure 6 shows that creep master curves for PB4 and PB5 demonstrate a similar trend. The PB4
content of 70% reached close to 25% strain in 1.8 y duration.
having a low rubber content of 30% exhibits a strain of just over 5%, while PB5 with a higher rubber
content of 70% reached close to 25% strain in 1.8 y duration.

30

25

20 PB5
Strain (%)

15

10
PB4
5

0
100 101 102 103 104 105 106
Time (min)

Figure
Figure 6. Master
6. Master creep
creep curves
curves of PB4
of PB4 andand PB5
PB5 at the
at the reference
reference temperature
temperature 30 30
◦ C.°C.

3.3.3.3. Modelling
Modelling of the
of the Creep
Creep Phase
Phase of Composites
of Composites viavia a Four
a Four Element
Element Burger
Burger Model
Model
TheThe four
four element
element Burger
Burger model
model comprising
comprising Maxwell
Maxwell andand Kelvin-Voigt
Kelvin-Voigt models
models was was usedusedto to
interpret the creep component [10]. Mechanistic model parameters
interpret the creep component [10]. Mechanistic model parameters were extracted from creep and were extracted from creep and
recovery curves of each composite (Table 2). Modulus (E 1) and viscosity (η1) were determined from
recovery curves of each composite (Table 2). Modulus (E1 ) and viscosity (η1 ) were determined from the
the equilibrium
equilibrium regionregion
of the of the curves.
creep creep curves.
E1 wasEmeasured
1 was measured by extrapolation of the linear portion of
by extrapolation of the linear portion of the
the creep curve to the time when the
creep curve to the time when the stress was applied, stress waswithapplied, with thedetermined
the modulus modulus determined from the
from the intercept.
intercept. Increasing rubber content of the composite reduced the
Increasing rubber content of the composite reduced the modulus significantly. Modulus, E1 of PB3 modulus significantly. Modulus,
E1 of
with 70%PB3 with particles
rubber 70% rubber (39 particles
MPa) is much(39 MPa) lower is much
than thelower than the
modulus modulus
of PB1 having ofaPB1 having
rubber a rubber
content of
content of 70% (192 MPa). Introduction of compatabiliser increased
70% (192 MPa). Introduction of compatabiliser increased the modulus: PB4 and PB5 showed higher the modulus: PB4 and PB5
showed
moduli higher with
compared moduli compared
the PB1 and PB3,with the PB1 Itand
respectively. PB3, respectively.
is expected It is expected
that the compatabiliser that the
(MA-g-PE)
should assist in promoting the connectivity of adjoining PE crystallites as well as interacting with as
compatabiliser (MA-g-PE) should assist in promoting the connectivity of adjoining PE crystallites
thewell as interacting
rubber with the
particles. Whereas rubber particles.
introduction of carbon Whereas
nanotubesintroduction of carbon
did not improve thenanotubes
elastic modulus, did not
improve
both C-PB4 the
andelastic
C-PB5modulus, both C-PB4
showed slightly and C-PB5
reduced modulishowed
compared slightly
withreduced
the PB4 moduli
and PB5compared
respectively. with
the PB4 and PB5 respectively. The equilibrium viscosity (as determined
The equilibrium viscosity (as determined from the slope of the linear portion) accounted for the from the slope of the linear
portion)
solid accounted
state viscous flowfor thatthe solid state
occurred withviscous
the applied flowstress.
that occurred
C-PB4 showed with the applied equilibrium
the highest stress. C-PB4
showed(η
viscosity, the) indicating
highest equilibrium
that a lower viscosity, (η1) indicating
flow occurred in thethat a lower
dashpot andflow occurred deformation
permanent in the dashpot
1
and permanent deformation decreased as shown in Figure
decreased as shown in Figure 6. C-PB4 composite with low rubber content reinforced with 6. C-PB4 composite with low rubber
carbon
content reinforced with carbon nanotubes is likely to be more dimensionally
nanotubes is likely to be more dimensionally stable than the others when under stress. Retardation stable than the others
when
time, (τ) under
is equal stress.
to theRetardation
ratio of thetime, (τ) is(η
viscosity, equal to the ratio of the viscosity, (η2) to the modulus (E2)
2 ) to the modulus (E2 ) of the Kelvin-Voigt component.
of the Kelvin-Voigt component. The non-linear
The non-linear curve fit function of Excel software was employed curve fit function to of Excelthe
define software
modulus was (E2employed
), and the to
define the
viscosity (η2 ).modulus
The modulus(E2), and(E2the viscosity
), which (η2). The
is related modulus
to the stiffness (E2of
), which is related chains
the amorphous to the stiffness
in short of
term, increased following the incorporation of compatabiliser into the composites. Both PB4 andinto
the amorphous chains in short term, increased following the incorporation of compatabiliser PB5the
composites. Both PB4 and PB5 showed a higher modulus (E
showed a higher modulus (E2 ) compared with the PB1 and PB3 respectively. The modulus (E2 ) of2) compared with the PB1 and PB3

respectively.
C-PB4 and C-PB5 The moduluscompared
decreased (E2) of C-PB4 with andthe PB4 C-PB5anddecreased compared
PB5 respectively. Thewith the PB4time
retardation and(τ) PB5
respectively. The retardation time (τ) and the viscosity (η 2) increased both for C-PB4 and C-PB5
and the viscosity (η2 ) increased both for C-PB4 and C-PB5 compared to PB4 and PB5, respectively.
compared to
Incorporation of PB4
carbonand PB5, respectively.
nanotubes did not introduceIncorporation of carbon
reinforcement in thenanotubes
Kelvin-Voigt didmodel,
not introduce
due to
lowreinforcement
viscosity of thein the Kelvin-Voigt
master batch. model, due to low viscosity of the master batch.
Polymers 2016, 8, 437 8 of 13

Polymers 2016, 8, 437 8 of 13

Table 2. Parameters of the mechanistic Burger model, creep component of composites.

Table 2. Parameters of the mechanistic Burger model, creep component of composites.
Composite code E1 (MPa)
Composite code E1E(MPa) η1 (MPa·ηs)1 (MPa·s)
2 (MPa) E2 (MPa) η2 (MPaη2·s) τ (s) τ (s)
(MPa·s)
PB1 PB1192 127
192 127448,200 448,200 8730 8730 69 69
PB3 PB339 3942 42176,829 176,829 7409 7409 176 176
PB4 258 299 479,916 13,287 44
PB5
PB452 25869
299169,956 479,916 8293 13,287 120 44
C-PB4 PB5226 52
177 691,020,917 169,956 40,838 8293 231 120
C-PB5 C-PB438 22659 177201,237 1,020,917 9177 40,838 154 231
C-PB5 38 59 201,237 9177 154
3.4. ABAQUS Implementation of the Four Element Burger Model
3.4. ABAQUS Implementation of the Four Element Burger Model
In ABAQUS, creep behaviour is specified by the equivalent uniaxial behaviour—the creep law.
Five commonIncreep ABAQUS,
laws arecreep behaviour
directly providedis specified
in ABAQUS:by thethe equivalent
power law, uniaxial behaviour—thelaw,
the hyperbolic-sine creep law.
Five common creep laws are directly provided in ABAQUS: the power
the double power law, the Anand law, and the Darveaux law and they are used for modelling secondary law, the hyperbolic-sine law,
the double power law, the Anand law, and the Darveaux law and
or steady-state creep [16]. However, in practical cases creep laws are typically of very complex form tothey are used for modelling
secondary
fit experimental or thus,
data; steady-state
the lawscreep [16]. However,
are frequently in practical
user-defined via thecases
use ofcreep
user laws are typically
subroutine CREEP of very
complex form to fit experimental data; thus, the laws are frequently
and included in a general time-dependent, viscoplastic material formulation [17–19]. Our four elementuser-defined via the use of user
subroutine CREEP and included in a general time-dependent, viscoplastic
model or Burger model, is not a standard model in ABAQUS and hence needed to be incorporated via material formulation [17–
the CREEP19].user
Our subroutine.
four element model or Burger model, is not a standard model in ABAQUS and hence needed
to be incorporated
As the CREEP user subroutinevia the CREEP
definesuser subroutine.of inelastic creep strain; ∆εcreep as functions
the increments
of the solutionAsdependent
the CREEPvariables,
user subroutine
such as defines the increments
the deviatoric of inelastic
stress, pressure, andcreep strain; ∆εand
temperature; as functions
creeptime

of the solution dependent variables, such as the deviatoric stress, pressure,

increment ∆t. Equation (4) is required to be discretised to fit available integration schemes. ABAQUS and temperature; and
time increment ∆t. Equation (4) is required to be discretised to fit
provides both explicit and implicit time integration of creep and the choice of the time integration available integration schemes.
scheme ABAQUS
depends on provides both explicit
the procedure type,and the implicit
procedure timedefinition
integration andofacreep and the
geometric choice of the time
non-linearity.
integration scheme depends on the procedure type, the procedure
The selected approach was based on the creep strain rate definition, shown in Equation (8), [20] definition and a geometric
and it non-
linearity. The selected approach was
was discretised to fit the both integration schemes. based on the creep strain rate definition, shown in Equation (8),
[20] and it was discretised to fit the both integration  schemes.

.
 (t) =
σ
+
σ σ
exp − σt (8)
η1 ϵ ( η)2= + τ exp − (8)
ƞ η τ
The following FORTRAN
The following code snippet
FORTRAN highlights
code snippet some ofsome
highlights the key aspects
of the of the model
key aspects of the model
implementation in ABAQUS.
implementation in ABAQUS.

C
SUBROUTINE CREEP(DECRA,DESWA,STATEV,SERD,EC,ESW,P,QTILD,
1 TEMP,DTEMP,PREDEF,DPRED,TIME,DTIME,CMNAME,LEXIMP,LEND,
2 COORDS,NSTATV,NOEL,NPT,LAYER,KSPT,KSTEP,KINC)
C

C
T1=QTILD/Nu1
T2=QTILD/Nu2
Tau=(Nu2/E2)
C
DECRA(1) = DTIME*(EXP(-TIME/Tau)*T2+T1)
DECRA(5) = DTIME*((1/Nu1)+(1/Nu2)*EXP(-TIME/Tau))

The validation of the developed creep model and the previously extracted parameters was
The validation of the developed creep model and the previously extracted parameters was
performed using a one-solid-element model shown in Figure 7 [21]. The correlation between the
performed using a one-solid-element model shown in Figure 7 [21]. The correlation between the
analytical creep strain, numerical creep strain obtained using ABAQUS Finite Element Analysis and
analytical creep strain, numerical creep strain obtained using ABAQUS Finite Element Analysis and
the experimental creep strain was found to be adequate. Hence, to avoid repetition, the results
the experimental creep strain was found to be adequate. Hence, to avoid repetition, the results were
were shown only for the low rubber content materials which have demonstrated higher conductivity
shown only for the low rubber content materials which have demonstrated higher conductivity
compared the low rubber content composites upon introduction of carbon nanotubes. Figures 8–10
compared the low rubber content composites upon introduction of carbon nanotubes. Figures 8–10
demonstrate the consistency of both analytical and numerical solutions with the experimental results
demonstrate the consistency of both analytical and numerical solutions with the experimental results
for rubber rich composites: PB3, PB5, and C-PB5 respectively.
for rubber rich composites: PB3, PB5, and C-PB5 respectively.
Polymers 2016, 8, 437 9 of 13
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Polymers 2016, 8, 437 9 of 13

Figure
Figure 7.
7.One-solid-element
One-solid-element finite
finite element
element model
model used
used in
in the
the validation.
validation.
Figure
Figure 7.
7. One-solid-element
One-solid-element finite
finite element
element model used in the validation.
0.09
0.09
0.09
0.08
0.08
0.08
0.07
0.07
0.07
0.06
(m/m)

0.06
(m/m)

0.06
(m/m)

0.05
0.05
0.05
Strain

0.04
Strain

0.04
Strain

0.04
0.03
0.03 Experimental
0.03 Experimental
0.02 Experimental
0.02 Analytical
Analytical
0.02 Analytical
0.01
0.01 Numerical
0.01 Numerical
00 Numerical
0 0 500 1000 1500 2000
0 500 1000 1500 2000
0 500 1000 1500 2000
Time
Time(s)
(s)
Time (s)

Figure
Figure 8.
8. Modelling
Modelling the
the creep
creep component
component of
of PB3
PB3 by
by aaaBurger
Burger model.
Burger model.
model.
Figure 8. Modelling the creep component of PB3 by a Burger model.

0.07
0.07
0.07
0.06
0.06
0.06
0.05
0.05
0.05
(m/m)
(m/m)
(m/m)

0.04
0.04
0.04
Strain
Strain

0.03
0.03
Strain

0.03
0.02 Experimental
Experimental
0.02 Experimental
0.02
Analytical
Analytical
0.01
0.01 Analytical
0.01 Numerical
Numerical
00 Numerical
0 0 500 1000 1500 2000
0 500 1000 1500 2000
0 500 1000 1500 2000
Time
Time(s)
(s)
Time (s)
Figure 9. Modelling the creep component of PB5 by a Burger model.
Figure
Figure 9.
9.Modelling
Modelling the
thecreep
creepcomponent
component of
ofPB5
PB5 by
by aaBurger
Burger model.
model.
Figure 9. Modelling the creep component of PB5 by a Burger model.
Polymers 2016, 8, 437 10 of 13
Polymers 2016, 8, 437 10 of 13

0.08
0.07
0.06

Strain (m/m)
0.05
0.04
0.03
Experimental
0.02
Analytical
0.01
Numerical
0
0 500 1000 1500 2000
Time (s)

Figure 10. Modelling the creep component of C-PB5 by a Burger model.

Figure 10. Modelling the creep component of C-PB5 by a Burger model.

3.5. Modelling of the Recovery Phase of Composites via a Weibull Distribution Function
3.5. Modelling of the Recovery Phase of Composites via a Weibull Distribution Function
A Weibull distribution function was used to model the recovery component of the experimental
A Weibull distribution function was used to model the recovery component of the experimental
creep curves. The value of viscoelastic strain recovery (ε ) and permanent strain (ε∞ ) are received
creep curves. The value of viscoelastic strain recovery (εve ve) and permanent strain (ε∞) are received
through the simulation of Weibull equation (Equation (6)) and the εmax is the maximum deformation
through the simulation of Weibull equation (Equation (6)) and the εmax is the maximum deformation
corresponding to the strain value for the longest time (t = 1800 s) during the creep test as shown in
corresponding to the strain value for the longest time ( 0 = 1800 s) during the creep test as shown in
Equation (9).
Equation (9).
εmax = εe + εve + ε∞ (9)
ε = +  +  (9)
Resultant parameters are shown in Table 3. Figures 11–13 show the modelling of the recovery
Resultant
phase of rubber parameters are shown in Table
rich composites—PB3, PB5,3.and
FiguresC-PB511–13 show the modelling
respectively—by meansof of
thearecovery
Weibull
phase of rubber rich composites—PB3, PB5, and C-PB5 respectively—by
distribution function. Viscoelastic strain recovery (εve ) decreased from 0.95% to 0.40% for low means of a Weibull
rubber
distribution function. Viscoelastic strain recovery (ε ve ) decreased from 0.95%
content composites (PB1 and PB4) and similarly εve it decreased from 2.85% to 1.73% for high rubber to 0.40% for low rubber
content
content composites
(PB3 and PB5) (PB1 and PB4) and
composites withsimilarly εve itof
the addition decreased from 2.85%This
the compatibilizer. to 1.73% for high
observation rubber
confirms
content (PB3 and
the enhanced PB5) composites
recovery behaviour of with
thethe addition with
composites of thethecompatibilizer. This observation
addition of compatibilizers. confirms
Viscoelastic
the enhanced recovery behaviour of the composites with the addition of compatibilizers.
strain recovery (εve ) increased from 0.40% to 0.68% for low rubber content composites (PB4 and C-PB4) Viscoelastic
strain recovery
and similarly εve(εincreased
ve) increased fromfrom
1.73% 0.40%
up toto 0.68%
2.02% forforhighlow rubber
rubber content
content composites
composites (PB5(PB4
and and C-
C-PB5)
PB4)
with and similarly of
the addition εvethe
increased
carbonfrom 1.73% up
nanotubes. to 2.02%
Hence, for be
it can high rubber content
concluded that thecomposites (PB5
addition of and
carbon
C-PB5)
nanotubes did not introduce an enhanced recovery behaviour. Similarly, characteristic life factor (ηofr )
with the addition of the carbon nanotubes. Hence, it can be concluded that the addition
carbon nanotubes
and shape parameter did(βnot introduce an enhanced recovery behaviour. Similarly, characteristic life
r ) are expected to show an increasing trend with the introduction of MWCNT
factor (ηr) andthe
by inhibiting shape parameter
slippage (βr) are expected
of molecular to show
chains hence an increasing
leading trendin
to an increase with the introduction
viscosity. However,
of MWCNT by inhibiting the slippage of molecular chains hence leading
in our studies, this trend was not clear, again most likely due to the introduction of MWCNT to an increase in viscosity.
via a low
However, in ourbatch.
viscosity master studies, this trend was not clear, again most likely due to the introduction of
MWCNT via a low viscosity master batch.
Table 3. Parameters of the Weibull distribution function—recovery phase of composites.
Table 3. Parameters of the Weibull distribution function—recovery phase of composites.
Composite code ε (%) ε (%) εve (%) ε (%) η (s) βr
max
Composite code εmax (%) e εe (%) εve (%) ε∞ ∞(%) ηr (s) r βr
PB1 PB1 2.56 2.56 0.640.64 0.95
0.95 0.47
0.47 591.180.48
591.18 0.48
PB3 7.17 3.07 2.85 1.25 221.77 0.47
PB4 PB3 1.32 7.17 0.463.07 2.85
0.40 1.25
0.45 221.77
340.340.47 0.46
PB5 PB4 5.30 1.32 2.290.46 0.40
1.73 0.45
1.28 340.34
356.550.46 0.45
C-PB4 PB5 1.42 5.30 0.552.29 1.73
0.68 1.28
0.19 356.55
720.600.45 0.49
C-PB5 C-PB4 6.29 1.42 3.170.55 2.02
0.68 1.10
0.19 186.310.49
720.60 0.46
C-PB5 6.29 3.17 2.02 1.10 186.31 0.46
Polymers 2016, 8, 437 11 of 13
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8
8 Experimental
78 Experimental
7 Analytical
Experimental
67 Analytical
6 Analytical
56

(%)(%)(%)
5
45
Strain
Strain 4
34
Strain
3
23
2
12
1
01
0 0 2000 4000 6000 8000 10000
0 0 2000 4000 6000 8000 10000
0 2000 4000Time (s)6000 8000 10000
Time (s)
Time (s)
Figure 11. Modelling the recovery component of PB3 by a Weibull distribution function.
Figure
Figure 11.
11. Modelling
Modelling the
the recovery
recovery component
component of
of PB3
PB3 by
by aa Weibull distribution function.
Weibull distribution function.
Figure 11. Modelling the recovery component of PB3 by a Weibull distribution function.
6
6 Experimental
6 Experimental
5 Analytical
Experimental
5 Analytical
5 Analytical
4
4
(%)(%)(%)

4
3
Strain

3
Strain

3
Strain

2
2
2
1
1
1
0
0 0 2000 4000 6000 8000 10000
0 0 2000 4000 6000 8000 10000
0 2000 4000Time (s)6000 8000 10000
Time (s)
Time (s)
Figure
Figure12.
12.Modelling
Modellingthe
therecovery
recoverycomponent
componentof
ofPB5
PB5by
byaaWeibull
Weibull distribution
distribution function.
function.
Figure 12. Modelling the recovery component of PB5 by a Weibull distribution function.
Figure 12. Modelling the recovery component of PB5 by a Weibull distribution function.
7
7 Experimental
67 Experimental
6 Analytical
Experimental
56 Analytical
5 Analytical
(%)(%)(%)

45
4
Strain

34
Strain
Strain

3
23
2
12
1
01
0 0 2000 4000 6000 8000 10000
0 0 2000 4000 6000 8000 10000
0 2000 4000Time (s)6000 8000 10000
Time (s)
Time (s)
Figure 13. Modelling the recovery component of C-PB5 by a Weibull distribution function.
Figure 13. Modelling the recovery component of C-PB5 by a Weibull distribution function.
Figure 13. Modelling the recovery component of C-PB5 by a Weibull distribution function.
Figure 13. Modelling the recovery component of C-PB5 by a Weibull distribution function.
Polymers 2016, 8, 437 12 of 13

4. Conclusions
Creep and recovery behaviour were evaluated for polyolefin-rubber nanocomposites developed
for additive manufacturing. The creep component was successfully modelled by means of a four
element Burger model. Model parameters enabled numerical modelling of the creep component
of the composites by means of finite element analysis (Abaqus Software). Both the analytical and
the numerical solutions were found to be consistent with experimental results. The recovery phase
of the creep experiments was modelled using a Weibull distribution function. Model parameters,
in particular change in viscoelastic strain (εve ), was indicative of the effect of compatibilizers and the
carbon nanotubes in time dependent recovery behaviour of the composites.

Acknowledgments: Special thanks go to Betul Dal for her assistance in the modelling and analysis of the
experimental creep and recovery data.
Author Contributions: Robert Shanks and Fugen Daver conceived and designed the experiments. Fugen Daver
performed the experiments. Fugen Daver, Robert Shanks, and Milan Brandt analyzed the data. Mladenko Kajtaz
developed and performed the numerical modelling and wrote the relevant section (Section 3.4) of the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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