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A non-affine micro-macro approach to strain-


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DOI: 10.1016/j.jmps.2017.10.007

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Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Contents lists available at ScienceDirect

Journal of the Mechanics and Physics of Solids


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

A non-affine micro-macro approach to strain-crystallizing


rubber-like materials
Reza Rastak, Christian Linder∗
Department of Civil and Environmental Engineering, Stanford University, Stanford, California, 94305, USA

a r t i c l e i n f o a b s t r a c t

Article history: Crystallization can occur in rubber materials at large strains due to a phenomenon called
Received 25 May 2017 strain-induced crystallization. We propose a multi-scale polymer network model to cap-
Revised 2 October 2017
ture this process in rubber-like materials. At the microscopic scale, we present a chain
Accepted 11 October 2017
formulation by studying the thermodynamic behavior of a polymer chain and its crystal-
Available online 13 October 2017
lization mechanism inside a stretching polymer network. The chain model accounts for the
Keywords: thermodynamics of crystallization and presents a rate-dependent evolution law for crystal-
Strain-induced crystallization lization based on the gradient of the free energy with respect to the crystallinity variables
Rubber-like materials to ensures the dissipation is always non-negative. The multiscale framework allows the
Micromechanics anisotropic crystallization of rubber which has been observed experimentally. Two differ-
Homogenization ent approaches for formulating the orientational distribution of crystallinity are studied. In
Maximal advance path constraint the first approach, the algorithm tracks the crystallization at a finite number of orienta-
tions. In contrast, the continuous distribution describes the crystallization for all polymer
chain orientations and describes its evolution with only a few distribution parameters. To
connect the deformation of the micro with that of the macro scale, our model combines
the recently developed maximal advance path constraint with the principal of minimum
average free energy, resulting in a non-affine deformation model for polymer chains. Vari-
ous aspects of the proposed model are validated by existing experimental results, including
the stress response, crystallinity evolution during loading and unloading, crystallinity dis-
tribution, and the rotation of the principal crystallization direction. As a case study, we
simulate the formation of crystalline regions around a pre-existing notch in a 3D rubber
block and we compare the results with experimental data.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction

Many polymeric materials such as natural and synthetic rubber, polyethylene, polyethylene terephthalate, and polylactide
are subject to polymer crystallization. This phenomenon is observed under certain conditions in vulcanized and unvul-
canized polymers well above the glass transition temperature. Extreme stretchability and the possibility to combine with
carbon nanotubes or conjugated polymers to create stretchable conductors or semiconductors makes these materials perfect
for future applications in devices such as epidermal electronics and implantable sensors (Wang et al., 2017; Xu et al., 2017).
The unique characteristics of rubber-like materials originate from their underlying polymer chain network. The covalent
bonds between monomers lead to long flexible polymer chains and create a soft structure for the material while crosslinks


Corresponding author.
E-mail address: linder@stanford.edu (C. Linder).

https://doi.org/10.1016/j.jmps.2017.10.007
0022-5096/© 2017 Elsevier Ltd. All rights reserved.
68 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

and chain entanglements provide elasticity and load carrying capability. The random distribution of chains in all orientations
results in an isotropic amorphous phase at room temperature. However, the polymer chains can undergo phase transforma-
tion at either lower temperatures or the application of a large amount of stretch. The latter mechanism is referred to as
strain-induced crystallization(SIC) and is the central focus of this work.
For SIC to occur, the chemical composition of the material must enable crystallization. Segments of the macromolecules
have to possess a mutually conforming atomistic structure so that they can arrange themselves into a regular crystalline or-
der. This transition turns an amorphous solid into a partially crystalline solid and is accompanied by volume change, which
is a first-order change. Unlike conventional crystallization, this transition is not rapid and does not cause any phase separa-
tion. In fact, amorphous and crystalline fractions coexist and the ratio between them changes gradually. This phenomenon
is possible because of the microscopic structure, which possesses certain gas-like and liquid-like features. Specifically, the
long flexible macromolecules are quite similar to gases and liquids, because they have a substantial internal freedom to
perform random thermal motion, and they interact by means of volume-exclusion intermolecular forces. Thus, the amor-
phous to semi-crystalline solid-solid transition locally at the microstructural level occurs as a transition from gas/liquid to
solid. The thermodynamics of this process is governed by the latent heat of fusion, and the entropic free energy change in
the amorphous fraction. The relation between these two factors indicates whether crystallization is thermodynamically ad-
missible. Accordingly, crystallization can be triggered through influencing this relation either by thermal action (decreasing
the temperature) or by mechanical action (stretching the material). Mechanical deformation is the key to SIC of rubber-like
materials. Regardless, crystallization is a kinetic process, for it is a result of the molecular motion. Under most conditions it
has a non-equilibrium nature and leads to a transient history-dependent material behavior with distinct hysteresis effects.
The process of SIC was first described by Katz (1925). This discovery was followed by a number of experimental ob-
servations of the structure of crystals formed by SIC (Gehman and Field, 1939; 1944; Luch and Yeh, 1973; Mitchell, 1984).
Most experimental studies perform tensile tests on rubber and use a variety of X-ray diffraction methods to quantify the
crystallization (Candau et al., 2014; Toki et al., 2003; Tosaka et al., 2004). In this process, the intensity of the diffracted
light is measured to compute the degree of crystallinity in the rubber and its directional distribution. The results show
that the process of crystallization during uniaxial tension creates a hysteresis in both the stress response and the evolution
of crystallinity (Toki et al., 20 0 0). Moreover, the results demonstrate that at high stretches, the crystalline regions are ori-
ented parallel to the stretching direction. In addition to uniaxial tests, researchers have focused on different aspects of SIC
such as rate dependence, temperature dependence (Candau et al., 2015; Marchal, 2006; Toki et al., 2013), multiaxial loading
(Pannier et al., 2011), crystalline morphology (Andrews, 1964), and the effect of chemical additives (Ren et al., 2015) and
fillers (Fu et al., 2015; Rault et al., 2006b).
Interestingly , this phenomenon has a dramatic effect on fracture properties of rubber (Brüning et al., 2013; Mars and
Fatemi, 2004; Rublon et al., 2013; 2014; Toki, 2014). Rubber materials fracture at very high local deformation levels which
means that SIC precedes and accompanies their failure. In particular, SIC occurs in the process zone in front of the crack tip,
where the loaded material undergoes significant tension in the direction perpendicular to the crack plane. Polymer chains
align correspondingly along this direction, which leads to the formation of oriented crystallites. In-situ X-ray diffraction
measurements fully confirm this picture and reveal a highly crystalline zone surrounding the crack tip with size and mor-
phology controlled by the crack geometry and the loading conditions. This anisotropic semi-crystalline microstructure has
an improved resistance to tearing, hence SIC increases the strength of rubbery polymers. Furthermore, as crystallization is
a time-dependent process, it affects transient aspects of fracture like the crack propagation velocity. Whereas a fast crack
has the chance to pass through the material with no or little crystallization, a slow or static crack will encounter material
reinforced by SIC to the full extent.
While the macroscopic responses of polymers can be evaluated experimentally, a theoretical understanding of the prop-
erties of rubber requires an in-depth study of the microscopic elements of the material and the upscaling of those to the
continuum scale. Early models for polymer elasticity were purely phenomenological. Those models used empirical equa-
tions for the description of strain energy and calibrated their parameters to experimental data in order to simulate various
behaviors of polymers. The subsequent models directly analyzed the polymer chains and their properties using statistical
mechanics leading to the development of the micromechanically-based models. Early examples include the 3-chain model
(James and Guth, 1943; Wang and Guth, 1952), which uses principal stretch values and computes the response of polymer
chains in the three principal directions. While the 3-chain model assumes an affine deformation, the 4-chain model (Flory
and Rehner Jr, 1943; Treloar, 1946) and the subsequent 8-chain model (Arruda and Boyce, 1993; Boyce et al., 1994) introduce
a network model that can simulate non-affine deformations of the material. In this context, an affine deformation is under-
stood as one where the microscopic elements of the network deform with the same deformation mapping that occurs on the
macroscopic scale, whereas a non-affine deformation allows the polymer chains to perform reorientation to redistribute the
stress in a more flexible manner. In other words, the non-affine microscopic deformation seeks to find a lower energy state
than the affine deformation while satisfying the kinematic compatibility conditions. One of the most recognized non-affine
models for polymer networks is the microsphere model (Miehe et al., 2004), which uses the notion of isotropic orientation
of similar chains in a continuous orientation space to impose a constraint onto the polymer network deformation. An al-
ternative constraint, accounting for the network functionality, is proposed in our previous work (Tkachuk and Linder, 2012).
Whereas the former model is expanded to inelastic responses of polymers, including SIC in Mistry and Govindjee (2014),
the latter model so far only accounts for elastic effects, and has so far not been applied to three-dimensional (3D) applica-
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 69

tions. In this study, we propose a SIC model that extends the non-affine elastic formulation of Tkachuk and Linder (2012) to
account for inelastic effects and apply it to 3D problems.
Early theoretical investigations of SIC using statistical mechanics were performed by Flory (1947). He considered the
partially crystalline polymer chains as containing freely rotating segments representing the amorphous part and a com-
pletely rigid portion as the crystalline portion. Using Gaussian statistics and simplifying assumptions, he developed a re-
lationship between temperature, elongation and amount of crystallinity in equilibrium condition, which was verified with
experimental observations (Arlman and Goppel, 1951). Later models extended Flory’s approach to include the effect of folds
in crystallized polymer chains (Gaylord, 1976; Roe et al., 1961) and the effect of the misorientation of the crystals with
respect to the polymer chain (Smith Jr., 1976). The extension of the model to include non-Gaussian statistics is performed
by Smith Jr. et al. (1964). The crystallization process during stretch is not in an equilibrium condition which motivated
the study of the kinematic aspects of SIC (Gent, 1954). Recent SIC models incorporate multiscale computational techniques,
which combine the existing micromechanical elasticity models with the description of crystallization at the polymer chain
scale. These models are able to explain stress hysteresis and the crystallinity evolution. Kroon (2010), who proposed one of
the first fully micromechanical models of SIC, classifies polymer chains based on their state as either fully amorphous or
partially crystalline. Using the thermodynamics of crystal nucleation, Kroon incorporates an Arrhenius-type evolution law for
the change in the ratio of the partially-crystalline chains. The calculations for the chains are done at a large number of dis-
crete orientations and the model is able to capture induced anisotropy during SIC. Mistry and Govindjee (2014) developed a
novel SIC formulation based on the non-affine microsphere approach (Miehe et al., 2004). They provide a constitutive model
for both Gaussian and non-Gaussian statistics and a rate-independent evolution equation to simulate the non-equilibrium
crystallization. Other notable recent contributions in modeling SIC include Guilié et al. (2015) and Dargazany et al. (2014a;
2014b).
To further our understanding of SIC, we have developed a non-affine micro-macro approach to gain a mechanics based
interpretation of the entropic and enthalpic processes of polymer chains within amorphous and crystalline domains during
SIC and have created an efficient finite element based homogenization scheme to investigate its influence at the experi-
mentally measurable macroscopic scale. Some of the important features of the model is the ability to simulate anisotropic
crystallization of the rubber and the newly formulated continuous crystallinity distribution which helps us describe the
crystallinity state of the microstructure with a reduced number of parameters. Furthermore, we will show that the pro-
posed model is thermodynamically consistent on both, the microscopic and the macroscopic scale. The outline of the paper
is as follows. Our micro-macro approach to strain induced crystallization is presented in Section 2. We start with a macro-
scopic description of SIC in Section 2.1, then outline microscopic aspects of our model in Section 2.2, and bridge the scales
for deformation and crystallinity in Sections 2.3 and 2.4, respectively. The resulting multiscale constitutive model can then
be implemented using the numerical algorithms explained in Section 3. Those are used in Section 4 to perform finite ele-
ment simulations. The presented results in Section 4 are compared with existing experimental data for uniaxial and three
dimensional settings. Finally, after the conclusions in Section 5, some of the advanced derivations of the equations used in
this work are explained thoroughly in the appendices.

2. A micro-macro approach to strain induced crystallization

Despite the underlying polymer chain network structure of rubber-like materials, they display an almost homogeneous
mechanical behavior at the continuum scale. Therefore, we will develop a continuum mechanics based formulation for these
materials and will link the microscopic polymer chain deformation and crystallinity to the macroscopic continuum deforma-
tion and a corresponding continuum crystallinity. Using a continuum model will allow us to study larger physical systems at
a lower computational cost compared to molecular dynamics or discrete network simulations. At the same time, the macro-
scopic behavior is linked to the microscopic properties of the individual chains and reflects the transformations that occur
in the micro-structure of the material.
The classification of state variables into macroscopic and microscopic groups as well as their relationships are illustrated
in Fig. 1. The deformation gradient F and the macroscopic crystallinity variables  constitute the macroscopic state variables.
The former represents the amount of strain and rotation in the material and the latter describes the amount of crystallinity
in the material and the orientational distribution of the crystals, from which a conjugate stress tensor P and the evolution
rate of crystallinity 
˙ can be obtained. The details about the macroscopic formulation are expressed in Section 2.1. The state
variables of the micro-scale are λ, the stretch of the polymer chain, and ω, its degree of crystallinity (DOC). In the following
sections the relationship between these variables are obtained. As shown in Fig. 1, our multiscale formulation consists of
three main components. In Section 2.2, a mathematical chain formulation is introduced that explains the influence of λ and
ω on the thermodynamic properties of a chain and the calculation of its internal force f and on ω˙ , the rate of change of the
DOC. Subsequently, a homogenization model for deformation, based on the maximal advance path theory, is introduced in
Section 2.3, connecting the deformation of the continuum material F with its micro-deformation counterpart λ and eventu-
ally obtaining an expression that relates the internal force f of the chains to the macroscopic stress measures P. Finally, in
order to track the anisotropic creation of crystals in the material, the macroscopic crystallinity parameters  is introduced
in Section 2.4 and its connection to the micro-crystallization variable ω is studied, leading to an evolution equation for the
rate of change of the crystallinity internal variables 
˙.
70 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 1. The different elements of the non-affine strain-induced crystallization model and its relationship with micro and macro scales are shown.

2.1. Macroscopic description of strain induced crystallization

Since rubber-like materials are soft and can easily be stretched to several 100% strain, we develop the constitutive model
in a large deformation setting. To do so, we consider the rubber-like body to be a collection of material points. At time
t ∈ R+ , those occupy the spatial configuration S ⊂ Rndim in terms of the space dimension 1 ≤ ndim ≤ 3, where the position
of an individual material point of the body at time t is given as x ∈ S. The changes these material points experience during
the deformation are described relative to a fixed reference configuration B ⊂ Rndim which for instance can represent the
configuration occupied by the body at the instant time t0 in which the material point is located at position X ∈ B. To avoid
any explicit reference to the body itself, the nonlinear deformation map ϕ (X ) : X −→ x = ϕ (X; t ) is introduced which maps
positions X ∈ B onto positions x ∈ S. Key kinematic quantities are the local deformation gradient F = ∇X ϕ (X; t ), represent-
ing the linear map between tangent vectors in the reference and the spatial configuration, as well as the covariant Cartesian
metric tensors G = δAB and g = δab of those configurations written in terms of the Kronecker symbol δ .
Since rubber is assumed to be nearly incompressible, a decoupled volumetric-isochoric formulation based on the decom-
position of F into volumetric Fvol and isochoric F̄ parts is assumed as
F = Fvol F̄ , where Fvol = J 1/3 I and F̄ = J −1/3 F (1)
with J = det F > 0 as the Jacobian, given as the ratio of the current local volume to its initial volume. We use the volumetric-
isochoric formulation of Miehe (1994) and Miehe et al. (2004).
Since the process of SIC is an inelastic mechanism, we introduce a set of internal variables to track the evolution of
crystallinity. This set, called the macro-crystallinity , represents the level of crystallization and the orientation of the crys-
tal. Two different methods for computing its evolution  ˙ will be proposed in Section 2.4. Using the concept of macro-
crystallinity, we define the free energy of the material as
(g, F , ) = U (J ) + (
¯ g, F̄ , ) (2)
by separating the volumetric and isochoric responses of the material, and assuming that the crystallization only affects the
isochoric part of the free energy. With the free energy specified in (2), the Kirchhoff stress tensor is computed as
τ = 2∂g  = pg−1 + τ̄ : P (3)
consisting of an isotropic and a deviatoric part. The former is given in terms of the pressure p = JU (J ) and the spatial metric
tensor g, while the deviatoric part of the expression is represented by τ̄ = 2∂g  ¯ and is given in terms of the projection
tensor Pi j kl = 12 (δ i k δ j l + δ i l δ j k ) − 13 δ i j δkl . The spatial consistent tangent C represents the rate sensitivities of the Kirchhoff
stress tensor τ and the associated Lie derivatives of the spatial metric as £ v τ = C : 12 £ v g, and can be written as
 2
 2 
C = 4∂gg
2
 = ( p + κ )g−1  g−1 − 2 pI + PT : C̄ + (τ̄ : g)I : P − PT : τ̄  g−1 + g−1  τ̄ : P (4)
3 3
where the bulk modulus κ = J 2U (J ) and the isochoric tangent C̄ = 4∂gg
2 ¯ are used. Although the above equations describe
the model in general curvilinear coordinates, only the Cartesian coordinates (gi j = δi j ) will be considered in the subsequent
sections.
In this work, we consider a phenomenological model for the volumetric part as
1
U (J ) = B ( J − 1 )2 (5)
2
where B is chosen to be several orders of magnitude larger than the shear modulus of the nearly incompressible material.
The isochoric response of rubber is related to the underlying structure of the material. The micromechanically motivated
derivation of the mechanical response is a key contribution of this work. The full expression for this free energy is explained
in Section 2.3.
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 71

Fig. 2. The physical parameters of a (a) fully-amorphous and of a (b) semi-crystalline polymer chain.

2.2. Microscopic description of strain induced crystallization

Polymer chains are considered as axial elements, meaning that their state can be determined primarily by their end-to-
end distance. As mentioned above, a partially crystallized chain is described by its stretch λ and its degree of crystallinity
ω. Stretch is the kinematic variable of the chain, whereas the degree of crystallinity will be used as the internal variable of
the chain controlling the transformation of the chain from its amorphous to crystalline state.
Most of the mechanical properties of rubber originates from the oscillation of molecules inside the long polymer chains
between the crosslinks. To study the statistical mechanics properties of these chains it is useful to assume that a polymer
chain consists of a series of rigid segments connected with freely rotating joints (Treloar, 2005). The number of these seg-
ments between two crosslink points and the length of each segment are denoted by N and l, respectively. Due to thermal
fluctuations, all
√ polymer chains are coiled in a random configuration and their end-to-end distance has the root-mean-square
value of r0 = Nl. Using this definition, the stretch of a chain λ = r/r0 represents the ratio between the current end-to-end
length of the chain and its original average value. These microscopic variables for a typical non-crystallized chain are shown
in Fig. 2(a).
The thermal oscillation of the molecules in the polymer chain pulls the endpoints of the chains towards each other. The
non-Gaussian theory (James and Guth, 1943; Kuhn and Grün, 1942) for a flexible fully-amorphous, i.e. ω = 0, chain states
that the averaged force required to keep a chain at a certain end-to-end length is equal to
 
 kB T 
F = β (6)
ω=0 l ω=0


where β  is the Langevin parameter corresponding to the stretch of the material, i.e.
ω=0
   
    r λ
 = L (β  ) = coth β  − β −1  = = √ . (7)
ω=0 ω=0 ω=0 ω=0 L N
In the above equation L(· ) is the Langevin function and L = Nl is the total contour length of the chain, which determines
its maximum possible elongation. Therefore, the ratio = r/L is the current end-to-end length of the chain divided by its
maximum value. The non-linear effect of limited extensibility can be seen in the non-Gaussian chain theory. If the length of
the chain gets close to the maximum length, i.e. r → L, then the relative stretch approaches 1, and based on (6) and (7),
the force resisted by the chain increases unboundedly as F → ∞.
Based on these well known results, we now propose a statistical representation of a partially crystalline polymer chain.
After stretching the rubber, some of the chains may form small crystals together with other surrounding chains. In a partially
crystalline chain, we therefore assume that a part of the chain belongs to a crystal and therefore does not fluctuate due to
temperature. Then, the degree of crystallinity of the polymer chain ω = Nc /N = Lc /L will be defined as the ratio of the
number of crystallized segments Nc to the total chain segments N of the material and Lc = Nc l represents the length of
this crystallized section. This definition of ω based on the length of the crystalline region is similar to the definitions of
Flory (1947), Mistry and Govindjee (2014), and Guilié et al. (2015). The DOC belongs to the unit interval [0, 1]. It is initially
zero but increases as the material crystallizes. The value of ω is directly related to the crystallinity internal variables 
based on the distribution function ω = ω (, λ0 ), explained in Section 2.4. In line with Flory (1947) or Kroon (2010), we
proceed by assuming that the existence of a crystalline phase competes with the existence of the amorphous phase and
thereby changes the overall thermodynamic condition of the chain. We define the effective end-to-end length ra and the
total length La of the amorphous portion of the chain as ra = (r − Lc )/2 and La = (L − Lc )/2, respectively, also illustrated in
Fig. 2(b). Using these definitions we can find an expression for the force similar to (6) and (7) as

kB T β ra r − Lc λ/ N − ω
F= with = L(β ) = coth β − β −1
= = = . (8)
l La L − Lc 1−ω
It is observed that is a decreasing function of ω and crystallization relaxes the amorphous parts of the polymer chain, as
validated by the experiments of Marchal (2006). Note that in Fig. 2(b) the amorphous sections on the right and left of the
crystalline region do not necessarily have to have the same length. In fact, (8) holds as long as we assume the ratio ra /La
72 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

is equal on both sides. One of the main assumptions in this chain formulation is that the crystalline segment lies in the
line connecting the ends of the chain. Although many models (Flory, 1947; Kroon, 2010) make similar assumptions, more
complicated representations can be obtained for a general location and orientation of the crystalline region (Smith Jr., 1976;
Mistry and Govindjee, 2014).
Since the amount of force is the first derivative of the free energy, i.e. F = ∂ ψ /∂ r, we obtain the free energy of the chain
ψ by integrating (8) as
 r
ψ (λ, ω ) = ψa (λ, ω ) + ψc (ω ) = F dr + ψc ( ω ). (9)
0
The first term is the amorphous energy of the partially-crystalline chain, which is computed by integrating the force with
respect to the length of the chain. The sign distinguishes the integration variable with the upper bound of the definite
integral. The constant of this integration ψ c (ω) is called the crystalline free energy. This free energy is independent of the
entropy of the system and depends only on the DOC of the chain. It is assumed to take the form
 ω ω
ψc ( ω ) = c ω − ξ + ln(1 − ) . (10)
ωmax ωmax
This expression consists of a linear term, similar to Flory (1947), Smith Jr. (1976), or Mistry and Govindjee (2014), related to
the change of enthalpy during crystallization and a penalty term, which prevents crystallinity from growing unboundedly.
The linear term cω represents the energy of fusion and the interface energy of the crystalline phase. If all the chains were
completely parallel, they could crystallize up to ω = 1. However, in reality, entanglements and the effects from other chains
in other orientations prohibit any single chain to crystallize more than a specific maximum value ωmax < 1 called the satura-
tion crystallinity. This effect from the surrounding chains is incorporated using a differentiable logarithmic penalty function
in the crystalline free energy expression (10). The use of a barrier function and the saturation DOC can also be seen in the
model of Guilié et al. (2015). The penalty parameter ξ controls how strong the higher values of ω are penalized. At ω = 0,
the penalty term equals zero with a zero derivative.
Substituting (8) and (10) into (9), we obtain the full form of the free energy as a function of the micro-mechanical
variables, λ and ω, as

 ω
β ω
ψ (λ, ω ) = kB T N (1 − ω ) β + ln +cω−ξ + ln(1 − ) . (11)
sinh β ωmax ωmax
This expression is plotted for various levels of crystallization in Fig. 3(a). When the chain is not stretched (λ is small),
the energy is minimized for ω = 0. However, when the chain is stretched (λ > 2), the free energy of the chains with zero
crystallinity exceed that of a partially crystallized chain, making crystallization favorable. The conjugate thermodynamic
variable with respect to the chain stretch is the normalized force
∂ψ √ √
f = = l N F = kB T N β (12)
∂λ
which is later used to calculate the stress tensor at the macroscopic scale. The force response of the chain is linear at small
stretches, as seen in Fig. 3(b). Nonetheless, due to limited extensibility of the chain, the force quickly increases for higher
stretches. Note that crystallization allows the chain to achieve higher length at any constant level of force. Therefore, the
partially crystallized chains show lower amount of force for an equal amount of elongation. In addition to this quantity, we
can define the driving force of crystallization as


∂ψ β ξω
fw = − = kB T N β + ln −c− (13)
∂ω sinh β ωmax (ωmax − ω )
describing the tendency of the material to crystallize. Hence, it is directly used to calculate the rate of crystallization of the
polymer chain. For each stretch λ, there is an equilibrium degree of crystallinity ωeq , shown in Fig. 3(c), which corresponds
to fw = 0. When the chain is at its equilibrium crystallinity, it does not have any tendency to crystallize or lose crystallinity.
Although various evolution laws, such as the Arrhenius equation used by Kroon (2010), the plasticity-like rate-independent
evolution equation of Mistry and Govindjee (2014), and the method similar to viscoplasticity proposed by Guilié et al. (2015),
can be used for this chain model, here we choose a linear relationship between the crystallization force and the rate of
crystallization as
ω˙ = q fw . (14)
This simplified evolution law allows us to capture rate-dependence of SIC but we note that for high-strain rates more ad-
vanced formulations containing both, rate dependent and rate-independent components, are needed. This expression for
the crystallization rate is demonstrated in Fig. 3(d). If the chain is not crystallized and the stretch is more than a certain
threshold, the chain will start to crystallize (ω˙ > 0). Conversely, for a chain already in the crystallized state, if the elonga-
tion λ is reduced, the rate of crystallization becomes negative and the chain begins to melt. Note that the crystallinity rate,
by construction, always has the same sign as the crystallization driving force, ensuring consistency with the second law of
thermodynamics, as it can be seen in the expression for the polymer chain dissipation
Dchain = f λ˙ − ψ˙ = fω ω˙ ≥ 0 . (15)
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 73

Fig. 3. The constitutive response of a polymer chain as a function of elongation λ and DOC ω based on the proposed model is shown in the form of (a) the
free energy of the chain, (b) the thermodynamic force of the chain (c), the equilibrium crystallinity ratio for each stretch value, and (d) the crystallization
rate of the chain.

In order to simplify the computation of chain quantities, the parameters and thermodynamic variable of chains are normal-
ized by the number of chains per volume n. The normalized quantities are shown using a bar on top of the symbol. We
define

ψ̄ = nψ , f¯ = n f , f¯w = n fw (16)
as the normalized thermodynamic variables. Additionally, the nomalized material parameters
1
μ = nkB T , c̄ = nc, ξ¯ = nξ , q̄ = q (17)
n
are used, where μ is the shear modulus of the polymer. The plots (a) and (b) in Fig. 3 make use of these normalized
variables along the vertical axis.
Alternative representations of partially crystalline polymer chains with amorphous and crystalline domains have been
recently proposed (Kroon, 2010; Mistry and Govindjee, 2014; Guilié et al., 2015), all of which are not fully compatible for
our bridging concept of micro- and macroscopic deformation outlined next in Section 2.3. The reason is that our framework
requires the computation of stretch λ as a function of the variable pair (f, ω) which is the inverse of the force-stretch
function (12). The force response in existing models cannot be inverted efficiently and accurately, whereas the proposed
chain model can use the Langevin function to obtain λ from f and ω in closed form.

2.3. Bridging of micro- and macroscopic deformation

As mentioned earlier, the isotropic response of the presented model is derived directly from the micro-structure of rub-
ber. This material consists of long crosslinked polymer chains that can resist deformation using their one-dimensional tensile
74 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 4. The difference between the macroscopic deformation ϕ(X) and the corresponding microscopic mapping λ(λ0 ) results in a non-affine deformation
of the rubber-like material undergoing strain induced crystallization. The physical reference and current configurations are shown in the top row with
corresponding boundary conditions in the displacements on ∂X B and tractions on ∂t B and loading t̄ and zooms into the material points in the reference
configuration (no crystallization) and current configuration (crystallization). The bottom row shows the orientation spaces corresponding to the physical
configurations and the microscopic mapping relating the stretch vectors λ0 and λ.

stiffness. Since tracking the response of every polymer chain in a three dimensional random network is not computation-
ally feasible, the quantities of the network are homogenized by making simplifying assumptions. Polymer chains generally
have different orientations and end-to-end lengths both in the undeformed and the deformed configuration. By assuming
identical length, stiffness and other properties for all the chains in the network, the orientation of the chains in the refer-
ence configuration becomes the main parameter that distinguishes different chains from each other. If we denote r0 as the
undeformed end-to-end vector of the chains, the reference orientation vector λ0 = r0 /|r0 | describes the orientation of the
chains in the reference configuration. All chains with the same reference orientation are assumed to have identical defor-
mation and thermodynamic variables including internal force, degree of crystallinity, and free energy. These assumptions,
visualized in Fig. 4, are similar to those presented by Wu and Van Der Giessen (1993), Miehe et al. (2004), Kroon (2010),
and Tkachuk and Linder (2012). Because rubber behaves isotropically in the undeformed state, it is reasonable to assume
that the polymer chains exist in all undeformed orientations with equal probability. This allows us to study the response of
the random network statistically by assigning each polymer chain orientation to a point on a surface of a unit sphere called
the orientation space (see Fig. 4). Therefore, using the area of the unit sphere S0 , the uniform probability distribution P (λ0 )
of the chain orientation has the form

1 1
P ( λ0 ) = = , P (λ0 )|dλ0 | = 1. (18)
|S0 | 4π S0

Once external deformation is applied to the material, the chains are stretched and rotated in order to provide compatibility
between the micro and the macro scales. The deformation state of the chain is shown by the end-to-end vector r in the
current configuration and the stretch vector λ = r/|r0 |. The chains do not experience equal amounts of stretch, so the end-
to-end vectors of the chains form an ellipsoid in the deformed state. The isochoric free energy of the deformed network,
introduced in Section 2.1, can be written as
     
¯ g, F̄ , ) = n ψ (λ, ω ) = ψ̄ (λ, ω ) = 1
( P (λ0 )ψ̄ λ(λ0 ), ω (λ0 ) |dλ0 | = ψ̄ λ(λ0 ), ω (λ0 ) |dλ0 |. (19)
S0 |S0 | S0
This energy is computed by taking the average, given by the average operator ·, of free energies ψ of all the polymer
chains in the vicinity of a material point. Since 
¯ is expressed as energy per unit volume of rubber, the number of chains
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 75

per volume n is used in (19). As described in more detail in Section 2.2, a partially crystallized chain is described on the
micro-scale by λ, its stretch, and by ω, signifying its degree of crystallinity. It is assumed that crosslinking points in the
polymer do not undergo any thermal motion, therefore the total free energy only depends on the thermodynamics of the
chains between the crosslink points.
The numerical method for integrating a symmetric function over the unit sphere, described by Bažant and Oh (1986), is
incorporated to compute the average of various quantities over the orientation space. The number of quadrature orientations
nint affects the accuracy of the results as well as the computation cost of the algorithm. Although Bažant and Oh (1986) use
21 × 2 and 37 × 2 integration schemes for describing small deformations, Verron (2015) showed that more than 300 quadra-
ture points are needed to obtain less then 5% error in computing the various invariants during large deformations. Using
this numerical integration scheme, we can approximate (19) as

nint

nint
(
¯ g, F̄ , ) = ψ̄l Wl = ψ̄ (λl , ωl )Wl (20)
l=1 l=1

where Wl is the weight coefficient for the lth integration orientation (λ0 )l , and λl represents the stretch value corresponding
to chains that are oriented along (λ0 )l in the reference configuration.
While the continuum deformation describes the mapping ϕ between the reference material vector dX and the deformed
material vector dx, the deformation of the micro-structure is defined here as the mapping between the uniformly distributed
reference chain vector λ0 and the deformed chain vector λ. The affine full-network model (Wu and Van Der Giessen, 1993),
used for SIC by Guilié et al. (2015), assumes the linear mapping λ = ϕ (λ0 ) = F̄ λ0 . However, this assumption is not always
applicable (Boyce and Arruda, 20 0 0) and hence we incorporate a non-affine model. In order to obtain the non-affine de-
formation of the chains, we find the microscopic mapping ϕ that minimizes the free energy of the network described in
(19). This method is denoted as the principle of minimum average free energy for random networks (Miehe et al., 2004).
In addition to this minimization principle, the microscopic deformation must be kinematically compatible with the external
large scale deformation. Thus, here we use the kinematic constraint equations known as the maximal advance path con-
straint (MAPC) proposed by Tkachuk and Linder (2012). This constraint depends on the functionality, the number of chains
connected to each crosslinking point, of the network. For networks with the functionality of four, which is a reasonable
assumption for any crosslinked polymer network, the tensorial micro-macro compatibility equation takes the form

1 1
λ  λ0  = λ(λ0 )  λ0 |dλ0 | = F̄ (21)
|S0 | S0 3
and leads to the constrained optimization problem

1
Minimize ψ̄  Subject to λ  λ0  = F̄ . (22)
λ 3

The deformed stretch vector λ is the main optimization variable and the crystallization of the chains is also dependent on
this variable. This optimization expression for the free energy allows us to obtain the deviatoric stress tensor

∂ ¯
P̄ = = f¯  λ0  (23)
∂ F̄
as function of the internal forces arising in the polymer chains. The normalized force vector of a chain f¯ is the vector
parallel to λ with the magnitude of f¯. The algorithm for solving this optimization problem and obtaining the stress tensor
and material tangent is explained thoroughly in Section 3.

2.4. Bridging of micro- and macroscopic crystallinity

Although the degree of crystallinity of individual polymer chains ω is a key quantity for studying SIC, it cannot be directly
measured experimentally because of the incredibly small size of polymer chains. However, many experimental procedures
such as X-ray diffraction provide information about the size and orientation of the crystals. We refer to these experimentally
measurable quantities as macroscopic crystallinity variables, one of which is the crystallinity ratio ω̄ of the material. This
quantity represents the mass or volume ratio of the crystallized regions to the total mass of the material and it is obtained
experimentally by measuring the intensity of the X-ray diffraction at various angles and performing a numerical integration
similar to the methods shown by Toki et al. (2003). In our micromechanical constitutive model, we consider the crystallinity
ratio ω̄ to be proportional to the average degree of crystallinity ω of the chains

nint
ω̄ = α ω = α ωl Wl (24)
l=1

by introducing the proportionality factor α and incorporating the integration weights Wl . The SIC model of Mistry and
Govindjee (2014) considers α = 1 and Kroon (2010) uses α = Nc /N because of the unique way of defining ω. Guilié
et al. (2015) also employ a non-unit proportionality coefficient α = 1 in computing ω̄. Here, α is calibrated as a material
76 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

parameter. Its value is on the order of 1 but may generally deviate from it due to possibly inconsistent assumptions be-
tween experimental measurements and theoretical assumptions.
Next, we will discuss two separate approaches for tracking the crystallinity ω of the chains in the orientation space.
Commonly (Guilié et al., 2015; Kroon, 2010), the crystallinity values are evaluated at discrete orientations over the orien-
tation space resulting in a discrete crystallinity distribution. Alternatively, we propose in this work a continuous distribution
function for ω, resulting in a memory efficient continuous crystallinity distribution.

2.4.1. Discrete crystallinity distribution


Experiments (Toki et al., 2003; Tosaka et al., 2004) show that crystallization mostly occurs in chains which are parallel to
the stretching direction, resulting in an anisotropic crystallization. Rubber is originally isotropic, but the formation of crystals
causes it to behave anisotropically. Nevertheless, it becomes isotropic once the crystals melt during unloading. Using the
MAPC approach in our model results in an anisotropic distribution of λ and subsequently an anisotropic distribution of ω in
the polymer chains. This ability to represent anisotropic crystallization should be contrasted with the non-affine microsphere
approach (Miehe et al., 2004) in which the amount of stretch for all the chains are uniform in the orientation space.
In order to keep track of the state of crystallinity, we can store the DOCs only for the chains that are oriented along the
quadrature orientations. This method, which is used by Kroon (2010) and Guilié et al. (2015), represents the orientational
distribution of DOC by specifying it at a number of representative orientations. In other words, the macro-crystallinity pa-
rameter introduced in (2), which represents the current state of crystallization in the material, is defined as
T
 = ω1 ω2 . . . ωnint (25)

a column vector containing the DOCs of the chains oriented along the integration directions. Hence, the distribution function
for the discrete formulation

ωl λ0 = (λ0 )l for l = 1, . . . , nint
ω (, λ0 ) = (26)
undefined otherwise

is only defined for the integration directions. This definition is sufficient for calculating the mechanical and crystallinity
response of the material using numerical integration methods. Thus, the number of internal variables is the same as the
number of integration orientations. The memory required for the history variables can be very large if we choose to increase
the accuracy of the integration over the sphere. For example using 770 quadrature orientations as in Guilié et al. (2015),
more than 4.5 GB of the program memory is required in order to store the history variables for a 3D simulation with 105
elements.
Although in our approach the stretches of the chains are not independent of each other due to the MAPC formulation,
the evolution of crystallinity is calculated independently using the rate of crystallization of individual chains as seen in (14).
We use an implicit time integration for the evolution of each chain as

ωl (tn+1 ) = max {ωl (tn ) + t ω˙ l (tn+1 ), 0} for l = 1, . . . , nint . (27)

Since the crystallization rates can be negative for small stretches, we enforce the constraint ω (tn+1 ) ≥ 0 using the max { · }
function while solving (27). During each iteration of our MAPC algorithm, the chain force of the current step f (tn+1 ) and
the DOC of the previous step ω(tn ) are used to compute the new stretch λ(tn+1 ) and DOC ω (tn+1 ). If the value of the chain
quantities such as λ or ω are needed for chains that are not parallel to any integration orientation, these quantities can be
interpolated to obtain a continuous distribution over the orientation space for postprocessing purposes.
Since the evolution of chains are independent, we can observe the change in DOC of a single chain as it undergoes axial
loading and unloading, allowing us to understand the microscopic chain formulation of SIC. The force-elongation relation-
ship for our proposed chain is plotted in Fig. 5(a). The dotted line represents the non-crystallized ω = 0 response of the
chain similar to the solid curve of Fig. 3(b). The solid curves in Fig. 5(a) correspond to two simulations for different stretch
rates λ˙ . Initially, the curve matches the non-crystallization result. However, it softens around λ = 1.7 when the chain starts
to crystallize. This crystallization is visualized in Fig. 5(b), showing that lower stretch rates lead to higher levels of crystal-
lization. Since crystallization has a softening effect on the material, the lower stretch rate simulation has a lower level of
internal force in the chain. When the strain rate approaches zero, i.e. λ˙ → 0, the chain follows the equilibrium crystallinity
path (dashed line) in both force and crystallinity response. The equilibrium crystallinity corresponds to the value of ω that
minimizes the free energy of the chain for a given value of λ, resulting in f w = 0 and ω˙ = 0. It can be seen in Fig. 5(b)
that when the amount of crystallinity is less than the equilibrium value, ω increases. Conversely, when DOC of the chain is
higher than equilibrium, the crystals melt and ω decreases. The unloading curve for ω is maximized at its intersection with
the equilibrium crystallinity curve.
The material parameters for our chain model are μ = 0.37 MPa, N = 18.5, α = 0.37, c̄ = 6.9 MPa, ξ¯ = 1.0 MPa, ωmax =
0.78, q̄ = 0.018 MPa−1 min−1 . These parameters and the parameters used to calculate the response of other chain models
are obtained by calibrating each model with experimental data from Toki et al. (2003) for sulfur-cured natural rubber (see
Section 4.1). For comparison, the similar graphs are plotted for other notable SIC chain models including those by Mistry and
Govindjee (2014) and Kroon (2010) in Fig. 5(c–d) and (e–f), respectively.
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 77

Fig. 5. Independent evolution of crystallinity in an individual chain for various chain models and strain rates. Left figures (a,c,e) show the force-elongation
response while the right figures (b,d,f) represent the evolution of crystallinity. The current model is presented in (a,b), while the chain model by Mistry and
Govindjee (2014) and the one by Kroon (2010) are shown in (c,d) and (e,f), respectively.

Remark 1. The model proposed by Mistry and Govindjee  (2014)  uses the non-affine microsphere formulation by
Miehe et al. (2004) to calculate the microscopic stretches λ = F̄ λ0 P from the deformation gradient, where P is the aver-
aging exponent. The stretch values of the chains computed with this method are uniform across all orientations. As a result,
the chain force and the chain DOC is also identical for all chains. Although this representation does not take into account
anisotropic crystallization in rubber, it is computationally very efficient both in terms of memory and cpu time because only
a single history variable is needed to store ω and the computations for the chains are performed only for one set of input
78 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

parameters. In addition to a Gaussian formulation, the model by Mistry and Govindjee (2014) also provides expressions for
the non-Gaussian theory. Focusing on the Gaussian model in this comparison, the resulting linear force response of the
chains can be expressed as
3μ  √ 
f¯ = λ − Nω . (28)
1−ω
The evolution law of Mistry and Govindjee (2014) is a rate-independent formulation similar to plasticity using the yield
function
 
 √ √ √ 
 ∂ ¯  ∂ ¯ T 3μ 1 2 N (λ − ω N ) ( λ − ω N )2

g=  − (gc + γ ω ) ≤ 0 with = −μd N 1 − 0 − + −
∂ω  ∂ω Tm 2 1−ω 1−ω ( 1 − ω )2
(29)
where μd is the heat of fusion and T and Tm0 )
are the current temperature and the crystallization temperature of the rubber.
It can be noted that the term −μd N (1 − T /Tm0 ) is equivalent to c̄ in our proposed model. Since this chain model is rate-
independent, changing the stretch rate does not change the loading and unloading curve in both plots. The topological
tube constraint arising from restricted chain movements due to surrounding chains is also considered in the free energy
expression of this model. However, this effect is not visible in Fig. 5(c) because the tube constraint free energy is not a direct
function of λ. Ignoring the tube constraint, Fig. 5 shows that the force response of the flexible chain starts to decrease after
the crystallization starts for the given set of material parameters. We note that since the MAPC model requires a one-to-
one non-decreasing force-elongation response of the chains, this chain model is not compatible with the SIC chain model of
Mistry and Govindjee (2014). The parameters used to create the plots shown in Fig. 5(c–d) are those calibrated by Mistry and
Govindjee (2014) for sulfur-cured natural rubber, i.e. μ = 0.62023 MPa, N = 195.15, μd = 0.110 MPa, gc = 18, γ = −65.

Remark 2. In the polymer chain formulation proposed by Kroon (2010), the main crystallinity variable ω represents the
ratio of partially-crystallized chains to the total number of chains for a particular orientation. The free energy expression
provided in the model includes a number of terms such as the viscous response of chains, a topological constraint, and a
non-affine penalty term. However, for comparing the chain formulation with our model, Fig. 5(e–f) only show the flexible
chain response of the material. The normalized chain force is computed as


∂ ψ̄ √ √ ∂λ √  
f¯ = = μ ( 1 − ω ) N β + 2ω N β
= μ N (1 − ω )β + ωβ (30)
∂λ ∂λ
√ √
where N = (N − Nc )/2 and λ = (λ N − Nc )/(2 N ) are the number of √ segments and the stretch of the amorphous portion
of a partially-crystalline chain, respectively. Additionally, β = L−1 (λ / N ) is the Langevin parameter for the stretch of the
amorphous segments. This force response is coupled with the crystallinity evolution equation


λ β
ω˙ = H (λ )gc (1 − ω ) exp(η ) − ga ω exp(−η ) where η = Nn Nc √ β + ln (31)
N sinh β
to obtain the behavior of the chain during loading and unloading. The parameter gc is the rate at which the chains crystallize
and ga is the rate at which the crystals melt into the amorphous phase. This evolution law includes the Heaviside function
H(λ ) that ensures the chains have been stretched enough. Note that in this chain model all the partially-crystalline chains
have√ the same constant number of crystallized segments. Therefore, Nc is constant and the chains stretched less than λmin =
Nc / N are physically impossible to crystallize. This condition is enforced using the Heaviside function, creating noticeable
sharp kinks in plots for both the chain force and the chain DOC. It can also be visualized by a large jump in the value of the
equilibrium crystallinity. This non-smoothness in the response makes it difficult to combine this chain model with the MAPC
homogenization method. One challenge is the convergence of the model after the first chain starts to crystallize. In addition,
the sudden changes in f¯ and ω lead to distinctive kinks in the homogenized macroscopic response of rubber if a small
number of integration directions are used. It can be noted that the hysteresis in the force response is rather small within
Kroon’s model so that an additional viscoelastic response should be added to it to produce the amount of hysteresis seen
in experimental data. The parameters used to create the plots in Fig. 5(e–f) are μ = 0.6 MPa, N = 22.4, Nc = 11.0, Nn = 0.1,
gc = 0.051min−1 , ga = 0.48 min−1 , which are identical to the calibrated results in Kroon (2010).

2.4.2. Continuous crystallinity distribution


Due to the large memory requirement when using a discrete representation of crystallinity, a continuous representation
is proposed in this work. The DOC of a chain is calculated using the crystallinity distribution function ω(, λ0 ) which
depends on a small number of crystallinity parameters  and on the reference orientation of the chain. This distribution
function must be continuous and even-symmetric (ω (, −λ0 ) = ω (, λ0 )) over the unit sphere. Since crystals created by
SIC are oriented mostly along a preferred direction, the function must be axisymmetric. The chains closer to the axis of
rotation possess the highest amount of crystallinity, whereas the chains perpendicular to that axis will not crystallize. The
axis of symmetry is close to the maximum principal stretch direction, but it can be different if non-proportional loading is
applied.
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 79

Fig. 6. Left: Orientation of the crystal and its angle θ with respect to the chains in the reference configuration. Right: The distribution of crystallinity as a
function of the angle θ between the chain and the crystal orientation is shown. The influence of the parameters a and b on this distribution can be seen,
where a1 > a2 and b1 > b2 .

Various expressions satisfy these requirements for the crystallinity distribution function. In particular, the function

ω = ω (, λ0 ) = a exp(−b(ln cos θ )2 ) (32)


is used to perform our numerical simulations in Section 4. The crystallinity internal variables
T
= φ1 φ2 a b (33)
include the spherical orientation of the crystal (φ 1 , φ 2 ), the intensity of crystallization a, and the spread (width) of crys-
tallinity b. The plot of this distribution as well as the effects of a and b can be seen in Fig. 6. The angle θ between the
crystal orientation and the reference orientation of the chain λ0 , which is shown on the left of Fig. 6, directly determines
the amount of crystallinity in a chain. Note that regardless of the number of quadrature directions, we only need to track
four internal variables in our constitutive model, resulting in a more memory-efficient method. The calculation of the chain
formulation is still performed at every integration orientation, but ω is not stored for every chain. Instead, the crystallinity
internal variables store the distribution information at every time step. The integration orientations are used to calculate
the micromechanical and the evolution of crystallinity, but they are not used to store crystallinity values. The accuracy of
the simulation can be improved by using adaptive quadrature rules, which is only possible if we incorporate the continuous
distribution of crystallinity. In contrast, attempting to use an adaptive quadrature with discrete representation of crystallinity
leads to interpolation challenges and possible inaccuracies. Using the rate of crystallization of the chains, obtained from the
chain formulation, we compute the evolution of the macroscopic crystallinity parameter by performing a homogenization
algorithm. The rate computed from (14) describes the true rate ω˙ of crystallization of the chain. On the other hand, if we
take the time derivative of (32) as
 T  
∂ ∂ω (, λ0 ) ∂
ω˜˙ = ω (, λ0 ) = (34)
∂t ∂ ∂t
we obtain the so called apparent rate ω
˜˙ of crystallization in the chain. The value of ∂ /∂ t in (34) is the only unknown value
which can be computed by equating the true rate and the apparent rate for all the chains. These rates cannot be exactly
equal but we can minimize the square of the difference between them, leading to a least square optimization problem
  T  
∂ 1 1 ∂  ∂ 
= arg min (ω˙ − ω˜˙ )  + γ
2
. (35)
∂t ∂ / ∂ t 2 2 ∂t ∂t

The objective function of the minimization computes the differences of the apparent rate and the actual crystallization
rate of the chains. Additionally, it contains a regularization term which ensures that the system has a minimum required
convexity to achieve reliable numerical results. The value of the regularization constant is chosen as a small positive number.
80 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 7. The evolution of crystallinity is shown as a function of the angle θ between each chain and the crystallinity direction and the difference between
the actual rate and the apparent rate of crystallization is presented.

The solution of this least square problem can be easily obtained as


    T
∂ ∂ω ∂ω ∂ω
˙ = = A−1 ω˙  where A =  + γ I4 (36)
∂t ∂ ∂ ∂
since the apparent rate is a linear function of the unknown. Here, the matrix I4 represents the 4 × 4 identity matrix. Com-
puting the local dissipation during isochoric deformation in the material, we get
  T   T    
¯˙ = P̄ : F̄˙ − ∂ ¯ ∂ 
¯ ∂ ¯ ∂ ψ̄ ∂ω T −1 ∂ω
Disochoric = P̄ : F̄˙ −  : F̄˙ + ˙ = − ˙ = −  A ω˙  (37)
∂ F̄ ∂ ∂ ∂ω ∂  ∂
  T     

nint
∂ω
nint
∂ω
= ( f¯w )l Wl A −1
Wm ω˙ m (38)
l=1
∂ l m=1
∂ m

resulting in Disochoric ≥ 0 assuming the evolution relationship of the chains is linear as shown in (14) and q̄ ≥ 0. This in-
equality is proved using the symmetry of (38) and the positive definiteness of A. Therefore, the macroscopic crystallinity
evolution model is consistent with the second law of thermodynamics.
The process of evolution of  is best explained by illustrating the distribution of crystallinity at various stages of loading
and unloading as shown in Fig. 7. The solid curve and the dashed curve represent the continuous distribution of ω in the
reference configuration at the current time step tn and the next time step tn+1 , respectively. The height of the vertical lines,
corresponding to the true rate of crystallization at the integration points, is equal to ω˙ t where ω˙ is computed using (14).
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 81

Although often a small time step t is chosen for obtaining accurate results, a rather large time step is used for creating
Fig. 7 to show an exaggerated, recognizable change in ω between tn and tn+1 . As seen in Fig. 7, we are only able to compute
the value of the true rate of crystallinity at the discrete set of integration points. On the other hand, the difference between
the solid line and the dashed line ω ˜˙ t is proportional to the apparent rate, which is computed as a continuous function of
θ based on (34). The value of ˙ is chosen to make the true rate and the apparent rate as close as possible using the least
squares method of (35). At the start of loading, see Fig. 7(a), only a small number of chains that are close to the stretch
direction crystallize and consequently, the value of crystallinity becomes non-zero by increasing the parameter a. At later
stages of loading, see Fig. 7(b), crystallinity continues to increase and more chains contribute to crystallization. This time in
addition to an increase in a the value of b decreases to widen the distribution function. When the unloading stage starts,
see Fig. 7(c), the chains close to the stretch direction face a decrease in the stretch while their ω is very high, therefore
they face a reduction in crystallinity ω˙ < 0. However, some of the chains in other orientations have not crystallized to their
equilibrium crystallinity value and they continue to crystallize. Therefore, using the averaging algorithm, the height of the
distribution function a remains constant, while the width of the distribution function increases by decreasing b. Finally, the
unloading continues, see Fig. 7(d), and all of the chains decrease their ω, resulting in a decrease in a. Note that the rotation
of the crystals, not considered in this figure but responsible for the change in φ 1 and φ 2 , is studied in Section 4.3.

3. Numerical algorithm

In order to create a numerical implementation based on the theory presented in Section 2, the MAPC equations describ-
ing the micro-structure and the equations representing the evolution of crystallinity must be solved. These expressions are
highly non-linear and we have to solve them numerically using the Newton–Raphson scheme. Although it is possible to
solve both of these equations simultaneously, we chose to solve them in a nested configuration in order to ensure numeri-
cal stability. During each iteration of the Newton loop for the MAPC process, the evolution equations are solved iteratively,
generally converging in less than 5 iterations. After updating the micro-structure and moving to the next iteration of MAPC,
the rate of crystallization is modified and the evolution equation must be solved again. The process of crystallinity evolution
differs for discrete and continuous representations of crystallinity. The algorithm for independent crystallization of chains
is discussed in Section 3.1 for the case of discrete crystallinity distribution. Additionally, the process of updating the crys-
tallinity internal variables for the continuous distribution of crystallinity is explained in Section 3.2. Using the results of the
MAPC algorithm we can compute the spatial stress tensor and consistent tangent (explained in Section 3.3).

3.1. Algorithm for obtaining a discrete distribution of crystallinity

As mentioned in Section 2.3, in order to obtain the microscopic deformation of the network, we need to minimize (19) by
imposing the constraint (21). Solving the equality constrained minimization is equivalent to finding the stationary point of
the Lagrangian form of the problem, written as
 1

L[λ, ν] = ψ̄ (λ, ω ) − ν : λ  λ0  − F̄ . (39)
3
Once solved, the Lagrange multiplier ν is shown (see Appendix C or Tkachuk and Linder (2012)) to be proportional to the
isochoric first Piola–Kirchhoff stress tensor
1
P̄ = ν. (40)
3
Furthermore, the normalized force vector f¯ of any chain can be computed based on
f¯ = n f = 3P̄ λ0 (41)
as a function of P̄ . Consequently, the stretch vector, which directly depends on the force vector, can be represented as a
function of P̄ . Using this dependency, we can write the MAPC constraint as a residual
1
Rλ (P̄ ) = F̄ − λ(P̄ )  λ0  (42)
3
only dependent on the stress tensor. Setting Rλ = 0, we can solve this non-linear tensorial equation to obtain the stress
tensor P̄ .
The computer algorithm solves (42) using the Newton–Raphson method. At the beginning of the first iteration, an initial
value is assigned to P̄ . This initial tensor can be the stored value from the previous time step, or the linear small-strain
approximation P̄ ≈ μF̄ . Using the initialized stress tensor, we find the set of force vectors along the quadrature orientations
using (41). The orientation of the force vector defines the orientation of λ and the force magnitude is used in the chain
formulation (12) to compute λ. The set of stretch vectors are then combined to form the residual (42). Unless the residual is
close to zero, the stress tensor P̄ is updated using the MAPC tangent operator. This iterative process of updating the stress
tensor is demonstrated in Table 1.
Note that the amount of force in polymer chains is used to compute its stretch and thus it requires inverting the rela-
tionship between stretch and force. In contrast, the force equation in most existing chain models is not easily invertible and
82 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Table 1
Algorithm of the constitutive model with a discrete crystallinity representation.

0. Given: isochoric deformation gradient F̄ at time tn+1 , the DOC of the chains (ω1 , ω2 , . . . , ωnint )n at time tn
1. Initialize the isochoric first Piola Kirchhoff tensor from previous step or from the linear approximation P̄ 0 = μF̄
2. Perform the MAPC Newton iteration loop (iteration k) to compute the stress tensor P̄n+1
a) Compute the normalized force and the deformed unit vector for the chains in all quadrature orientations
   
f¯lk = 3P̄ k (λ0 )l , f¯lk =  f¯lk  and λ
ˆ k = f¯ k / f¯k  for l = 1, 2, . . . , nint
l l l
b) Compute the Langevin parameters for each chain

βl = fl /(μ N ) and l = coth βl − 1/βl
k ¯ k k k k

c) Initialize the DOC for the chains as ωlk,0 = (ωl )n


d) For every orientation (index l) of chains, perform Newton iteration (iteration m) to obtain the crystallinity ratio ω at time tn+1
(i) Compute the crystallization rate of the chain
k,m  
( f¯w ) = μN β k + ln(β k / sinh β k ) − c̄ − ξ¯ ωk,m /(ωmax (ωmax − ωk,m )) and ω˙ k,m = q̄ ( f¯w )k,m
l l l l l l l l
(ii) Calculate the crystallinity evolution residual (rw )k,m
l
= −ωlk,m + (ωl )n + t ω˙ lk,m
(iii) Check
 the tolerance and make sure ω k,m
l
≥ 0
if (rw )k,m
l
 ≤ tol go to 2e
if ω˙ l < 0 and ωl = 0 go to 2e
k,m k,m

(iv) Calculate the chain crystallinity tangent


(kw )k,m
l = 1 + t ξ¯ q̄/(ωmax − ωlk,m )2
(v) Update the DOC of the chains ω√lk,m+1 = max{ωlk,m + (rw )k,m
l
/(kw )k,m
l
, 0}
e) Compute the stretch λkl = N ωlk + (1 − ωlk ) kl for l = 1, 2, . . . , nint
f) Compute MAPC residual
 int k ˆ k
Rλk = 13 F̄ − nl=1 λl λl  (λ0 )l Wl
g) Check the tolerance: if ||Rλk || ≤ tol exit the algorithm
h) Compute the Jacobian matrix Klk and the stiffness k̄kl of the chains using (48) and (50)
i) Formulate the MAPCtangenttensor
 λkl λk ˆ k
K k = 3 nint
λ 1+ 1 − l λ λ ˆ k ((λ0 )l  (λ0 )l )Wl where (AB )abcd = Aac Bbd
l=1 f¯lk k̄kl f¯lk l l
−1
j) Update the stress tensor P̄ k+1 = P̄ k + Kλk : Rλk

may require additional Newton–Raphson iterations. Our proposed model provides a closed-form expression to compute the
stretch value as a function of the force value and the DOC by combining (12) and (7) in the form
√  1

λ = N ω + (1 − ω )(coth β − ) where β = √ . (43)
β μ N
Before calculating the chain stretch, it is necessary to update the DOC of the chains during the time step. At the beginning
of the simulation the DOC of the chains are set to zero. When the stretch is small, the driving force of crystallinity and
consequently the rate of crystallization are negative. In this case, since we have to ensure ω ≥ 0, the chain remains fully
amorphous. However, once fw > 0, the chain starts to crystallize and we have to update ω. During unloading, the driving
force becomes negative and decreases the DOC until it reaches zero. The algorithm makes sure that ω does not become
negative at any point. This evolution of crystallinity for each chain orientation is performed by solving (27) iteratively using
the following residual and tangent, namely
rw = −ω (tn+1 ) + ω (tn ) + t ω˙ (tn+1 ) (44)
and 
∂ rw  q̄ξ¯ t
∂ω  f =cst
kw = − =1+ . (45)
(ωmax − ω )2
This chain crystallization tangent can also be computed from the 2 × 2 chain Jacobian K as
 K12 K21

kw = 1 − t K22 − . (46)
K11
The chain Jacobian matrix K provides the derivatives of the force and rate of crystallization with respect to the thermody-
namic variables of the chain, stretch and DOC. The value of used in the following equation is calculated from β using
(7) and its derivative can be calculated from L (β ) = d /dβ = β −2 − (sinh β )−2 . Thus,
⎡ ⎤
  ∂ f¯ ∂ f¯
K11 K12 ⎢ ∂λ ∂ω ⎥
K= =⎢ ⎥ (47)
K21 K22 ⎣ ⎦
∂ ω˙ ∂ ω˙
∂λ ∂ω
with
μ √ √ q̄ξ¯
K11 = , K12 = N ( − 1 )K11 , K21 = −q̄K12 , K22 = N ( − 1 )K21 − . (48)
( 1 − ω )L ( β )
(ωmax − ω )2
After updating the crystallinity of the chains and computing the stretch vectors, the MAPC iteration is performed by cal-
culating the MAPC residual (42) and the associated tangent operator. The MAPC tangent required for updating the stress
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 83

tensor P̄ depends on the stretch λ, force f¯, and stiffness k̄ = ∂ f¯/∂λ of the chains, as well as the unit vector oriented along
the deformed chain λˆ = λ/λ = f / f, and can be written as



∂ (Rλ )iJ λ 1 λ ˆ ˆ
(Kλ )iJkL = − = 3 δik + − λi λk (λ0 )J (λ0 )L  . (49)
∂ P̄kL f¯ k̄ f¯
This tangent operator is a fourth order tensor with 81 entries. Nevertheless, in the computer implementation, P̄ and Kλ are
stored as a 9 dimensional column vector and a 9 × 9 matrix, respectively. The chain stiffness
 
K11 = μ/ (1 − ω )L (β ) ω˙ = 0
k̄ = (50)
K11 + tK12 K21 (1 − tK22 )−1 ω˙ = 0
equals K11 when the chain is fully amorphous. However, if the chain is crystallizing, we have to take into account the
softening due to crystallization. The details about calculating the MAPC tangent Kλ and the chain stiffness k̄ is thoroughly
explained in Appendix C.
The steps required to compute the microscopic deformation field, the stress tensor and the evolution of crystallinity for
the discrete representation of the chains are summarized in Table 1. For simplicity, the quantities that correspond to time
tn+1 are written without any time subscript whereas the quantities of time tn are shown with subscript n.

3.2. Algorithm for obtaining a continuous distribution of crystallinity

The numerical algorithm used to calculate the evolution of crystallinity and the state of stress for a continuous crys-
tallinity distribution has similarities to the previous case (discrete distribution of crystallinity). In contrast, in the continuous
crystallinity formulation, the state of crystallinity is solved for all the chains at the same time instead of using independent
evolution equations. At each step, instead of ω,  is updated iteratively and as a result, the state of each chain has higher
impact on the other chains in the material.
In addition to an initial value for P̄ , as discussed in 3.1, we also need to provide an initial value for the crystallinity
internal variables. Since there are no crystals in the material at the beginning of the simulation, we can set a = 0 and
therefore, based on (32), the DOC is initially zero for chains in all orientations regardless of the value of φ 1 , φ 2 , and b. The
polar angles φ 1 and φ 2 , representing the orientation of the crystals, are set to arbitrary numbers initially and their value
are irrelevant as long as no crystal has been formed. When the material is deformed and starts to crystallize for the first
time, we set the polar angles to the orientation which has the largest value of chain stretch in the micro-structure. The
orientation with the maximum stretch of the chain also has the maximum chain force and according to (41), its direction is
obtained by computing the singular-value decomposition of the stress tensor as

3
P̄ = σζ u ζ  vζ (51)
ζ =1

where the vector vζ corresponding to the largest singular value σ ζ is chosen as the initial crystal orientation in the reference
configuration. During this initial calculation of the spherical coordinates φ 1 and φ 2 of the crystal orientation, we can choose
any coordinate axis (X, Y, or Z) as the main axis for spherical coordinates. For example, the Z axis is used in Fig. 6 as
the main spherical axis and φ 1 is defined according to the Z axis. After this initialization, the orientation of the crystal is
updated through the evolution law described in (36) and the singular value decomposition method is not used anymore.
During each iteration of the MAPC algorithm, the crystallinity internal variables must be updated, which is performed by
an additional Newton–Raphson algorithm nested inside the main MAPC iteration loop. Along this process, after calculating
the force vectors using (41), the crystallinity (DOC) of the chains are calculated from (32). The unit orientation vector of the
crystal
uˆ = sin φ1 cos φ2 e1 + sin φ1 sin φ2 e2 + cos φ1 e3 (52)
 
is obtained from the two polar coordinates of the macroscopic crystallinity. Substituting cos θ = uˆ · λ0  into (32), we get
   
ω = ω (, λ0 ) = a exp −b(ln uˆ · λ0  )2 (53)
which allows us to calculate the DOC of the chains. Hence, the DOC of the chains are not stored as a history variable and
the simulation only keeps track of 4 numbers included in , thus avoiding an otherwise needed large storage requirement
when using a large number of quadrature orientations. The gradient of this quantity with respect to the crystallinity internal
variables
⎡ ⎤ ⎡          ⎤
∂ ω/∂ φ1 −2ab (ln uˆ · λ0 /uˆ · λ0  ) exp −b(ln uˆ · λ0  )2 (∂ uˆ · λ0 /∂φ1 )
   
∂ω ⎢
⎢∂ ω/∂ φ2 ⎥ ⎢−2ab (ln uˆ· λ0 /uˆ ·λ0  ) exp −b(ln uˆ · λ0  )2 (∂ uˆ · λ0 /∂φ2 )⎥
=⎣  ⎥
∂ ω/∂ a ⎦ ⎣exp −b
=  2 (54)
∂ ⎦
 (ln uˆ · λ0 )    
∂ ω/∂ b −a(ln uˆ · λ0  )2 exp −b(ln uˆ · λ0  )2
 
is essential for calculating the evolution of the crystallinity. Here, the derivative of uˆ · λ0  with respect to the polar coordi-
nates can be written as
84 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

 
∂ uˆ · λ0 
= sign(uˆ · λ0 )[cos φ1 cos φ2 (λ0 )1 + cos φ1 sin φ2 (λ0 )2 − sin φ1 (λ0 )3 ] (55)
∂φ1
and
 
∂ uˆ · λ0 
= sign(uˆ · λ0 )[− sin φ1 sin φ2 (λ0 )1 + sin φ1 cos φ2 (λ0 )2 ]. (56)
∂φ2
In addition to the gradient [∂ ω/∂ ], also the Hessian [∂ 2 ω/∂ ∂ ] must be calculated, whose closed form expression is
omitted here for the sake of brevity. Note that based on (56), we need to make sure that φ 1 > 0 at all times in order to
obtain a non-zero gradient for the variation of φ 2 . Thus, we try to choose the spherical axis that is not parallel to the
crystal orientation.
Using the chain parameters f¯ and ω, the stretch λ and the rate of crystallization ω˙ of each chain are calculated directly
using (43) and (14). Now, using (36) and (54) the rate of change of the crystallinity internal variables ˙ can be calculated
and the crystallinity Jacobian ∂ 
˙ /∂  is obtained from
 
   2  T   T   2  
∂ ˙ ∂ω K12 K21 ∂ω ∂ ω ˙ ∂ω ˙ ∂ ω
=A −1
(K22 − ) −   + ω˙ −   . (57)
∂ ∂ K11 ∂ ∂ ∂  ∂ ∂ ∂ 
These calculated quantities allow us to update the value of the crystallinity internal variables using a Newton–Raphson
scheme. The evolution of the crystallinity internal variables can represent the growth or shrinking of the crystal (updating
a), the rotation of the crystal (updating φ 1 , φ 2 ), and the change in the angular width of the crystalline region (updating b).
The residual R and the tangent K for updating the crystallinity internal variables are calculated as
R = −(tn+1 ) + (tn ) + t (
˙ tn+1 ) (58)
and
∂ R ∂ ˙
K = − = I4 − t (t ). (59)
∂ (tn+1 ) ∂  n+1
The calculation of the MAPC residual and its tangent is performed after the crystallinity internal variables are converged.
Although the MAPC residual is obtained identical to (42), the expression for the tangent must be modified to include the
softening effect of the evolution of the internal variables. The full expression of the MAPC tangent
 
  
∂ Rλ  4
∂ Rλ  ∂ i 
Kλ = −  +    (60)
∂ P̄ =cst i=1 ∂ i P̄=cst ∂ P̄ R =0
is similar to (49), but it includes a new term representing the effect of the evolution of  on the tangent operator. The first
term corresponds to the derivative of the residual for constant  and it is equal to (49) with k̄ = K11 . However, the second
term explains how the MAPC tangent changes due to the change in the crystallinity internal variables while the stress tensor
is kept constant. The expressions to compute these quantities are presented as

∂ Rλ  K12 ∂ω ˆ
= λ  λ0 
∂ i P̄=cst
(61)
K11 ∂ i
and
 4
∂ i  4
K ∂ω ˆ
 = 3t (K )−1 A−1 21 λ  λ0  . (62)
∂ P̄ R =0 11 ∂ k
ij jk K
j=1 k=1

The complete algorithm for the continuous crystallinity distribution is summarized in Table 2 through a pseudo-code and
the proofs for some of the equations are provided in Appendix B and C.2

3.3. Computing the stress and consistent tangent

The deviatoric part of the first Piola–Kirchhoff stress tensor obtained from the MAPC algorithm can be transformed into
the spatial deviatoric stress tensor
τ̄ = P̄F̄ T (63)
and be used to compute the total stress from (3) as
τ = p1 + τ̄ : P (64)
assuming the coordinate system is Cartesian (gi j = δi j ). Furthermore, the MAPC tangent operator can be transformed to the
spatial tangent tensor corresponding to the deviatoric stress using
∂ P̄iA ∂ P̄ 1 −1
C̄i jkl = F̄lB F̄jA − δik τ̄ jl where = K (65)
∂ F̄kB ∂ F̄ 3 λ
which must be combined with (4) to represent the total spatial tangent operator.
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 85

Table 2
Algorithm of the constitutive model with a continuous crystallinity distribution.

0. Given: isochoric deformation gradient F̄ at time tn+1 , the crystallinity internal variables n at time tn
1. Initialize the isochoric first Piola Kirchhoff tensor from previous step or from the linear approximation P̄ 0 = μF̄
2. Perform the MAPC Newton iteration loop (iteration k) to compute the stress tensor P̄n+1
a) Compute the normalized force and the deformed unit vector for the chains in all quadrature orientations
   
f¯lk = 3P̄ k (λ0 )l , f¯lk =  f¯lk  and λ
ˆ k = f¯ k / f¯k  for l = 1, 2, . . . , nint
l l l
b) Compute the Langevin parameters for each chain

βl = fl /(μ N ) and l = coth βl − 1/βl
k ¯ k k k k

c) Initialize the crystallinity internal variable for the iteration as k,0 = n


T
d) Perform Newton iteration (iteration m) to obtain the crystallinity internal variables  = φ1 φ2 a b at time tn+1
(i) Compute the DOC of the chains for all  orientations
  
ωlk,m = ω (k,m , (λ0 )l ) = ak,m exp −bk,m (ln uˆ k,m · (λ0 )l  )2
(ii) Compute the crystallization rate of the chains for all orientations
k,m  
( f¯w ) = μN β k + ln(β k / sinh β k ) − c̄ − ξ¯ ωk,m /(ωmax (ωmax − ωk,m )) and ω˙ k,m = q̄( f¯w )k,m
l l l l l l l l
(iii) Calculate the gradient [∂ ωl /∂ ]k, m using (54) and the Hessian [∂ 2 ωl /∂ ∂ ]k, m of the crystallinity distribution function at all of the chain orientations
(iv) Calculate the rate of change of the crystallinity internal variables
 k,m  k,m T  k,m
nint ∂ωl ∂ωl nint ∂ωl
Ak,m = Wl + γ I4 and ˙ k,m = (Ak,m )−1 Wl ω˙ lk,m
l=1 ∂ ∂ l=1 ∂
(v) Calculate the crystallinity evolution residual R k,m
= −k,m + n + t 
˙ k,m
(vi) Check the
 k,m  tolerance and make sure a k, m
≥ 0
if R  ≤ tol go to 2e
if ˙ k,m = a˙ k,m < 0 and 0 ≤ k,m = ak,m ≤ tol go to 2e
3 3
k,m
˙ /∂ 
(vii) Compute the Jacobian matrix Klk,m of the chains and the crystallinity Jacobian ∂  using (48) and (57).
(viii) Calculate the crystallinity tangent
k,m
K k,m = I4 − t ∂ 

˙ /∂ 
(ix) Update the crystallinity internal variables k,m+1 = k,m + αline (K ) R
k,m −1 k,m

The parameter α line ≤ 1 is a positive line-search parameter


√  that guaranties the crystallinity magnitude (3 = a) always remains non-negative
e) Compute the stretch for all orientations λl = N ωl + (1 − ωl ) l
k k k k

f) Compute the MAPC residual Rk = 1 F̄ − nint λk λ
ˆ k  (λ0 )l Wl
λ 3 l=1 l l
g) Check the tolerance: if ||Rλk || ≤ tol exit the algorithm
h) Formulate the MAPC
 tangent
 tensor 
 int λkl λk ˆ k 
Kλk = 3 nl=1 ¯k 1 +
1
( K )k
− ¯kl λ λˆ k  (λ0 )l  (λ0 )l Wl
fl
 l
11 l l f

l k  
k 
4 nint (K12 )kl ∂ωl 4 4 nint ( K )k ∂ωl
−3t λˆ kl  (λ0 )l Wl  (K )−1 A−1 21 l
λˆ kl  (λ0 )l Wl
i=1 l=1 ( )
K11 kl ∂ i j=1 p=1 l=1 ij jp (K )k 11 l ∂ p
−1
i) Update the stress tensor P̄ k+1 = P̄ k + Kλk : Rλk

4. Numerical results

4.1. Uniaxial tension test

To calibrate the material parameters for our model, we investigate the uniaxial loading and unloading experiments of
Toki et al. (2003) for sulfur vulcanized natural rubber (NR-S). The macroscopic tensile stretch λ̄ is applied with the rate of
0.4/min through the deformation gradient
⎡ ⎤
λ̄ 0 0
F = F̄ = ⎣0 λ̄−1/2 0 ⎦ (66)
0 0 λ̄ −1/2

ensuring an isochoric deformation. The total Piola stress tensor P = τ F −T is obtained from the value of τ defined in (64) for
a certain value of the pressure p which corresponds to the stress free lateral boundary condition τyy = τzz = 0. Fig. 8 shows
the experimental data for natural rubber alongside our simulation results for both discrete and continuous representations
of crystallinity. As observed from the figure, our numerical simulation is able to capture the fundamental behaviors of the
SIC process. Initially, the material has no crystals and deforms elastically with the applied load. When loading beyond λ̄ =
3 is applied, the material starts to crystallize and the slope of the crystallinity ratio changes accordingly. Since both the
chain model and the crystallinity evolution are described as differentiable mathematical expressions, the crystallinity ratio
changes smoothly in the numerical simulation. Maximum stress is seen at λ̄ = 6 after which the specimen is unloaded.
The crystallinity grows slightly in the initial unloading stage because SIC is a rate dependent process and it is not fully
equilibrated at the maximum-stretched state. When the amount of stretch goes below λ̄ = 5.5, the degree of crystallinity
decreases until it almost vanishes at the end of the unloading stage. The degree of crystallinity is less than the equilibrium
crystallinity during loading. In contrast, it becomes larger than the equilibrium crystallinity in the unloading stage (except for
λ̄ > 5.5), thus forming a hysteresis in the plot of the degree of crystallinity. Since higher levels of crystallinity correspond
to lower mechanical stresses, the rubber material experiences lower amounts of stress during unloading. Therefore, the
86 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 8. Uniaxial loading simulation (the solid lines) compared with experimental data (the dashed lines) for sulfur vulcanized natural rubber (Toki et al.,
2003). The stress-stretch relationship is plotted in (a) and (c) and the evolution of crystallinity during the test is demonstrated in (b) and (d). The top Figs.
(a,b) refer to the discrete crystallinity representation while the bottom graphs (c, d) represent the continuous crystallinity distribution.

hysteresis in the crystallinity response corresponds to a hysteresis in the amount of stress in the material. It is assumed that
no other dissipative effects such as viscoelasticity are present in this uniaxial test and the hysteresis is solely the result of
crystallization. Experimentally, Marchal (2006) shows that the hysteresis in the stress response of rubber is primarily due to
DOC whereas viscous effects are very small. The simulations are performed for both discrete and continuous distributions
of crystallinity. The calibrated parameters for these two cases are exactly the same as the values mentioned in Section 2.4.1.
In the case of continuous crystallinity formulation, the initial value for the width parameter is chosen as b = 2.0. For all
simulations presented here, 37 × 2 integration orientations are incorporated.
Next we examine the experimental observations of Marchal (Marchal, 2006; Rault et al., 2006a). The material is sulfur
vulcanized natural rubber with 1.2 g of sulfur per 100 g of rubber and it is stretched to various maximum elongations
for which the unloading paths are measured in the experiment. Fig. 9 shows the experimental data as well as simulation
results we obtained with our model. Material parameters, calibrated for the maximum elongation λ̄max = 6.5, are μ = 0.203
MPa, N = 23.8, α = 0.388, c̄ = 7.22 MPa, ξ¯ = 0.187 MPa, ωmax = 0.7833, q̄ = 0.0215MPa−1 min−1 for the discrete crystallinity
distribution, and μ = 0.22 MPa, N = 23.1, α = 0.33, c̄ = 7.6 MPa, ξ¯ = 0.051 MPa, ωmax = 1.0, q̄ = 0.019 MPa−1 min−1 for the
continuous crystallinity distribution model. The size of the specimen used by Rault et al. (2006a) is 2 × 5 × 30 mm and the
displacement is applied with a rate of 0.035 mm/s. The plots show reasonable agreement between the experimental and
simulation results. During initial portion of unloading, the proposed model predicts higher levels of crystallinity and larger
decrease in the uniaxial force. This is due to the rate-dependent evolution law of (14).
Various softening and hardening stages of SIC can be seen in Fig. 9(c) with the notation defined in Albouy et al. (2005).
These transition points are named A, B, C, D, and E. From λ̄O to λ̄A , rubber behaves elastically. From λ̄A to λ̄B , crystallization
starts and the stress remains relatively constant, after which the hardening region between λ̄B and λ̄C occurs. In this part
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 87

Fig. 9. Uniaxial loading simulation (the solid lines) compared with experimental data (dots) for sulfur vulcanized natural rubber (Rault et al., 2006a). The
stress-stretch relationship is plotted in (a) and (c) and the evolution of crystallinity during the test is demonstrated in (b) and (d). The top Figs. (a,b) refer
to the discrete crystallinity representation while the bottom graphs (c, d) represent the continuous crystallinity distribution.

Fig. 10. The evolution of the half-width angle hf during uniaxial tension simulation (solid curves) in comparison with the experimental results of material
NR-04 (dashed lines) described by Tosaka et al. (2004). (a) the discrete crystallinity distribution approach (b) the continuous crystallinity distribution
method.
88 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 11. The simulation for two-step tension and shear loading using the continuous formulation for different values of initial stretch λ̄y . (a) The schematic
representation of the two-stage simulation (b) the evolution of crystallinity ratio ω̄ (c) rotation of the reference angle of the crystals (d) rotation of the
deformed angle of the crystals together with experimental data from Pannier et al. (2011).

of loading, the value of ω has grown close to the value of ωmax for some of the chains and because of the penalty term in
(10), further crystallization is slowed down. Additionally, Since the elongation of the chain is near its limiting extensibility,
hardening is observed. During unloading (C, D, E, O), the same process is observed in the reverse order. The stress remains
relatively constant between λ̄D and λ̄E .

4.2. Half-width angle

Since the directional distribution of crystallinity is explicitly monitored in our model, we try to validate this distribution
by experiments. The peaks in the x-ray diffraction intensity plot provide information about the distribution of crystallinity.
The orientation with the maximum intensity shows the orientation of the crystal in a specific point in the material. This
intensity is reduced when we look at orientations further from the peak. The plot of X-ray diffraction intensity versus angle
can be approximated by a normal distribution function expressed as (Tosaka et al., 2004)


θc2
I = Imax exp − (67)
2w2
where θ c is the angle between the deformed chain orientation and the peak intensity direction. Imax is the peak intensity
and w is the distribution width parameter. This distribution of intensity allows us to define the half width angle hf as the
angle between two orientations in the deformed state which correspond to the intensity of Imax /2. The half width angle is
calculated as

h f = 2w 2 ln 2. (68)
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 89

Fig. 12. The 3D notched specimen: (a) The schematic geometry. (b) The finite element mesh. (c) A close up of the mesh.

Fig. 13. Distribution of the crystallinity ratio ω̄ in the vicinity of the tip of one of the notches: (a) Numerical simulation contour results (b) experimental
observations from Rublon et al. (2014). (c) Simulation results along the horizontal x-axis (d) simulation results along the vertical y-axis.

In our simulations, in order to calculate the angle of the chains in the deformed state with respect to the main crystalline
orientation, we use the stress tensor as the mapping based on (41). The uniaxial loading is applied in the X direction and
crystals are forming along the same axis. Then the stress tensor takes the diagonal form
 
P̄11 0 0
P̄ = 0 P̄22 0 (69)
0 0 P̄22
90 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Fig. 14. Three dimensional views of the distribution of crystallinity around the notch corresponding to strain values of (a) ε = 0 (b) ε = 20% (c) ε = 40%
(d) ε = 60% (e) ε = 80% (f) ε = 92%.

and allows us to compute the deformed chain orientation. Assuming that the chain originally exists in the X − Y plane
λ0 = cos θ e1 + sin θ e2 , the deformed orientation is

f 3P̄ λ0 3 
λˆ = = = P̄ cos θ e1 + P̄22 sin θ e2 (70)
f ¯f ¯f 11

which makes the angle θc = tan−1 (P̄22 /P̄11 ) tan θ with the crystallinity axis. In addition to computing the orientation of the
chains in the current configuration, we can obtain the degree of crystallization in the deformed state ωc using the concept
of area transformation on a unit sphere

ωc (θc ) sin θc dθc = ω (θ ) sin θ dθ (71)

which is also used in Kroon (2010). The X-ray diffraction intensity is assumed to be proportional to ωc , so by fitting ωc (θ c )
to a normal distribution and using (68) we can calculate the half-width parameter.
Tosaka et al. (2004) computed the half width of the crystals inside a rubber specimen at various stages of the uniaxial
loading and unloading. Fig. 10 compares those experimental data for natural rubber NR-4 with the values computed from
our simulations. The displacement rate is 10 mm/min applied to a 24 mm specimen. The material parameters for this simu-
lation are calibrated by the uniaxial data provided by Tosaka et al. (2004). The calibrated parameters are μ = 0.37 MPa,
N = 32, α = 0.25, c̄ = 8.5 MPa, ξ¯ = 1.1 MPa, ωmax = 0.92, and q̄ = 0.015 MPa−1 min−1 for both discrete and continuous
crystallinity simulations. Similar to Section 4.1, the initial value of the width parameter is set to b = 2.0 for the continuous
crystallinity formulation. Two different phenomena contribute to the change of the half-width angle. Increasing crystallinity
ratio causes more chains to crystallize and should cause the half-width to increase, but this effect can only be seen if we
look at the angle of the chains in the reference orientation. However, during uniaxial tension, the crystallized chains are
aligned toward the principal strain direction and this effect decreases the half-width angle in the deformed configuration.

4.3. Rotation of the crystals

During uniaxial loading simulations, the crystals grow in the direction of the loading and they will not rotate unless
the load changes its direction. In order to examine how the computational model simulates the rotation of the crystals, a
non-proportional loading scheme is used. First the specimen is pulled in Y direction up to a certain stretch λ̄y , after which
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 91

Fig. 15. Orientation of the polymer crystals in the region surrounding the notch in the current configuration. φ c is the positive angle between the polymer
crystal orientation and the vertical axis. (a) Numerical simulation contour results (b) experimental findings from Rublon et al. (2014). (c) Simulation and
experimental results along the vertical axis (d) schematic view of the definition of φ c and the coordinate axes.

a shear strain γ xy is applied in X direction. Therefore, the deformation gradient is set to


⎡ −1/2 ⎤
λ̄y γxy λ̄y 0
F = F̄ = ⎣0 λ̄y 0 ⎦. (72)
0 0 λ̄−1
y
/2

The shear strain rotates the principal axis of stretch and consequently, the chains in the first and third quadrant of the X − Y
plane crystallize more than the chains in the second and fourth quadrants. Therefore, the crystal axis rotates toward the
first and third quadrants by changing the spherical angle φ 2 . This rotation occurs automatically by solving the crystallinity
evolution residual (58).
Fig. 11 shows the results of this non-proportional loading with our continuous crystallinity distribution model. Three
different simulations are performed with different values of initial stretch λ̄y . In the case of λ̄y = 2, the crystallinity is
negligible at the end of the tensile region, and the shear displacement allows the first crystals to grow. However, in the
other cases, strain-induced crystallization already happens before any shear is applied. The rotation of the crystals are visible
when looking at the angle between the crystal axis and the Y axis in the reference configuration φ r . When the crystals are
small, they are easier to rotate, thus enabling higher rotation for the simulations with lower λ̄y . However, this difference in
rotation angles is not clearly distinguishable when looking at the crystallinity angle in the current configuration φ c because
the rigid-body rotation coming from the shear strain contributes strongly to this rotation. Moreover, at these large strains,
the deformation of the networks rotates almost all of the chains into the same orientation and the different angles in the
reference configuration are mapped into the same narrow region in the current configuration.
92 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Pannier et al. (2011) performs this combined tensile and shear loading and measures the angle φ c . Those experimental
results are also shown on Fig. 11(d). The tensile and shear loading speed is set to λ˙ y = 0.05/min and γ˙ xy = 0.25/min, based
on the values used in the experiment. Since there is no stress-strain information of the material used in the experiment, the
same material parameters (expressed in Section 2.4.1) are employed except for N = 28 and c̄ = 8 MPa in order to allow large
amounts of tensile stretch. The simulation results are close to the experimental values for the case of λ̄y = 2.0. However,
one of the points of the experiment for λ̄y = 4.0 has a large discrepancy with respect to the simulation curve.

4.4. 3D notch simulation

Using our 3D network model allows us to study the behavior of rubber under complex loading conditions, which provides
more insight into the effectiveness of the SIC model. We recreated the experiments of Rublon et al. (2014) as a 3D numerical
simulation to study the effects of SIC in the vicinity of cracks and high-stress regions. Since Rublon et al. (2014) use sulfur
vulcanized natural rubber and do not provide uniaxial test results, we incorporate the continuous crystallinity distribution
model with the same parameters as in Section 4.1 to perform these simulations. When a specimen with a notch is pulled,
we observe strain localization in the vicinity of the notch. This region becomes crystallized due to SIC and this crystalliza-
tion helps reinforce the material, thereby reducing the tendency to form a crack. The geometry and the dimensions of the
simulation are shown in Fig. 12(a). This simulation uses 2436 hexahedral elements and 4020 nodes, refined in the areas
close to the notches as shown in Figs. 12(b–c). The tip of the notches are modeled as half circles with the radius of 0.2
mm in order to avoid stress singularities. The simulation does not consider tearing or the formation of cracks and thus the
length of the notch is constant. The specimen experiences up to 92% strain perpendicular to the notch axis while clamping
the ends of the specimen.
The distribution of crystallinity close to the notch tip can be seen in Fig. 13, showing qualitative and quantitative agree-
ment with the experimental results. In addition to the contour data, the variation of the crystallinity is shown in two
perpendicular axes around the notch. The crystalline region is relatively small and it diminishes as we get further from
high-strain areas. The three dimensional snapshots of the crystallization around the notch are also shown in Fig. 14.
Since our constitutive model stores the orientation of the polymer crystals at every material point, we can plot the orien-
tation of the crystals surrounding the simulated notch. At the beginning of the simulation, the material has zero crystallinity
at every point, the direction of the crystals is undefined. When the crystallization starts, the singular value decomposition
method is used to compute the initial orientation of crystallinity, which continues to rotate afterward based on the evolution
of . Because the stored crystal orientations belong to the reference configuration, we have to consider the finite rotation of
the material to calculate the orientation of the crystal in the current configuration. The calculated crystal orientation in the
current configuration is performed by considering P̄ as the rotation operator in the microscale based on (41). The results
can be viewed in Fig. 15, which are very close to the experimental findings.

5. Conclusion

A micromechanical homogenization model for studying strain-induced crystallization is presented which connects the
deformation and phase transformation of polymer chains with the large scale measurable properties of the material such as
the deformation or the X-ray diffraction intensity. A new polymer chain model is introduced based on non-Gaussian statis-
tical mechanics which takes into account the change of the flexible length of the chain during crystallization and provides
an evolution law for crystallization using the gradient of the free energy expression. The MAPC model is incorporated in
the proposed framework to compute the microscopic stretch and rotation of the chains from the large scale local contin-
uum deformation field. Furthermore, in accordance with experimental evidence, the anisotropic crystallization of rubber is
observed computationally due to the non-uniform stretch of chains in different orientations. In addition to the traditional
representation of crystallinity values at discrete orientations, a new continuous crystallinity distribution is presented and
the respective mathematical expressions for computing the evolution of crystallinity are derived. The material parameters
can fit experimental uniaxial tension tests with great accuracy. It is shown that the model accurately predicts the rotation of
the crystals as well as the change in the half-width angle. The accumulation of a crystalline phase in the high-strain region
around a notch is simulated using the proposed model and the results agree with the experimental data.
Our model can be improved in the future by incorporating various mechanical phenomena such as viscosity, damage, and
fracture. At high strains, rubber material can be damaged due to the Mullins effect (Göktepe and Miehe, 2005; Mullins, 1948)
causing softer response in subsequent loading cycles, which can have a combined effect with SIC. Therefore, introducing the
Mullins effect in the SIC model is one of the future directions for expanding this model. Incorporating viscous effects based
on Linder et al. (2011) is another direction of future research to be pursued. Additionally, in order to better study the role
of SIC in the vicinity of a crack tip, it is necessary to combine this presented model with fracture formulations such as the
phase field approaches (Miehe et al., 2010; Zhang et al., 2016) or the strong discontinuity methods (Linder and Raina, 2013;
Linder and Zhang, 2013; 2014; Raina and Linder, 2015).
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 93

Acknowledgements

Financial support for this research was provided by Samsung Electronics and the National Science Foundation through
CAREER Award CMMI-1553638. This support is gratefully acknowledged.

Appendix A. Derivation of quantities of partially crystallized chains

Based on Fig. 2, in a partially-crystallized chain, the end-to-end length and the total length of the effective random walk
can be calculated as

ra = r − Lc and La = L − Lc . (A.1)
This result is used to calculate the relative stretch of the freely jointed chains compared to the maximum possible stretch
as
√ √
ra λ Nl − ωNl λ/ N − ω
= = = . (A.2)
La Nl − ωNl 1−ω
The variation of this quantity versus the change in λ or ω, given as


dλ dω (λ/ N − 1 ) dλ
d = √ + = ( 1 − ω ) −1
√ + ( − 1 ) d ω (A.3)
N (1 − ω ) ( 1 − ω )2 N
is useful for calculating the derivatives of the free energy later in this appendix. The main thermodynamic quantity of a
chain formulation is its free energy. This free energy is defined in (9) based on the force response of a non-Gaussian chain.
The amorphous portion of the free energy can be calculated by substituting (8) into (9), yielding
  λ
r
k T β (λ ) √
ψa (λ, ω ) = F ( r )d r = ( B )( Nldλ ). (A.4)
0 0 l
This integral represents the mechanical work done when stretching the chain from zero end-to-end length to its current
length. The star symbol is used to distinguish the integration variable from the upper bound of the definite integral.
During this stretch, the amount of crystallization and the temperature
√ remains constant. In order to solve the integral we
change the integration variable from λ to by using dλ = N (1 − ω )d from (A.3) (considering dω = 0). We then
replace with β using integration by parts. Thus,
  β

√ √
ψa (λ, ω ) = kB T Nβ ( )( N (1 − ω )d ) = kB T N (1 − ω ) ( β − 0 ) − (β )dβ . (A.5)
−ω / ( 1 −ω ) 0

The lower bound of the integral is changed from λ = 0 to its equivalent = −ω/(1 − ω ) leading to a negative relative
stretch. This case refers to the condition that the end-to-end length of the chain is shorter than the crystallized segment.
For calculating this integral, the entropic force at this initial stage is considered to be zero. Thus, we can substitute 0 instead
of −ω/(1 − ω ) as the lower bound of the integral. Now we use the anti-derivative of the Langevin function
   1
β
− (β )dβ = − coth β − dβ = −(ln(sinh β ) − ln β ) = ln (A.6)
β sinh β
to obtain the expression in (11). The thermodynamic force and the crystallization force are formed by calculating the differ-
ential of the free energy as



β β
dψ = kB T N (−dω ) β + ln + kB T N (1 − ω )d β + ln + c dω
sinh β sinh β


dω dω ω −1
−ξ − (1 − ) . (A.7)
ωmax ωmax ωmax
From (A.6) we know that d(ln(β / sinh β ) ) = − dβ . Thus, combining it with (A.3), we get




β β β dλ
d β + ln = dβ + β d + d ln = β d = √ + ( − 1 )dω (A.8)
sinh β sinh β (1 − ω ) N
and


β √ ξ ω dω
dψ = f dλ − fw dω = −kB T N β + ln dω + kB T Nβ dλ + kB T Nβ ( − 1 )dω + c dω + .
sinh β ωmax (ωmax − ω )
(A.9)
94 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

Regrouping the terms in (A.9) results in the expression for the chain force and the crystallization force shown in (12) and
(13). These equations can be differentiated once more to formulate the jacobian matrix K, i.e.


√ ∂β √ 1 dλ μdλ + μ N ( − 1 )dω
d f¯ = μ N d = μ N (1 − ω )−1 √ + ( − 1 )dω = = K11 dλ + K12 dω
∂ L (β ) N L (β )(1 − ω )
(A.10)
and


q̄ξ¯ dω q̄μN (1 − ) dλ q̄ξ¯ dω
dω˙ = q̄d f¯w = q̄μN (dβ − dβ ) − = √ + ( − 1 )dω −
(ωmax − ω )2 L (β )(1 − ω ) N (ωmax − ω )2
= K21 dλ + K22 dω. (A.11)

Appendix B. Derivation of the rate of change of the crystallinity internal variables

As mentioned in Section 2.4.2, the amount of change of the crystallinity internal variable is computed by minimizing the
expression in (35). The crystallinity rates of the chains are considered constants and the optimization variable is the rate of
crystallinity internal variables 
˙ . It can be easily seen that we are minimizing a quadratic function of ˙ and the solution
can be obtained by solving a linear system of equations. First we substitute the apparent rate from (34) to get
  T  2
˙ = 1 (ω˙ − ω
˜˙ )2  + 1 γ  ˙ = 1 ∂ω 1
f () ˙ T ω˙ − ˙  + γ ˙ T ˙ (B.1)
2 2 2 ∂ 2

and then we expand the expression and factor 


˙ out of the sphere average because it does not depend on the orientation
of the chains. Thus,
  T   T
˙ = 1 ω˙ 2 + 1  ∂ω ∂ω ∂ω 1
f () ˙T ˙ − ω˙ ˙  + γ ˙ T ˙ (B.2)
2 2 ∂ ∂ ∂ 2

  T   T
1 ˙T ∂ω ∂ω ∂ω 1
=   + γ I4  − ω˙
˙  ˙ + ω˙ 2  (B.3)
2 ∂ ∂ ∂ 2

Minimizing this familiar quadratic form leads to the linear system


  T   
∂ω ∂ω ∂ω
min f ()
˙ →  + γ I4 ˙ = A˙ = ω˙  (B.4)
˙ ∂ ∂ ∂
which can be solved because the matrix A is guaranteed to be positive definite due to the regularization term. In order
to find the tangent for the non-linear evolution Eq. (58), the derivative of the crystallization rate with respect to the crys-
tallinity variables are needed. This can be achieved by taking the derivative of (B.4) with respect to , i.e.

4
∂ 2 ω ∂ω ∂ω ∂ 2 ω 4
∂ ˙ k ∂ ω˙ ∂ω ∂ 2ω
+  ˙ k + Aik = + ω˙  (B.5)
k=1
∂ i ∂  j ∂ k ∂ i ∂ k ∂  j k=1
∂ j ∂  j ∂ i ∂ i ∂  j
or
   T   
 2  T   T  2 
∂ 2ω ∂ω ∂ω ∂ ω ˙ ∂ ˙ ∂ω ∂ ω˙ ∂ ω
 +
˙   +A = + ω˙ . (B.6)
∂ ∂  ∂ ∂ ∂ ∂  ∂ ∂ ∂ ∂ ∂ 
Using the chain rule we can relate [∂ ω˙ /∂ ] to [∂ ω˙ /∂ω], which is non-trivial to calculate, because we have to assume that
the normalized force f¯ of the chain is constant. The MAPC loop determines the chain force based on the stress tensor and
it remains constant throughout the crystallinity iterations. Consider the chain variables in differential form
d f¯ = K11 dλ + K12 dω and dω˙ = K21 dλ + K22 dω. (B.7)
Applying the fact that the chain force is constant , we can solve for dω˙ and find our desired derivative as
 
K12 K21 dω˙  K12 K21
d f¯ = 0 → dω˙ = K22 − dω →  = K22 − . (B.8)
K11 dω f¯=cst K11
Hence we can substitute
       ∂ω 
∂ ω˙ dω˙  ∂ω K12 K21
∂
= 
dω f¯=cst ∂ 
= K22 −
K11 ∂
(B.9)

into (B.6) and, after some algebraic manipulations, we obtain (57).


R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 95

Appendix C. Derivation of the MAPC residual and tangent

As discussed in Section 3.1, solving for the MAPC deformation field is the same as finding the stationary point of the
Lagrangian (39). Setting ∂ L/∂ λ = 0, where λ is the deformed vector of an arbitrary chain orientation, we can find an ex-
pression relating the normalized force of the chains and the Lagrange multiplier, i.e.

∂ L ∂ ψ̄
0= = − νλ0 = f¯ − νλ0 → f¯ = νλ0 . (C.1)
∂λ ∂λ
The stress tensor P̄ is obtained by taking the derivative of the macro free energy with respect to the isochoric deformation
gradient to

∂ ¯ ∂ ψ̄ ∂λ
P̄ = = · . (C.2)
∂ F̄ ∂λ ∂ F̄
Using the result of (C.1) and the MAPC constraint (21), the expression for the isochoric stress tensor can be simplified as
∂λ ∂λ ∂λ  λ0 1
P̄ = f¯ ·  = νλ0 ·  = ν : = ν (C.3)
∂ F̄ ∂ F̄ ∂ F̄ 3
as mentioned earlier in (40). The stationary condition of the Lagrangian with respect to ν is equivalent to the MAPC con-
straint. We use this constraint as a residual described in (42) and solve this residual considering P̄ as the independent vari-
able. This residual requires a corresponding tangent that guaranties quadratic convergence of the Newton–Raphson solver.
In the following, this step to obtain the expression for the tangent operator is explained for two separate cases: The discrete
and the continuous crystallinity representation.

C1. Discrete crystallinity representation

We can write the differential form of the residual to observe its dependency on various variables especially the stress
tensor, i.e.
1 1
d Rλ = d F̄ − λ  λ0  = dF̄ − dλ  λ0  . (C.4)
3 3
The change in the stretch vector λ = λλ
ˆ originates from changes to its magnitude and the changes to its orientation. We
calculate each of them and show its dependency on the force vector of the corresponding chain as

d f¯ λˆ · d f¯ ∂ f¯ ∂ 2 ψ̄
dλ = = where k̄ = = (C.5)
k̄ k̄ ∂λ ∂λ2



f¯ f¯d f¯ − f¯ d f¯ d f¯ − λ
ˆ (λ ˆ · d f¯ ) 1−λ
ˆ λ
ˆ

ˆ =d = = = d f¯ (C.6)
f¯ ¯f 2 ¯f ¯f


λ λˆ  λˆ
dλ = λdλ
ˆ +λ
ˆ dλ = 1−λ
ˆ λ
ˆ + d f¯ . (C.7)
f¯ k̄
Next we consider the dependence of the chain force on the stress tensor using (41), i.e.
 
d f¯ = d νλ0 = 3dP̄λ0 . (C.8)
Now we can substitute the results from (C.7) and (C.8) into (C.4) to obtain the expression for the local tangent tensor. During
the calculation of the microscopic deformation using MAPC, the deformation gradient remains constant during the iterations
(dF̄ = 0). Thus,



1 λ 1 λ ˆ ˆ
d Rλ = dF̄ − 3 1+ − λ  λ dP̄λ0  λ0  (C.9)
3 f¯ k̄ f¯
and



∂ Rλ λ 1 λ ˆ ˆ
Kλ = − = 3 1+ − λ  λ  ( λ0  λ0 )  . (C.10)
∂ P̄ f¯ k̄ f¯

This latter expression can also be written in index notation as mentioned in (49). The stiffness of the chain k̄ represents the
additional amount of force required per unit of additional elongation. When the chain is not crystallizing, its value is given
as
∂ f¯
k̄ = = K11 (not crystallizing) (C.11)
∂λ
96 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

but during the change in crystallization, we must account for the softening due to crystallization. In the MAPC algorithm, the
crystallization occurs while the chain crystallization residual rw remains zero. So replacing drw = 0 in (44) and incorporating
(B.7) we obtain
0 = drw = −dω + t (K21 dλ + K22 dω ) (crystallizing) (C.12)

tK21
dω = dλ (crystallizing) (C.13)
1 − tK22


tK21
d f¯ = K11 dλ + K12 dω = K11 + K12 dλ (crystallizing) (C.14)
1 − tK22
tK12 K21
k̄ = K11 + (crystallizing). (C.15)
1 − tK22

C2. Continuous representation of crystallinity

As described in (60) the MAPC tangent for the continuous crystallinity distribution is composed of the tangent with con-
stant crystallinity and the adjustment required for the change in  during the iteration. The first expression, corresponding
to no change in crystallinity, is the same as substituting K11 for k̄ in (49) because K11 refers to the change in the chain force
for no change in stretch assuming the crystallinity is constant. Thus,
 nint
k

∂ Rλ  λl 1 λkl ˆ k ˆ k
−  =3 1+ − λl  λl ((λ0 )l  (λ0 )l ) where (AB )i jkl = Aik B jl . (C.16)
∂ P̄ =cst l=1
f¯lk (K11 )kl f¯lk
The second part of the tangent expression requires the calculation of the change in the MAPC residual with change in the
crystallinity parameter ∂ Rλ /∂ i and the evolution of the crystallinity internal variables as a function of the change in the
stress tensor ∂ i /∂ P̄ . The calculation of ∂ Rλ /i must be carried out assuming that the stress tensor is constant because the
variation of the MAPC residual with respect to the stress tensor is already included in (C.16). Thus,

∂ Rλ ∂λ ∂λ  ∂ω ˆ
= −  λ0  = − λ  λ0  .
∂ω  f¯=cst ∂ i
(C.17)
∂ i ∂ i
Note that since the stress tensor is kept constant, it implies that the chain force is also assumed to be constant during this
calculation, i.e.

∂λ  K12
0 = d f¯ = K11 dλ + K12 dω →  =− (C.18)
∂ω f¯=cst K11
and
∂ Rλ K12 ∂ω ˆ
= λ  λ0  . (C.19)
∂ i K11 ∂ i
The final expression to calculate is ∂ i /∂ P̄ . This parameter is zero when the material is not crystallizing, i.e. when the
crystallinity is zero, a = 0, and the crystallinity rate is not positive, a˙ ≤ 0. In the case when the crystallinity internal variables
are changing, this derivative must be calculated assuming that the crystallinity evolution residual is identically zero during
the time step, i.e.

 
∂ω
0 = dR = −d + t d A ω˙  .
−1
(C.20)
∂
 
∂ω
Both A and do not depend on the value of P̄ . Therefore, this expression can be simplified as
∂


 
∂ R ∂ R ∂ ˙ ∂ ω˙ ∂ω
0= d + : dP̄ = − I4 − t d + t A−1 : dP̄  (C.21)
∂ ∂ P̄ ∂ ∂ P̄ ∂
   ∂ω 
−1 ∂ ω ˙ 
0 = −K d + t A  3λ · dP̄ λ0
ˆ  (C.22)
∂ f¯ ω=cst ∂
where the equality d f¯ = λˆ · d f¯ = 3λ
ˆ · dP̄ λ0 is incorporated. The calculation of ∂ ω˙ /∂ f¯ is performed with no change in ω
because this variation is already included in d. Thus,


d f¯ − 0 ∂ ω˙  K21
dω = 0 ⇒ dω˙ = K21 dλ + 0 = K21 ⇒  = . (C.23)
K11 ∂f ¯ ω = cst K11
By substituting (C.23) into (C.22) and solving for ∂ i /∂ P̄ , expression (62) is obtained.
R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99 97

Appendix D. Derivation of the Cauchy stress and the consistent tangent

For computing the consistent tangent of the material we first find the relationship between the change in P̄ and the
change in F̄ , using (C.4). In all steps of the iteration, the MAPC residual is kept identically zero and thus we can incorporate
dRλ = 0 as
1
0 = d Rλ = dF̄ − Kλ : dP̄ (D.1)
3

∂ P̄ 1 −1
= K (D.2)
∂ F̄ 3 λ



∂ P̄iJ 1 λ 1 λ ˆ ˆ
= δik + − λi λk (λ0 )J (λ0 )L −1 . (D.3)
∂ F̄kL 9 f¯ k̄ f¯
In order to convert ∂ P̄ /∂ F̄ to the isochoric consistent tangent C̄ we have to write the expression for the rate of change of
the isochoric stress


∂ P̄ ˙ T
£¯v (τ̄ ) = τ̄˙ − l¯τ̄ − τ̄ l¯T = P̄˙ F̄ T + P̄ F̄˙ T − l¯τ̄ − P̄ F̄ T l¯T = : F̄ F̄ + P̄ (l¯F̄ )T − l¯τ̄ − P̄ F̄ T l¯T (D.4)
∂ F̄


∂ P̄ ¯
£¯v (τ̄ ) = : (l F̄ ) F̄ T − l¯τ̄ (D.5)
∂ F̄
and extract the velocity gradient tensor l¯ using the index notation


  ∂ P̄iA ¯ ∂ P̄iA
£¯v (τ̄ ) = lkl F̄lB F̄jA − l¯il τ̄l j = F̄lB F̄jA − δik τ̄l j l¯kl . (D.6)
ij
∂ F̄kB ∂ F̄kB
The 4th order tensor appearing in equation (D.6) can be shown to be symmetric with respect to the indices k and l (the
proof is presented in Remark 3). Thus, we can replace l¯kl with its symmetric component d¯kl = (l¯kl + l¯lk )/2, to get
1
£¯v τ̄ = C̄ : d¯ = C̄ : £¯v g (D.7)
2
where
∂ P̄iA
C̄i jkl = F̄lB F̄jA − δik τ̄l j . (D.8)
∂ F̄kB
Remark 3. To prove the minor symmetry of the isochoric spatial modulus, we can write the spatial modulus as
 ∂ (P̄ F̄ ) ∂ F̄jA  ∂ τ̄
F̄lB − δik τ̄l j = − P̄iA δ jk δAB F̄lB − δik τ̄l j
iA jA ij
C̄i jkl = − P̄iA (D.9)
∂ F̄kB ∂ F̄kB ∂ F̄kB
∂ τ̄i j  
C̄i jkl = F̄lB − δ jk τ̄il + δik τ̄l j . (D.10)
∂ F̄kB
The second term in (D.10) has obvious minor symmetry. For proving the minor symmetry of the first statement assume
 = τ̄i j is the scalar value of one of the components of τ̄ .  is a function of F̄ and since τ̄ is objective,  is also a function
of C̄ . Thus,
∂ ˙
˙ = : F̄ (D.11)
∂ F̄
and
∂ ˙ ∂  ˙ T  ∂  T ˙   ∂ ˙
˙ = : C̄ = : F̄ F̄ + F̄ T F̄˙ = : 2F̄ F̄ = 2F̄ : F̄ (D.12)
∂ C̄ ∂ C̄ ∂ C̄ ∂ C̄
Since F̄˙ is arbitrary, equating expressions (D.11) and (D.12) results in
∂ ∂
= 2F̄ (D.13)
∂ F̄ ∂ C̄
∂ ∂ T ∂ T
F̄lB ek  el = F̄ = 2F̄ F̄ → symmetric . (D.14)
∂ F̄kB ∂ F̄ ∂ C̄
∂ τ̄i j
Therefore, F̄lB is symmetric with respect to the indices k and l. As a result, the minor symmetry of C̄ is proved.
∂ F̄kB
98 R. Rastak, C. Linder / Journal of the Mechanics and Physics of Solids 111 (2018) 67–99

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