Nano Materials Science 4 (2022) 64–82

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Nano Materials Science

journal homepage: www.keaipublishing.com/cn/journals/nano-materials-science/

A comparative study of 85 hyperelastic constitutive models for both unfilled

rubber and highly filled rubber nanocomposite material
Hong He a, b, Qiang Zhang a, b, Yaru Zhang a, Jianfeng Chen a, Liqun Zhang a, c, **, Fanzhu Li a, c, *
a
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China
b
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing, 100029, China
c
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing, 100029, China

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

Keywords: Nonlinear finite element analysis is widely used for structural optimization of the design and the reliability
Rubber-like materials analysis of complex elastomeric components. However, high-precision numerical results cannot be achieved
Hyperelastic constitutive model without reliable strain energy functions (SEFs) of the rubber or rubber nanocomposite material. Although
Strain energy function
hyperelastic constitutive models have been studied for nearly 80 years, selecting one that accurately describes
Phenomenological model
Micromechanical network model
rubber's mechanical response is still a challenge. This work reviews 85 isotropic SEFs based on both the
UHYPER subroutine phenomenological theory and the micromechanical network theory proposed from the 1940s to 2019. A fitting
algorithm which can realize the automatic fitting optimization and determination of the parameters of all SEFs
reviewed is developed. The ability of each SEF to reproduce the experimental data of both the unfilled and highly
filled rubber nanocomposite is quantitatively assessed based on a new proposed evaluation index. The top 30 SEFs
for the unfilled rubber and the top 14 SEFs for the highly filled rubber nanocomposite are presented in the ranking
lists. Finally, some suggestions on how to select an appropriate hyperelastic constitutive model are given, and the
perspective on the future progress of constitutive models is summarized.

1. Introduction tions, including nearly 60 papers with “hyperelastic”, “model”, and

Rubber and rubber-like materials (RLMs) exhibit many unique
physical and chemical properties [1,2], such as elasticity, resilience,
flexibility, shock absorption, damping, sealing capability, insulation, etc.
These properties of RLMs enable them to meet a wide range of re-
quirements in industrial and engineering applications [3,4], such as tire,
hose, conveyor belt, seal, damping component, artificial soft tissue, etc.
The study of the stress-strain response of rubber is extremely important
and an active research topic. With the fast development of computing
power and non-linear numerical simulation techniques, finite element
analysis (FEA) has been applied successfully to the structural optimiza-
tion of the design and the reliability analysis of complex rubber com-
ponents with large deformation [5–7]; however, a high-precision
numerical result of strain and/or stress distribution cannot be achieved
without reliable hyperelastic constitutive models of the RLMs used [8].
According to search in Google Scholar, a considerable amount of
scientific literature on hyperelastic constitutive models of RLMs has been
steadily accumulating since the 1940s, producing over 16,000 publica-
“rubber” in the title. For example, the pioneering work by Boyce and
Arruda [9] focused on comparison of the accuracy of 5 hyperelastic
constitutive models based on the well-known experimental data of Tre-
loar [10] under three deformation modes, i.e., uniaxial tension (UT),
pure shear (PS), and equibiaxial tension (ET). Attard and Hunt [11] then
verified the validity of their rubber constitutive model with the different
types of experimental data of UT, ET, planar tension (PT), biaxial tension
(BT) and uniaxial compression (UC). Hoss and Marczak [12,13] classified
and sorted 40 strain energy functions (SEFs) based on strain invariants
proposed from the year 1944–2010. They found that the models
including the eI1 term could represent the softening characteristic at small
strain while the models containing the ln I2 term could easily capture the
stress hardening at high strain. Another outstanding work was done by
Marckmann and Verron [14]. They compared 20 different hyperelastic
constitutive models, ranking them by their ability to reproduce the
experimental data. Steinmann and Hossain [15,16] systematically
reviewed 25 hyperelastic constitutive models and found that it was
difficult to reliably predict the mechanical behavior of RLMs under all

* Corresponding author. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China.
** Corresponding author. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China.
E-mail addresses: zhanglq@buct.edu.cn (L. Zhang), lifz@buct.edu.cn (F. Li).

https://doi.org/10.1016/j.nanoms.2021.07.003
Received 2 April 2021; Accepted 21 June 2021
Available online 16 July 2021
2589-9651/© 2021 Chongqing University. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
H. He et al. Nano Materials Science 4 (2022) 64–82

Fig. 1. The classification of 85 hyperelastic SEFs for RLMs.

Table 1
14 phenomenological models in the form of the series function based on invariants (Params represents the number of material parameters).
Model Name Year Strain Energy Function Params Parameters

Mooney-Rivlin [49] 1940 W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ 2 C10 ; C01

Neo-Hookean [48] 1943 W ¼ C10 ðI1  3Þ 1 C10
Isihara [51] 1951 W ¼ C10 ðI1  3Þ þ C20 ðI1  3Þ2 C01 ðI2  3Þ 3 C10 ; C20 ; C01
Biderman [52] 1958 W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ þ C20 ðI1  3Þ2 þ C30 ðI1  3Þ3 4 C10 ; C01 ; C20 ; C30
James-Green-Simpson 1975 W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ þ C11 ðI1  3ÞðI2  3Þ þ C20 ðI1  3Þ2 þ C30 ðI1  3Þ3 5 C10 ; C01 ; C11 ; C20 ; C30
[53]
Haines-Wilson [54] 1979 2 2
W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ þ C11 ðI1  3ÞðI2  3Þ þ C02 ðI2  3Þ þ C20 ðI1  3Þ þ 6 C10 ; C01 ; C11 ; C02 ; C20 ; C30
C30 ðI1  3Þ3
P
Yeoh [55] 1990 W ¼ 3i¼1 Ci0 ðI1  3Þi 3 C10 ; C20 ; C30
Lion [56] 1997 W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ þ C50 ðI1  3Þ5 3 C10 ; C01 ; C50
Haupt-Sedlan [57] 2001 W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ þ C11 ðI1  3ÞðI2  3Þ þ C02 ðI2  3Þ2 þ C30 ðI1  3Þ3 5 C10 ; C01 ; C11 ; C02 ; C30
Hartmann-Neff [58] 2003 P P 3=2 pffiffiffi j 2Nþ1 α; Ci0 ; C0j
W ¼ αðI13  33 Þ þ Ni¼1 Ci0 ðI1  3Þi þ Nj¼1 C0j ðI2  3 3 Þ , N ¼ 1; 2; 3:::
Carroll [59] 2011 W ¼ AI1 þ BI14 þ CI2
1=2 3 A; B; C
Nunes [60] 2011 4 2 C1 ; C2
W ¼ C1 ðI1  3Þ þ C2 ðI2  3Þ3=4
3
Bahreman-Darijani [61] 2014 W ¼ A2 ðI1  3Þ þ B2 ðI2  3Þ þ A4 ðI12  2I2  3Þ þ A6 ðI13  3I1 I2 Þ 4 A2 ; B2 ; A 4 ; A 6
Zhao [62] 2019 W ¼ C1
1
ðI2  3Þ þ C11 ðI1  3Þ þ C21 ðI12  2I2  3Þ þ C22 ðI12  2I2  3Þ
2 4 1
C1 ; C11 ; C21 ; C22

deformation modes when only one type of test data was provided. Hor-
gan and Saccomandi [17–19] introduced the theory of limiting chain
extensibility in detail and reviewed the related hyperelastic constitutive
models of rubber-like and biological materials. Martins et al. [20] eval-
uated the accuracy of 7 hyperelastic constitutive models to study the
nonlinear mechanical response of soft tissue and silicone rubber via
correlations between experimental and theoretical data. Beda [21]
summarized 29 phenomenological hyperelastic constitutive models of
RLMs and explained the derivation process of some classical constitutive
models such as the Takamizawa-Hayashi model, the Hart-Smith model,
the Gent model, and the Beda model. Dal et al. [22] reviewed the
reproducibility of experimental data according to 40 hyperelastic
constitutive models using the multi-objective optimization parameter
identification toolbox. Ding et al. [23] showed the derivation relations of
31 hyperelastic constitutive models including phenomenological models
and statistical mechanics models. In addition, the similarity and quan-
titative equivalence of different models were given using the coefficient
of determination and the Fr
echet distance between models.

65
H. He et al. Nano Materials Science 4 (2022) 64–82

Table 2
26 phenomenological models in the form of the power law, exponential or logarithmic functions based on invariants.
Model Name Year Strain Energy Function Params Parameters
  
Knowles [65] 1977 μ bðI1  3Þ n 3 μ; b; n
W ¼ 1þ 1
2b n
 1þαi  1þβi
Swanson [66] 1985 3 XN Ai I1 3 XN Bi I2 4N Ai ; α i ; Bi ; β i
W ¼ þ , N ¼ 1; 2; 3:::
2 i¼1 1 þ αi 3 2 i¼1 1 þ βi 3
Yamashita-Kawabata [67] 1992 C3 Nþ1 4 C1 ; C2 ; C3 ; N
W ¼ C1 ðI1  3Þ þ C2 ðI2  3Þ þ ðI1  3Þ
Nþ1
Davis-De-Thomas [68] 1994 A 2 ð1n=2Þ 4 A; n; C; k
W ¼ ðI1  3 þ C Þ þ kðI1  3Þ2
2ð1  n=2Þ
Gregory [69] 1997 A B 5 A; B; C; m; n
W ¼ ðI1  3 þ C2 Þð1n=2Þ þ ðI1  3 þ C2 Þð1þm=2Þ
2ð1  n=2Þ 2ð1 þ m=2Þ
modified Gregory 2021 A B 6 A; α; M; B; β; N
W ¼ ðI1  3 þ M 2 Þ1þα þ ðI1  3 þ N 2 Þ1þβ
1þα 1þβ
Beda [70] 2005 C1 C3 K0 7 C1 ; C2 ; C3 ; α; ς; β
W ¼ ðI1  3Þα þ C2 ðI1  3Þ þ ðI1  3Þς þ ðI2  3Þβ
α ς β
Amin [71] 2006 C2 C3 6 C1 ; C2 ; C3 ; C4 ; N; M
W ¼ C1 ðI1  3Þ þ ðI1  3ÞNþ1 þ ðI1  3ÞMþ1 þ C4 ðI2  3Þ
Nþ1 Mþ1
Lopez-Pamies [72] 2010 PN 31αi αi α
2N αi ; μi
W ¼ i¼1 μi ðI1  3 Þ, N ¼ 1; 2; 3:::
i
αi
gen-Yeoh [73] 2019 W ¼ K1 ðI1  3Þm þ K2 ðI1  3Þp þ K3 ðI1  3Þq 6 K1 ; K2 ; K3 ; m; p; q
Hart-Smith [74] 1966 ∂W ∂W k2 3 G; k1 ; k2
¼ G exp½k1 ðI1  3Þ2 , ¼G
∂I1 ∂I2 I2
Veronda-Westmann [75] 1970 W ¼ C1 ðeαðI1 3Þ  1Þ þ C2 ðI2  3Þ 3 C1 ; C2 ; α
Fung-Demiray [76,77] 1972 μ 2 μ; b
W ¼ ðebðI1 3Þ  1Þ
2b
μ μ; b; α
Vito [78] 1973 W ¼ ðebðαðI1 3Þþð1αÞðI2 3ÞÞ  1Þ 3
2b
Humphrey-Yin [79] 1987 W ¼ C1 ðeC2 ðI1 3Þ  1Þ 2 C1 ; C2
modified Yeoh [80] 1993 α 5 C10 ; C20 ; C30 ; α; β
W ¼ C10 ðI1  3Þ þ C20 ðI1  3Þ2 þ C30 ðI1  3Þ3 þ ð1  eβðI1 3Þ Þ
β
Martins [81] 1998 2
W ¼ C1 ðeC2 ðI1 3Þ  1Þ þ C3 ðeC4 ðλf 1Þ  1Þ 4 C1 ; C2 ; C3 ; C4
Chevalier-Marco [82] 2002 ∂W P ∂W P bi 2(Nþ1) ai ; bi
¼ expf Ni¼0 ai ðI1  3Þi g, ¼ Ni¼0 i , N ¼ 1; 2; 3:::
∂I1 ∂I2 I2
Gornet-Desmorat [83] 2012 R 2 R 1 3 h1 ; h2 ; h3
W ¼ h1 eh3 ðI1 3Þ dI1 þ 3h2 pffiffiffiffidI2
I2
Mansouri-Darijani [84] 2014 W ¼ A1 ½em1 ðI1 3Þ  1 þ B1 ½en1 ðI2 3Þ  1 4 A1 ; m1 ; B1 ; n1
 
Gent-Thomas [85] 1958 I2 2 C1 ; C2
W ¼ C1 ðI1  3Þ þ C2 ln
3
 
Alexander [86] 1968 R ðI2  3Þ þ γ 5 C1 ; k; C2 ; γ; C3
W ¼ C1 exp kðI1  3Þ2 dI1 þ C2 ln þ C3 ðI2  3Þ
γ
R P2 R P1
Lambert Diani-Rey [87] 1999 W ¼ expf i¼0 ai ðI1  3Þ gdI1 þ expf i¼0 bi ðln I2 Þi gdI2
i 5 a0 ; a1 ; a2 ; b0 ; b1
  
Hoss-Marczak-I [13] 2010 α ðI 3Þ μ bðI1  3Þ n 5 α; β; μ; b; n
W ¼ ð1  eβ 1 Þ þ 1þ 1
β 2b n
    
Hoss-Marczak-II [13] 2010 α ðI 3Þ μ bðI1  3Þ n I2 6 α; β; μ; b; n; C2
W ¼ ð1  eβ 1 Þ þ 1þ  1 þ C2 ln
β 2b n 3
 
Exp-Ln [88] 2013 1 1 3 A; a; b
W ¼ A eaðI1 3Þ þ bðI1  2Þð1  lnðI1  2ÞÞ   b
a a

Although hyperelastic constitutive models of RLMs have been studied
for nearly 80 years, how to construct and select a reasonable constitutive
model to accurately describe the mechanical response of rubber is still
one of the major active research fields of RLMs. The sea of scientific
papers and the constantly evolving constitutive models make it chal-
lenging for researchers and engineers to select the most reliable
hyperelastic constitutive model from among all the models existing.
To gain a clearer picture, this article is organized as follows: This
work first comprehensively reviews 85 isotropic hyperelastic SEFs based
on both the phenomenological theory and the micromechanical network
theory proposed from the 1940s to the year 2019. Then a fitting algo-
rithm using the nonlinear least square optimization method is developed
that can simultaneously realize the automatic fitting optimization and
parameters determination of all the hyperelastic SEFs. The ability of each
SEF to reproduce the experimental data of both the unfilled and highly
filled rubber materials is quantitatively assessed based on a new pro-
posed evaluation index. The top 30 SEFs for the unfilled rubber and the
top 14 SEFs for the highly filled rubber materials are presented in the
ranking lists. We also list the suggested value regions of the material
parameters for all the micromechanical network models and part of the
phenomenological models based on the literature survey and our fitting
results. Finally, some suggestions are given on how to select an
appropriate isotropic hyperelastic constitutive model of RLMs, and the
perspective on the progress of constitutive models of RLMs is
summarized.
2. Some basic concepts of hyperelastic constitutive models
Before the review work, we simply introduce some basic concepts of
hyperelastic constitutive models. Different from the microstructure of
metal, ceramic, or plastic, the very flexible and long macromolecular
chains together with crosslinking and entangled macromolecular
network render rubber a special mechanical response; for example, it can
deform nonlinearly with large deformation, and it can almost completely
recover its original configuration when the external force is removed [24,
25]. Due to the strong geometrical and physical nonlinearity and the
nearly incompressible nature of rubber, the constitutive models of rubber
materials are generally represented by a strain energy function (W)
rather than a direct stress-strain relation. The complex and highly
non-linear behavior of rubber is generally studied from the following five
main aspects [26]: (i) the hyperelastic behavior under static or
quasi-static load, (ii) the viscoelastic behavior under cyclic loadings such
as hysteresis [27] and the Payne effect [28–30], (iii) the permanent set
and stress-softening phenomenon also called the Mullins effect under

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H. He et al. Nano Materials Science 4 (2022) 64–82

Table 3
11 phenomenological models considering the limiting chain extensibility based on invariants.
Model Name Year Strain Energy Function Params Parameters
 
Warner [90] 1972 1 I1  3 2 μ; Im
W ¼  μIm ln 1 
2 Im  3
  rffiffiffiffiffiffiffiffiffiffiffiffiffi  rffiffiffiffiffiffiffiffiffiffiffiffiffi 
Kilian [91] 1981 I1  3 I1  3 2 μ; JL
W ¼  μJL ln 1  þ
JL JL
Van der Waals [92–94] 1986  3 4 μ; λm ; β; a
2 I3 2
W ¼ μ  ðλ2m  3Þ½lnð1  ΘÞ þ Θ  a
3 2
 
Gent [89] 1996 E I1  3 2 E; Im
W ¼  ðIm  3Þln 1 
6 Im  3
   
Takamizawa-Hayashi [95] 1987 I1  2 2 2 c; Jm
W ¼  c ln 1 
Jm
0 1
Yeoh-Fleming [96] 1997 I1  3   4 A; B; Im ; C10
A B B
C I1  3
W ¼ ðIm  3Þ@1  e Im  3 A  C10 ðIm  3Þln 1 
B Im  3
   
3 Parameters Gent [97] 1999 μ I1  3 3 α; μ; Im
W ¼  αðIm  3Þln 1  þ ð1  αÞðI2  3Þ
2 Im  3
   
Pucci-Saccomandi [98] 2002 I2 μ I1  3 3 K; μ; Jm
W ¼ K ln  Jm ln 1 
3 2 Jm
 2 
Horgan-Saccomandi [99] 2004 μ J  J 2 I1 þ JI2  1 2 μ; J
W ¼  J ln
2 ðJ  1Þ3
 
Beatty [100] 2007 Im ðIm  3Þ 1  ðI1  3Þ=ðIm  3Þ 2 c; Im
W ¼ c ln
2Im  3 1 þ ðI1  3Þ=Im
 
Horgan-Murphy [101] 2007 2μðIm  3Þ λc þ λc2 þ λc3  3 3 μ; c; Im
W ¼  ln 1  1
c2 Im  3

cyclic loadings [31–33], (iv) the orthotropic or even anisotropic me-
chanical response [34,35], and (v) damage, failure, and aging [36–38].
In this work, the RLMs are considered to be homogeneous, isotropic,
incompressible or nearly incompressible, and all inelastic phenomena
such as permanent set, hysteresis, Payne effect, Mullins effect or damage
are tacitly ignored. We only focus on the isotropic hyperelastic response
of RLMs under the static or quasi-static load.
Based on the continuum mechanics method [39,40], for homoge-
neous, isotropic, and incompressible or nearly incompressible rubber, the
SEF can be written in a polynomial form composed of strain invariants (or
expressed in the form of a stretch ratio). The three strain invariants of the
right Cauchy-Green deformation tensor are as follows:
I1 ¼ λ21 þ λ22 þ λ23
I2 ¼ λ21 λ22 þ λ22 λ23 þ λ21 λ23
I3 ¼ λ21 λ22 λ23
where I is the strain invariant and λ is the stretch ratio. The subscripts 1,
2, and 3 stand for the three principal directions.
For the nearly incompressible rubber, the SEF can be expressed as the
sum of the deviatoric hyperelasticity (WDev) for shape change and the
dilatational hyperelasticity (WDil) for volume change, shown in Eq. (4).
 
W ¼ WDev I1 ; I2 þ WDil ðJÞ
pffiffiffiffi
where I1 ¼ I1 =J 2=3 , I2 ¼ I2 =J 4=3 , J ¼ I3 .
For incompressible rubber, the SEF can be expressed only as devia-
toric hyperelasticity without dilatational hyperelasticity. This means the
third strain invariant I3 equals one.
W ¼ WDev ðI1 ; I2 Þ
This work focuses on the deviatoric strain energy function WDev of
incompressible RLMs.
3. Review of hyperelastic constitutive models of RLMs
Vahapo glu and Karadeniz [41] pointed out that Green first theoreti-
cally dealt with the mechanical response of RLMs in 1839. Since then, the
term “hyperelastic” has been used to express the elasticity of rubber. The
general equation of the theory of large deformation elasticity was greatly
developed in the 19th century. But unfortunately, it developed slowly
from 1900 to 1940. Until the 1940s, Rivlin's work [42–44] opened a new
era in the research field of rubber hyperelasticity. He pointed out that the
SEF can be used to express the stress-strain relationship of RLMs under
finite strain or large deformation. After that, a large number of SEFs for
the elastic response of rubber were reported.
The SEFs of RLMs can be roughly divided into two main categories:
(1) phenomenological models based on continuum mechanics and micro-
mechanical network models based on microstructure. The 85 SEFs of
(2) RLMs we review are shown in Fig. 1. The detailed introduction of the
model classification is shown in a later section.
(3)
3.1. Phenomenological models
Phenomenological models are based on the fitting of experimental
data of mechanical response via mathematical equations, and, in most
cases, the material parameters do not have physical meanings [45]. As
mentioned earlier, the phenomenological model can be expressed by the
combination of the strain invariants and/or stretch ratio. Such models
(4) can be further divided into phenomenological models based on strain
invariants, phenomenological models based on stretch ratio, and mixed
phenomenological models based on both strain invariants and stretch
ratio.
3.1.1. Phenomenological models based on strain invariants
The phenomenological models based on strain invariants can be
(5) further divided into three types: (1) series function models; (2) power
law, exponential or logarithmic function models; and (3) limiting chain
extensibility models.

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H. He et al. Nano Materials Science 4 (2022) 64–82

Table 4
6 phenomenological models based on stretch ratio.
Model Name Year Strain Energy Function Params Parameters
P3
Valanis-Landel [102] 1967 W ¼ 2μ i¼1 ½λi ðln λi  1Þ 1 μ
 
Peng-Landel [103] 1972 P 1 1 1 1 E
W ¼ E 3i¼1 λi  1  ln λi  ðln λi Þ2 þ ðln λi Þ3  ðln λi Þ4
6 18 216
Ogden [104] 1972 P 2μ 2N αi ; μ i
W ¼ Ni¼1 2i ðλα1i þ λα2i þ λα3i  3Þ
αi
Attard [11] 2004 PN Ai Bi 2N Ai ; B i
W ¼ i¼1 ½ðλ1 Þ2i þ ðλ2 Þ2i þ ðλ3 Þ2i  3 þ ½ðλ1 Þ2i þ ðλ2 Þ2i þ ðλ3 Þ2i  3, N ¼ 1; 2; 3:::
2i 2i
P3 Pn
Shariff [106] 2000 W ¼ i¼1 ωðλi Þ, ωðλi Þ ¼ E j¼0 αj φj ðλi Þ 5 E; α1 ; α2 ; α3 ; α4
Arman-Narooei [107] 2014 P αi αi αi P βj βj βj
6N Ai ; Bj ; mi ; nj ; αi ; βj
W ¼ Ni¼1 Ai ½emi ðλ1 þλ2 þλ3 3Þ  1 þ Nj¼1 Bj ½enj ðλ1 þλ2 þλ3 3Þ  1, N ¼ 1; 2; 3:::

Table 5
Mixed phenomenological models.
Model Name Year Strain Energy Function Params Parameters

Continuum Hybrid [108] 2003 I2 μ 4 K 1 ; K 2 ; α; μ

W ¼ K1 ðI1  3Þ þ K2 ln þ ðλα1 þ λα2 þ λα3  3Þ
3 α
P2 P2 r
Bechir-4term [109] 2006 W ¼ C1 ðI1  3Þ þ n¼1 r¼1 Cnr ðλ2n
1
1 þ λ2 þ λ3  3Þ
2n 2n 4 C11 ; C12 ; C21 ; C22
 
WFB [110] 2017 R Lf 1 4 A; B; C; D
W ¼ 1 fFðλ1 ÞAðλ1 eBI1 Þ þ Cðλ1 I1D Þg λ1 
2
dλ1
λ1

Table 6
Gaussian chain network models.
Model Name Year Strain Energy Function Params Parameters

Gaussian [113] 1943 1 1 NkT

W ¼ NkTðλ21 þ λ22 þ λ23  3Þ
2
Affine [114–116] 1946 G 1 G
W ¼ ðλ21 þ λ22 þ λ23  3Þ, G ¼ υkT
2  
Phantom [117,118] 1947 υkT 2 1 Gc
W ¼ 1 ðλ21 þ λ22 þ λ23  3Þ, Gc ¼ υkTð1  2 =f Þ
2 f
Edwards-Tube [119] 1967 W ¼ Ge ðλ21 þ λ22 þ λ23  3Þ 1 Ge
0 1
Slip-Link [120] 1981 3 Ge ; η; α
1 X3 B B ð1 þ ηÞð1  α2 Þλ2i P C
C
W ¼ Ge B
i¼1 @
P þ lnð1 þ η 3i¼1 λ2i ÞC
2 ð1 þ ηλ2i Þð1  α2 3i¼1 λ2i Þ A

  2  
Constrained Junctions [121,122] 1982 νkT X
λ2t  1 λ þκ 3 Gc ; νkT; κ
W ¼ Wph þ þ ln t
κ  ln λ2t
2 λ2t þ κ
t
1þκ
0 1
Edwards-Vilgis [123] 1986 4 Gc ; Ge ; α; η
  X B C
Gc ð1  α ÞI1
2
1 3 B ð1 þ ηÞð1  α Þλi
2 2 P C
W ¼ þ lnð1  α2 I1 Þ þ Ge B P þ lnð1 þ η 3i¼1 λ2i ÞC
2 1  α2 I1 2 i¼1 @
ð1 þ ηλ2i Þð1  α2 3i¼1 λ2i Þ A

MCC [124] 1989 1 X 1 X 3 ξkT; μkT; κ

W ¼ ξkT ðλ2i  1Þ þ μkT ½Bt þ Dt  lnð1 þ Bt Þ  lnð1 þ Dt Þ
2 i
2 i
2
Bt ¼ κ 2 ðλ2t  1Þðλ2t þ κÞ , Dt ¼ λ2t Bt =κ
Tube [125] 1997 P Gc 2Ge 3 Gc ; Ge ; β
W ¼ 3i¼1 ðλ2i  1Þ þ 2 ðλβ i  1Þ
2 β
 
Nonaffine-Tube [126] 1997 P3 λ2i P 1 2 Gc ; Ge
W ¼ Wph þ Went ¼ Gc i¼1 þ Ge 3i¼1 λi þ
2 λi

(1) Series function models W ¼ C10 ðI1  3Þ þ C01 ðI2  3Þ (8)

The most general series expansion of SEF based on strain invariants where C10 and C01 are material parameters. The Mooney-Rivlin model
was proposed by Rivlin [46,47]. has been widely used in the analysis of rubber components with medium
deformation. According to Tschoegl [50], the main shortcoming of the
X
∞
Mooney-Rivlin model is that not enough expansion terms are retained
W¼ Cij ðI1  3Þi ðI2  3Þj (6)
i¼0;j¼0
based on the Rivlin polynomial series. Many other researchers have
proposed high-ordered series function models based on the form of the
where Cij are the material parameters. If i ¼ 1 and j ¼ 0, the simplest and Rivlin model. In general, the high-ordered series function models based
widely used Neo-Hookean model [48] can be obtained. on the Rivlin give people the impression that their fitting accuracy is
much higher and the scope of application is wider for these models.
W ¼ C10 ðI1  3Þ (7) However, we think specific analysis is required for some special rubber
materials, which will be discussed later. A full list of the model name, the
If only the first two terms in Eq. (6) are retained, the Mooney-Rivlin
year, the strain energy function, the number of material parameters
model [47] can be obtained.

68
H. He et al. Nano Materials Science 4 (2022) 64–82

Table 7
Non-Gaussian chain network models.
Model Name Year Strain Energy Function Params Parameters
 
Three-Chain [117] 1943 μN X3 pffiffiffiffiffiffiffiffiffi βi 2 μ; N
W ¼ N 1 λi βi þ ln
3 i¼1 sinh βi
Four-Chain [128] 1943 – – –
 
Arruda-Boyce [129] 1993 βchain 2 μ; N
W ¼ μN βchain λchain þ ln
sinh βchain
modified Flory-Erman [9,119] 1993 P μ 3 μ; N; κ
W ¼ W8ch þ 3i¼1 ½Bi þDi lnðBi þ1Þ lnðDi þ1Þ
2
2
Bt ¼ κ2 ðλ2t 1Þðλ2t þ κÞ Dt ¼ λ2t Bt =κ
 
Extended-Tube [130] 1999 Gc ð1  δ2 ÞðI1  3Þ 2Ge X3 4 Gc ; Ge ; δ; β
W ¼ þ lnð1  δ2 ðI1  3ÞÞ þ 2 ðλβ  1Þ
i¼1 i
2 1  δ2 ðI1  3Þ β
Meissner-Matejka (ABGI) [131,132] 2004   γ  P 2μ 4 μ; N; μe ; β
W ¼ μN γλc;r þ ln þ 3i¼1 2e ðλβ  1Þ
sinh γ β i
 
Micro-Sphere [133] 2004 1
L ðλr Þ 5 μ; N; P; U; q
W ¼ μ λr L1 ðλr Þ þ ln
sinh L1 ðλr Þ
   
Bootstrapped-8-Chain [134,135] 2009 λ1 þ λ2 þ λ3 λc λc 2 μ; N
W ¼ W8ch pffiffiffiffiffiffiffi  pffiffiffiffi þ W8ch pffiffiffiffi
3N N N
 
Davidson-Goulbourne [136] 2013 1 P 1 3 Gc ; Ge ; λmax
W ¼ Gc I1  Gc λ2max lnð3λ2max  I1 Þ þ Ge λi þ
6 i λi
Network Averaging Tube [137] 2016   q 4 μc κ; n; q; μt
π I1 2
sin pffiffiffi  1 
n 3 I2 2
W ¼ μc κn ln q þ μt 1
    3
π I1 2
sin pffiffiffi
n 3
0 1
SpT [138] 2018 1 3 Gc ; Ge ; N
3N þ I1 P1
B 2 C
W ¼ Gc N ln@ A þ Ge
3N  I1 i λi

Table 8
Mixed micromechanical network models.
Model Name Year Strain Energy Function Params Parameters
   
Wu-Giessen (Full Network) [139–141] 1992 μ pffiffiffiffi X3 pffiffiffiffi βi βchain 3 μ; N; ρ
W ¼ N λi βi þ N ln ð1  ρÞ þ μN λchain βchain þ ln ρ
3 i¼1 sinh βi sinh βchain
  sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Zuniga-Beatty [142] 2002
λ1 λ1 þ λ2 þ λ3
2 2 2 3 μ; N3 ; N8
W ¼ W3ch 1  pffiffiffiffiffiffi þ W8ch
N3 3N8
Lim [143] 2005 W ¼ WGaussian ð1  f Þ þ fW8ch 4 NkT; μ; N; f
2 0 13
Bechir-Chevalier [144] 2010 h  β i μ Xj¼3 βj 5 μ0 ; η; ρ; N3 ; N8
W ¼ μf N8 λr β þ ln c
þ N3 4 βj λjr þ ln @ A5
sinh β 3 j¼1 sinhβj

involved, the material parameter symbols and the original reference for
each series function model is presented in Table 1.
(2) Power law, exponential or logarithmic function models
Previous studies showed that most rubber materials soften under
small deformation but rapidly stiffen as the strain increases. However
many classical SEFs failed to reproduce such mechanical responses under
all deformation modes [63,64]. For this reason, power law, exponential
and logarithmic functions were introduced to achieve a good prediction
of the mechanical behavior of RLMs. Similar to Table 1, such SEFs are
listed in Table 2. Specifically, inspired by the Gregory model [69], we
propose a modified Gregory model. The expression of the modified
Gregory model is shown in Table 2. Gregory introduced the concept of
variable power to improve the flexibility of the fit. The strain invariants
(I1-3) from the former and latter items in the Gregory model share the
same material parameter C. We changed the material parameter C into
two different material parameters M and N. The newly proposed modi-
fied Gregory model is also a phenomenological model and contains six
material parameters (A, B, M, N, α, and β).
(3) Limiting chain extensibility models
Yeoh [55] modified the SEF by using high-ordered I1 terms in order to
improve the fitting precision of the model for a wide range of strains.
After the high-ordered term was introduced, the model fitting results
were in good agreement with the test data under the condition of large
strains. In addition, the model parameters determined by UT test data
were suitable for other deformation modes (e.g. PT, ET). However, the
Yeoh model was not accurate at small deformation. Gent [89] solved the
problem by introducing the concept of the stretch ratio limit of the
macromolecular chain of rubber. He believed that there was a maximum
value Im; then he proposed the following famous SEF.
 
E I1  3
W¼  ðIm  3Þln 1  (9)
6 Im  3
where E and Im are material parameters. E is the tensile modulus at small
strains. The Gent model can be equivalent to the Neo-Hookean model
when Im tends to infinity. Other models related to the limited extensi-
bility of macromolecular chains are introduced in Table 3.
3.1.2. Phenomenological models based on the stretch ratio
Valanis and Landel [102] proposed a simple phenomenological SEF
based on the stretch ratio for incompressible rubber materials, shown in
Eq. (10).

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H. He et al. Nano Materials Science 4 (2022) 64–82

the Mooney-Rivlin model. The Ogden model can be utilized in a wide

strain range with great flexibility. Other typical phenomenological
models based on the stretch ratio are shown in Table 4.

3.1.3. Mixed phenomenological models

The phenomenological SEF expressed in terms of both strain in-
variants and stretch ratio is called the mixed phenomenological model in
our work. Most of the SEFs are not applicable to the loading conditions of
both small deformation and large deformation; therefore, the emergence
of mixed SEFs is a good solution. Not only can the mixed models ensure
the accuracy of the simulation, but they also take into account the
respective characteristics of the two SEFs. Typical mixed phenomeno-
logical models include the continuum hybrid model proposed by Beda
and Chevalier [108], the Bechir-4term model [109] and the WFB model
[110]. Mixed phenomenological models are shown in Table 5.

3.2. Micromechanical network models

Micromechanical network models are based on the physical and

Fig. 2. The Treloar's test data (UT, PT and ET) for unfilled rubber. Replotted
from Ref. [10].
statistical methods of polymer chain networks and material microstruc-
ture. Different from the parameters in phenomenological models, the
material parameters of micromechanical network models do have
physical interpretations. So they are superior to the purely phenomeno-
logical models when the models are adopted to explain the relations
between microstructures and properties of RLMs. According to the sta-
tistical characteristics of macromolecular chains, micromechanical
network models can be divided into three types: Gaussian chain network
models, non-Gaussian chain network models and mixed micro-
mechanical network models.

3.2.1. Gaussian chain network models

Kuhn [111,112] first proposed the use of statistical theory to calculate
the conformation of the polymer chain. He considered that the proba-
bility density function of the end distance of the polymer chain in small
deformation and the free state is a Gaussian function. Treloar [113]
applied Gaussian statistical theory to the molecular chain network to
describe the macroscopic behavior of RLMs and obtained the SEF shown
in Eq. (13).

1
W ¼  TΔS ¼ NkT λ21 þ λ22 þ λ23  3 (13)
2
ΔS represents the change in conformational entropy of the molecular
Fig. 3. The test data (UT and UC) of a highly filled hydrogenated nitrile-
chain per unit volume, N is the number of network chains in the cross-
butadiene rubber (HNBR) compound for a typical packer seal. Replotted
linked network per unit volume, T is the thermodynamic temperature,
from Ref. [73].
k is the Boltzmann's constant, NkT represents the initial shear modulus.
The Gaussian model is based on the assumption that the end distance is
X
3
W ¼ 2μ ½λi ðln λi  1Þ (10) much smaller than the total length of the chain. It can only be used to
i¼1 approximate the situation of small deformation. The Gaussian model is
equivalent to the Neo-Hookean phenomenological model, and it assumes
where μ is a material parameter. Based on the hypothesis proposed by that the ideal polymer network is composed of chains that freely pass
Valanis and Landel, Peng and Landel [103] obtained a SEF in the through each other without considering the intermolecular forces.
following form. However, in real macromolecular networks, the polymer networks have
topological constraints due to the formation of entangled and cross-
X3  
1 1 1 linked states. A series of micromechanical models based on Gaussian
W ¼E λi  1  ln λi  ðln λi Þ2 þ ðln λi Þ3  ðln λi Þ4 (11)
i¼1
6 18 216 chain distribution, shown in Table 6, was developed after considering
such effects. These models can only describe the stress-strain responses
where E is a material parameter. To reduce the complexity of using in- from small to moderate deformations and fail to describe stress hard-
variants to describe the SEF, Ogden [104] ignored the assumption that ening under large deformation.
the SEF was an even function of the principal stretch ratio and proposed a
new SEF, shown in Eq. (12). 3.2.2. Non-Gaussian chain network models
When the end distance of the molecular chain reaches 40% of the
X
N
2μ
W¼ n
λα1 n þ λα2n þ λα3n  3 (12) fully extended length, the influence of non-Gaussian chains should be
n¼1
α2n considered. Therefore, to improve the accuracy and applicability of the
models, a new model considering the non-Gaussian statistical charac-
where αn, βn are material parameters. Rivlin, Sawyers [105] and Treloar teristics of molecular chains is needed.
[25] pointed out that the Ogden model was a special equivalent form of Kuhn and Grǜn [127] used Langevin statistical theory to explain the

70
H. He et al.
Fig. 4. The top 10 SEFs used to fit the Treloar's data.
effect of molecular chain elongation based on the random walk statistical
theory of the ideal affine chain. The non-Gaussian chain network models
are obtained by applying the mechanical property of the non-Gaussian
single chain to the molecular chains of the rubber network. The
earliest non-Gaussian chain network model is the three-chain model
[117]. This model assumed that the molecular chains of the network
were distributed along three principal directions, and the molecular
chains would show affine deformation with the deformation of the rub-
ber materials (affine hypothesis). Later, Flory [128] proposed the
four-chain network model based on the three-chain network model,
which assumed that four molecular chains were connected to the center
by the four vertices of a tetrahedron. The three-chain network model and
the four-chain network model can describe stress-strain behavior under a
certain deformation mode (e.g. UT) well, but they can't predict the me-
chanical behavior of rubber materials under multiple deformation modes
simultaneously. Based on this, Arruda and Boyce [129] proposed the
Arruda-Boyce model to capture the hardening behavior of the rubber
materials by considering the limited chain extensibility of a single chain.
After the introduction of the effect of chain entanglement and cross-
linking into non-Gaussian theory, a series of non-Gaussian chain models
appeared, shown in Table 7.
3.2.3. Mixed micromechanical network models
Due to the defects of Gaussian chain network models and non-
Gaussian chain network models, some researchers paid attention to the
mixed micromechanical models. Wu and Van der Giessen [139–141]
combined the three-chain model and the Arruda-Boyce model by a
constant or a physical quantity related to the deformation process.
Eli-as-Zuniga and Beatty [142] proposed a combination model of the
three-chain model and the Arruda-Boyce model, to replace the full
network model. Lim [143] proposed a mixed model based on the
Gaussian chain network model and the Arruda-Boyce model in his work,
that is, the Gaussian chain network model is adopted when the length of
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Nano Materials Science 4 (2022) 64–82
the molecular chain end vector is r < 0.8Nl, while the Arruda-Boyce
model is adopted when 0.8Nl < r < Nl. Bechir et al. [144] considered
the influence of the interaction between the chains of the cross-linked
network into a mixed model. The free energy function of the constraint
network is simply processed using the three-chain model, and that of the
unconstrained network is constructed utilizing the Arruda-Boyce model.
See Table 8 for the mixed micromechanical network models.
The phenomenological constitutive models based on continuum me-
chanics can describe the stress-strain response of material under a wide
deformation range. But they could not provide an understanding of the
nature of the molecular structure, and these models may produce unre-
alistic results beyond the deformation mode and strain range determined
by the fitting parameters of the material. The micromechanical network
model based on microstructure is suitable for the establishment of a
correlation between the microstructure of the material and the me-
chanical properties. The parameters in the micromechanical network
model have real physical meanings, so more and more attention has been
paid to the physically-based model by the research community. On the
other hand, with the increasing needs of FEA in the design and optimi-
zation of rubber products, in-depth study of constitutive models for
rubber is essential to improve the accuracy of the FEA.
Tables 1–8 give full lists of the model name, the year, the strain en-
ergy function, the number of material parameters involved and material
parameter symbols. We didn't list the physical meanings of the material
parameters involved one by one in the tables. But we gave the original
reference of each model. There is a clear description of each material
parameter for every model. For the known regions of the material pa-
rameters involved, we listed the suggested value regions for the material
parameters of all the micromechanical network models. Due to the un-
clear physical meaning of the material parameters of the phenomeno-
logical model, the acquisition of such parameters mainly depends on the
fitting optimization algorithm. Similarly, based on the literature survey
and some calculation results, the suggested value regions of the material
H. He et al.
Fig. 4. (continued).
parameters of some phenomenological models are also given. See
Table S1 for details.
The SEFs of RLMs have been studied for nearly 80 years. In the above
section, we comprehensively reviewed 85 hyperelastic SEFs of RLMs
based on phenomenological theory and micromechanical network theory
proposed from the 1940s to the year 2019. Although many pioneering
studies have been done to assess the pros and cons of various SEFs,
especially on the description of unfilled rubber, it is still a burdensome
endeavor to select an appropriate SEF for the RLM at hand. In the
following, we carry out the work on how to evaluate the SEFs and select
the proper one or ones.
4. Determination and evaluation of SEFs for RLMs
The determination and evaluation of hyperelastic constitutive models
are mainly based on the fitting precision that a specific SEF can realize in
reproducing the mechanical response of RLMs. In general, an ideal SEF
should (1) contain as few material parameters as possible; (2) accurately
reproduce a complex mechanical response under multiple deformation
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Nano Materials Science 4 (2022) 64–82
modes and a wide range of strains; (3) contain the material parameters
that do have physical meanings; (4) satisfy the requirement of Drucker
stability [145,146]; (5) take less computational time when used in the
engineering application.
Some outstanding works have been done in this field. Marckmann
and Verron [14] analyzed 20 different models and ranked them for the
Treloar's data. The results showed that the extended-tube model, the
micro-sphere model, the Shariff model and the Ogden model provide the
best results. Dal et al. [22] gave a ranking list of models based on two
groups of experimental data reported by Treloar and Kawabata et al.
[147]. The top five models were the micro-sphere model, the Alexander
model, the Lambert-Diani-Rey model, the extended-tube model, and the
Shariff model. However, considering that the material parameters should
have physical significance, they believed that models with tube con-
straints such as the micro-sphere model and the extended-tube model are
better than the models without tube constraints. Seibert and Schüche
[148] compared the prediction ability of six different models using the
UT and ET test data of carbon black filled rubber, and concluded that the
high-ordered term was very important to reproduce the typical stress
H. He et al.
Fig. 5. The top 14 SEFs used to fit the UT and UC test data for the highly filled HNBR compound.
stiffening characteristics under large deformation. Considering their
experimental data, they found that the Van der Waal model, the
Arruda-Boyce model and the Yeoh model could reliably predict equi-
biaxial tensile response when only the UT test data was provided.
Steinmann and Hossain [15,16] derived accurate stress tensors and
tangent operators from different phenomenological and micro-
mechanical network models, and they revealed the abilities of 25 SEFs to
predict the mechanical response under other deformation modes when
only one kind of experimental data (e.g. UT, PT or ET) was provided.
Because of the shortcomings of the Arruda-Boyce model, which was
known to be significantly deficient in predicting the ET response, Hossain
et al. [149] compared 5 modified versions of the Arruda-Boyce model
and two modified versions of the full network model with the classic
Arruda-Boyce model. He concluded that the Gornet-Desmorat model, the
modified Flory-Erman model, the bootstrapped-8-chain model and the
Meissner-Matejka model could predict the stress-strain response under
all three deformation modes better than the Arruda-Boyce model. Horgan
et al. [150] compared the fitting quality of the Vito model and the
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Nano Materials Science 4 (2022) 64–82
Fung-Demiray model for the experimental data under different defor-
mation modes, and concluded that the SEF with the second strain
invariant of the right Cauchy-Green deformation tensor could more
accurately describe the mechanical response of RLMs. Fujikawa et al.
[151] used the experimental data of UT, PS and BT of vulcanized
styrene-butadiene rubber with different carbon black content to evaluate
the Arman-Narooei model, the SpT model, the Exp-Ln model, and the
Mansouri-Darijani model, and they found that the SEF with the first
strain invariant of the right Cauchy-Green deformation tensor had good
repeatability and predictability for the RLMs studied.
Many pioneering works have been done on the identification of the
parameters of hyperelastic constitutive models of RLMs. These works laid
the in-depth foundation of the research in this field. Benjeddou et al.
[152], N€ orenberg and Mahnken [153], Ogden et al. [154], and Twizell
and Ogden [155] utilized a non-linear least squares optimization method
to estimate the material parameters of the Ogden model. The main dif-
ficulty in the parameter identification process is to determine appropriate
initial values. Dal et al. [156] developed a multi-objective optimization
H. He et al. Nano Materials Science 4 (2022) 64–82

Fig. 5. (continued).

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H. He et al. Nano Materials Science 4 (2022) 64–82

method together with a MATLAB genetic algorithm to identify the pa-

Fig. 6. The evaluation index (EI) values of the top 10 SEFs used to fit the
Treloar's data.
Fig. 7. The evaluation index (EI) values of the top 10 SEFs used to fit the UT and
UC test data for the highly filled HNBR compound.
rameters of 10 SEFs, and obtained the accurate material parameters for
each model. Yevgen et al. [157] developed a program based on
computer-aided engineering to identify and verify the material parame-
ters of 9 SEFs by fitting the Treloar's data.
In addition, with the increasing need for a high quality hyperelastic
constitutive model, lots of fitting tools appeared. For example, the
commercial finite element software ABAQUS provides 17 SEFs in six
categories for the fitting operation. The users can also write UHYPER or
UMAT subroutines to define a specific hyperelastic constitutive model
according to their own design needs. Another commercial finite element
software, ANSYS, can also perform the parameter-fitting calculations of
the hyperelastic constitutive models. Hyperfit [158] is a famous fitting
software for hyperelastic and/or viscoelastic constitutive models. Mate-
rial parameters can be identified from the user's test data. It provides a
large number of isotropic/anisotropic, compressible/incompressible
SEFs to be calibrated for FEA. In addition, MCalibration [159] is a
powerful calibration tool, which can extract the material parameters for
all SEFs in ABAQUS and ANSYS. Plagge developed an on-line platform for
the fitting of hyperelastic constitutive models for RLMs. The platform is
convenient and easy to use. Users can also customize their own proposed
or modified SEFs [160].
However, we need to mention two points here in particular. Firstly,
the hyperelastic SEFs studied by all the previous pioneering work are up
to around 40 types, that we know of. None of these completed works fully
demonstrate the fitting effects of the 85 hyperelastic SEFs we reviewed
above. Secondly, many reported works focused on the experimental data
of unfilled rubber; for example, the classical Treloar's data. Some work
[161,162] concluded that the work on unfilled rubber would be signifi-
cant for filled rubber because the shape of the stress-strain curves with
different filler contents are similar; however, this may be not true for
some highly filled rubber materials.
In this work, we selected the experimental data of two hugely
different rubber materials - the Treloar's data (UT, PT and ET) [10] for
unfilled rubber, shown in Fig. 2, and the test data (UT and UC) [73] for a
highly filled hydrogenated nitrile-butadiene rubber (HNBR) compound,
shown in Fig. 3, for a typical packer seal to compare the reproducibility of
each SEF. The stress-strain responses of the Treloar's data mainly show
that the stiffness decreases at small strains, then a linear interval with
almost constant stiffness appears at medium strains, and finally the
stiffness increases at large strains. This phenomenon is due to the com-
bined effect of the limited extensibility of macromolecular chains and
strain-induced crystallization [25]. The stress-strain curve of the highly
filled HNBR is very different from that of unfilled rubber. Due to the
Payne effect, the filler network is destroyed at low strains and the stiff-
ness decreases rapidly. The UT and UC stress-strain curves show more
prominent nonlinear characteristics.
The nonlinear least square optimization method based on the

Fig. 8. The three-dimensional finite element model and dimensions of the dumbbell rubber specimen composed of 125,307 elements with a thickness of 1 mm.

75
H. He et al. Nano Materials Science 4 (2022) 64–82

Table 9
The computational time and Mises stress distribution of the dumbbell rubber specimen under uniaxial tensile loading for the cases using the Lambert Diani-
Rey model, the Alexander model and the Gornet-Desmorat model implemented with user-defined material subroutines in Abaqus/Standard (UHYPER).
Hyperelastic SEF Computational time (s) Mises stress (MPa)

Lambert Diani-Rey 720

Alexander 698

Gornet-Desmorat 645

 
lsqcurvefit tool from MATLAB software was adopted. We developed an ∂W 2 ∂W 1
σi ¼ 2 λ  p (14)
algorithm program that can realize the automatic fitting optimization ∂I1 i ∂I2 λ2i
and parameters determination of 85 SEFs in turn. The core of this algo-
rithm program is the simultaneous fit of the specific experimental data by ∂W ∂I1 ∂W ∂I2 1
Pi ¼ þ  p (15)
using the derived nominal stress vs. nominal strain expression from each ∂I1 ∂λi ∂I2 ∂λi λi
corresponding SEF under every deformation mode provided from the
test. The criterion for the end of the fitting operation is that the coeffi- In the formula, p represents the hydrostatic pressure. Using the above
cient of determination (R2) reaches the maximum value. The derived formula, the stress-stretch expressions under every simple deformation
nominal stress vs. nominal strain (or stretch ratio) expressions for each mode (UT, PT and ET) can be derived.
corresponding SEF under all deformation modes are given below. To For the deformation mode of uniaxial tension:
describe the large deformation of the RLMs, two types of stresses are   
∂W 1 ∂W 1
classically defined: the true (or Cauchy) stress σ and the engineering (or PUT
1 ¼2 þ λ 2 (16)
∂I1 λ ∂I2 λ
nominal) stress P.

PUT UT
2 ¼ P3 ¼ 0 (17)

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H. He et al. Nano Materials Science 4 (2022) 64–82

Table 10
The computational time and Mises stress distribution of the dumbbell rubber specimen under uniaxial tensile loading for the cases using the modified Gregory
model, the Gregory model and the Davis-De-Thomas model implemented with user-defined material subroutines in Abaqus/Standard (UHYPER).
Hyperelastic SEF Computational time (s) Mises stress (MPa)

modified Gregory 601

Gregory 602

Davis-De-Thomas 598

For the deformation mode of planar tension:

PET
3 ¼0 (22)
  
∂W ∂W 1
PPT
1 ¼ 2 þ λ  (18) where the subscripts 1, 2, and 3 stand for the three principal stretch di-
∂I1 ∂I2 λ3
rections.
   To compare the fitting accuracy of each SEF, the coefficient of
∂W 2 ∂W 1
PPT
2 ¼ 2 þ λ 1  (19) determination, R2, is defined by Eq. (23).
∂I1 ∂I2 λ2
Pn test 2
P  Pfit i
PPT
3 ¼0 (20) R2 ¼ 1  P 1 i 2 (23)
n test test
1 Pi P
For the deformation mode of equibiaxial tension:
   In Eq. (23), n is the total number of measurement points. Ptest is the
∂W 2 ∂W 1 i
PET
1 ¼ PET
2 ¼ 2 þ λ λ  (21) i . Pi is the fitting
test data of the engineering stress at specific stretch λtest fit
∂I1 ∂I2 λ5

77
H. He et al.
Fig. 9. Comparison between test data and simulation data of the stress vs. strain
curves for the Treloar's data with user-defined material subroutines in Abaqus/
Standard (UHYPER).
Fig. 10. Comparison between test data and simulation data of the stress vs.
strain curves for the highly filled HNBR with user-defined material subroutines
in Abaqus/Standard (UHYPER).
data of the engineering stress corresponding to specific engineering
test
strain λtest
i . P is the mean value of the engineering stress for all the
measurement points.
The top 10 hyperelastic SEFs used to fit the Treloar's data are shown
in Fig. 4. The coefficient of determination (R2) and the number of pa-
rameters (Params) are shown at the bottom right of the figure. The scatter
data represent the test data and the lines stand for the fitting data by the
specific SEF. The name of each model is shown at the top of the figure.
The abbreviation “Ni” means the model is i-ordered. For example,
Swanson N2 model and Swanson N3 model are the second-ordered and
the third-ordered Swanson model, respectively.
The top 10 SEFs used to fit the Treloar's data based on the R2 value are
the Lambert Diani-Rey model, the Alexander model, the Gornet-
Desmorat model, the micro-sphere model, the Zuniga-Beatty model,
the Swanson N3 model, the Swanson N2 model, the Beda model, the
extended-tube model and the Shariff model. Considering the good fitting
results, we also provide the top 30 SEFs in the supplementary data (See
Fig. S1).
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Nano Materials Science 4 (2022) 64–82
The R2 values and the comparison between the test data and the
fitting data for each deformation mode show that the top 10 (even the top
30) SEFs can accurately reproduce complex mechanical responses under
multiple deformation modes and a wide range of strains. But we have
mentioned above that a good SEF should also contain as few material
parameters as possible, and the material parameters of that SEF should
have physical meanings.
Six SEFs with only three parameters are located in the top 30 ranking
list. They are the Gornet-Desmorat model, the Zuniga-Beatty model, the
Carroll model, the Lion model, the modified Flory-Erman model, and the
Pucci-Saccomandi model. It is worth mentioning that the Zuniga-Beatty
model and the modified Flory-Erman model are micromechanical
network models. Other excellent micromechanical network models
include such models as the micro-sphere model, the extended-tube
model, the Edward-Vilgis model, and the network averaging tube
model. In addition, the bootstrapped-8-chain model with only two pa-
rameters performs better than 50 more SEFs for the Treloar’ data of
unfilled rubber.
If we don't focus on the micromechanical network models when
pursuing simulation accuracy for the unfilled rubber or the filled rubber
material with similarly shaped stress-strain curves, phenomenological
models such as the Lambert Diani-Rey model, the Alexander model, the
Gornet-Desmorat model, the Shariff model, the Carroll model and the
Ogden N3 model are good choices.
The top 14 hyperelastic SEFs used to fit the UT and UC test data for
the highly filled HNBR compound are shown in Fig. 5. The top 6 SEFs
based on the R2 value are the modified Gregory model, the Gregory
model, the Davis-De-Thomas model, the gen-Yeoh model, the Alexander
model, and the modified Yeoh model. It is worth mentioning that all top
14 SEFs are phenomenological models. None is a micromechanical
network model. This is because the stress-strain response of the highly
filled HNBR is very different from the unfilled rubber or some conven-
tional carbon black filled natural rubber material. The UT and UC stress-
strain curves exhibit highly prominent nonlinear characteristics due to
the formation of a filler network different from the entropic macromo-
lecular network. It is worth mentioning that the modified Gregory model
we propose in this work is perfect to describe the stress-strain response of
the highly filled HNBR nanocomposite.
We also provide the calculated PT and ET data obtained from Eq. (18)
and Eq. (21) for the top 14 SEFs. They share the same optimal material
parameters fitted based on the UT and UC test data. All 14 SEFs can
predict a fairly reasonable PT and ET mechanical response in a wide
range of strains when only UT and UC test data are provided. The results
are shown in Fig. S2.
In Figs. 4 and 5, we can find that there is a very tiny difference in the
R2 values used to describe the nonlinear fitting accuracy for the top 10
hyperelastic constitutive models no matter whether the rubber material
is unfilled or highly filled. Here we compared the number precision (or
parameters sensitivity [163,164]) influence of the material parameters
on the R2 value. Two cases were taken into consideration: material pa-
rameters with single float and material parameters with double float.
The R2 comparison for the top 30 SEFs used to fit the Treloar's data
and the top 14 SEFs used to fit the highly filled HNBR using the material
parameters with single float precision and double float precision are
shown in Table S4 and Table S5, respectively. Compared with the R2
value calculated by the material parameters with double float precision,
the R2 value corresponding to the parameters with single float precision
has almost no change, or the values only change slightly in the eighth or
ninth decimal place. The background of these numbers has been marked
in yellow, see Table S4 and Table S5. In summary, the fitting algorithm
based on the nonlinear least square optimization method in this work is
relatively stable. The minimal difference in R2 comes from the model
itself rather than numeric uncertainty.
To magnify the difference between R2 values, we define an evaluation
index (EI) that can assess which models are better than the others.
H. He et al.
r  rmin
EI ¼  100 (24)
rmax  rmin
In Eq. (24), r is an R2-based quantity that can be obtained from Eq.
(25). rmin is the minimum value of r for the poorest hyperelastic model,
and rmax is the maximum value of r for the best hyperelastic model. The
greater value of R2 leads to the bigger value of EI, and the EI of the best
hyperelastic model is 100.
r ¼ log 10 1  R2 (25)
The EI values of the top 10 hyperelastic SEFs used to fit the Treloar's
data and the test data for the highly filled HNBR compound are shown in
Fig. 6 and Fig. 7, respectively. The SEFs in the top 10 ranking list based on
EI values are identical to those in the top 10 ranking list based on R2
values. The interesting part is the changing trend in the EI values. Fig. 6
shows that all the 10 SEFs perform well because the EI value of the Shariff
model, ranked 10th, is still more than 90. However, Fig. 7 indicates that
the first four SEFs reproduce the stress-strain response much better than
the following ones. We also provide the R2, EI and Params values of the
top 30 SEFs for the Treloar's data of unfilled rubber and the top 14 SEFs
for the highly filled HNBR nanocomposite in the supplementary data (See
Table S2 and Table S3).
From the fitting results of both unfilled and highly filled rubber
compounds, it can be concluded that the models performing excellent
fitting results for the Treloar's data usually could not display superior
performance for the test data of highly filled rubber. It is worth noting
that among the top 10 SEFs, only the Alexander model and the Beda
model achieve satisfactory fitting results with high accuracy for both
experimental data. Therefore, it is difficult to simply indicate which SEF
is valid for some specific experimental data from the above comparison
and discussion. The researchers and engineers need to take care when
deciding the best constitutive model for the specific rubber compound at
hand. But what is certain is that at least one of the 85 SEFs we reviewed is
relatively suitable to describe the hyperelastic response of the RLMs. By
utilizing all the SEFs to fit a specific experimental data in turn, we can
help researchers and engineers carefully select the most appropriate SEF
for further finite element analysis with relatively high precision.
In addition, we take the Alexander model as an example to make a
general introduction of the algorithm program that can determine the
final material parameters, which can be found in the last part of our
supplementary file.
5. Finite element implementation of the top ranked SEFs
The determination and evaluation of the hyperelastic SEFs could not
rely solely on the fitting accuracy of the model, the number of material
parameters, etc. It is also important to take the computational cost into
account when the SEF is used in the engineering application.
The top three SEFs (the Lambert Diani-Rey model, the Alexander
model and the Gornet-Desmorat model) for the Treloar's data and the top
three SEFs (the modified Gregory model, the Gregory model and the
Davis-De-Thomas model) for the test data of the highly filled HNBR are
all implemented with user-defined material subroutines in Abaqus/
Standard (UHYPER) [73] for a three-dimensional uniaxial tensile loading
problem of a dumbbell rubber specimen.
In order to distinguish the difference in computational cost of
different models, we artificially refine the mesh of the finite element
model. The three-dimensional model of the dumbbell rubber specimen
consists of 125,307 elements (shown in Fig. 8). The element type of the
model was an 8-node linear hybrid, constant pressure, reduced integra-
tion brick element with enhanced hourglass control (i.e. C3D8RH in
Abaqus nomenclature). The nodes at the left surface were fixed, and a
displacement of 40 mm was applied to the nodes at the right surface. All
the simulation work was done by using full nodal precision and 6 pro-
cessors on an 8 Intel(R) Core(TM) i7-6700K CPU @ 4.00 GHz.
79
Nano Materials Science 4 (2022) 64–82
All simulation work shares the identical geometrical model, mesh
model and boundary conditions. Only the SEFs differ. The computational
time and Mises stress distribution of the dumbbell rubber specimen for
each case are listed in Table 9 and Table 10.
From Table 9, we can see that the Gornet-Desmorat model with only
three material paramaters has the shortest calculation time, followed by
the Alexander model, and the Lambert Diani-Rey model has the longest
calculation time. The calculation results of the Mises stress distribution
for the three models are very close to each other, all indicating the
relatively precise prediction ability, which can be seen in Fig. 9.
From Table 10, we can see that the computational time of the
modified Gregory model, the Gregory model and the Davis-De-Thomas
model are almost the same by using the UHYPER subroutine in Aba-
qus. Similarly, the Mises stress distribution calculation results of the three
models are also very close to the test data, indicating that they all have
very good predictive capabilities, as shown in Fig. 10. The material pa-
rameters corresponding to these six models are shown in Table S6.
6. Summary
We comprehensively reviewed 85 hyperelastic constitutive models of
rubber-like materials based on the phenomenological theory and the
micromechanical network theory proposed from the 1940s to the year
2019. Also, we proposed a new hyperelastic constitutive model based on
the Gregory model. Then we compared all the SEFs using a nonlinear least
square optimization algorithm to fit both the unfilled and highly filled
rubber materials. For the unfilled rubber, the uniaxial tension, equibiaxial
tension and planar tension test data of Treloar were simultaneously used.
For the highly filled HNBR nanocomposite, both the uniaxial tension and
the uniaxial compression test data were adopted. The ability of each SEF to
reproduce the experimental data was quantitatively assessed and sorted
based on a proposed evaluation index closely related to the coefficient of
determination. Finally, the top three SEFs for the Treloar's data and for the
test data of the highly filled HNBR were all implemented with UHYPER
subroutines for a three-dimensional uniaxial tensile loading problem of a
dumbbell rubber specimen to compare the computational cost.
For the unfilled rubber, the top 5 models just considering the R2 value
are the Lambert Diani-Rey model, the Alexander model, the Gornet-
Desmorat model, the micro-sphere model, and the Zuniga-Beatty
model. Six models with only three parameters are shown in the top 30
ranking list. They are the Gornet-Desmorat model, the Zuniga-Beatty
model, the Carroll model, the Lion model, the modified Flory-Erman
model, and the Pucci-Saccomandi model. It is particularly worth
mentioning that the Zuniga-Beatty model and the modified Flory-Erman
model are micromechanical network models. Other excellent micro-
mechanical network models include the micro-sphere model, the
extended-tube model, the Edward-Vilgis model, and the network aver-
aging tube model. The bootstrapped-8-chain model with only two pa-
rameters performs better than 50 more models for the Treloar's data of
the unfilled rubber. If we don't focus on the micromechanical network
models when pursuing simulation accuracy for the unfilled rubber or the
filled rubber material with similarly shaped stress-strain curves,
phenomenological models such as the Lambert Diani-Rey model, the
Alexander model, the Gornet-Desmorat model, the Shariff model, the
Carroll model, and the Ogden N3 model are excellent alternatives.
For the highly filled HNBR nanocomposite, the top 5 hyperelastic
constitutive models used to fit the UT and UC test data are the modified
Gregory model, the Gregory model, the Davis-De-Thomas model, the
gen-Yeoh model, and the Alexander model. It is worth mentioning that
the top 14 models are all phenomenological models. None is a micro-
mechanical network model. We can conclude that the models performing
excellent fitting results for the Treloar's data could not display superior
performance for the test data of the highly filled HNBR. Among the top
10 models, only the Alexander model and the Beda model achieve
H. He et al.
satisfactory fitting results for the experimental data of both the unfilled
rubber and the highly filled rubber nanocomposite.
The computational time of the Lambert Diani-Rey model, the Alex-
ander model and the Gornet-Desmorat model using the UHYPPER sub-
routine are 720s, 698s, and 645s, respectively. The computational time of
the modified Gregory model, the Gregory model and the Davis-De-
Thomas model are almost the same. From the calculation results of the
Mises stress distribution and the comparison between the test data and
the simulation data of the stress vs. strain response, we can conclude that
the top three ranked SEFs accurately reproduce the corresponding
experimental data.
Of course, as we know, the mechanical responses of RLMs are highly
nonlinear and extremely complex (not limited to hyperelasticity); for
example, viscoelasticity, hysteresis, permanent set, Payne effect, Mullins
effect, orthotropy or even anisotropy, aging, crack, damage, failure, etc.
The stress-strain responses are also closely related to temperature, strain,
frequency, strain rate, pre-stress and deformation mode. On the other
hand, not so many constitutive models (compared with the number of the
existing phenomenological models) are very concerned with how to
quantitatively establish the relations between the complex mechanical
responses and the microstructures of the rubber materials. The micro-
structures include the crosslinking, entanglement, orientation and crys-
tallization of the macromolecular chains, the concentration, size,
morphology, dispersion and network formation of the fillers, the inter-
face interactions and so on. Fortunately, nowadays more and more
micromechanical network models are emerging and gradually devel-
oping [165].
Putting in perspective the progress of constitutive models of RLMs in
the future, we notice that a good constitutive model should quantitatively
bridge the gap between the above-mentioned microstructure and the
mechanical property, and accurately predict the complex mechanical
responses under different working conditions and temperatures. Consti-
tutive models of RLMs will surely and constantly develop, and they will
help to predict and optimize the performance of rubber products. In
addition, some novel and disruptive ideas inspired by the constitutive
models, especially from the micromechanical network models, can help
find better rubber-like materials.
Declaration of competing interest
None.
Acknowledgements
We gratefully acknowledge the National Key Research and Develop-
ment Program of China (2018YFB1502501), and the National Natural
Science Foundation of China (52003024). The authors declare that they
have no conflict of interest.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https
://doi.org/10.1016/j.nanoms.2021.07.003.
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