e-Polymers 2015; 15(4): 205215

Review
Sukhwinder K. Bhullar*

Three decades of auxetic polymers: a review

Abstract: Developments in design and technology in the
engineering and medical fields necessitate the use of
smart and high-performance materials to meet higher
engineering specifications. The general requirements of
such materials include a combination of high stiffness
and strength with significant weight savings, resistance
to corrosion, chemical resistance, low maintenance, and
reduced costs. Over the last three decades, it has been
demonstrated that auxetic materials offer a huge potential for the fields of engineering, natural sciences, and
biomedical engineering, and for many other industries,
including the aerospace and defense industries, through
their unique deformation mechanism and measured
enhancements in mechanical properties. To meet future
engineering challenges, auxetic materials are increasingly
being recognized as integral components of smart and
advanced materials. Although materials with a negative
Poissons ratio have been known since the early 1900s,
they did not capture researchers attention until the late
1980s. Since 1991, these materials have been known as
auxetic materials. Since then, their benefits and applications have been expanded to all major classes of materials
such as metals, ceramics, polymers, and composites, and
they are also now being used in engineering applications.
The goal of this review was to present the development of
auxetic polymers, which were first fabricated in the form
of polyurethane foam approximately three decades ago
and are now used in the fabrication of non-woven nano/
micropolymeric structures. This review could provide
useful information for the future development of auxetic
polymers.
Keywords: auxetic patterns; auxetic polymers; polymeric
foams; polyethylene; woven and non-woven structures.
DOI 10.1515/epoly-2014-0193
Received October 21, 2014; accepted March 11, 2015; previously
published online April 25, 2015

*Corresponding author: Sukhwinder K. Bhullar, Department of

Mechanical Engineering, Bursa Technical University, Bursa, Turkey
and Department of Mechanical Engineering, University of Victoria,
Victoria, BC, Canada, e-mail: sbhullar@uvic.ca

1 Introduction
The development of structural materials is focused on
improving their mechanical or physical properties, often
saving in weight or cost, whereas that of functional materials is designed to detect or respond to events or stimuli
that occur during their lifetime. These materials often
display novel and counterintuitive behavior; examples
include electrically (semi-) conducting polymers and
materials that contract when heated. Another example is
a remarkable class of materials known as auxetic materials, which become wider rather than thinner when
stretched. Most engineering materials become thinner in
cross section when stretched; a rubber band for example
gets thinner when it is stretched, and an iron bar would
display the same behavior if it were stretched. The Poissons ratio v in this situation is positive, typically between
0 and +0.5. However, some materials or structures expand
laterally when stretched or contract in the transverse
direction under uniaxial compression, and these materials or structures are said to have a negative Poissons ratio.
Such materials have been called auxetic materials since
1991 (1). This behavior does not contradict the classical
theory of elasticity, based on the thermodynamic considerations of strain energy. The Poissons ratio of isotropic
materials not only can have negative values, but also can
have a range of negative values twice as many as that of
positive ones (2). Poissons ratio is bounded by two theoretical limits: it must be >-1 and 0.5, i.e. 1<v 0.5. The
upper bound corresponds to the incompressible limit
(infinite bulk modulus), typically applicable to rubberlike materials (3), whereas the lower bound corresponds
to an infinite shear modulus. Also, it has been reported
by the authors in Ref. (4) that, in a two-dimensional
system, the Poissons ratio can be as large as +1. A study
of materials with a negative Poissons ratio was made in
1987 by Roderick Lakes who fabricated a material that
became fatter when stretched, as illustrated in Figure 1,
and thinner when compressed. The key to their auxetic
behavior is the negative value of Poissons ratio (5, 6).
Although auxetic materials have been known for over 100
years, it was only during the last three decades (late 1980s
to the present) that they have received renewed attention.

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206S.K. Bhullar: Three decades of auxetic polymers: a review

Figure 1:(A) Auxetic vs. (B) non-auxetic behavior of materials.

The auxetic property was first reported in the early 1900s

by the German physicist Woldemar Voigt when he experimented with a mineral called iron pyrite (7). His work suggested that the crystals of this mineral somehow become
thicker laterally when stretched longitudinally. Voigt did
not explain this peculiar behavior, and possible applications of this property were not considered at that time,
and it was ignored for decades. Also, in 1927, Love (8)
described a material with a negative Poissons ratio and
presented an example of a cubic single-crystal pyrite as
having a Poissons ratio of -0.14. He suggested that the
effect may be caused by twinned crystals. In 1982, Gibson
(9) described the auxetic effect using a two-dimensional
silicone rubber or an aluminum honeycomb that can be
deformed by flexure of the ribs. Then, in the late 1980s
(1015), researchers managed to intentionally make an
auxetic foam from a commercially available one. This was
a major breakthrough because it showed that it is possible
to induce auxeticity in materials and structures through
their design. With this discovery, researchers started to
realize that these materials had a vast number of applications. Since then, a whole range of synthetic auxetic
materials have been produced for all major classes of
materials, such as metals, ceramics, polymers, and composites (1634). However, natural auxetic materials do
exist, examples being single crystals of arsenic (35) and
cadmium (36), -cristobalite (37), and many cubic elemental metals (38). In addition, some biological materials have been found to be auxetic, including certain forms
of skin, for example, cat skin (39), salamander skin (40),
and cow teat skin (41), and load-bearing cancellous bone
from human shins (42). Furthermore, the mechanisms
of auxetic materials depend on either their microstructure or their geometrical structure and on the deformation mechanisms of these structures when they deform.
Upon applying a load on an auxetic material or structure
in one direction, it expands in the perpendicular direction and exhibits a negative Poissons ratio. Therefore, a
correct cooperation between the internal structure of the
material and the way it deforms when loaded gives rise to
auxeticity (4349). The classification of auxetic behavior
into complete auxetic, auxetic, partially auxetic and nonauxetic has been reported in Refs. (5052). A number of

reviews on this subject are available from long ago, e.g.,

Refs. (27, 28, 43, 5358), which focused mainly on the fabrication, structures, deformation mechanism, mechanical
properties, and applications of auxetic materials.
Here, the main focus is to present a review of polymers tailored with an auxetic effect from the late 1980s to
the present, spanning almost three decades of studies on
auxetic polymers. Synthetic polymers have uniformity, less
immunogenicity, and well-known structures and properties, with reliable source materials. Polytetrafluoroethylenes (PTFE), ultra-high-molecular-weight polyethylenes
(UHMWPE), and polyurethane (PU) foams are polymers
with properties ranging from very brittle and hard to very
tough, soft and tacky, and viscous. Their molecular structure can be tuned based on their ability to be modified for
desired properties. They are generally easier and cheaper
to process than conventional materials and are well suited
as candidates for the development of nano- to macrostructures for the biomedical and engineering industries.
These biocompatible synthetic materials are already being
used in other industries. However, polymers tailored with
auxetic patterns to achieve appropriate mechanical properties and unique deformation mechanisms called auxetic
polymers offer a number of benefits to different industries, including, but not limited to, the engineering and
biomedical industries, tissue engineering fields, and the
packaging industry. In the following review, auxetic polymeric foams, polyethylenes, and piezomorphic polymers
are discussed followed by a summary and a brief discussion of the future of auxetic materials.

2 Auxetic polymeric foams

Polyurethane foams are one of the most important foams
studied for various applications such as in medical devices,
coatings, and automotive interiors. However, alterations to
the mechanical properties of PU foams may be of benefit
where enhanced mechanical properties are beneficial.
Smart polymeric and metallic foams called auxetic foams
were first fabricated by Roderick Lakes in 1987 (3, 59) from
conventional polyester low-density open-cell polymeric

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S.K. Bhullar: Three decades of auxetic polymers: a review207

foams. These foams exhibit a negative Poissons ratio,

which was obtained by changing the microstructure of
conventional foams. A sample of a conventional polyurethane (PU) foam is illustrated in Figure 2.
Since then, a large number of research papers, patents,
and theses have been published related to the fabrication,
characterization, theoretical, and mechanical modeling of
such foams (22, 6078). Their enhanced mechanical properties such as indentation resistance, shear resistance,
fracture toughness, viscoelastic loss, sound absorption,
and high-density were reported by authors in Refs. (79
100). Other mechanical properties including improved
stiffness and high-energy dissipation under compressive
cyclic fatigue loading were studied in Refs. (22, 62, 71,
101, 102) using a manufacturing route for auxetic opencell thermoplastic foams. Furthermore, a very detailed
study using a large number of samples manufactured
with modified processes had been discussed in Refs. (103,
104). Recently, an auxetic behavior in foam cellular materials, due to a mechanism called rotation of rigid units,
produced from conventional open-cell cellular materials,
was developed by the authors in Ref. (105) and the auxetic
behavior was demonstrated through the ribs of the cells,
which were slightly thicker at the joints compared to the
centre of the ribs. In the study in Ref. (106), the authors
found that the energy dissipated by auxetic foams is significantly higher than that by conventional foams. The
schematic developed by these authors (106) for the manufacturing process and the micrographs of the conventional
and auxetic foams are shown in Figure3.
Evaluation of the homogeneity and gradient properties of auxetic foam was reported by the authors in Ref.
(106). They found that the auxetic effect occurs owing to
the existence of concavity of the cells. To exploit further
the benefits of auxetic foams, very recently, heterogeneous strain distributions due to a complex microstructure
(107) and fabrication of flat and curved auxetic foam
sheets were reported by the authors in Ref. (108). Also,

some other properties of auxetic PU foam such as the

effect of solvents were reported by the authors in Ref.
(109). According to these authors, auxetic PU foams do
not change their microstructure if they are subjected to
high temperature or solvent exposure in a contained
state, which does not permit the expansion. This means
that auxetic foams can still be used in such environments
provided that the right precautions are taken (e.g., putting
them in a cover, thereby constraining them to retain their
volume). Characterizations of two-dimensional auxetic
foams were studied by computer simulations using soft,
normal, and hard joints. It was found through the simulations that, by applying harder joints, foams with more
auxetic properties can be achieved (110)

3 Auxetic polyethylene
After the successful fabrication of auxetic foams, research
further extended to the investigation of the auxetic effect
in more dense materials such as polyethylenes (12, 13, 34,
36, 81, 111128) based on the internal microstructure of
nodules and fibrils. A bead-spring model of polymer networks and flexural grid models of micropolar continua,
an array of regular or irregularly shaped particles, a set
of springs to store elastic energy, and a set of topological
constraints had been discussed in the literature (12, 127,
128). The deformation mechanisms of these microstructures were achieved through elastic energy stored via
simple tensile springs, as opposed to the flexural beams
of the foam structure models reported in Ref. (129).

3.1 Auxetic PTFE

Polytetrafluoroethylene was the first auxetic polymer
fabricated in the form of a sheet or a cylindrical ribbon

Figure 2:Microstructure of (A) conventional and (B) auxetic foam.

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208S.K. Bhullar: Three decades of auxetic polymers: a review

Before processing
Z

Y
The transformation process consists of
triaxial compression combined with heat
treatment (~30 min @135C).*

After processing
Global reduction in length:
X~22%
Y~22%
Z~17%

Global volume change~50%

Local volume change~50 to 75%
to resulting auxetic behavior

Figure 3:Optical images of a foam (A) before and (B) after processing (105). (Adapted with permission from Springer).

to exploit the auxetic behavior of polymers with higher

density (11) using extrusion, uniaxial, and biaxial
drawing. The authors reported (11) that the auxetic effect
occurs owing to tensile deformation mechanisms or to
micro-rotational degrees of freedom. Furthermore, tailored enhanced mechanical properties of auxetic PTFE
such as flexural rigidity and plane strain fracture toughness were studied and reported in Refs. (13, 128). The
morphology and deformation mechanism models given
in Ref. (56) are illustrated in Figures 4 and 5, respectively.
Also, the mechanism to obtain an auxetic effect exhibiting
a negative Poissons ratio of up to -12 has been discussed
in the literature (120, 130133).

The studies on auxetic polymers have been further

expanded to include other polymers, such as UHMWPE.
Using the same mechanism that was found in PTFE using
a novel thermoforming route, the authors in Ref. (118) discussed the fabrication of UHMWPE and they obtained a
large negative Poissons ratio through its complex microstructure. The improved mechanical properties owing to
auxeticity were studied in Ref. (121), and an increase in
indentation resistance up to a factor of 2 compared that of
conventional UHMWPE was reported. A simple geometric
model consisting of rectangular nodules interconnected
by fibrils was studied, and a good agreement between
the experimental and the theoretical Poissons ratios was
reported (118). Also, the effects of different fabrication procedures were studied the authors in Refs. (120, 134) who
found that indentation resistance can be up to 2.5 times
higher than that of conventionally processed UHMWPE
using a double-sintered processing route.

4 Geometrical pattern-based
auxetic polymers

Figure 4:Scanning electron microscopy images of the microstructure of a PTFE (56). (Adapted with permission from Academic
Journals; http://academicjournals.org).

The microstructure and geometrical structure tailored

on materials give arise to the auxetic effect. Double
arrowhead, star honeycomb, and hexagonal re-entrant
honeycomb; and lozenge grids, square grids, sinusoidal ligaments, chiral units, and rotating units (triangle,
square, rectangle, tetrahedron), anti-chiral structures,

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S.K. Bhullar: Three decades of auxetic polymers: a review209

Figure 5:(A) Initial compressed and (B) stretched structure due to rotation of nodes (56). (Adapted with permission from Academic Journals; http://academicjournals.org).

cyclic hexamers, and cyclic trimers (4, 14, 15, 4449, 135
138) are two- and three-dimensional re-entrant structures,
respectively, that have been studied by various authors.
Some examples of auxetic patterns are illustrated in
Figure 6 (56).
Based on this property of auxetic structures, polymers
were fabricated with auxetic patterns using both nonwoven and woven techniques. Vacuum casting technique,
three-dimensional imaging, and laser cutting at nano- to
macroscale were used in Refs. (139143) for tailoring the
auxetic patterns on polymers, which are shown in Figure 7.
Research on woven polymeric auxetics, including
auxetic fibers, yarns, and fabrics, is also available in the
literature, and these materials have been introduced
commercially already. The first polypropylene fibers that
displayed auxetic behavior were reported in Ref. (139),
which were fabricated using a continuous partial melt

extrusion process. To date, a variety of auxetic fibers, such

as auxetic polyester fibers and nylon fibers (144148), and
fabrics made from auxetic yarns using knitting, weaving,
and both the warp and the weft-knitting technologies
based on different geometrical arrangements, have been
developed (149152).

5 R
 ecent developments in auxetic
polymers
5.1 Piezomorphic PU foam
Large strain deformation is necessary to produce an elastic-gradient material. In recent developments in auxetic

Figure 6:Some geometrical structure-based auxetic patterns (56). (Adapted with permission from Academic Journals; http://academicjournals.org).

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210S.K. Bhullar: Three decades of auxetic polymers: a review

Figure 7:(A) Auxetic polyurathylene sheet in crimped form and (B) femtosecond laser-cut auxetic metallic expanded tubular structure (141).

polymers, the elastic response of a material undergoing

large strain deformation has been reported by the authors
in Ref. (153) through tailored Youngs modulus and Poissons ratio to control morphing behavior. Through X-ray
tomography images, the authors showed a transition
region from an initially thick to a thin cross section of
the converted and unconverted foam, as illustrated in
Figure 8. They reported that the auxetic effect, as shown

in the bottom of the image, is due to the higher density

re-entrant foam.
Also, upon the application of a uniaxial stress, auxetic
foams changed to a bottle-shaped square cross section
from regular elongated cuboid and recovered the original
shape on release, as shown in Figure 9.
Furthermore, the authors in Ref. (112) produced higher
density polymer samples such as ex-PTFE with a wedge
shape and an hourglass shape. Video stills showing the
response under tensile testing induced by the shape
memory effect, gradient elasticity, and piezomorphic
response of the samples are shown in Figure 10 (153).
Nanolevel re-entrant honeycombs exposed to solvent
molecules such as ethanol, propanol, and benzene at
different concentrations were studied by the authors in
Ref. (154) using Monte Carlo-based sorption simulations
to determine the structural and mechanical properties of
porous polyphenylacetylene auxetic organic networked
polymers. It was observed that the effect on stiffness was
highly dependent on the properties of the network and on
the type and amount of solvent adsorbed (154). Also, characterization of PU foam for a soft tissue implant through
a nonlinear elastic model was presented by the authors in
Ref. (155).

6 S
 ummary and development of
auxetic polymers in the future

Figure 8:X-ray tomographs of the converted PU foam (153).

(Adapted with permission from Wiley).

The research involving auxetic materials and their applications is highly interdisciplinary and is being increasingly recognized as an integral component of smart
materials. They are considered as one of the 16 smart
materials of the 21st century and have a significant impact
on the biomedical, aerospace, and defense industries and
on many other fields globally. In addition, more research

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S.K. Bhullar: Three decades of auxetic polymers: a review211

Figure 9:Elastic-gradient piezomorphic PU foam with the auxetic region at the bottom. (A) Before gripping (relaxed unstressed state), (B)
after gripping (relaxed unstressed state); (C) bottle shaped foam (153). (Adapted with permission from Wiley).

not limited to, the biomedical, aerospace, defense, and

textile industries. Their development has been growing
since the last three decades. The technology has already
been transferred from the university to the industry, but
more effort should be made to exploit their properties

work needs to be done to further understand these materials. To date, man-made auxetic materials are synthesized
and fabricated in all major categories of materials including polymers, metals, composites, and ceramics using a
variety of methods and techniques for application in, but

Referencce
11.6 mm

Hourglass

8.5 mm

10.9 mm

Wedge

8.7 mm

15.2 mm

Rectangle
5.3 mm

5.1 mm

L=0%

L=0%

L=1.75%

L=5%

L=3.5%

L=10%

L=5.25%

L=15%

L=7%

L=18%
14.7 mm
T=24%
=-1.31

15.9 mm

16.9 mm

T=60%
=-3.35

T=10%
=-0.57

14.9 mm
T=56%
=-3.12

15.1 mm
T=33%
=-1.83

6.3 mm
T=16%
=-2.31

5.6 mm
T=9.4%
=-1.34

Figure 10:Video stills of (A) unconverted, (B) piezomorphic wedge-shaped, (C) hourglass-shaped, and (D) rectangular-shaped ex-PTFE
samples (153). (Adapted with permission from Wiley).

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212S.K. Bhullar: Three decades of auxetic polymers: a review

and commercial benefits. The development of auxetic
polymers has been extended in recent years to woven and
non-woven structures with auxetic patterns, but they are
still limited. Tailored with auxetic patterns, smart polymeric structures could be a good choice for the further
development of auxetic medical devices such as implants,
biodegradable stents, wound bandages, and scaffolds
for tissue engineering. For example, stents with auxetic
nano- and microfibrous drug delivery structures tuned
with auxetic effect can deliver drugs when pores open
and can cease drug delivery in a relaxed position due to
their shape memory ability. Also, implementation of a
multidisciplinary approach such as the combination of
high-tech techniques and auxetic effect with other functions, such as shape memory effect and electromagnetic
effect, to make multifunctional auxetic materials could
enhance their potential for further applications in engineering and biomedical fields. Fully exploited, the auxetic
effect in polymeric structures through systematic studies
could enhance their mechanical properties and deformation mechanism. In the future, with the implementation
of a multidisciplinary approach and collaboration with
researchers from other disciplines such as those from the
textile, materials, chemical, and biological industries, it
is believed that auxetic polymers will be developed successfully to explore further potential applications in the
future.

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