6 Smart Polymers
L. Peponi, M.P. Arrieta, A. Mujica-Garcia and D. López
Institute of Polymer Science and Technology, ICTP—CSIC, Madrid, Spain
6.1 Smart Materials: Polymers and
Nanocomposites
In recent years, the increase in life expectancy
has led to a growing demand for both new materi-
als and new technologies. In this scenario polymers
fit very well, considering that they are very versa-
tile materials, exist in many forms, and also can be
embodied as the desired properties and their final
applications. In this sense we can speak about natu-
ral polymers (starch, cellulose, protein, natural rub-
ber, etc.), synthetic (obtained by different routes of
polymerization), or semisynthetic (for processing of
natural polymers), according to their origins.
The last two to three decades have witnessed
enormous growth interest in “smart materials”
based on polymers and on polymeric nanocompo-
sites. However, to find a unique definition of a
“smart” polymer is quite difficult, considering that
all the polymers able to be stimuli-responsive,
soluble-insoluble, or environmentally sensitive have
defined as “intelligent” or “smart” materials and
they have found application in many areas, such as
biotechnology, medicine, and engineering. It is
worth noting that proteins, carbohydrates, and
nucleic acids, considered as basic components of
living organic systems, are themselves, polymers.
For this reason it is possible to say that Life is
polymeric in its essence, as reported by Galaev and
Mattiasson (1999).
Initially, the name “smart” polymers was coined
for their similarity to biopolymers as pioneeringly
reported by Dagani in 1995 (Dagani, 1995).
Synthetic polymers, which are designed to mimic
these biopolymers, have been developed into a vari-
ety of functional forms to meet the industrial and sci-
entific applications (Kumar et al., 2007). To classify
the smart synthetic polymers with a unique manner
is quite difficult; however, they can be classified into
different categories considering their physical or
chemical properties. As a result, different names are
Modification of Polymer Properties. DOI: http://dx.doi.org/10.1016/B978-0-323-44353-1.00006-3
© 2017 Elsevier Inc. All rights reserved.
coined in the scientific literature for describing smart
polymers, such as “intelligent polymers” (Kikuchi
and Okano, 2002), “stimuli-responsive polymers”
(Hoffman et al., 2000), or “environmental-sensitive”
polymers (Qiu and Park, 2001). The general charac-
teristic they present is their ability to respond to very
slight changes in the surrounding environment. In
particular, the environmental triggers responsible for
these transitions can be physical such as temperature,
light, electric or magnetic fields, mechanical stress,
or chemical, such as pH shift, wet, ionic strength,
presence of metabolic chemicals.
A very important aspect, when working with
smart polymers, is that they are not only able to
change macroscopically their structure but also these
transitions are reversible and the system returns to its
initial state when the external stimulus is removed.
These polymers can change shape, solubility, sur-
face characteristic, but also the formation of molec-
ular assemblies, sol
gel transitions, etc. can occur.
Since the first articles published in the early 1990s
on the topic of “smart polymers,” more than 6000
scientific work and more than 500 reviews have been
published, based on data from Scopus source, as evi-
denced in the graphic of Fig. 6.1, where the trend on
the scientific works published from 1990 to 2014 has
been reported. It is clear that the interest about smart
polymers has exponentially increased in recent years,
because of the desire to design new materials able to
answer to more complex requirements from
advanced industrial sectors.
At the same time, the applications of smart poly-
mers reported in these works are copious and they can
be reflected in many fields. Biotechnology and bio-
medicine were the initial uses and nowadays continue
to be the most diffuse applications. This fact is a con-
sequence of the smart polymers’ behavior which ini-
tially was mainly observed in water (Galaev and
Mattiasson, 1999) and, occasionally, in polymer blends
(Sato et al., 1998) and in organic solvents (Osada and
Gong, 1998). The hydrophobicity/hydrophilicity
131
132 MODIFICATION OF POLYMER PROPERTIES

Thermally Reversibly
Immobilized
controlled soluble
viable cells
biocatalyst biocatalyst

Immobilized
Drug
biocatalyst
delivery
Biomimetic
actuators

Smart Chemical
polymer valve

Figure 6.1 Trend on the scientific works published

from 1990 to 2014. From Scopus. Thermoresponsive
Bioseparation
surfaces

Trends in biotechnology
Aqueous
two-phase
balance in the molecular structure of the polymer in polymer Thermoresponsive Cell
water solution was the responsible for the phase systems chromatography detachment

transition in the stimulus-responsive polymers and Affinity

hydrogels and there were numerous works published precipitation

in the 1990s on responsive gels and hydrogels (Gels,

1993; Hoffman, 1995; Yoshida et al., 1993).
Thus, considering the case in which the
stimulus-responsive behavior occurs in aqueous
solutions, these polymers and hydrogels are becom-
ing increasingly attractive for biotechnology and
medicine (Galaev and Mattiasson, 1999). Fig. 6.2
schematically represents the uses of smart polymers
in biotechnology and medicine.
Moreover, analyzing the previous results related
to the reviews published so far on smart polymers,
Figure 6.2 Uses of smart polymers in biotechnology
and medicine. Reprinted with permission of Elsevier
Galaev, I.Y., Mattiasson, B. 1999. ‘Smart’ polymers
and what they could do in biotechnology and medi-
cine. Trends Biotechnol. 17, 335
340.
62% Hydrogels

four different classes of smart materials can be

summarized. Not only hydrogels, but also shape- 5%
memory polymers and nanocomposites, self-healing 22% Smart packaging
11%
polymers and nanocomposites, as well as polymers Shape memory
Self-healing
and nanocomposites for smart packaging, can be
evidenced, as summarized in Fig. 6.3. As reported
previously, the hydrogels were the first class of Figure 6.3 Four different classes of smart materials.
smart materials studied and the percentage of arti-
cles published in this field is the highest: 65%. materials, i.e., polymers and polymeric nanocompo-
However, in the last 15 years the attention has been sites for:
focused also on shape memory polymers (22%) and
self-healing polymers (11%). More recently an • smart packaging;
increasing interest in polymers for smart packaging • shape memory;
can be pointed out (5%).
So, in this chapter we focus the attention on the • self-healing;
mechanisms of these four different classes of smart • hydrogels.
6: SMART POLYMERS
However, it is quite difficult to generate an accu-
rate cut between the different classes, and in this
chapter the attention will be focused on the
mechanisms of shape memory polymers.
Maybe it is possible to separate the polymers for
smart packaging applications from the others due to
their new features as smart materials, but hydrogels,
shape memory, and self-healing polymers and nano-
composites are strongly correlated with each other.
This correlation, based on the reviews published so
far in Scopus, is represented in the graphic of
Fig. 6.4, confirming that it is quite difficult to sepa-
rate definitely each item.
However, if the four classes of smart materials
are considered, another common factor can be evi-
denced, regarding the type of polymers used. In
fact, most of them are biopolymers, both bio-based
or biodegradable polymers and polymeric-based
nanocomposites.
Polymer nanocomposites refer to multiphase
polymeric-based materials reinforced with nanopar-
ticles characterized by at least one dimension below
100 nm, i.e., in the nanoscale range (Raquez et al.,
2013; Peponi et al., 2014b; Chivrac et al., 2009).
As a consequence of their nanoscale dimensions,
nanoparticles possess a large surface area for a given
volume (Raquez et al., 2013). Moreover, it is widely
known that nanoparticles can considerably improve
the nanocomposite properties compared with those
of the neat polymeric matrix, thanks to the strong
and large polymer
nanofiller interactions as well as
to the good particle dispersion into the polymer
matrix. It is important to underline that one of the
most difficult challenges when working with nano-
composites, is to reach a good compatibilization
between nanoparticles and polymeric matrix avoid-
ing nanoparticle agglomerations.
Hydrogels
65
7 4
2
Shape Self-healing
memory 4 11
22
Figure 6.4 Percentage of correlation between the
different classes of smart materials.
133
It is possible to classify the nanoparticles into
three main categories depending on their geometry
as represented in Fig. 6.5:
• isodimensional nanoparticles (3D), are struc-
tures with three nano dimensions, such as vesi-
cles, spherical micelles, metal, metal oxides,
and ceramic nanoparticles (Peponi et al.,
2008a,b,c, 2009a,b, 2011; Monti et al., 2015);
3D nanoparticles require a narrow range of
particle sizes distribution and dispersion. Their
surface area per unit volume is inversely pro-
portional to their diameters. In fact, the 3D
nanoparticles present a surface area to volume
ratio equal to 3/r, where r is the radius of the
nanoparticle (Raquez et al., 2013).
• acicular or fibrous ones (2D), are nanoparticles
with two dimensions at nano-level. Some
examples of 2D nanoparticles are the cylindri-
cal micelles, DNA, whiskers, some proteins,
and carbon nanotubes (CNTs) (Peponi et al.,
2014b). In this sense, CNTs are the most inves-
tigated 2D nanofillers due to their exceptional
mechanical resistance as well as electrical and
thermal conductivity which can be potentially
used in many applications, ranging from nano-
devices to macroscopic materials. Also in this
case their surface area per unit volume is
inversely proportional to their diameters and in
particular, their surface area to volume ratio is
equal to (2/r 1 2/l), where r is the radius and l
is the longitude of the nanoparticle. However,
the second term is generally omitted because it
presents a very small influence with respect to
the first term showing a difference of three
orders of magnitude (Raquez et al., 2013).
• layered particles (1D) also called plate-like nano-
fillers, present their thickness on the order of
1 nm and present an aspect ratio of at least 25
(Raquez et al., 2013). The most well-known 1D
nanoparticles are layered silicates and graphene
sheets.
For instance, metal nanoparticles have been
extensively incorporated in polymer matrices to
Figure 6.5 Nanoparticle geometries.
134
produce functional nanocomposites for numerous
applications, such as the use of iron nanoparticles
to provide electromagnetic properties (Wilson
et al., 2004), silver nanoparticles for antibacterial
activity (Dallas et al., 2011), or gold nanoparticles
for electrical conductivity (Bryan, 2005). Metals
undergo the most considerable property change by
size reduction. For this reason nano-sized metals
have special characteristics that can be tuned by
changing the nanoparticle dimension. Although
metallic nanoparticles were traditionally produced
by the top-down approach, the bottom-up strategy
produce better results for these kinds of size-
dependent particles via chemical processes (Peponi
et al., 2014b). 3D nanoparticles require a narrow
range of particle size distribution and dispersion.
Moreover, since nano-sized metals are very
instable and tend to aggregate, the use of surfactant
is of considerable interest (Peponi et al., 2009a,b;
Peponi et al., 2008a,b,c, 2011).
CNTs are the most investigated 2D nanofillers
due to their exceptional mechanical resistance as
well as electrical and thermal conductivity which
can be potentially used in many applications, rang-
ing from nanodevices to macroscopic materials
(Raquez et al., 2013; Peponi et al., 2009a, 2010). In
recent years, cellulose nanocrystals (CNCs) have
also been deeply studied due to their bio-based
nature. In general, the morphology of nanocellulose
is strongly affected by the origin of the cellulose
fibers, and they can be theoretically prepared from
any botanic sources containing cellulose (Raquez
et al., 2013; Navarro-Baena et al., 2014; Arrieta
et al., 2016; Mujica-Garcia et al., 2016). However,
their dimensions depend on several factors even if
the most important are the cellulose source, the
hydrolysis conditions, and the ionic strength. In
general the width of the CNCs is on the order of a
few nanometers while their length on the order of a
few hundred nanometers (Raquez et al., 2013).
Regarding 1D nanoparticles, layered silicates
montmorillonites (MMT) are the most investigated
for their potentially high aspect ratio and their
unique intercalation/exfoliation characteristics
(Peponi et al., 2014b). In this sense, clay particles
should be exfoliated to increase the surface area.
Nanocomposites with MMT are able to achieve
remarkable thermal, barrier, thermomechanical, and
fire-resistance properties at low nanofiller content
(Raquez et al., 2013). To improve the clay/matrix
affinity the use of hydrophilic surfactants, such as
MODIFICATION OF POLYMER PROPERTIES
carbohydrate surfactants, has been proposed to
modify the nanofiller polarity and reach exfoliation
(Chivrac et al., 2009).
Graphene exhibits exceptional properties due to
its unique structural and electrical characteristics
(Peponi et al., 2009c). Instead of pristine graphene,
results have show that it is easier to obtain gra-
phene oxide, which is a water dispersible interme-
diary obtained by chemical modification of
graphite (Peponi et al., 2014b). Graphene oxide
reaches better dispersion within polymeric materi-
als, but it exhibits poor electric conductivity.
In general, there are four main routes that can be
used to obtain polymer-based nanocomposites:
• solution method. The polymeric matrix within
the incorporated dispersed nanoparticles are
dissolved in an adequate solvent and the final
nanocomposite is obtained for solvent evapora-
tion or precipitation;
• melt-mixing. When the polymer and the nano-
fillers are directly melt-mixed together;
• in situ polymerization. In this case the nano-
particles are firstly dispersed in the liquid
monomer or in a monomer solution followed
by its polymerization;
• template synthesis. The nanoparticles are syn-
thesized from precursor solution using polymer
as template (Raquez et al., 2013; Peponi et al.,
2014b).
However, the main goal of this chapter is to
point out the attention on the principles behind the
“smart” effects on both polymer and polymeric
nanocomposites. Therefore, after this short intro-
duction on polymers and nanocomposites, special
attention will be focused on smart packaging, shape
memory, self-healing, and hydrogel materials.
6.2 Stimuli Responsive Materials
in Smart Packaging
Traditionally, packaging is required to contain
food products and protect them from the surround-
ings avoiding contamination, humidity, and oxida-
tions process (Galaev and Mattiasson, 1999; Arrieta
et al., 2015). However, as a consequence of some
changes in consumers habits, new quality and
safety requirements as well as the appearance of
6: SMART POLYMERS
new regulations in the food supply chain (food
transport, distribution, and storage), nowadays there
is a demand of more advanced packaging systems
(López-Gómez et al., 2015). Therefore, smart mate-
rials are also gaining interest in the food packaging
field which continuously demands innovative food
packaging to guarantee food safety, quality, and
traceability (Vanderroost et al., 2014). There are a
new generation of smart packaging materials with
specific characteristics which allows monitoring the
condition of packaged food or contributes to pre-
serving and extending their shelf life (López-
Gómez et al., 2015; Vanderroost et al., 2014).
These two concepts are included in two packaging
approach technologies which can be differentiated
in active packaging and intelligent packaging sys-
tems (López-Gómez et al., 2015).
Active packaging are systems in which the food
product, the packaging, and the environment inter-
act in a positive way to extend the shelf life or to
achieve some specific characteristics (Biji et al.,
2015). Active packaging systems take advantage of
the interactions between packaging materials and
foodstuff. The development of active packaging is
mainly based on the inclusion of active agents
(antimicrobials, antioxidants (AOs), flavors, vita-
mins, or nutritional supplements) in the packaging
material instead of the direct addition of them into
the foodstuff. Active packaging technologies are
based on physical, chemical, or biological actions
between the packaging and the packed food or the
head space (López-Gómez et al., 2015). When
active compounds migrate from the packaging to
Figure 6.6 Schematic representation of release process.
135
the foodstuff they chemically or biologically
interact with the foodstuff to slow down the
deterioration processes, increasing their shelf-life
(Gómez-Estaca et al., 2014; Sanches-Silva et al.,
2014). The effective incorporation of the active
agent as well as the ability to subsequently release
the active agent to the foodstuff is the major chal-
lenge in the development of active packaging.
Fig. 6.6 shows the schematic representation of the
release process of active compound from the pack-
aging to the packed food.
Some components of the packaging can also
migrate to the food, thus, the evaluation of materi-
als compliance with regulations includes migration
monitoring for both package component (i.e., oligo-
mers, plasticizers, etc.) and the active compound
itself (Jamshidian et al., 2010). On the other hand,
active compounds could show higher affinity for
the packaging material than the foodstuffs.
Therefore, the design of active packaging systems
is expected to obtain an successful release ability of
active compound from the polymer matrix (Osada
and Gong, 1998). In this context, the addition of
plasticizer has shown to be an effective way to
improve the release of the active compound from
the polymer matrix due to the increased polymer
chain mobility which increases the mass transport
of the active agent (Arrieta et al., 2014; Castro
López et al., 2012). Another strategy is the nano-
encapsulation of active substances in which the
active compound is encapsulated within another
material at nanoscale sizes by applying specific
methods of nanocomposite, nano-emulsification,
136
and nanostructuration, thereby increasing the func-
tionality of the final material by controlled release
of the active core (Tekiner et al., 2015).
In active packaging the active agents are mainly
oxygen scavengers, antioxidant and antimicrobial
agents, moisture and ethylene adsorbers, and etha-
nol and carbon dioxide emitters (López-Gómez
et al., 2015).
Lipid oxidation is one of the main cause of spoil-
age of several food products (i.e., fish, meats, nuts,
whole milk powders, sauces, and oils), which leads
to the loss of nutritional and sensorial quality of
foodstuff, while it may also result in the formation
of toxic aldehydes (Gómez-Estaca et al., 2014).
Therefore, many research and industry efforts have
been focused on the limiting the oxygen presence in
packaged foods, such as the direct addition of AOs
to the food, the development of high-barrier packag-
ing materials, and the use of vacuum or modified-
atmospheres. However, in order to reduce or avoid
the direct addition of antioxidant to the food pro-
ducts and due to the fact that some food products (i.
e., fresh red meat or fish products) cannot be pack-
aged without oxygen (Gómez-Estaca et al., 2014),
new strategies focused on the development of anti-
oxidant packaging materials are growing in the food
packaging field. A lot of oxygen-scavenging sys-
tems have been successfully commercialized (Tian
et al., 2013). For instance, the most frequently used
oxygen-scavenging systems in commercial applica-
tions are sachets and labels which are included in
the packaging that contain active substance (mainly
metals, enzymes, and small natural/biological mole-
cules) (Caleb et al., 2012). There are also films with
immobilized oxidizing enzymes (i.e., alcohol oxi-
dase and glucose oxidase) on the inner surface (Tian
et al., 2013).
AOs can be also incorporated into packaging
materials to prevent food oxidation processes and
thus find a compromise between the antioxidant
role and the pleasant taste and aroma of packed
food (Bonilla et al., 2011). In particular, the incor-
poration of natural AOs into packaging materials is
of high interest since this approach may reduce
lipid oxidation and can even increase food nutri-
tional value (Gómez-Estaca et al., 2014). In this
context, green tea extract, which is a great source
of flavonoids and thus serves as a rich source of
polyphenol AOs, mainly catechins, has the status of
a food additive (Carrizo et al., 2014). Catechins
have aroused considerable interest as antioxidant
MODIFICATION OF POLYMER PROPERTIES
additives for the food packaging field, not only for
their potential beneficial effects on human health,
but also because of they are nonvolatile, which is a
great advantage compared to other AOs (i.e., essen-
tial oils), reducing the loss of active agents during
packaging manufacturing by melt blending technol-
ogies (Arrieta et al., 2014; Carrizo et al., 2014;
López de Dicastillo et al., 2011; Castro López
et al., 2013). Both traditional plastic and bio-based
plastic have been loaded with catechin (Arrieta
et al., 2014; Castro López et al., 2012, 2013). For
instance, López de Dicastillo et al. developed
catechin-loaded maleic anhydride modified poly-
propylene using two different maleic concentra-
tions. They found that increasing the degree of
grafted polypropylene (PP) decreased the amount
of catechin released from the composites to the
food simulants (Lopez de Dicastillo et al., 2013).
Arrieta et al. developed composites based on poly
(lactic acid) (PLA) and PLA-poly(hydroxybutyrate)
(PLA-PHB) blends plasticized with a citrate acid
and further loaded with catechin. It was observed
that the PHB presence produced an induction
period in the diffusion process, due to the higher
crystallinity limiting the polymer chain mobility in
PLA-PHB-based blends. Meanwhile, a higher
amount of catechin was released when these sys-
tems were plasticized owing to the ability of plasti-
cizer to increase the polymer chain mobility and,
thus, the release of catechin (Arrieta et al., 2014).
To control undesirable microorganisms in foods
during storage and distribution, and to reduce or
avoid the addition of antimicrobial substances into
the food product they can be also incorporated into
the food packaging materials. In particular, there is
a growing interest in the development of antimicro-
bial packaging materials incorporated with natural
antimicrobial agents (Irkin and Esmer, 2015;
Vergis et al., 2015). Several antimicrobial agents
have been incorporated into food packaging materi-
als for the development of antimicrobial packaging
systems, including biotechnology antimicrobial pro-
ducts, natural occurring antimicrobials, antimicro-
bial polymers, essential oils, etc. (Malhotra et al.,
2015). The well-known antimicrobial activity of
chitosan has allowed it to be proposed as a bio-
based and biodegradable polymer matrix for food
packaging applications. However, the antimicrobial
effectiveness of chitosan films is highly dependent
on environmental conditions (pH, humidity, tem-
perature), microbial targets, and also on intrinsic
6: SMART POLYMERS
factors (the chitosan type and the film forming pro-
cesses) (Fernández-Pan et al., 2015). Several essen-
tial oils have been proposed as antimicrobial agents
for active food packaging (i.e., oregano, lemon,
clove, cinnamon, citronella, eucalyptus, etc.).
Recently, bioactive nanocomposite films based on
fish gelatin loaded with chitosan nanoparticles and
incorporated with oregano essential oil were devel-
oped. Those films containing essential oil exhibited
antibacterial activity against four different patho-
genic and spoilage bacteria: gram-positive bacteria
(Staphylococcus aureus and Listeria monocyto-
genes) and gram-negative bacteria (Salmonella
enteritidis, and Escherichia coli). Meanwhile, the
nanocomposites without essential oil did not pres-
ent antimicrobial activity against the studied micro-
organisms due to chitosan nanoparticles with low
polarity diffusing slowly from the films to the agar
plates, giving time to colonies to grow on the agar
plates (Hosseini et al., 2016). Silver nanoparticles
have been widely used in the development of anti-
microbial packaging materials due to the strong
biocidal effects of silver ions and silver-based com-
pounds which are highly toxic to microorganisms
(Tripathi et al., 2011). Chitosan-silver oxide nano-
composite films showed significant antibacterial
effect against E. coli, St. aureus, Bacillus subtilis,
and Pseudomonas aeruginosa. Bionanocomposites
based on PLA reinforced with CNCs and silver
nanoparticles have shown antibacterial activity
against St. aureus and a greater effect against
E. coli. The antibacterial effectiveness was
improved by to the presence of silver nanoparticles.
The antibacterial activity was significantly higher
in bionanocomposites with CNCs because of the
release of silver ions was higher in those formula-
tions (Fortunati et al., 2014).
Ethylene adsorbers or removals have been widely
used in the removal of ethylene from packed food
based on activated carbon systems, silicon dioxide,
or potassium permanganate (Tian et al., 2013;
Church, 1994). Carbon dioxide removals have been
also used, for instance in the packaging of freshly
roasted coffee it extended its shelf life by more than
three times (Church, 1994).
Intelligent packagings are packaging or articles
contained in the packaging which monitor the con-
dition of packaged food or the environment sur-
rounding the food (Biji et al., 2015). Intelligent
packaging systems have the ability to detect, sense,
or be sensed and also to communicate when its
137
contents are spoiling or some specific conditions
have changed and, thus, provide the consumers with
information on the conditions of the food, its envi-
ronment (temperature, pH), or the packaging integ-
rity (Biji et al., 2015; Tian et al., 2013; Neethirajan
and Jayas, 2011). Therefore, it represents an exten-
sion of the communication function of traditional
packaging. Intelligent packaging often produces a
visible change in the properties of the indicator
used, such as color change, which allows the possi-
bility to monitor the safety and shelf life of the food
products (Tian et al., 2013). The main purpose of
intelligent packaging is to indicate whether the
packed food quality has decreased before it deterio-
rates (López-Gómez et al., 2015). Most smart pack-
aging materials incorporate indicators or sensors
into the packaging material. A sensor is made up of
a receptor and a transducer, which first detects,
locates, or quantifies energy or matter by detecting
or measuring a physical or chemical property to
which the device responds and then provides a con-
tinuous output of a signal (Park et al., 2015).
Meanwhile, an indicator is much simpler in design
and communicates information throughout a direct
visually observable change (Park et al., 2015). The
most used intelligent packaging applications are
time
temperature indicators (Joshi et al., 2012),
freshness indicators and tracking services via intelli-
gent expiry date labels (López-Gómez et al., 2015).
The time
temperature indicators are stimulated
by temperature and respond with a mechanical,
chemical, or biological (enzymatic or microbiolog-
ical) irreversible change, which is usually expressed
as a visible response in the form of a mechanical
deformation, color development, or color move-
ment (López-Gómez et al., 2015). The reactions
involved in these types of IP systems are
temperature-dependent and the rates of the reac-
tions increase at high temperatures (Park et al.,
2015). Thus, they provide indirect information
about the freshness and safety of packed food in
terms of the temperature to which the product was
exposed from the manufacturer to the final con-
sumer (López-Gómez et al., 2015). Most commer-
cially available TTIs show the color change in a
time
temperature-dependent manner based on their
specific properties (Park et al., 2015). The
main causes for the lack of current commercial
time
temperature indicators in foodstuffs are cost,
reliability, and applicability (Brizio and Prentice,
2015). Nevertheless, the direct indicators are
138 MODIFICATION OF POLYMER PROPERTIES

generally preferred because of their ability to pro-

vide more precise and targeted information on qual-
ity attributes (Puligundla et al., 2012). The use of
dyes for the development of the time
temperature
indicators is a very common approach. For
instance, extracts of some plants containing antho-
cyanins can be used as natural pH indicators, since
they show color changes due to the presence of
phenolic or conjugated substances which are sub-
jected to structural changes when there is a varia-
tion in pH. The time
temperature indicators films
based on poly(vinyl alcohol)/Chitosan added with
anthocyanins were recently developed to indirectly
Figure 6.7 Radio frequency identification device.
indicate food quality changes through the detection
Reprinted with permission of American Chemical
of changes in the pH revealed by color changes of
Society. Potyrailo, R.A., Nagraj, N., Tang, Z.,
the films of packaged foods when subjected to
Mondello, F.J., Surman, C., Morris, W. 2012.
improper storage temperatures (Pereira et al.,
Battery-free Radio Frequency Identification (RFID)
2015). Another color change detector has been
sensors for food quality and safety. J. Agric. Food.
recently developed in which the operating principle
Chem. 60, 8535
8543, Potyrailo et al. (2012).
is based on the complexation reaction between
starch and iodine and the subsequent action of an
optically-based sensor systems to continuously
amylase enzyme on this complex, causing discolor-
monitor the headspace gas composition of packed
ation at a rate dependent on time and temperature
mushrooms. They added porphyrin, a phosphores-
of the medium (Meng et al., 2014).
cent dye, and α-naphtholphthalein, a colorimetric
Radio frequency identification (RFID) tags
pH indicator, in a poly(isobutyl methacrylate)
involve a wireless transfer and collection of data. A
matrix and a phase transfer agent, tetraoctyl
reader emits radio waves which capture data from a
cetyltrimethylammonium hydroxide (TOA-OH) or
RFID tag and the data are then transferred onto a
cetyltrimethylammonium hydroxide (CTA-OH).
host computer for analysis and interpretations (Tian
The emission energy is transferred from porphyrin (the
et al., 2013). Thus, RFID are electronic devices that
donor) to a-naphtholphthalein (the acceptor) which
transmits real-time information to trace and track
absorbs in the same region as the donor emission.
history of more complex information including
They showed that sensors containing higher amounts
temperature and relative humidity (Park et al.,
of TOA-OH are useful for lower CO2 concentrations,
2015; Fig. 6.7). Such technology is currently used
while sensors containing CTA-OH are preferred for
for agricultural and food traceability systems
higher CO2 concentrations (Borchert et al., 2014).
(Meng et al., 2014).
When designing an ideal intelligent packaging,
There are also gas indicators, biosensors, etc.
there are various criteria to be considered. A sensor/
(Tian et al., 2013; Meng et al., 2014). Gas sensors
indicator should be composed of nontoxic materials.
are used for detecting the presence of gaseous ana-
The change measured in the environment should be
lytes in the packaging (i.e., oxygen sensors, carbon
an irreversible reaction with the intention of contin-
dioxide sensors, water vapor sensors, ethanol sen-
uously monitoring changes and determining whether
sors, etc.) (Biji et al., 2015). During the food fer-
the product has ever been exposed to adverse condi-
mentation or spoilage due to microbe action,
tions (Park et al., 2015).
oxygen gas decreases and carbon dioxide gas
accumulates. Thus, carbon dioxide sensors are
widely used in IP systems, including fluorescent 6.3 Mechanisms of Shape Memory
carbon dioxide sensors, dry optical carbon dioxide
sensors, sol
gel-based optical carbon dioxide sen- Shape memory materials are a class of smart
sors, photonic crystal sensors, and pH-based wet materials able to change their shape on application
optical carbon dioxide indicators (Meng et al., of an external stimulus, fixing a temporary shape
2014). Borchert et al. recently developed when the external stimulus is removed. Then, the
6: SMART POLYMERS
Figure 6.8 Photographs representing the shape memory effect in a polymeric material.
shape memory materials are able to recover their
initial shape when the external stimulus is applied
again (Fig. 6.8). Not just polymers (Peponi et al.,
2014a; Wei et al., 1998; Lendlein and Kelch, 2004)
are able to present shape memory properties but
also this phenomenon can be found in metal alloys
(Wei et al., 1998; Van Humbeeck, 1999; He et al.,
2005; Chau et al., 2006; Gil et al., 2004; Rossi
et al., 2008) as well as in ceramics (Heuer et al.,
1990; Wang et al., 1991). As we might expect, the
shape memory mechanisms are different in the dif-
ferent types of materials (Peponi et al., 2014a; Liu
et al., 2007). In particular, the deformation that can
be presented in both the metal alloy and the cera-
mics, are very small compared with the deforma-
tion achieved by polymers (Knight et al., 2009).
Moreover, when working with polymers, their big
strains give more possibility for fixing the tempo-
rary shape in contrast with metallic alloys and cera-
mics. In general, polymers are cheaper than the
other materials; conversely, they present the worst
mechanical properties. So with the aim of exceed-
ing this drawback, the incorporation of nanofillers
into the polymeric matrices has been also studied in
order to obtain increased mechanical performance.
However, in this chapter the attention will be
focused only on polymeric-based materials.
As mentioned above, when speaking about shape
memory polymers it is referred to as “one way shape
memory.” Some differences are presented with
respect to materials able to present “two-way” or
“multiway” shape memory behavior. In general, in
order to obtain one-way shape memory polymers,
simply referred to as shape memory polymers, two
active phases are necessary and an external stimulus
needs to be able to activate the changing from one
phase to the other. In particular, one is the fixity
phase, which is able to memorize the initial shape of
the polymer, and the other one acts as the “switch
phase” allowing to fix the temporary shape.
139
Figure 6.9 One-way shape memory mechanisms:
programming and recovery stage.
These changes are achieved throughout a “pro-
gramming” and “recovery” stage, regulated by the
external stimulus.
In particular, the programming stage fixes the
temporary shape from the fixity shape. In the recov-
ery stage the material is able to recover its fixed
shape form the temporary shape (Fig. 6.9).
There are many stimuli able of producing the
shape memory effects in polymeric materials.
Meng and Hu (2009) reported a general classifica-
tion of the external stimuli dividing them into two
categories—direct and not-direct stimuli.
The direct ones allow programming and recover-
ing stages such as temperature. In this case the phe-
nomenon is named thermally activated shape
memory effect.
On the other hand, not-direct stimuli only act dur-
ing the recovery process making necessary the
application of another stimulus for the temporary
fixation. Moisture and electric and magnetic fields
are examples of indirect stimuli. In this case the
programming stage is performed through the appli-
cation of temperature, obtaining a temperature-
sensitive programming procedure similar to the one
for the direct stimuli.
Light can act as both direct and not-direct
stimulus.
140
Therefore, in the thermally activated shape mem-
ory processes, once the transition temperature
(TTRANS) is chosen, the sample is heated above the
TTRANS during the programming stage, changing
shape from the fixity to the temporary one. In order
to fix the temporary shape the sample is cooled
down below the TTRANS, “freezing” the sample at
the new temporary shape. Then, during the recov-
ery stage, the sample is reheated above its TTRANS
and recovers its fixity shape (Fig. 6.10).
The fixity phase memorizes the initial shape of the
polymer while the switch phase allows fixing the
temporary shape. In addition the switch phase has a
transition temperature TTRANS, which enables the
recovery of the primary shape. This temperature can
be the melt temperature (Tm) or the glass transition
temperature (Tg) of the polymer depending on the
crystalline or amorphous nature of the switch phase.
In order to characterize the thermally activated
shape memory behavior on polymeric materials,
thermo-mechanical cycles is the common procedure
used (Liu et al., 2007; Peponi et al., 2013; Chen
et al., 2009). However, there are not standard proce-
dures for the characterization of the shape memory
effects of polymeric materials. Also, microscopy
analysis of the materials during the recovery stage
has been reported (Lendlein and Langer, 2002).
In Fig. 6.11, a 3D stress
strain
temperature
diagram is schematically shown with the different
programming and recovery stages of the sample.
Moreover, two main parameters have to be chosen
before starting the shape memory tests, i.e., the
deformation at which the shape memory has to be
studied and the TTRANS of the system used for the
thermally activated shape memory behavior.
The whole thermomechanical cycle used to char-
acterize the shape memory process can be divided
into four main steps, synthesized as follows:
• Once the TTRANS is chosen, the sample is
heated above the TTRANS, without applying
any stress.
T < TTRANS
Temporary
Fixity T > TTRANS T > TTRANS
shape
shape
Figure 6.10 Thermally activated one-way shape
memory mechanisms.
MODIFICATION OF POLYMER PROPERTIES
• After the programming time, a stress is applied
to the sample until it reaches the deformation at
which the shape memory has to be studied (εm).
• The stress is maintained until the sample is
cooled down below the TTRANS, fixing the
temporary shape. Then the stress is removed.
In this step it is possible to determine the abil-
ity of the material to fix the temporary shape.
• Finally, the polymer is reheated above the
TTRANS in order to recover its initial shape,
determining the capability of the material to
recover its original shape.
This procedure should be cyclically repeated.
There are two main parameters used to quantify
the shape memory ability of a polymer, the strain
recovery ratio, Rr and the strain fixity ratio, Rf
(Peponi et al., 2013).
In particular, Rf describes the capability of the
polymer to fixity its mechanically imposed tempo-
rary shape
εu ðN Þ
Rf 5 3 100% (6.1)
εm
εm 2 εp ðN Þ
Rr 5 3 100% (6.2)
εm 2 εp ðN 2 1Þ
while Rr indicates the capability of the polymer to
recover its original shape, where, N is the number
of cycle, εm is the deformed strain, εu the fixed
strain and εp is the recovered strain.
Also a bending test can be used in order to char-
acterize the shape memory behavior of the poly-
mers (Knight et al., 2009; Luo et al., 2008; Zheng
et al., 2006, 2008; Zhou et al., 2007).
Another important parameter to be considered in
shape memory polymers characterization is the
recovery time. However, there is not uniformity in
the literature to quantify this parameter. There are
different ways to represent it, such as a strain recov-
ery versus time graph (Knight et al., 2009; Song
et al., 2010b), photographs (Zhang et al., 2007;
Fixity
Navarro-Baena et al., 2015), or giving a value of the
shape
recovery process (Luo et al., 2008; Zini et al., 2007).
However, considering the application of shape-
memory polymeric devices in real-life, one major
drawback of the shape memory effect, is the missing
reversibility of the shape change in the “one-way”
6: SMART POLYMERS 141

ion
shape fixat
150 Temporary

Co
oli
Reco ng
very
100

Strain (%)
50

on
ati
rm
Firs

fo
t he

De
0 atin 600
0 g
Te 30 300 a)
mp
era 60 (KP
tur e ss
e (°C 90
0 Str
)
T < TTRANS T > TTRANS T < TTRANS T > TTRANS

Fixity Recovered
shape fixity shape

Temporary shape

Figure 6.11 Thermomechanical cycle uses to characterize the thermally activated shape memory behavior of
polymers.

Figure 6.12 “One-way” and “two-way” shape memory effects. From Progress in Polymer Science-Volumes
49–50, October–November 2015, Pages 3–33.

shape memory polymers as described above (Hager
et al., 2015).
The situation is different for the “two-way”
shape memory polymers (Fig. 6.12). In fact, in this
case, a reprogramming phase is not required due to
the fact that the temporary shape is able to reform
by itself as soon as the stimulus is terminated.
Materials able to present two-way shape memory
effects are quite rare, due to the fact that they need
an internal driving force for achieving the reverse
transformation. One designed principle for such
materials is based on liquid crystal elastomers (Xie
and Zhang, 2005; Ohm et al., 2010; Qin and
Mather, 2008; Agrawal et al., 2014). Pandini et al.
reported that poly(ε-caprolactone) (PCL), PCL, is
also able to reveal the two-way shape memory
142
effects under a constant stress (Pandini et al.,
2012). In this case the melting induced expansion
while crystallization induced contraction under con-
stant stress (Chung et al., 2008).
However, we refer to “one-way” and “two-way”
shape memory polymers as “dual” shape memory
materials. It means that the temporary shape is
transformed into the permanent shape.
In contrast with “dual” shape memory effects,
there are the triple shape memory polymers consti-
tuted by two temporary shapes (A and B in Fig. 6.12)
and a permanent one (shape C, in Fig. 6.12) (Hager
et al., 2015; Behl and Lendlein, 2010).
In general in the triple shape memory polymers,
a programming stage and two triggers are required.
One is responsible for the transient shapes, chang-
ing from A to B, and the other one induces the
change back to the original shape (shape C). In par-
ticular, firstly, the temporary shape B has to be pro-
grammed, followed by the programming of the
second temporary shape A.
In principle, multiple (n) shape memory polymers
can be also designed. They should be characterized
by one permanent shape and (n-1) temporary shape
(Hager et al., 2015; Hu et al., 2012).
Shape memory behavior is not an intrinsic prop-
erty of the materials but it is necessary that poly-
mers present an adequate phase morphology in
order to show this behavior (Peponi et al., 2014a).
In particular, two phases have to exist, a “hard
phase” and a “soft phase.” The hard stable phase is
able to retain the original shape. Its deformation is
the driving force for the shape recovery. This phase
can be formed by both chemical or physical
domains, obtained by the introduction of chemical
cross-links, crystalline phases, or interpenetrating
networks (Peponi et al., 2014a; Liu et al., 2007; Hu
et al., 2012; Meng and Li, 2013; Behl et al., 2010;
Behl and Lendlein, 2007).
A second phase, influenced by the external stim-
ulus, is able to fix the temporary shape. This phase
can be also composed by chemical or physical
domains. In particular, it can be composed by
chemical reversible bonds such as covalent or
supramolecular bonds and by physical domains
characterized by reversible phase transition, such as
melting temperature with low Tm, glass transition,
and transition between different liquid crystalline
phases. The main difference between Tm and Tg is
that Tm presents a narrow interval respect to the
wide interval of Tg making the choice of Tm
MODIFICATION OF POLYMER PROPERTIES
preferable as a switch temperature (Peponi et al.,
2014a; Behl et al., 2010; Behl and Lendlein, 2007;
Nagata and Yamamoto, 2009; Lendlein et al.,
2009).
However, when working with shape memory
polymers it can be possible to divide the materials
into Tm-type and Tg-type shape memory effects, as
briefly discussed below.
The melting temperature can be utilized in
chemically cross-linked rubbers, in semicrystalline
polymeric networks as well as in physically cross-
linked polymers. The glass transition temperature
can be utilized in chemically cross-linked thermo-
sets as well as physically cross-linked thermoplas-
tics (Peponi et al., 2014a).
Most investigated Tm-type shape memory poly-
mers are based on polyolefins (including the prime
example polyethylene in heat-shrinkable films)
(Morshedian et al., 2003; Kolesov et al., 2009;
Maksimkin et al., 2014; Zhao et al., 2013), natural
rubbers (Katzenberg et al., 2011; Heuwers et al.,
2012, 2013), polyethers (Ahmad et al., 2012; Chun
et al., 2007; Niu et al., 2012; Li et al., 2014), or
polyesters (in particular PCL), which are used also
as soft block in polyurethanes (PU) (Peponi et al.,
2013; Hu et al., 2005; Kim et al., 1996; Saralegi
et al., 2014; Rabani et al., 2006; Ping et al., 2005).
There are several ways to generate cross-links in
the matrix in order to obtain shape memory poly-
mer (SMP) (Liu et al., 2002; Nagata and
Yamamoto, 2009; Helminen et al., 2002; Zhu et al.,
2006; Nair et al., 2010) even if the two more dif-
fuse ways are by using a cross-linking agent or
through electromagnetic radiation. In the first case
it can be possible to add peroxide to the polymer
matrix to create covalent bonds (Morshedian et al.,
2003; Liu et al., 2002; Helminen et al., 2002).
Regarding the second case, there are different
wavelengths that are able to get polymer cross-
linking with electromagnetic radiation. In fact, the
first polymer with shape memory behavior was
obtained by radiation of polyethylene with gamma
rays (Liu et al., 2007). Additionally, gamma radia-
tion has been used to generate shape memory in
PCL (Zhu et al., 2003) and its blend with poly
(methyl-vinyl-siloxane) (Zhu et al., 2006).
Moreover, ultraviolet (UV) radiation has been used
by incorporating photoinitiators or light-sensitive
monomers to produce a polymer network. Knight and
coworkers (Knight et al., 2009) synthesized a cova-
lent network from poly(lactide-co-glicolide) with
6: SMART POLYMERS
polyhedral oligomeric silsesquioxanes using tetra
thiol as a cross-link agent and (2,2-dimethoxy-2-phe-
nylacetophenon) as a radical photoinitiator.
Another way to get a cross-linked network with
UV radiation consists of the addition of functional
monomers to polymer chains which can create
covalent bonds when they are exposed to UV-light.
In this manner it is easy to control the initial shape
of the polymer and the degree of cross-linking and
the network points are formed by photo curing
(Song et al., 2010b; Helminen et al., 2002;
Schoener et al., 2010; Kelch et al., 2007; Choi and
Lendlein, 2007).
Nagata et al. (Nagata and Yamamoto, 2009,
2010) developed SMP from PCL, poly(ethylene
glycol) (Rossi et al., 2008) and PLA using two dif-
ferent chain extenders. With the same approach,
A. Lendlein has obtained SMP with reversible light
cross-linking by means of acid cinnamic molecules
addition (Lendlein et al., 2005).
Different to Tm-type shape memory polymers,
the Tg-based shape memory polymers present a Tg
above room temperature which can be used as a
switch temperature for the shape memory effects.
However, the Tg-type materials present a slower
shape recovery due to the broad transition, in com-
parison to the Tm-types, indicating that they are not
ideal for applications where a sudden shape recov-
ery is required (Hager et al., 2015), making them
interesting candidates for biomedical applications
where a slow recovery is necessary (Hager et al.,
2015; Hu et al., 2012).
We discussed before about natural rubber as Tm-
type shape memory polymers. However, epoxidized
natural rubber with an increasing cross-linking den-
sity resulted in higher glass transition temperatures
and, therefore, in higher switching temperatures.
Moreover, with epoxy-based materials the glass
transition could be tuned by the thermoset composi-
tion (Hager et al., 2015). Consequently, a higher
cross-linking density resulted in a faster shape
recovery (Kumar et al., 2013).
As for the epoxy-based materials, also PU can
present shape memory effect controlled by Tg
instead of Tm. In this case the Tg-type PU are trans-
parent and more favorable to the degradation due to
the absence of crystallinity in the switch phase
(Alteheld et al., 2005; Jeong et al., 2000).
Another class of material based on the Tg-type
of shape memory effect is the acrylate-based cova-
lently cross-linked shape memory polymers (Hager
143
et al., 2015; Safranski and Gall, 2008; Song et al.,
2010a). Moreover, the methacrylate structure was
also studied in shape memory hydrogels
(Hao and Weiss, 2013) confirming the strong
interaction between the different classes of smart
materials.
Generally, the studied Tg-type shape memory
polymers present a transition temperature lower
than 100°C. A very few shape memory polymers
present high switching temperatures. However, an
example is polyimide and graphene-reinforced
polyimide nanocomposites with low cross-link den-
sity, which are able to present a switch temperature
of about 220°C (Koerner et al., 2013; Yoonessi
et al., 2012).
6.4 Mechanisms of Self-Healing
Nowadays, the field of self-healing is growing
quite fast (Fig. 6.13), encompassing a whole range
of self-healing polymer systems. Inspired by nature,
researchers have developed engineered materials
with an even further extended life time by autore-
pairing the inevitable damage events that occur
during use.
Therefore, since the 1990s, the self-healing
capacity has inspired many researchers to design
polymer composites that are capable of healing
damage rather than preventing it (Zhong and Post,
2015). This field was pioneered by Dry who
included hollow glass fibers containing liquid adhe-
sive in a concrete matrix (Zhong and Post, 2015;
Dry, 1996).
It is very difficult to realize a classification of
these materials. However, when speaking about
self-healing polymers it is worth distinguishing
between those able to recover their material proper-
ties fully autonomously and those that require the
application of an external stimulus, such as heat or
UV-light, to initiate the recovery process
(Hillewaere and Du Prez, 2015).
Within the autonomous ones it is possible to dis-
tinguish two different categories of self-healing
polymers, namely, external and internal self-healing
polymers (Hillewaere and Du Prez, 2015). Yuan
et al. (2008) and later many other groups world-
wide (Hager et al., 2010; Blaiszik et al., 2010;
Murphy and Wudl, 2010; Garcı́a et al., 2011;
Guimard et al., 2012) refer to these two categories
as extrinsic and intrinsic materials.
144
Figure 6.13 Review publications from 2000 to 2015 on self-healing.
Zhong et al. (Zhong and Post, 2015) reported an
interesting review on composites with intrinsically
self-healing polymeric matrices, summarizing their
mechanisms, schematically reported in Fig. 6.14.
Hillewaere et al. (Hillewaere and Du Prez, 2015)
named them as external and internal, a definition we
also adopt. In particular, external refers to the mate-
rials able to show its self-healing capabilities by
adding supplementary healing agents in any kind of
container (capsules, vascular network, etc.) while
internal refers to materials where the self-healing
capability is due to its own chemical nature.
As examples of internal self-healing polymers we
can take into account the work of Herbst et al.,
where they studied self-healing polymers obtained
via supramolecular forces (Herbst et al., 2013).
Another example is presented by Billiet et al. (2013)
where they reported a study on the chemistry of
cross-linking processes for self-healing polymers.
Moreover, there are different material functions
that can be recovered, obtaining the so-called func-
tional self-healing polymers. Recently, there have
been publications on the recovery ability of the
material functions, such as corrosion protection or
conductivity (Garcı́a et al., 2011; Hughes et al.,
2010; Amendola and Meneghetti, 2012).
Hillewaere et al. (Hillewaere and Du Prez, 2015)
recently reviewed external self-healing polymers.
They reported different self-healing chemistries and
for each one they highlighted if there is a catalyst
MODIFICATION OF POLYMER PROPERTIES
Figure 6.14 Schematic representation of intrinsic
self-sealing by external stimuli; thermal, photochem-
ical, electrical, and moisture activation. Reprinted
with permission of Elsevier Zhong, N., Post, W.
2015. Self-repair of structural and functional compo-
sites with intrinsically self-healing polymer matrices:
a review. Composites, Part A. 69, 226
239.
required, the different types of damage, and the
efficiency of each system (Table 6.1).
In particular, they reported that for the self-
healing chemistry based on the ring-opening
metathesis polymerization of dicyclopentadiene
(DCPD) and 5-ethylidene-2-norbornene (ENB) the
use of catalyst is required and considered as the
drawback of the system. Moreover, the choice of
the catalyst is strongly influenced by the final self-
healing application temperatures, Fig. 6.15.
White et al. proposed the original concept of
using microcapsules in a thermosetting matrix to
deliver liquid healing agents to a location of
damage (White et al., 2001). In particular, liquid
Table 6.1 Summary of External Self-Healing Systems

Epoxy
Matrix Healing Vynil Unsaturated
Agent Ester Acrylates Poly (diethoxysiloxane) Poly (methacrylimide) Poly (isobutylene) Poly (isocyanurate) Polyester
DCPD/ENBa
Siloxanesa
Epoxy a
Amine-Epoxy
Thiol-Epoxy a
Thiol-Isocyanate
Azide-alkynea
Acylhydrazine/
methacrylatesa
Glycidylmethacrylate
Maleimides
Isocyanates
Cyanoacrylates
Vinyl ester a
Unsaturated
polyester a
a
Catalyst required, Maximal healing efficiencies higher than 80% (green-diagonal lines [dark grey in print version]), from 50% to 80% (orange-horizontal lines [light grey in print version]),
and from 0% to 50% (red-vertical lines [black in print version]).
Adapted from Hillewaere, X.K., Du Prez, F.E. 2015. Fifteen chemistries for autonomous external self-healing polymers and composites. Prog. Polym. Sci. 49–50: 121–153.
146
Figure 6.15 (A) Ruthenium-based Grubbs’ catalyst
initiates ring-opening metathesis polymerization
(ROMP) of endo-dicyclopentadiene (endo-DCPD).
Reprinted with permission of Hillewaere, X.K., Du
Prez, F.E. 2015. Fifteen chemistries for autonomous
external self-healing polymers and composites.
Prog. Polym. Sci. 49
50: 121
153.
endo-DCPD and first generation Grubbs’ catalyst
particles were introduced into an epoxy matrix to
generate a self-healing material. The idea is that
when the epoxy material ruptures, these microcap-
sules break and release the liquid DCPD into the
crack, where it comes into contact with the dis-
persed Grubbs’ catalyst and undergoes polymeriza-
tion, thus forming a cross-linked network that
adheres the epoxy crack surfaces back together.
Rule et al. studied paraffin wax protection to
more easily disperse the catalyst in the epoxy matrix
and to shield the Grubbs’ catalyst from deactivation
by the amine hardener at the same time (Rule et al.,
2005).
Biggs et al. combined the DCPD-Grubbs’ cata-
lyst self-healing system with poly(methyl methacry-
late) bone cement for anchoring joint replacements
(Biggs et al., 2009).
6.5 Mechanisms of Hydrogel
Hydrogels consist of a polymer
solvent system.
The polymer has to be cross-linked, physically or
chemically, so that a three-dimensional network that
is submerged in water is formed, swells, and retains
some of the water within its structure. This requires
that the polymer chain possesses hydrophilic
groups. The temperature sensitive hydrogels are
those that change their swelling properties when
subjected to temperature changes. Two types of
hydrogels with different behavior versus tempera-
ture exist—the “lower critical solution temperature”
(LCST) and the “high critical solution temperature”
(HCST). As the temperature increases LCST
decrease swelling while HCST increase in swelling.
MODIFICATION OF POLYMER PROPERTIES
Figure 6.16 Stimuli-responsive shape changing
polymers: (A) shape changing polymers (SCPs) and
(B) liquid crystalline elastomers. Reprinted with
permission of Elsevier Zhao, Q., QI, H. J. & Xie,
T. 2015. Recent progress in shape memory
polymer: New behavior, enabling materials, and
mechanistic understanding. Progress in Polymer
Science, 49
50, 79
120, Zhao et al., 2015.
Hydrogels are belonging to the class of stimuli-
responsive shape changing polymers (SCPs)
(Fig. 6.16A) with the liquid crystalline elastomers
(Fig. 6.16B).
Stimuli-responsive SCPs commonly refer to those
for which shape changes are either macroscopic or
at least visible under microscopes (Zhao et al.,
2015). However, in this case the programming stage
is not necessary. In fact, after the materials are fabri-
cated, the shape change can only occur between a
fixed numbers of equilibrium shapes (often two).
That is, their shape shifting cannot be manipulated
externally after fabrication, a nonprogrammable
shape changing behavior (Zhao et al., 2015).
This behavior is in contrast with the abovemen-
tioned features of the shape memory polymers in
which a programming stage is required.
However, shape memory hydrogels can be
designed. In particular, shape memory hydrogels
can be developed to realize additional functions not
offered by solid dense shape memory polymers
(Zhao et al., 2015). The programmable nature of
shape memory hydrogels sets them apart from typi-
cal stimuli-sensitive hydrogels. In fact, stimuli-
sensitive hydrogels can change their shapes in
6: SMART POLYMERS
Figure 6.17 Review publications from 2000 to 2015 on hydrogels.
response to external stimuli (temperature, pH, light,
electric signal, or chemicals). A typical example of
stimuli-sensitive hydrogel is a cross-linked water-
swollen network with environment-sensitive groups
able to change their affinity with water. They are
able to form additional cross-linking points upon
stimulation. In this case, stimuli-sensitive hydrogels
show only nonprogrammable shape transformation
between swollen states and shrunken states.
Starting from 2000, there have been numerous
reviews published on smart polymers hydrogels, as
summarized in Fig. 6.17.
Stimuli-sensitive hydrogels have been extensively
studied for drug delivery, cell culture, fluid control,
separation, and sensing applications, not only
because of their stimuli sensitivity, but also because
of their unique softness, high hydrophilicity, biocom-
patibility, and ability for rapid diffusion of molecules
(Drury and Mooney, 2003; Chung et al., 2012).
The first example of shape memory hydrogel was
reported by Osada and coworkers in the mid 1990s
(Osada and Matsuda, 1995; Kagami et al., 1996).
A thermally triggered shape memory hydrogel was
formed by water swelling of a polymer network
obtained by copolymerizing of acrylic acid, stearyl
acrylate, and methylenebisacrylamide (the cross-
linker) (Zhao et al., 2015). In this case they used the
crystalline/melting transition as the switching seg-
ments while the cross-linker set the permanent shape.
The presence of water in hydrogels creates even
more opportunities for designing shape memory
147
hydrogels using molecular switches. Theoretically,
the same principle can be applied to organogels
although not much has been reported in the litera-
ture (Zhao et al., 2015).
6.6 Conclusions
Polymer materials, in their early days, were
mostly studied for their use as static structural
parts. In the modern days, however, advanced poly-
mer materials that exhibit special functions in
response to external conditions have attracted more
and more attention. Such behavior is similar to the
biological intelligence observed in nature.
Accordingly, such polymers are also called smart
polymers, or in a more scientific term, stimuli-
responsive polymers. Within smart polymers, there
are the SCPs, sol hydrogels, for which, after their
fabrication, the shape change can only occur
between a fixed number of equilibrium shapes
(often two) such as swelling and deswelling. This
behavior indicates a nonprogrammable shape
changing behavior. In contrast, SMPs are a class of
stimuli-responsive SCPs for which shape shifting
behavior can be programmed. This is the single
most important feature that distinguishes SMPs
from other stimuli-responsive SCPs. Self-healing
polymers are another important class of stimuli-
responsive materials.
Active packaging systems take advantage of the
interactions between the packaging material and the
148
food. Active agents are incorporated into the pack-
aging material instead of the direct addition to the
foodstuff. Controlled release packaging offers the
potential for extending the shelf life of foodstuffs
by slowly releasing active agents (AOs and antimi-
crobials) over time. The addition of nanoparticles
can modulate the release process allowing to obtain
nanocomposites with the required release time.
Intelligent packaging monitors the condition of
packaged food or the environment surrounding the
food.
So, based on this chapter, it is worth concluding
that the vast potential to enable technological inno-
vations that are highly relevant for the human soci-
ety (e.g., health) has been the driving force for
active research on shape memory polymers.
Acknowledgments
We are indebted to the Spanish Ministry of
Economy and Competitiveness (MAT2013-48059-
C2-1-R and MAT2014-55778-REDT) and to the
Regional Government of Madrid (S2013/MIT-
2862) for their economic support. LP and MPA
acknowledge MINECO for the “Ramon y Cajal”
(RYC-2014-15595) and “Juan de la Cierva” (FJCI-
2014-20630) contracts, respectively.
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