Int J Adv Manuf Technol (2010) 49:803–826
DOI 10.1007/s00170-009-2428-6
ORIGINAL ARTICLE
Multifunctional materials: engineering applications
and processing challenges
Konstantinos Salonitis & John Pandremenos &
John Paralikas & George Chryssolouris
Received: 28 May 2009 / Accepted: 6 November 2009 / Published online: 17 December 2009
# Springer-Verlag London Limited 2009
Abstract Multifunctional materials are designed so as to
meet specific requirements through tailored properties.
Smart materials can be considered as multifunctional ones
that have the ability to react upon an external stimulus,
simulating, in this way, the behavior of nature’s materials.
Furthermore, the introduction of biomemetics in the
material science, allows the designing of materials with
similar processes as nature does: building from molecules
to complete structures. This paper focuses on the presen-
tation of the various multifunctional materials reported in
the literature and the processing means developed.
Keywords Multifunctional materials . Smart materials .
Composites . Material processing
1 Introduction
The multifunctional materials can be defined as those present-
ing specific desirable electronic, magnetic, optical, thermal, or
other properties to satisfy previously unattainable performance
metrics. These properties are combined with each other, or with
specific mechanical properties including stiffness, ductility,
and strength. The introduction of such materials to production
will significantly alter the design philosophy itself and the form
and capabilities of the products designed.
The composite materials can be considered multifunc-
tional, since they can achieve multifunctionality through the
K. Salonitis : J. Pandremenos : J. Paralikas : G. Chryssolouris (*)
Laboratory for Manufacturing Systems & Automation,
Department of Mechanical Engineering & Aeronautics,
University of Patras,
26500 Patras, Greece
e-mail: xrisol@mech.upatras.gr
proper selection of different materials combined together to
form the material. On the other hand, the ultimate
multifunctional materials are provided by nature; virtually,
all biology material systems are composites that are typically
endowed with a superior set of properties since they must be
able to perform well a variety of functions (e.g., the bones are
natural organic/inorganic composites made of hydroxyapa-
tite and collagen that have various important functions such
as supporting the body, moving the muscles, and producing
blood). Furthermore, biology exhibits a diverse number of
multifunctional materials, e.g., material systems with struc-
tural capability fully integrated with sensing, actuation, and
healing functions [1]. Thus, the multifunctionality of a
material could be achieved by designing the material from
the micro- to macroscales (bottom-up design approach),
mimicking the structural formations created by nature. This
is the case of the nanomaterials as it will be discussed later.
The theoretical design of materials is quite an old
practice. The prediction of coordination geometries by
simply considering the ratios of radii as well as by other
more sophisticated approaches, such as the determination of
stereochemistry with the use of the symmetry-based Wood-
ward–Hoffmann rules, are some of the methods that have
been applied for many years [3]. Computational-based
material development in material synthesis is a new
alternative approach. It is based on multiscale material
and process modeling spanning, on a large spectrum of time
as well as on length scales. Distinct models are used,
starting with the atomistic ones. Subsequent stages include
the realm of modeling processes and system modeling, as
shown in Fig. 1 [2]. The maturity of this research will
enable the designing, at the atomic/molecular level, to be
multifunctional via the specification of particular properties.
In general, the cost of designing and producing a novel
multifunctional material can be considered high and the risk
804
Fig. 1 Computationally driven material development [2]
of this investment is significant. Therefore, the economic
fostering of such an attempt depends largely on the acceptance
of this type of a material, both by the industry and the
customers. Moreover, the utilization of such materials is
limited by the processing techniques available. The processing
cost is still high, characterized by expensive and time-
consuming processes. During the processing, special care is
required in order for the functionality and properties of the raw
materials not to be disturbed; furthermore, each material
family poses different limitations, e.g., the difficulty in
forming pre-coated or sandwich material. Therefore, in
tandem with the ongoing research in the development of
new materials, significant research has to be focused on the
eco-efficient and mass processing of such materials. Eco-
efficiency, in particular, is nowadays considered a prerequisite
for the wide acceptance of a new technology by industries,
governments, and people. Producing more goods and services,
while using fewer resources and creating less waste and
pollution, is the current trend [4]. As far as mass processing is
concerned, only technologies that can afford high production
volume at a considerable low cost, will allow the commer-
cialization of multifunctional materials-based products.
Another key factor for the wide acceptance of these
advanced materials is the identification of their unique
capabilities and the freedom they give to the designer. For
the application of these materials in real world mass
produced goods, the design of the parts, subassemblies,
and eventually the product itself has to be altered in a
fundamental way. The current design philosophy is tailored
to meet the needs of homogenous materials and not of
composite materials with specific multifunctionalities.
The present paper aims to present the evolution in the
multifunctional materials and discuss the major processing
issues and challenges. Three major families of multifunc-
tional materials have been identified and are considered:
& Structural composite materials
& Smart or intelligent materials
& Nanostructured materials
Int J Adv Manuf Technol (2010) 49:803–826
2 Structural composite materials
Composites are composed of individual phases; the matrix
and the reinforcement ones. The matrix phase surrounds
that of the reinforcement, providing in such a way a
supporting structure for maintaining its position. The
reinforcement phase contributes with special properties
and enhances those of the matrix.
Composites are made up from a combination of
materials, each of them providing a unique character to
the final product [5]. Reinforcing materials could be also
found in ancient times, as ancient Greeks used to cement
iron rods into marbles so as to increase the span in marble
building constructions [6]. In the late 1930s, research and
development started the incorporation of composite materi-
als into aircrafts. In the First World War, the glass fiber was
developed as a substitute for asbestos, but this technology
was not developed further [7].
During the Second World War (WWII), the development
of composite materials was accelerated. Since then,
composites were used in tooling, but after that, they were
adopted as structural and semi-structural parts. Spectacular
steps, taken into processing structural composites and new
materials, were developed. The processing of composites
was also improved during WWII. Innovative manufacturing
processes were developed as filament winding and sand-
wich structures, using a cellular core, fire resistance
composites, and pre-preg materials, were some of the
innovative structural composites [8, 9].
During the post WWII period, some of the war-oriented
applications turned into commercial ones for the structural
composite materials. These applications focused mainly on
the aerospace, automotive, and appliances industries.
During this period, processing advancements in the com-
posites sector include pultrusion, vacuum bag molding, and
large-scale filament winding [8–10]. In the late 1960s and
early 1970s, new fibers were introduced with a boron
filament, such as aramid and ultra high molecular weight
polyethylene fibers. The development of new matrix resins
was implemented and the composites expanded into fields
such as high temperature and high corrosion resistance
applications.
The development of composite materials has evolved,
providing engineering applications with special material
combinations that can address strict requirements and
withstand very demanding environments. Composites such
as glass and carbon fiber reinforced plastics that can be
easily tailored (as far as strength and stiffness are
considered) to suit the requirements of their end applica-
tions can only be manufactured to meet a single combina-
tion of properties. New emerging challenging applications
and mixtures are in the background of developing multi-
functional composite structures, as shown in Fig. 2.
Int J Adv Manuf Technol (2010) 49:803–826
Fig. 2 Synthesis of multifunc-
tional composite structures
[11]
Intrinsically smart structural composites are multifunction-
al structural materials, which can perform additional functions
(Fig. 3) such as sensing strain, stress, damage or temperature,
damage (crack) propagation prevention, thermoelectric ener-
gy generation, electromagnetic interference (EMI) shielding
electric current rectification, self-healing internally, and
active noise and vibration control [12]. Polymer-matrix
composites are important for lightweight constructions.
2.1 Self-sensing composites
The simplest way of adding multifunctionality to a compos-
ite material is by incorporating sensors for monitoring its
own situation (self-damage detection and assessment). The
damage state of composite materials is determined by using
non-destructive techniques such as radiography or ultrasonic
testing that cannot provide continuous reporting during
service. Smart composites incorporate, besides the polymer
Fig. 3 Main functions of multifunctional structural composite
materials
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or metallic matrix material, non-structural elements such as
piezoelectric ceramics (PZT), optical fibers, etc. that allow
the real time monitoring of the damage state of the composite
material. Smart composite materials, which can monitor their
own strain, are valuable for structural vibration control. Self-
monitoring of strain has been achieved in carbon fiber
epoxy-matrix composites, without the use of embedded or
attached sensors, since the electrical resistance of the
composite in the through-thickness or longitudinal direction
changes reversibly with longitudinal strain due to alterna-
tions in the degree of fiber alignment. Continuous carbon
fiber epoxy matrix composites provide temperature sensing
as well by acting as thermistors and thermocouples. The
thermistor function stems from the reversible decrease of the
contact electrical resistivity at the interface between the fiber
layers (laminae) and the temperature [12]. Parthenios et al.
[13] used aramid fibers for measuring the stress concentra-
tion and its development into composite structures. Their
inhibited high Raman activity and their minute dimensions
make them suitable as stress sensors embedded in, or even
attached to other materials for the accurate monitoring of
local stresses or strains. Alternatively, the fiber Bragg grating
(FBG) sensors that can perform internal and surface
monitoring of strain and temperature can be used [14]. The
special characteristic of FBG sensors and optical fibers is
that they can provide structural health monitoring for the
entire lifetime of the composite, both during its production
phase (i.e., composite material cure monitoring) [15] and
during its service life [16]. Alternatively, micro-sensors can
be embedded in the composite material for assessing its
health as network nodes (Fig. 4 [17]).
Damage in the form of delamination increases the
resistivity in a perpendicular direction to the fiber layers,
whereas damage in the form of fiber breakage increases the
resistivity in the direction of the fibers [18]. Thus, its detection
with the use of optical fibers can be achieved by monitoring
the evolution of the properties of the laser light transmitted
through them [19]. Steward et al. [20] monitored the damage
occurring within a composite material by measuring locally
the temperature response with permanently embedded fiber
optic sensors.
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Fig. 4 Integration of network nodes in a composite plane [17]
2.2 Composites with embedded optical cabling
Wiring and communication requirements between sensors
and electrical components affect significantly the design
and manufacturing of a product. In the case of automotive
vehicles, the wiring poses a significant percentage of the
entire vehicle’s weight. In addition, the vehicle structures
must be designed to accommodate the volume of wiring,
introducing cutouts and channels that can compromise
structural design. An approach for such structural integra-
tion is to embed optical cabling in the structure (Fig. 5).
Optical waveguides possess much higher bandwidth and
data rates than electrical conductors, so that the total
volume of cabling can be greatly reduced. Furthermore,
the integration of such optical fibers into the structural
elements, results in the improvement of their robustness and
survivability [21]. Such a multifunctional material structure
serves the role of traditional structural materials (supporting
loads) in addition to their serving as a local area network,
shuttling data between the vehicle’s systems. These optical
communication buses are modular, redundant, not-invasive,
and inexpensive. Furthermore, information can be easily
ported into and out of the material, using it also for
structural health monitoring. These devices could signifi-
cantly reduce vehicle manufacturing and design costs,
while improving survivability and modularity.
2.3 Metal–intermetallic laminate composites
Composite materials are developed so as to present both
intrinsic and embedded functionality. Multilayered or
laminate composite materials may incorporate multiple
functions such as crack propagation prevention, self
healing, improved strength, etc. and simultaneously without
adding weight or increasing the cost. These composite
materials could be ceramic–ceramic, metal–ceramic, metal–
metal, metal–ceramic–intermetallic, or metal–intermetallic
systems. Improved damage resistance of these composites,
combined with enhanced strength and toughness, can be
Int J Adv Manuf Technol (2010) 49:803–826
achieved where the crack tip is shielded by the closure
imposed by the plastic deformation of ductile ligaments
[22]. A number of toughening strategies have been
proposed [23] to improve the critical stress intensity for
crack propagation. One of the most effective toughening
techniques is the introduction of a ductile phase, which
remains intact and bridges the crack faces in the wake of a
growing crack. Then, the crack tip is shielded by the
closure traction imposed by the plastic deformation of
ductile ligaments.
Metal–intermetallic laminate (MIL) composites, such as
Ti-Al3Ti, and Ni-Ni3Al systems, have a great potential in
aerospace, automotive, and other structural applications
because of their lower density than other laminate systems
and furthermore, their excellent specific mechanical proper-
ties, such as high strength, toughness, and stiffness [22, 24].
The design concept of these composite materials during the
reactive foil sintering process is illustrated in Fig. 6. In this
process, the initial sheet foils of Ti, Ni, and Al react with
chemically bonded layers of the remaining unreacted Ti or
Ni and the fully reacted Ti3Al and Ni3Al intermetallic phase.
The fully reacted phases give high hardness and stiffness to
the composite, while the unreacted phases provide the
necessary high strength, toughness, and ductility to the
system in order to be concurrently flexible [22].
The multilayered structure of the composite allows for
variations in the layer thicknesses and layer volume
fractions of the metal components, thus permitting the
optimization of mechanical and thermal management
properties for practical applications.
The MIL composites can be processed by stacking
alternative layers of two different types of metals (Ti with
Al, Ni with Al, etc) and placing them into a composite
synthesis apparatus [22, 24]. Pressure and heating are applied
in the open air. Pressure/temperature excursion in the MIL
process is selected such as the metals react completely and
no gaps are left in the final product. Several steps and
combinations of these process parameters are applied to the
metal layers, as this ensures that the reaction has reached the
entire product and the uniformity has been achieved [23].
The thicknesses of the initial metal alloy sheets are selected
Fig. 5 Schematic of integrated into structural composite optical
communication buss [21]
Int J Adv Manuf Technol (2010) 49:803–826 807

Fig. 6 A schematic cross

section of MIL (Ti-Ti3Al and
Ni-Ni3Al) composites a before
and b after the reactive foil
sintering process [22]

in such a manner so as for the desirable thickness and ratios
between the final phases to be produced.
2.4 Thermal energy storage composites
Thermal energy storage (TES) composites are utilized for the
effective use of thermal energy and have applications in
diverse areas, such as building heating/cooling systems, solar
energy collectors, power, and industrial waste heat recovery
[25]. TES sandwich structures that combine heat storage
function with structural functionality are described by Wirtz
et al. [26]. For example, the TES composites can be
configured as structural elements whilst at the same time being
part of the temperature control system; a possible application
of such a system could be in avionic systems for reducing
weight, enhancing system reliability, and allowing the use of a
smaller, less power-consuming power module cooler.
The use of phase change materials (PCMs) for TES has
gained a considerable importance in recent years [27] and
can be classified into two main categories: inorganic and
organic compounds [28]. Inorganic PCMs include salt
hydrates, salts, metals, and alloys, whilst organic PCMs are
composed of paraffin, fatty acids/esters, and polyalcohols.
PCMs that undergo a “dry” phase transition (no liquid
phase) are attractive TES materials since packaging
difficulties associated with solid–liquid PCMs are avoided
[29]. The most widely used solid–liquid materials are
paraffins. Zhang et al. [28] considers paraffin as the most
promising PCM due to its large latent heat, low cost,
stability, non-toxicity, and non-corrosiveness. Wirtz et al.
[30] introduced a novel multifunctional plate that consisted
of paraffin impregnated porous graphite core (the energy
storage volume) encapsulated between rigid graphite/epoxy
composite skins. Heat storage is via solid–liquid phase
transition of the paraffin and stacked laminations form a
sandwich structure with load bearing properties. They also
developed a lightweight TES sandwich structure where the
structural/thermally conductive elements are a metal,
typically an mm-scale hollow aluminum extrusion or
casting. The TES volume is a solid–solid or solid–liquid
PCM, which may include a thermal conductivity enhancer
or another property modifier such as a paraffin immobilizer.
The primary advantage of such TES composite sandwich
structures is that multifunctionality results in a smaller sized
thermal control/structural system. In addition, the TES
component of the system is passive, having essentially no
moving parts. Bauer et al. [29] introduced a TES-composite
that had a plate-like structure and consisted of a central core
of foamed aluminum impregnated with a PCM (pentagly-
cerine) and thin aluminum plates, in order to serve two
purposes: the cooling module and the structural component
(Fig. 7). By combining these two materials in the central
core, the effective thermal conductivity of the composite is
significantly increased so that it can readily respond to
changes in heat loading.
The TES fabrication includes the adhesive bonding of
thin metal plates (aluminum plates) with thick sheets of
aluminum foam with a thermally conductive epoxy [29].
Subsequently, the fill of the aluminum foam with the PCM
take place. A form made from balsa wood is fitted to three
edges of the plate/foam composite, and the PCM, in
powder-form, is poured and packed into the void space of
the foam material. Care is taken to avoid air pockets. A
fourth balsa wood edge is then glued to the composite.
Balsa wood, an insulator, is chosen for the edge seal so that
Fig. 7 Thin aluminum plates are bonded to the foamed aluminum
impregnated with PG [29]
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nearly one dimensional plate-to-plate heat flow may be
obtained. This allows for measurement of the plate-to-plate
effective thermal conductivity of the composite independent
of sample size. Aluminum alloys are ideal for the
fabrication of TES-composites. They are lightweight with
a high thermal conductivity, attractive strength, and great
manufacturability [26]. Effective thermal performance and
desirable mechanical properties can be achieved by care-
fully designing the detailed structures. Since most alumi-
num alloys have similar thermal conductivity, a high
strength aluminum alloy will be desirable. 7075-T6 meets
the high strength requirement with a desirable ductility.
2.5 Self-healing composites
Strategies for the repair or replacement of composite compo-
nents are essential for their safe operation in many applications.
Microcracking is one of the fatal deteriorations generated in
service life, which would bring about the catastrophic failure of
composites and hence, significantly shorten the lifetime of
structures. Considering that damages inside the composites are
difficult to be perceived and be repaired manually, the
materials had better have the ability of self-healing. These
composites’ main ability to maintain their structural integrity is
their main function, and their multifunctionality relies on their
intelligent internal repair system. Also, other functions such as
electromagnetic and interactive functionalities can be embed-
ded into the composite structure [32].
With regard to self-healing two categories exist: self-
healing without and with the aid of healing agents [31]. The
former category consists of highly cross-linked polymeric
material with multi-furan and multi-maleimid via Diels–
Alde reaction. At temperatures above 120°C, the “intermo-
nomer” linkages disconnect, reconnecting however upon
cooling. The process is fully reversible and can be used for
restoring the fractured parts of the polymers. The latter
Fig. 8 Self-healing concept
based on microcapsules that
contain liquid healing agent [33]
Int J Adv Manuf Technol (2010) 49:803–826
category contains an agent in the liquid state at least at the
healing temperature. The healing agent is generally encap-
sulated and embedded into the composites’ matrix. As soon
as the cracks destroy the capsules, the healing agent is
released into the crack planes due to the capillary effect and
heals the cracks. The healing agent can be further
categorized into single-component and two-component.
The single component agents, such as the cyanoacrylate
and the polyvinyl acetate, must be cured under the
existence of air. Thus, they are not suitable for the crack
healing deep inside the composite matrix. The two-
component agent consists of a polymerizable resin and a
hardener. When they mix, polymerization is activated so
that the cracked part can be bonded. The agent is embedded
into a composite matrix using capsules with fragile walls.
Kessler et al. [33] demonstrated a self-healing fiber
reinforced structural polymer matrix composite material
(Fig. 8). In the composite, a micro-capsulated healing agent
and a solid chemical catalyst are dispersed within the
polymer matrix phase. Healing is triggered by the crack
propagation through the microcapsules, which then release
the healing agent into the crack plane. Polymerization of
the healing agent is triggered by contact with the embedded
catalyst, bonding the crack phases and achieving ca 90%
recovery of the virgin fracture toughness.
Yin et al. [31] discussed a healing method based on
external manual intervention (i.e., heating). Its application is
related to the development of intelligent structural health
monitoring or to the damage self-sensing techniques. It uses
a two-component healing system, for producing self-healing
epoxy, with the objective of improving healing efficiency.
This complex process shows long-term stability and curing
of the released epoxy healing agent catalyzed by 2-
methylimidazole (i.e., cracks healing) that can be triggered
at a temperature between 130 and 170°C, being higher than
the curing temperature for making the composites.
Int J Adv Manuf Technol (2010) 49:803–826
An alternative method applied for achieving self-healing
is the use of a new cross-linked polymer with the ability to
heal internal cracking through thermo reversible covalent
bonds. Combined with an electromagnetic wire medium
composite, it has a tremendous potential for further multi-
functionality. The healing mechanism is a result of the
Diels–Alder (DA) reaction, since most are thermally
reversible [32]. The electromagnetic properties of the
polymer are well-suited for devices of communication,
and furthermore, for the presence of the braided wire
elements allowing for the tuning of the dielectric constant
of the bulk material. Moreover, the wires enhance the self-
repairing properties of the polymer. Acting as both
electrical and thermal conductors, the wires provide
channels through which heat is transported to heal cracks
within the material. Since the wires are distributed
throughout the composite, heat is also uniformly distribut-
ed. Furthermore, the reinforcing fibers may also contribute
to the healing mechanism.
The materials referred above suffer from a number of
deficiencies. The main disadvantage is that they can only be
healed one time, since once the microcapsules have broken,
there is no healing agent left to perform its function again.
A first attempt to overcome this disadvantage is the
“mendomer” [34, 35], a multifunctional material that shows
both structural and self-healing properties after a repeated
damage. This is a highly cross-linked polymer (Furan–
Maleimide crosslinked solid) with thermally reversible
linkages, resulting from multiple DA connections. When
the “mendomer” material is heated, its polymer chains gain
enough mobility and the terminals of the broken linkages
appear to find their counterparts to reconnect. Upon
cooling, the connection remains intact and, over time, the
cracks are healed. This process is fully reversible and can
be used for repairing the cracks multiple times.
Other materials have been shown to heal when punctured
where energy in the form of heating is attributed to the
resealing of ionomeric membranes after bullet penetration
[35]. These ionomers have been demonstrated to self-heal
with the use of embedded magnetic particles in a related
approach for wire insulation applications as shown in Fig. 9.
These ionomeric magnetic particle composites are suitable
for compliant self-healing applications, requiring a Young’s
modulus in the 200 MPa range whereas, the mendomer
magnet particle composites are suited to structural applica-
tions requiring a modulus greater than 2 GPa.
Self-healing composites can be manufactured in the
same way as regular composite sandwich structures.
Kessler et al. [33] fabricated specimens with hot pressing
of woven graphite fiber and an epoxy matrix. The central
layers where the delamination was introduced were filled
with 20 wt% with microcapsules of a monomeric healing agent
of dicyclopentadiene and 5 wt% of a ring-opening metathesis
809
Fig. 9 a Cleaved surface remains unhealed where heating is not
applied, b cleaved surface has healed where site specific healing has
been applied [35]
polymerization catalyst (Grubbs’ catalyst). The panel was
subsequently clamped with aluminum plates and released a
film that was pressed at 25°C for 24 h. Cured panels were then
placed in an oven to be post cured at 30°C for 48 h. At room
temperature, the healing efficiency was found to be ca. 38%
with a maximum of almost 45%. Elevating the healing
temperature to 80°C resulted in the healing efficiency being
increased to 66% on the average and to 80% in the maximum.
An important step forward for processing self-healing compo-
sites is the introduction of smaller microcapsules distributed
throughout the entire matrix phase.
2.6 Electromagnetic interference shielding composites
The reliability of many electronic components depends on
their successful isolation from EMI. Metals are by far the
most suitable materials for such shielding. Carbon materials
(conventional short carbon fibers, carbon filaments with
submicron diameter, carbon black, flexible graphite, and
colloidal graphite) are also effective for shielding, while
most polymers are transports to electromagnetic interfer-
ence shielding [36]. Composites can also acquire combined
functions more than one, such as structural integrity,
electromagnetic, self-healing, thermal transport, and sensing
properties. Plaisted et al. [32] incorporated arrays of
conductive electromagnetic scattering elements, such as
straight copper wires and copper coils into fiber-reinforced
polymer composites, resulting in materials with improved
structural and electromagnetic functionality. The scattering
elements introduce a controlled electromagnetic response.
Embedded periodic metal scattering elements can pro-
duce electromagnetic enhancements in the form of a tunable
index of refraction and RF absorption and create an effective
medium response over the desired RF frequency ranges. The
radius of the embedded (copper) wires is in the order of tens
of micron and is spaced in the order of millimeters for the
medium to behave as plasma at microwave frequencies.
Processing such thin wires into host materials such as fiber
810
composites and the uniform integration into them have posed
manufacturing challenges [37].
Many methods for EMI shielding have been introduced.
The most typical method to shield electronics is by
applying coatings containing conductive additives such as
paint with metal flakes or particulates or metalized coatings.
The reliability of these methods is poor, due to the flaking
off of the surface or to the coating being damaged by
scratches [38]. A more reliable method is to use a polymer
with metal fibers incorporated into a matrix. Bagwell et al.
[37] introduced this type of method with the incorporation
of short-shaped copper fibers in an epoxy matrix. Copper
was chosen for its high ductility, formability, strength, and
electrical properties. Optimization of the fiber shape and
surface treatment can result in a multifunctional composite
with improved mechanical, electrical, and thermal proper-
ties. Moreover, besides the fracture and impact toughness of
a thermoset polymer matrix being improved, short-shaped
copper fibers also improve the electromagnetic shielding
efficiency and the electrical conductivity of the composite.
The size of the fiber is the most important factor of the
shielding efficiency in transmission. Furthermore, the
required mechanical properties of the composite are
essential for determining the optimum fiber size for each
application. Fu et al. [39] indicated that due to the skin
effect, small fibers (higher surface area) provide better
shielding. Vapor grown carbon nanofibers are ideal rein-
forcing fillers for polymers, owing to their high strength
and modulus, very small size, large surface area, and
excellent thermal and electrical properties.
EMI shielding composites (Fig. 10) are produced by
pouring thermoset epoxy matrix into a silicon mold that
holds fibers [37]. Then, the fibers are evenly distributed
throughout the mold, attempting to keep a single layer at a
random fiber orientation. Diameters of fibers of 0.325 mm
and 0.162 mm were used in 15 vol%.
Fig. 10 EMI composite with 15 vol% of 0.162-mm diameter rippled
fibers [37]
Int J Adv Manuf Technol (2010) 49:803–826
Due to a large number of fibers at the smaller fiber diameter,
it is difficult to create an effective single layer structure with all
fibers in one plane (without vertical fiber overlaps). The curing
phase is accomplished in 48 h, at room temperature, before the
composite can be removed from the mold.
2.7 Functionally graded materials
Functionally graded materials (FGMs) are usually fabricated
by combining metals and ceramics in a controlled manner to
optimize specific functional properties [40]. They can be
considered multi-functional materials, which contain spatial
variations in composition and/or microstructure for the
specific purpose of controlling variations in thermal,
structural, or functional properties. Engineers accomplish
this by using reinforcements of different properties, sizes,
and shapes, as well as by interchanging the roles of the
reinforcement and matrix phases in a continuous manner.
The result is a microstructure that produces continuously or
discretely changing thermal and mechanical properties at
the macroscopic or continuum scale [41].
The combination of the materials science and the
mechanics of materials areas can bring into light a new
concept of engineering material’s microstructure, which can
integrate the material and structural considerations into the
final design of structural components [41].
Multifunctionality in a material can be integrated into
several dimensional scales with increasing interconnectivity
between phases and engineering difficulty as the scale
decreases [42]. These scales have been categorized into
different types of materials, as shown in Fig. 11. Type I
materials are comprised of phases in which one function is
simply mounted, coated, or laminated to another, usually a
structural component. Type II materials are comprised of
distinct phases in which one function is embedded in
another, usually a structural component. Type III materials
are truly integrated; the phases are intermeshed, blurring the
physical distinctions between them.
FGM are ideal candidates for applications involving
severe thermal gradients, ranging from thermal structures in
advanced aircraft and aerospace engines to computer circuit
boards. Owing to the many variables that control the design
of functionally graded microstructures, full exploitation of
the FGMs potential requires the development of appropriate
modeling strategies for their response to combined thermo-
mechanical loads. Up to now, most computational strategies
for the response of FGMs do not explicitly couple the
material's heterogeneous microstructure with the structural
global analysis. Rather, local effective or macroscopic
properties at a given point within the FGM are first
obtained through homogenization, based on a chosen
micromechanics scheme and then, subsequently, are used
in a global thermomechanical analysis.
Int J Adv Manuf Technol (2010) 49:803–826
Fig. 11 Types of functionally grades materials [42]
2.8 Composite materials processing issues
As mentioned in Section 1, the processing of such
composite materials is of great significance, since special
care is required in order for the functionality and properties
of the raw materials not to be altered or even ruined. In
general, five major processing categories have been
identified for all kind of materials: primary forming
processes, deforming processes, removing processes, join-
ing processes, and modifying material properties processes
[43]. With regards to composite materials, the processes
that are usually encountered are the primary forming and
the joining ones.
Primary forming processes are used for producing parts
from composite materials. Various rapid manufacturing
processes have been developed for this reason such as
selective laser sintering and melting that require zero use of
tooling and seconding processes [44, 45]. These processes
are well-suited to manufacture parts in composite material
by applying powders that contains the two different
materials to compose the composite. This can be used to
produce polymer-metal, polymer-ceramic, metal-metal, or
metal-ceramic composites. Furthermore, rapid manufactur-
ing systems are basically additive manufacturing ones, thus,
allowing the manufacturing of parts of virtually any
complexity of geometry. The basic limitations and chal-
lenges of the future for the rapid manufacturing processes
are the relative low production rate that does not meet the
mass production requirements, the surface finish of the
manufactured parts, and the accuracy and the repeatability
of the process.
The metal matrix composites (MMCs) could offer new
possibilities for providing multifunctionality through em-
bedded elements during processing. The MMCs types are
distinguished into monofilaments, whiskers/staples fibers,
and particulates [46], and are based on aluminum, titanium,
copper, and magnesium. The composites with a metal
matrix can be produced by two primary forming processes
by casting and powder metallurgy [47].
Casting of molten metal alloys can be combined with
dispersion particles and short fibers, as producing
composites [48].
Powder metallurgy is based on blending the matrix
powder with reinforcing elements, further cold pressing,
811
sintering and, finally, forging and/or extrusion [47].
Mechanical alloying is used for the production of compo-
sites with a metal matrix and fine grains, amorphous
materials, and magnetic materials [49]. This process is
performed on a high-energy ball mill in which hard
dispersion particles are combined with a soft matrix. Then,
the powder could be formed in cold and hot plastic working
[50]. Spray forming is another way of producing MMCs by
injection of dispersion powders into the substrate [51]. This
production method enables a second or a third phase to be
added by entraining a stream of the added phase into the
atomized spray before deposition.
Joining processes are also widely used in composite
materials. Unless all the parts are co-cured, it is inevitable
that joints will be used to connect the parts. The
development of suitable joining techniques is one of the
main challenges for the future development of the compos-
ite materials [52]. Both conventional (such as mechanical
bonding, riveting and adhesive bonding) and non-
conventional (friction stir, explosive, and solid state weld-
ing to name few) joining methods are under research.
Mechanical fastening is still one of the main methods
used for joining composite components, with the advantage
of no special surface preparations, easy disassembly and
inspection [53]. The mechanical behavior of composite
bolted joints has been extensively studied in the past by
means of experimental, analytical, and numerical
approaches, mainly focusing on the determination of the
load capability, the load and stress distributions, and failure
criteria of single and multi-row bolted joints under the
influence of varying laminate configurations and joint
geometries [54]. The brittleness of most composite materi-
als, the possibility of using highly orthotropic laminates,
promoting high stress concentrations, and the anisotropy in
both stiffness and strength properties have to be taken into
account when designing composite joints. The joints are
often the critical part of a composite structure; therefore, the
soundness of the joint design procedure used is reflected on
the overall weight and cost of the composite structure [55].
The use of metallic inserts bonded to the hole of the
laminate can be used to repair cracked holes in metallic
structures. It is also a technique widely used in mechani-
cally fastened joints, in both metallic and composite
sandwich structures. However, designing an optimum scarf
repair for composite structures is complex due to the large
number of material and geometric parameters that influence
the joint performance (Fig. 12) [56]. Riveting is also a
mechanical bonding process, however, it is difficult to
control the interference of riveted joints in composite
structures. The expansion of the rivet produced by
conventional riveting is non-uniform damaging the com-
posite structure. Electromagnetic riveting technique has
been proposed for overcoming this problem. It is based on
812
Fig. 12 Common bonded joints [56]
eddy current repulsion between a copper pancake coil and a
copper driver plate resulting in uniform expansion along the
rivet shaft [57].
Laser welding process has been attempted for joining
aluminum metal matrix composites showing promising
results [58]. Friction stir welding (FSW) process is also
under research for the composites. The sub-melting temper-
atures and relatively short weld times allows many
combinations of metal matrix composites to be welded
[59, 60]. FSW is a very promising candidate for joining
particulate reinforced aluminum matrix composites since
this method is a solid state process, and thus no brittle
solidification products are produced; the energy input and
distortion are significantly lower than in fusion welding
techniques, improving the welding properties [61]. Addi-
tionally, FSW leads to an improvement in tensile properties
and joint hardness due to modification in solidification
microstructure of the base composite [60].
In low stress/low temperature applications, adhesives
have been used extensively. Joining components of poly-
mer composites through adhesive bonds is becoming
increasingly popular. Polymer-based adhesives provide a
simple means of joining adjacent brittle layers at room
temperature [62]. Adhesively bonded assemblies allow for
a gradual transfer of load from one structural element to
another and a reduction of stress concentrations arising
from material discontinuities inherent to mechanical fasten-
ing methods [63]. With the increasing proliferation of the
adhesives in structural applications and the hindrance posed
due to their brittleness, research is ongoing towards
toughening of the adhesive [64]. In adhesive bonding, the
bonded joint cannot be disassembled without damage. The
joints are very sensitive to environmental factors like
humidity and temperature and the bonded joints tend to
fail instantaneously, not progressively. In mechanical
fastening, the fasteners themselves are an important source
of weight increase. Particularly, in weight-sensitive struc-
tures like aircraft, reducing the number of fasteners is a
research priority. Few studies have been reported on hybrid
joints. The hybrid joint uses mechanical fastening in
Int J Adv Manuf Technol (2010) 49:803–826
addition to adhesive bonding in an effort to overcome the
potential weaknesses of adhesive bonding. Optimally
designed mechanical fastening might induce more progres-
sive failure propagation and increase joint strength [65].
3 Smart or intelligent materials
Almost all the materials that have been used up to now, are
designed and processed to offer only a limited set of
responses to external stimuli and are characterized by their
inability to adapt to the environmental changes in real time.
However, nature has taught us that all structures lacking in
adaptability are keen to extinction. The field of biomimetics
that focuses on the extraction of engineering design
concepts from biological materials and structures has much
to teach us on the design of future man-made materials
[66]. During the last decade, a lot or research has been
focused on designing materials that will be able to adapt to
external changes. The smart or “intelligent” materials, as
they are known, respond to environmental stimuli with
particular changes in some of their variables. They can act
simultaneously as actuators and sensors, as shown in
Fig. 13. The natural world is full of examples of responding
materials, e.g., the ability of plants to adapt their shape in
real time (for example, to allow leaf surfaces to follow the
direction of sunlight). The materials and structures involved
in natural systems have the capability to sense their
environment, process these data and respond accordingly.
The state-of-the-art smart materials are able to change
their properties (mechanical, electrical, and appearance),
their structure or composition, or their functions depending
on the stimuli received. In Table 1, indicative smart
materials are listed along with their changing characteristic.
A lot of applications exist in buildings, on airplanes, and
in the automotive industry for such materials and structures,
in order for vibrations, noise, and deformations to be
actively controlled. Currently, the smart materials are
embedded in systems, whose inherent properties can be
Fig. 13 Smart materials can act simultaneously as actuators and
sensors as well
Table 1 Indicative smart materials

Changing Material family Typical materials Operating and manufacturing issues Typical applications Research status
characteristic

Color-changing Photochromic Change color in response to light intensity. Changes Light-sensitive sunglasses that Commercialized
materials materials from one color to another color are possible mixing darken when exposed to bright
photochromic colors with base colors. They are used sunlight
in paints, inks, and mixed to mold or casting materials
for different applications
Thermochromic They are made as semi-conductor Change color depending on their temperature. They are Temptoos—thin films attached to Commercialized
materials compounds, from liquid crystals used to make paints, inks, or are mixed to molding or the skin and change color
or using metal compounds casting materials for different applications according to body temperature
Electrochromic Change color or opacity on the application of a voltage Liquid crystal display Commercialized
materials
Int J Adv Manuf Technol (2010) 49:803–826

Halochromic
materials
Light-emitting Electroluminescent They are made from insulating
materials materials substance with electrodes on
each side. One of the electrodes
is transparent and allows the
light to pass. The insulating
substance that emits the light
is usually made of zinc sulfide
Fluorescent
materials
Phosphorescent They are polycrystalline
materials or inorganic zinc sulfide (green
afterglow materials afterglow) or alkaline earth
sulfides (red or blue afterglow)
Moving materials Conducting They are conjugated polymers,
polymers namely organic compounds
that have an extended p-orbital
system, through which electrons
can move from one end of the
polymer to the other. The most
common are polyaniline (PAni)
and polypyrrole (PPY)
Piezoelectric Typically they are manufactured
materials using soft molding (both master
and transfer molds used).
Forming, deforming , and
sintering is also an option
Change color as a result of changing acidity, could be Under research for
used for indicating corrosion on metals application
Produce a light of different colors when stimulated Theater decoration. Arrow light Commercialized
electronically (e.g., by AC current). While emitting decoration, e.g., for industrial
light, no heat is produced and public vehicles safety
precautions
Produce visible or invisible light as a result of incident Under research for
light of a shorter wavelength (i.e., X-rays, UV-rays, etc.). application
Could be used for paints, inks, or mixed to molding or
casting materials
Produce visible or invisible light as a result of incident Under research for
light of a shorter wavelength (i.e., X-rays, UV-rays, etc.), application
detectable only after the source of the excitement has
been removed. Could be used in paints, inks, or mixed
to molding or casting materials for different applications
A current flow reduces one side and oxidizes the other. Polipyrrole is used in micro Still at a research
Ions are transferred. One side expands and the muscles. PAni films level. Commercial
other contracts, resulting in a bending of the sandwiched around an applications are not
sandwich. Electrical and chemical energies are ion-conducting film are expected before
so transformed in mechanical energy considered for artificial 1-10 years
muscles for robots
Produce an electric field when exposed to a Actuators structures made Commercialized
change in dimension caused by an imposed from these materials can
mechanical force (piezoelectric or generator be made that bend, expand
effect). Conversely, an applied electric field or contract when a voltage
will produce a mechanical stress (electrostrictive is applied
or motor effect). They transform energy from
mechanical to electrical and vice-versa. The
stress is very small, 0.1–0.3%. They are used
813
Table 1 (continued)
814

Changing Material family Typical materials Operating and manufacturing issues Typical applications Research status
characteristic

for sensing purposes (e.g., microphone,

transducer), and for actuating applications
Electrostrictive The most common are Exhibit mechanical strain when subjected to an Dielectric elastomers
materials (also PMMA-based electrostrictive electric field. Their striction capability very high are still at a research
known as Dielectric polymers and Lead magnesium as they strain proportionally to the square of the level, but they have
Elastomers) niobate (PMN) applied voltage of the applied electric field. In an the potential to be
electric field, the elastomer expands in the plane produced at a
of the electrodes, amplifying the normal compression low cost
due to the electrostatic charges on the electrodes.
The result is a muscle with large strain capability,
and a large actuation pressure. PMMA-based
electrostrictive polymers can be sandwiched
between two electrodes to emulate the operation
of muscles. By rolling a tube of a thin film with
many layers, larger strains can be achieved. They
do not show any sign of degradation
Electroactive PVDF (Polyvinylidene It can be shaped such that it acts as a natural filter Recently introduced
polymers fluoride) depending on the mode of interest. PVDF sensors
and actuators can be operated in air, vacuum,
or water and throughout a wide temperature range
Polymer gels The most common are Polymer gels consist of a cross-linked polymer Many potential applications Under research
polyvinylalcohol (PVA), network inflated with a solvent such as water. (e.g., artificial muscles,
polyacrylicacid (PAA), They can reversibly swell or shrink (up to 1,000 robot actuators, adsorbers
and polyacrylonitrile (PAN) times in volume) due to small of toxic chamicals), but
changes in their environment (pH, temperature, presently, few of them
salinity electric field). Micro-sized gel fibers present commercial interest.
contract in milliseconds,
while thick polymers layers require minutes to
react. Thus, it is still not fast enough for artificial
muscles. Furthermore, the lifetime of a gel actuator
is very short and their structure
gradually degrades. However, they present high
strength and can deliver sizeable stress (approximately
equal to that of human muscles)
Shape memory Most common is the NiTi. Present the ability to return to its initial shape when Mainly for medical Commercialized
alloys Also copper- and heated above a transformation temperature. Described applications
iron-based alloys in detail in other section
Self-assembling Self-assembling Bottom-up method for fabricating materials on the
materials materials nanometer scale.
Self-diagnostic Optic fibers Composites incorporating non-structural elements Under research
materials composite (micro-sensors and local network communication
Smart composites nodes) for real time and in situ damage detection
Smart-tagged and assessment
composites
Int J Adv Manuf Technol (2010) 49:803–826
 Int J Adv Manuf Technol (2010) 49:803–826 815

favorably changed to meet performance needs. In the future,

it is highly expected that more and more structures will use
Research status

Under research

Under research
smart materials for both safety and maintenance reasons.
Engineering structures could operate at the very limit of their
structural performance without fear of exceeding it. These
structures could provide full report on performance history,
location of defects, whilst having the ability to counteract
unwanted or potentially dangerous conditions, namely the
excessive vibration and attempted self-repair [67].

isolation mounts using

Actuator and vibration
Typical applications

3.1 Piezoelectric materials

magnetostrictive
materials Piezoelectric materials produce a voltage when stress is
applied. Since this effect also applies in a reverse manner, a
voltage across the sample will produce stress within the
sample. Suitably designed structures of these materials can
up, and the effect is reversible. Thermoelectric cooling

be made in such a way so as to bend, expand, or contract

is moved in the direction of the current. Usually, they

(to obtain larger cooling capacity) are combined. One

light devices, high reliability and precise temperature

Magnetostriction is the material property that causes a

face of the module cools down while the other heats

fields when they are deformed by an external force

control, and quiet operation. Disadvantages include
are used for thermoelectric modules where a single

when a voltage is applied. Piezoelectric materials are

material to change its length when subjected to an
electro-magnetic field. Magnetostriction properties
By applying a low voltage DC power source, heat

also cause materials to generate electro-magnetic

high prices and high operating costs, due to low

widespread used for shape control and vibration attenua-

tion. Also, they are used in a form of thin patches bonded in
the upper and lower surfaces of plate and shell structures.
Emerging applications of piezoelectric materials are the
Operating and manufacturing issues

integration of piezoelectric fibers into host structures [68].

A wide variety of materials are piezoelectric, including pole
allows for small size and
couple or many couples

polycrystalline ceramics (e.g., lead zirconate titanate, PZT),

single-crystal, or highly oriented polycrystalline ceramics (e.g.,
energy efficiency

zinc oxide and quartz), organic crystals (e.g., ammonium

dihydrogen phosphate), and polymers (e.g., polyvinylidiene
fluoride), as shown in Fig. 14. These piezoelectrics are
classified based on whether they are ferroelectric or not [69].
For piezoelectric MEMS, a key processing challenge is
to create a piezoelectric thin film with the desired structure
and properties [70]. In processing PZT piezoelectric thin
semiconductors that, when

films, several routes are available, including physical and

Thermoelectric materials

chemical vapor deposition, and solution deposition. Each

coupled, function as
are special types of

method has its advantages and disadvantages. Physical and

Typical materials

a "heat pump"

chemical vapor deposition routes offer uniform thickness

films and good step coverage. These routes are standard in
microfabrication. In contrast, solution deposition offers
excellent control of the chemistry of the thin film but it is
not appropriate when uniform film thickness over surface
Magneto-rehological

features is required. Solution deposition methods have three

basic steps: synthesis of a metalorganic solution, deposition
Material family

fluids (MRFs)
Thermoelectric

onto a substrate by a spin-casting or dip-coating method,

materials

and heat-treatment to remove organics and crystallize the

ceramic microstructure (Table 2).
Temperature-changing
Table 1 (continued)

3.2 Shape memory alloys

Thickness-changing

The shape memory alloys are smart materials (metal alloys)

characteristic

materials

materials

that present a remarkable thermomechanical behavior

Changing

(shape memory effect, super-elasticity, and damping). Arne

Olander first observed these unusual properties in 1938, but
816
Fig. 14 Piezoelectric effect [69]
it was not until 1962 that any serious research was
undertaken in the field of shape memory alloys. The term
shape memory refers to their ability to return to their
original shape after they have undergone large deforma-
tions. This recovery either takes place spontaneously at the
end of the deformation or by heating to a specified
temperature without leaving any residual deformations.
The shape memory effect results from a crystalline phase
change known as “thermoelastic martensitic transforma-
tion” that occurs at a transformation temperature depending
on the composition of the alloy. Below the transformation
temperature, the alloys are in martensitic phase and can be
easily deformed. If they are heated though, above the
transformation temperature, they recover the original shape
and they change their phase into austenitic [71].
Sandwich composite materials, having shape memory
capabilities, have been presented [72]. These lightweight
structural panels can both support loads and undergo
reversible shape changes as a result of the thermal stimulus.
These panels are consisted of SMA face sheets attached to
stainless steel truss and have, as shown in Fig. 15.
Processing of formed to shape materials involves
strategically placing the reinforcements while manipulating
the matrix properties to achieve a melding event at or near
the beginning of the component life cycle. A variety of
methods are used according to the end item design
Table 2 Properties of some piezoelectric materials [70]
No Material Formula
1 Ammonium dihydrogen phosphate (ADP) NH4H2PO4
2 Barium titanate BaTiO3
3 Barium titanate BaTiO3
4 Lead zirconate titanate (PZT) PbZr0.6 Ti0.40O3
5 Lead lanthanum zirconate titanate (PLZT) Pb0.925La0.5Zr0.56Ti0.44O3
6 Polyvinylidene fluoride (CH2CF2)n
7 Potassium dihydrogen phosphate (KDP) KH2PO4
8 Quartz SiO2
9 Zinc oxide ZnO
Int J Adv Manuf Technol (2010) 49:803–826
requirements. These fabrication methods are commonly
named molding or casting processes, as appropriate, and
both have numerous variations. The principle factors
impacting the methodology are the natures of the chosen
matrix and reinforcement materials. Another important
factor is the gross quantity of the material to be produced.
Large quantities can be used in order to justify high capital
expenditures for a rapid and automated manufacturing
technology. Small production quantities are accommodated
with lower capital expenditures whilst higher labor costs are
at a correspondingly slower rate.
Typical SMAs are the nickel-titanium (NiTi), various
copper- and iron-based alloys. However, at least other 20
different binary, ternary, and quaternary alloy types have been
discovered that exhibit shape changes and unusual elastic
properties consequent to deformation, as shown in Table 3.
The NiTi (commercially known as Nitinol [73]) is the
most common shape memory alloy; it presents great strain
memory (up to 8%), it is thermally stable, has high
corrosion resistance, and is biocompatible. Furthermore, it
presents super- or pseudo-elasticity, meaning that in its
elastic form, it can undergo a deformation, approximately
ten times greater than that of a spring steel equivalent, and
subsequently it can fully recover to the original geometry
for several million cycles. The geometry of the required
part is achieved through fusion. However, because of the
hyper-reactivity of titanium, vacuum furnaces are used for
its melting. The melting of the alloy is typically achieved
by electron beam and arc melting or by induction
hardening. NiTi is very sensitive to changes in composition,
since changing the percentage of nickel to titanium (ideally
50%-50%) affects the properties and the transformation
temperature. It can be processed using forging, bar rolling,
and extrusion in the air since contamination is less of a
problem after ingots of the alloy have been made. The
ingots can be worked cold, but the alloy tends to harden
quickly, thus requiring frequent annealing [74]. Special
Form Piezoelectric constant
(pm/V or pC/V)
Single crystal d36=48
Single crystal d15=587
Polycrystalline ceramic d15=270
Polycrystalline Ceramic d33=117
Polycrystalline Ceramic d33=545
Oriented film d31=28
Single crystal d36=21
Single crystal d11=2.3
Single crystal d33=12
Int J Adv Manuf Technol (2010) 49:803–826 817

The copper-based alloys being commercially available

are the copper-zinc-aluminum and copper-aluminum-nickel
alloys. They are cheaper than nickel-titanium alloys since
they are manufactured from relatively inexpensive metals
using conventional metallurgical processesand as they can
be melted in the air with ease. They present shape-memory
strain up to 4–5%. The most common method of producing
these alloys is induction melting. Powder metallurgy
processes can also be used to produce fine-grained
structures without the need of grain size control additives.
Hot work in air is well suitable, while cold work is suitable
only for low aluminum content alloys (<6% wt.). The major
disadvantages of these alloy systems are that the martensitic
phase is stabilized by long-term aging causing an increase
of the transformation temperature, and the alloy structure
decomposes when exposed to temperatures above 100°C.
Recently, a new alloy has been presented where the nickel
is replaced by beryllium. Adding less than 0.5% of
beryllium to the copper-aluminum alloys extends the
transformation temperature from 100°C to −200°C. This
Fig. 15 Shape memory sandwich composite structure [72]
CuAlBe alloy exhibits excellent super-elastic and damping
properties. The most important iron-based shape memory
alloy is iron-manganese-silicon. They base their shape
tools are used for turning and milling the material that memory effect on a different physical principle from that
presents, however, excessive tool wear. Welding, brazing, of the conventional shape memory alloys. Their memory
and soldering are also difficult due to the resulting excessive properties are modest with a maximum recoverable strain of
oxidation of the titanium. Forming is performed with about 4%.
difficulty due to the significant springback or the thermal The first industrial application occurred in 1969 when
recovery of the material. For this reason, the forming is SMA couplings were used for joining hydraulic pipes in the
performed by thermal shape setting with the use of cold F-14 aircraft [78]. The cylindrical coupling, having internal
worked material [75]. Since the properties of the material diameter slightly smaller than that of the pipes, is cooled at
depend on the temperature on the designing of the final cryogenic temperatures to produce the martensitic phase.
parts and on the processing required it is performed with The fitting of the coupling is achieved by radially
specialized finite element analysis tools [76, 77]. Its expanding it and sliding the pipes within. On heating
commercial raw form is in wires, strips, rods, bars, and above the transformation temperature, the coupling tries to
sheets. Over the last decade, alloy foams sintering powders return to its original size, but is constrained by the pipes
and sputtering targets of high purity are also produced. within. The stresses that result from this constraint are
sufficient to create a secure joint, as shown in Fig. 16. This
application has been extended to the joining of many other
types of pipe, sometimes using a liner that is squeezed onto
Table 3 Shape memory alloys
the pipes to make a joint. Furthermore, applications in
Titanium–palladium–nickel Iron–manganese–silicon electrical, aerospace, civil, and mechanical engineering
Nickel–titanium–copper Nickel–titanium have been reported [79–84]. Typical examples of applica-
Gold–cadmium Nickel–iron–zinc–aluminum tion of shape memory alloys are presented in Table 4.
Iron–zinc–copper–aluminum Copper–aluminum–iron Currently, shape memory alloys are mainly applied in
Titanium–niobium–aluminum Titanium–niobium medical sciences due to their biocompatibility. A typical
Uranium–niobium Zirconium–copper–zinc example of shape memory alloys application in medical
Hafnium–titanium–nickel Nickel–zirconium–titanium science is the stent that travels through human arteries to a
Silver–cadmium Copper–tin specified position where the artery has blocked (Fig. 17).
Iron–platinum Copper–zinc–aluminum The stent enters the human body contained within a
Manganese–copper Indium–titanium
catheter in a deformed state as to have them minimum
Nickel–aluminum
possible diameter. Once the blocked conduit has been
reached, the stent is deployed and expands due to the body
818 Int J Adv Manuf Technol (2010) 49:803–826

Fig. 17 Application of nitinol in human arteries [80]

Fig. 16 Coupling machined at its original shape (a), after cryogenic

3.3 pH-sensitive polymers
cooling and radial expansion (b), and installed on the pipes (c)

pH sensitive polymers are materials which respond to the

changes of the pH of the surrounding medium by varying
warmth to its original diameter with sufficient force to open their dimensions. Such materials swell or collapse depend-
the vessel lumen and reinstate blood flow. Stents made of ing on the pH of their environment. This behavior is
nitinol in most cases are manufactured by laser cutting from exhibited due to the presence of certain functional groups in
nitinol tubing. However, tubes with wall thickness less than the polymer chain (Fig. 18).
0.05 mm, as required in neurovascular applications, are The pH sensitive materials are categorized into two
very difficult to produce with this method, and vapor groups depending on their behavior in an acidic and basic
deposition is used in this case [87]. environment. The first group contains acidic group
(-COOH, -SO3H) and swells in basic pH, and others which
have basic groups (-NH 2) and swell in acidic pH.
Table 4 Current examples of applications of shape memory alloys Polyacrylic acid is an example of the former, and chitosan
[75, 85, 86]
is an example of the latter. The mechanism of response is
Aids for disabled Micro-actuators the same for both; it is just the stimuli that vary.
Aircraft flap/slat adjusters Mobile phone antennas
Anti-scald devices Orthodontic archwires 3.4 Polychromic, chromogenic, and halochromic materials
Arterial clips Penile implant
Automotive thermostats Pipe couplings Polychromic, chromogenic, and halochromic materials
Braille print punch Robot actuators change color due to external influences. These external
Catheter guide wires Rock splitting influences can be alterations in pH, temperature, light, or
Cold start vehicle actuators Root canal drills electricity. Materials that change color due to temperature
Contraceptive devices Satellite antenna deployment are normally known as thermochromic, and those that alter
Electrical circuit breakers Scoliosis correction due to light as photochromic.
Fiber-optic coupling Solar actuators Chromogenics cover any visible switchable technology
Filter struts Spectacle frames useful for glazing, mirrors, transparent displays, and a variety
Fire dampers Steam valves
of other applications [88]. Other chromogenic effects are
Fire sprinklers Stents
photochromic and thermochromic. Photochromic materials
Gas discharge Switch vibration damper
change color upon exposure to ultraviolent illumination and
have been used in ophthalmic products for many years [89].
Graft stents Thermostats
Thermochromic materials change color with temperature,
Intraocular lens mount Underwired bras
many based on transition metal oxides such as theVO2. The
Kettle switches Vibration dampers
aerospace industry uses mainly such materials to change the
Keyhole instruments ZIF connectors
emissivity of surfaces upon heating. In addition, organic
Key-hole surgery instruments MEMS
thermochromic inks are used as temperatures indicators.
Int J Adv Manuf Technol (2010) 49:803–826
Electrochromic materials change their optical properties
in response to an electric field and can be returned to their
original state by a field reversal. Their major advantages
are: (1) have a small switching voltage, (2) have specular
reflection, (3) possess a gray scale, (4) require power only
during switching, and (5) exhibit adjustable memory. One
such application is the smart electrochromic window
(Fig. 19), which darkens when voltage is added and is
transparent when the voltage is taken away [90, 91].
4 Nanostructured materials
Nanostructured materials are among the major outcomes of the
nanotechnology research undertaken during the last decade.
Nanotechnology as defined by Siegel et al. [92] is the direct
control of materials and devices on a molecular and atomic
scale. Chryssolouris et al. [93] have reviewed comprehen-
sively the critical issues of nanomanufacturing from the cost,
production rate, quality, and flexibility point of view and have
identified “precision” as the key element of developing
nanomanufacturing technologies. This turning of the academia
interest in nanotechnology issues has resulted in knowledge
being gained as to how materials are formed and what their
characteristics and properties in atomic and molecular scale are.
Nanomaterials can be fabricated using two different
approaches as indicated by Chryssolouris et al. [93], the
top-down and the bottom-up approaches. The top-down
method was firstly introduced by Taniguchi [94] and it is
also known as the transformative approach. In this case,
nanostractures are progressively miniaturized from larger
scale structures. The top-down processes are basically based
on existing manufacturing facilities. Typical examples of the
top-down processes include lithography (electron beam, ion
beam, scanning probe, and optical near field), thin film
deposition and growth, laser beam processing, mechanical
(machining, grinding, lapping, polishing), and electrochem-
ical material removal processes (electroforming and hot
embossing lithography; Table 5). Although this method can
be used for building nanostructures (e.g., MEMS, nano-
electronics, etc.), it is not suitable for the fabrication of
nanomaterials.
On the other hand, using the bottom-up (or synthetic)
approach, structures are built from their atomic or molecular
Fig. 18 pH-sensitive polymer swelling/collapse mechanism [113]
819
components. It is considered that the bottom-up approaches
will be the long-term solution. The bottom-up approach was
introduced by Drexler [96] and deals with organizing the
individual atoms/molecules into particular configurations in
order for complex products to be formed. Within the bottom-
up nanomanufacturing approaches, atoms and/or molecules
are specifically placed and connected similar to the processes
found in living organisms. Typical examples of the bottom-
up processes include contact printing, imprinting, spinodal
wetting/dewetting, laser trapping/tweezer, assembly and
joining (self- and directed-assembly), template growth,
electrostatic (coatings, fibers), colloidal aggregation, and
2-photon confocal processing (Table 6).
4.1 Biomemetics
As already stated, materials provided by nature present the
highest multifunctionality. Biomemetics is the science that
attempts to replicate and even mimic the structural
formations created by nature. Over the last decade,
engineers have been collaborating with biologists, and
now they have started presenting biologically inspired
technologies and materials of economic fostering [97].
The two basic mechanisms that nature is using for the
fabrication of blocks of buildings are those of self-
replication and self-assembling. Research is focusing on
mimicking self-replication is in its primitive stages [98].
The prospects, should self-replication be achieved, are very
promising: materials that self replicate and thus multiply
themselves in a controlled way that would allow the
dramatic reduction of their fabrication cost.
In self-assembly, the atoms or molecules required for the
construction of the structure or material desired are brought
together in a suitable environment in order to arrange
themselves and form it without any external intervention.
Self-assembling bimolecular material science lies at the
intersection of molecular biology, physical sciences, and
materials engineering [99]. Self-assembling is a bottom-up
nanofabrication process and there are several routes for
fabricating nanoscaled structures. These can be divided into
photolithography and non-photolithography techniques. Pho-
tolithography is widely used for fabricating patterns on to
semiconductor materials, which are used in integrated
circuits. Non-photolithography-based approaches are used in
both microfabrication and nanofabrication. Examples of self-
assembly of large molecules are widely found in chemistry
and biology and the field of supramolecular chemistry.
4.2 Nanocoatings
In general, the coating’s thickness is at least an order of
magnitude lower than the size of the geometry to be coated.
This means that for the surface treatment of a parent solid
820
Table 5 Top-down processes
[95, 96] Top-down processes
Process
Mechanical milling
Plasma arc spparying or plasma ionization
Etching (chemical)
Electro-explosion (thermal/chemical)
Sputtering (kinetic)
Laser ablation (thermal)
of 100 nm or so in dimension, the coating’s thickness will
be less than 10 nm. This sort of coating is called
nanocoating [100]. In contrary to the regular coatings, the
grain size of nanocoatings is so small and their number so
large, that any impurity is super-diffused. This is called
“homogenization by segregation”. Such a coating is said to
be stronger and more resistant to stress and corrosion
cracking. A number of potential applications of nano-
coatings can be summarized in Fig. 20.
The technology of microwave plasma thin film deposi-
tion is of vital importance to several manufacturing
industries due to its potential applications, including
protection (e.g., anti-corrosion), interfacial adhesion pro-
motion, optical modifiers, and diffusion membranes. Plas-
ma coating is evolving as a modern technology owing to its
ability to excite gaseous atoms and molecules into transient
and non-equilibrium conditions with very high densities.
Plasma thereby alters the normal pathways through which
surface modification is performed and thus, enables the
production of novel materials [102]. Mukhopadhyay et al.
[100] discussed in their work the microwave plasma
deposition technique for the production of a nanocoating.
It has been proven that this method can provide strongly
Table 6 Bottom-up processes
[95, 96] Bottom-up processes
Process
Sol-gel
Aerosol based processes
Chemical vapor deposition
Pulsed laser deposition
Atomic or molecular condensation
Supercritical fluid synthesis
Spinning
Use of templates
Self-assembly
Int J Adv Manuf Technol (2010) 49:803–826
Nanomaterials produced
Mixtures of elemental or prealloyed powders, alloys and alumina
Synthesize deposits on surfaces rather than new solid structures
Arrays of nanoscale shapes
Metallic nanopowders, fullerenes, metallofullerenes, nanotubes
Similar to vapor phase techniques
Broad of nanoparticles
bound films that completely cover the surface and provide
full functionality within 2–3 nm of film thickness.
Additionally, two functions of the coating were achieved:
(a) more reactive surface for enhanced bond strength with
other phases, increased dispersion of nanosolids in matrix
materials, increased wettability of polar fluids etc. and (b)
more inert and moisture resistant surfaces for increased
degradation resistance of stand-alone nanostructures and in
preventing agglomeration of nanoparticles. The first func-
tion can be obtained by a reacting mixture of hexa-methyl-di-
siloxane and O2 gas in plasma to form oxygen-containing
groups on the surface. The latter effect can be produced by
fragmenting the fluorocarbons in plasma to deposit CF2
and/or CF3 groups on the surface.
Furthermore, nanocoatings can have a range of applica-
tions in medicine. A methodology was developed in [103],
based on the “layer-by-layer electrostatic assembly” process
that allows molecular control over the components of the
coating, for building coatings capable of releasing sub-
stances in an exact sequence and at a predetermined rate.
The method is based on heating a layer among different
components, so that polymers form covalent bonds and
keep the components from mixing. This method could be
Nanomaterials produced
Colloidal nanoparticles, oxide nanoparticles, composite
nanopowders
Industrila production of nanoparticles such as carbon black,
titania, fumed silica etc.
Carbon nanotubes, partial surface coatings
Various nanoparticles
Metal-containing nanoparticles
Various nanoparticles
Thin polymer fibers
Porous alumina, zeolites, di-block copolymers, dendrimers, proteins
Variety of organic and biological compounds, inorganic oxides,
metals, and semiconductors
Int J Adv Manuf Technol (2010) 49:803–826
Fig. 19 Smart electrochromic module incorporated in a double-pane
window [91]
used for the fabrication of multi-graded materials. The
anticipated cost of this process is not significant; consequent-
ly, the cost of the fabricated material/coating will be most
probably determined from the materials used. Bolte [104]
presented in his study the use of aerosols in the production of
nanocoatings. According to this technique, aerosol drops are
deposited on the surface to be coated and after their
evaporation, a coating formed is only of some nanometers
thickness. Depending on the use of the coating, the
application of the floating aerosol droplets is carried out in
the process via three parameters: condensation about a
temperature difference between aerosol and surface temper-
ature, electrical charging in a high electric field, and gravity.
Bond strength, antistatic behavior, and surface tension with
long-time effect are some of the benefits of the method.
Fig. 20 Application possibili-
ties for different nanocoatings
[101]
821
An approach to coat electrodes with molecular layers
relies on the ability of certain compounds to adsorb
spontaneously, on solid supports, from liquid or vapor
phases. In particular, the affinity of certain sulfurated
functional groups for gold can be exploited to encourage
the self-assembly of organic molecules on microscaled and
nanoscaled electrodes. The electrode/monolayer/electrode
junction in Fig. 21, incorporates a molecular layer between
two gold electrodes mounted on a silicon nitride support.
This device can be fabricated by combining chemical vapor
deposition, lithography, anisotropic etching, and self-
assembly processes [105].
4.3 Nanoparticles
The materials have a significantly different behavior as well
as properties when they are manufactured as nanoparticles
in comparison with the bulk material. For instance, inert
metals may become highly effective catalysts when
manufactured as nanoparticles; opaque particles may
become transparent, conductors may become insulators
and vice versa. Nanoparticles can comprise a range of
different morphologies including nanotubes, nanowires,
nano whiskers, nanofibers, etc.
NEC, a Japanese electronics company, produced the first
carbon nanotubes with electrical/laser discharge. When this
discharge occurs in a highly pressurized atmosphere of
carbon-rich gasses, some of the carbon atoms bind together
to form long, hollow cylinders of 1 nm in diameter and up
to several thousand nanometers in length. Nanotubes are
heat resistant heat conductors, and with the appropriate
manufacturing procedure they can become electrical con-
ductors, semiconductors, or insulators. Some of the appli-
cations they may have include the creation of transparent
films capable of transferring heat or glow, medicine use as
822
Fig. 21 A molecular layer is embedded between two gold electrodes
maintained in position by a silicon nitride support [105]
molecular “deliver containers” for the active ingredients
and for the manufacturing of lighter and stiffer products
such as tennis rackets [106]. Furthermore, the template
synthesis is the easiest way of preparing nanomaterials
involving chemical synthesis or electrochemical deposition
of the desired material within the pores of a nanopore
membrane or other solid surfaces (Fig. 22). This method
has been used for the preparation of nanowires, nanotubes,
and composite nanostructures composed of many types of
materials, including metals, polymers, semiconductors, and
carbons [107]. Some of the recent successful syntheses of
semiconductor nanowires are based on the so-called vapor-
liquid-solid (VLS) mechanism of anisotropic crystal
growth. The proposed growth mechanism (Fig. 23)
involves the absorption of source material from the gas
phase into a liquid droplet of catalyst. Upon super
saturation of the liquid alloy, a nucleation event generates
a solid precipitate of the source material. This seed serves
as a favorite site for further deposition of the material at
the interface of the liquid droplet, promoting the elonga-
tion of the seed into a nanowire or a whisker, and
suppressing further nucleation events on the same catalyst.
Since the liquid droplet catalyzes the incorporation of
material from the gas source to the growing crystal, the
deposit grows anisotropically as a whisker, whose diam-
eter is dictated by the diameter of the liquid alloy droplet.
The nanowires thus obtained are of high purity, except for
their end which contains the solidified catalyst as an alloy
particle [105].
Fig. 22 Schematic illustration
of template synthesis [107]
Int J Adv Manuf Technol (2010) 49:803–826
Xu et al. [108] produced nanowhiskers of ZnO and
mixed them uniformly with acrylic resin so as to generate a
multifunctional coating. These nanoparticles were synthe-
sized by means of hybrid induction and laser heating or
induction heating. Multi-function was determined by the
characteristic structure of the nanoZnO and included
optical, chemical, biological, and semiconductor properties.
The multifunctionality gained by the formation of this
composite resin was an anti-electrostatic and, at the same
time, antibacterial coating. Furthermore, Lin et al. [109]
developed a strategy for the synthesis of multifunctional
uniform tumbler like mesoporous silica nanoparticles (Mag-
Dye@MSN) that simultaneously possessed magnetic, lu-
minescence, and porous properties. This srt of particles may
have a great potential for biological applications such as the
magnetic resonance imaging contrast agent, the drug
delivery carrier, the cell sorting, and labeling. The above
strategy is briefly described in Fig. 24.
Parkansky et al. [110] produced nanoparticles by pulsed
arcing in ethanol between Ni or W electrodes in order to
determine their size distribution in a nanorange as well as
their electrical and magnetic properties. They found out that
the size of the particles was distributed in the range of 3-
30 nm. In addition, the particles produced displayed a linear
dependence corresponding to Ohm’s law as well as a soft
ferromagnetic behavior at room temperature.
4.4 Nanostructured materials joining issues
Various processes can be used for the joining of nano-
stractured materials. Conventional welding processes like gas
tungsten arc welding (GTAW) and gas metal arc welding
(GMAW) might not be the best solution for joining nano-
composites due to the high temperatures that are developed,
however, nanocarbides and other stable ceramics that are
used in cermats would be easily arc joined. These nano-
particles could also be employed in the filler and used to join
standard metals together allowing greater flexibility in the
joint design and better control of the joining strength,
toughness, and electrical properties. Ultrasonic welding that
is based in friction heat for welding together pieces might be
Int J Adv Manuf Technol (2010) 49:803–826
Fig. 23 Schematic diagram il-
lustrating the growth of silicon
nanowires by the VLS mecha-
nism [105]
also a good solution for joining nanostructured materials,
since the heat generated is localized and the temperatures are
quite lower than arc welding.
A tested nanojoining technique used to join nanosized
materials is the atomic force microscope (AFM). Using AFM,
nanowires of 60-70 nμ can be repaired. This process is very
time-consuming since only a few atoms can be moved to the
damaged part of the wire at a time [111]. Alternatively, for
joining difficult to weld nanostractured materials, the pressur-
ized reaction synthesis or self-propagating high-temperature
synthesis (SHS) can be used. SHS is an advanced material
processing method that uses highly exothermic reactions
between powdered constituents. As a combination of SHS
processing and joining technology, the reactive synthesis
joining process has been introduced. The near net-shape
fabrication capabilities of the reactive synthesis joining
process are attractive due to lower cost for post-processing
and material and higher degree of design freedom [112].
5 Processing challenges
Five major processing categories have been identified for all
kind of materials: primary forming processes, deforming
Fig. 24 Synthetic procedure of
tumblerlike mesoporous silica
nanocomposites [109]
823
processes, removing processes, joining processes, and modi-
fying material properties processes [43]. However, multifunc-
tional materials are usually fabricated in the parts’ final form.
Therefore, material removing processes are seldom used for
the processing of such materials. Furthermore, the fabrication
of the final part is a holistic one, and thus, no post-processing
is required for modifying the material properties.
On the other hand, a number of different joining
processes are used for joining parts into products. These
joining processes can be either conventional ones that have
been modified in such a way that the multifunctionality of
the part is not affected or new joining processes developed
for specific materials only. The joining processes and their
limitations for both structural composite materials and
nanostructured ones were discussed within this paper.
The research effort is mainly focalized in different
fabrication methods that fall under the category of primary
forming processes. As described, there are different ways of
producing multifunctional materials that depend largely on
whether these materials are structural composites, smart
materials, or nanostructured materials. The latter category
presents the most challenging and innovative processes,
introducing, in the manufacturing, science biology
approaches such as self-assembly and self-replication.
824
6 Outlook
The introduction of multi-functional materials to the mass
production will alter significantly the way products are
designed. This introduction is prohibited mainly by the lack
of cost-efficient processing methods. A comprehensive
description of the advanced materials that will gradually
be the focus of the manufacturing research community has
been attempted. Some concrete orientations for future
research works and strategic developments have been
presented in order for industrial, technical, and financial
goals to be achieved.
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