EUROPEAN

POLYMER
European Polymer Journal 41 (2005) 645–662
JOURNAL
www.elsevier.com/locate/europolj
Review

Interfaces and interphases in multicomponent materials:

past, present, future
a,b,*
Béla Pukánszky
a
Department of Plastics and Rubber Technology, Budapest University of Technology and Economics, P.O. Box 91,
H-1521 Budapest, Hungary
b
Institute of Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences, P.O. Box 17,
H-1525 Budapest, Hungary

Received 7 February 2004; accepted 27 October 2004

Abstract

Interfacial interactions and interphases play a key role in all multicomponent materials irrespectively of the number
and type of their components or their actual structure. They are equally important in particulate filled polymer, polymer
blends, fiber reinforced advanced composites, nanocomposites or biomimetic materials. Recognition of the role of the
main factors influencing interfacial adhesion and proper surface modification may lead to significant progress in many
fields of research and development, as well as in related technologies. Although the role and importance of interfaces and
interphases are the same for all multicomponent materials, surface modification must be always selected according to the
objectives targeted, as well as to the characteristics of the particular system. Efficient surface treatment or coupling alone
might not achieve the desired goal, we must always keep in mind that an interphase forms always in such materials and
the control of interphase properties must be part of the modification philosophy. The use of multiphase, multicomponent
materials is expected to grow with a larger than average rate also in the future. It is important to keep the interdisciplin-
ary nature of the area, since principles and techniques developed by one field may find application also in other areas.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Interfacial interactions; Multicomponent materials; Heterogeneous structure; Surface modification; Polymer blends;
Particulate filled polymers; Fiber reinforced composites; Biomimetic polymers

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
1.1. The conference series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
1.2. Paradigm shift. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647

*
Corresponding author. Address: Department of Plastics and Rubber Technology, Budapest University of Technology and
Economics, P.O. Box 91, H-1521 Budapest, Hungary. Tel.: +36 1 463 2015; fax: +36 1 463 3474.
E-mail address: bpukanszky@mail.bme.hu

0014-3057/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2004.10.035
646 B. Pukánszky / European Polymer Journal 41 (2005) 645–662

2. General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647

2.1. Interphase. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648
2.2. Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649

3. The role of interphases in various multicomponent materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649

3.1. Fiber reinforced composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
3.1.1. General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
3.1.2. Traditional fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
3.1.3. Natural reinforcements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
3.2. Particulate filled polymers and blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
3.2.1 Particulate filled polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
3.3. Wood flour, hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
3.3.1. Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
3.4. Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
3.4.1. Spheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
3.4.2. Fibers and tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
3.4.3. Layered silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
3.5. Bio-related materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657

4. Technological consequences and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657

5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659

1. Introduction 1.1. The conference series

Multicomponent materials are used in increasing
quantities in all fields of the economy. They are present
in tools, utensils and devices used everyday at home, in
offices or in plants. Parts of our car or washing machine
are made of particulate filled or fiber reinforced compos-
ites, dental filling is a polymer nanocomposite, packag-
ing films are prepared from polymer blends or
multilayered structures, garden furniture usually con-
sists of CaCO3 filled polypropylene (PP), while racing
cars, parts of airplanes, rockets and helicopters contain
numerous parts of advanced composites. And the list
is endless. Most of these multicomponent materials
practically always consist of several phases, in which
interfaces exists between the phases. Interaction of the
phases across the interphase is one the factors determin-
ing the properties of these materials, thus the study and
modification of interfacial interactions are of utmost
importance for their further development. With the ad-
vance of science and technology and the introduction
of new materials the importance of interfacial interac-
tions does not diminish, on the contrary it considerably
intensifies, especially if we think of the rapid develop-
ment of nanocomposites, in which interfaces of enor-
mous size develop.
Recognition of the facts mentioned in the previous
paragraph brought into life two conference series in the
80s. Since fiber reinforced composites cannot be pre-
pared without the perfect adhesion of the phases and ad-
vanced composites for military applications were very
much in the center of attention at that time, both series
focused on interfaces and interphases in composite mate-
rials. The idea of creating such a series was raised in Ja-
pan at a conference by the accidental meeting of Prof.
Hatsuo Ishida from Case Western Reserve University
and Prof. Frans Maurer from DSM. Their discussion ini-
tiated the series of ICCI (International Conference on
Composite Interfaces) organized by Prof. Ishida in
Cleveland. He was the chairman of the meeting for sev-
eral years and organized the conference at the same loca-
tion every other year. Later the meeting moved around
the world, the last meeting took place in China in 2002.
The second series, IPCM (Interfacial Phenomena in
Composite Materials), was initiated by Prof. Frank
Jones at the University of Sheffield, who organized the
first meeting with the journal Composites in 1989.
The overall scope of both conferences was the same
with slight differences in focus. Both invited papers on
interfaces and interphases in polymer (PMC), ceramic
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662 647

Table 1 was selected accordingly. The goals of the meeting were

Scope and distribution (%) of papers presented at various to provide the scientific community with the opportunity
conferences on interfaces to present their latest results for discussion at a world-
Topic ICCI88 IPCM89 IIMM03 wide forum, to create a friendly atmosphere for socializ-
Polymer composites, fibers 61 68 47 ing and strengthening personal ties, to offer young
Materials 11 9 2 scientists an opportunity to present their work and inter-
Mechanics 12 23 13 act with the community, to enable scientists from East
Surface characterization 22 20 16 and West to meet and discuss issues of common interest
Surface modification 16 16 16 and coordinate to some extent worldwide scientific activ-
MMC, CMC 27 30 4 ities. Although the traditional fields of glass, carbon and
Blends, particulate filled 11 2 16 aramid fiber reinforced composites were maintained in
polymers the scope together with MMC and CMC composites,
Nanocomposites 1 0 27
numerous other fields, like nanocomposites and other
Others 0 0 6
nanostructured materials, biomimetic materials and tis-
sue engineering were also included into the program.
(CMC) and metal matrix composites (MMC). ICCI fo- The topics of oral papers presented at IIMM03 reflect
cused more on surface chemistry and modification, while both the shift in the interest of the scientific community as
IPCM on micro- and macromechanical testing, model- well as the success of the organizers in creating a meeting,
ing of interfaces and the determination of interfacial which reflects properly these changes. Table 1 compares
adhesion. Table 1 compares papers published in the con- the scope of the papers to those presented at ICCI88
ference proceedings of ICCI88 and IPCM89, respec- and IPCM89. Only about 50% of the presentations dealt
tively [1,2]. Since the proceedings contained different with ‘‘traditional’’ composites, and the rest with new
numbers of papers, the numbers in the table are given areas, the most important of which was nanocomposites.
as percentages. We must emphasize here that categoriza- Blends and composites maintained or increased their
tion is very difficult and arbitrary. Most of the papers fit role. Unfortunately the number of presentations on
into more than one category, thus the numbers in Table bio-related materials remained low; the organizers have
1 are intended only to give a qualitative picture about not reached scientists active in this area.
the main topics dealt with at the meetings. We can see Selected papers based on communications presented
though, that papers on PMC represented about 70%, at the Hungary meeting in 2003 are published in Com-
while those on CMC and MMC approximately 30% of posite Interfaces and European Polymer Journal. The
the contributions at both meetings. Basically all papers, editor of the latter asked the chairman of IIMM03 to
98% of the total, were presented on ‘‘traditional’’ com- write this paper and present his views on the past, present
posites at IPCM89, while close to 90% at ICCI88. The and future of research in interfaces and interphases in
slight difference in focus, i.e. mechanics vs. modification multicomponent materials. We must emphasize here that
and chemistry can be also seen in Table 1. this is not a review paper offering a comprehensive survey
The focus of the two meetings remained more or less of a specific area. It rather gives the personal, often sub-
the same for more than 15 years. The number of papers jective ideas of the author about the topic. Since he is less
presented on MMC and CMC decreased continuously familiar with some areas included in the scope of the
and so did the attendance. It became obvious relatively IIMM meeting, these views might be prejudiced or even
soon that the area would hugely benefit from the merge erroneous, and most probably not in line with the ideas
of the two meetings and the shift in scientific and com- of experts. Nevertheless, we hope that the thoughts and
mercial interest required topical changes as well. Negoti- views expressed here may raise some thoughts and in-
ations to merge started in the middle of 90s and the final crease the interest in this very important field, which will
decision was taken in 2001. The first joint meeting was gain even further significance in the future.
organized in 2003 in Hungary.

1.2. Paradigm shift 2. General aspects

With the advance of détente, the interest of industry
as well as the academia partly shifted from advanced
composites to other heterogeneous systems, like nano-
composites, biomaterials, or natural fiber reinforced
composites. As a consequence, the scope of the new, uni-
fied conference was changed to reflect these develop-
ments and also the name of the meeting, Interfaces
and Interphases in Multicomponent Materials (IIMM)
The importance of interfaces and interphases is rec-
ognized by all those who are involved in the study of
heterogeneous multiphase materials. In some cases inter-
facial interactions are claimed to determine the proper-
ties of composites [3,4]. On the other hand, the
important role of interactions is often neglected com-
pletely and good adhesion of the phases is assumed a
priori, especially in advanced composites. Books on
648 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
advanced composites occasionally dedicate only a very
short section of a few pages to interaction, surface mod-
ification and characterization [5,6]. The difficulty of esti-
mating the role of interfaces and interphases may arise
from the fact that the type, mechanism and strength of
interaction developing between the phases in multicom-
ponent materials may vary in a very wide range as a
function of component characteristics. Even larger is
the number of methods used for the modification of
interactions, and surface treatment or coupling must
be adjusted to each individual system specifically. As a
consequence, different areas treat interactions separately
and rarely compare methods, phenomena or processes,
or try to draw conclusions of general validity from
observations. Conferences on topics dedicated to specific
areas, like fiber reinforced composites, blends, nanoma-
terials, or even bio-related substances usually accommo-
date a section on interfaces and interphases, but rarely
try to go out of their field and discover the findings of
others. However, interfacial interactions have some
common features, which are present in all heterogeneous
systems and they are worth to consider.
2.1. Interphase
The properties of all heterogeneous materials are
determined by the same four factors, by the characteris-
tics of the components, composition, structure and inter-
facial interactions. As a first approximation one could
assume that the interface is a well defined area with only
two dimensions. However, in heterogeneous systems an
interphase forms practically always, which has a thick-
ness, and properties differing from those of the compo-
nents. Such an interphase forms by the adsorption of
the polymer on the surface of the inclusion in particulate
filled polymers, by interdiffusion of the components in
blends or by various chemical reactions on fibers. These
latter are influenced also by the composition of the siz-
ing material and by changes in curing reactions. Because
of the multitude of interaction mechanisms and the com-
plicated structure developing as an effect, generalization
is difficult. However, the existence of the interphase is an
accepted fact now. As a consequence, more effort must
be done to determine its thickness and properties.
The interphase can be characterized by a large num-
ber of methods and numerous attempts were and are
done to do so. Spectroscopic methods are used for the
characterization of the chemical composition of surfaces
and interphases, as well as to follow the effect of surface
modification. Such methods like X-ray photoelectron
spectroscopy (XPS), secondary ion mass spectroscopy
(SIMS), Auger electron spectroscopy (AES), diffuse
reflectance infrared spectroscopy (DRIFT) and other
methods have different resolution and penetration
depth. However, it is very difficult to obtain information
about interphases which form by adsorption or interdif-
fusion. If the interaction forces are weak—sometimes
only dispersion forces act between the components like
in the blends of olefin polymers [7,8]—spectroscopic
methods do not help in their detection and even less in
the determination of their strength.
The effect of the interphase on the properties of a
multicomponent material depends on its amount and
characteristics. These latter depend very much on the
mechanism of interphase formation and on the proper-
ties of the components. If the interphase forms in chem-
ical reactions, the prediction of its properties is very
difficult. This happens during the silane treatment of fi-
bers or fillers, where usually a polysiloxane layers forms
around the inclusion. The thickness of this layer is deter-
mined mainly by the amount of silane used for treat-
ment, while its properties by the organofunctional
group of the compound [9,10]. If the interphase forms
by physico-chemical interactions, its thickness is deter-
mined by the strength of the interaction, while its prop-
erties by the characteristics of the components. The
effect of the strength of interaction is amply demon-
strated by Fig. 1, where the correlation of interphase
thickness and acid base interaction is presented for var-
ious particulate filled thermoplastic matrices containing
the same CaCO3 filler [11]. Besides the strength of inter-
action, the amount of material bonded in the interphase,
which depends also on the size of the interface and on
the contact area between the components, also influ-
ences the properties of the material. This factor becomes
extremely important in nanocomposites and is claimed
to endow these materials with exceptional properties.
In the previous paragraph we discussed interphase as
a phase with well defined properties, dimensions and
Fig. 1. Dependence of interphase thickness on the strength of
interfacial interaction in polymer/CaCO3 composites [11].
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662 649

Table 2
Interphase thicknesses determined by different methods in particulate filled composites
Matrix polymer Dispersed component Determination method Thickness (lm) Ref.
HDPE SiO2 Extraction 0.0036 [19]
HDPE ’’ ’’ 0.0036 [20]
PP ’’ ’’ 0.0041 [20]
PP Graphite Model calculation 0.001 [21]
PS Mica Dyn. mech. spectra 0.06 [22]
PMMA Glass ’’ 1.4 [22]
PU Polymer ’’ 0.36–1.45 [23,24]
PP CaCO3 Modulus 0.012 [25]
PP ’’ Yield stress 0.15 [25]
PP ’’ Tensile strength 0.16 [25]

effect. We do not have sufficient space to discuss all de-
tails of these factors, but we must emphasize the con-
tradictions prevailing in this field and the need for
further study. Opinions are divided about the properties
of the interphase even in such simple materials as silica
filled PE. According to some sources a soft interphase
forms in such composites, while others claim the forma-
tion of a hard interlayer [12,13]. Models exist, which
take into consideration the formation of an interphase,
but assume a definite thickness and homogeneous prop-
erties inside the layer [14,15]. Opinions and models exist,
which assume that the properties of the interphase
change continuously from one phase to the other
[16,17]. In such cases either these graded properties or
average values must be taken into account during the
prediction of composite properties. Finally, the effect
of the interphase is different for each individual prop-
erty. Modulus is influenced very slightly by interaction,
while properties measured at larger deformation may
change considerably [18]. Similarly, the thickness of
the interphase determined indirectly from a composite
property depends very much on the method of determi-
nation. This point is demonstrated by Table 2 presenting
interphase thicknesses in various heterogeneous systems,
mainly particulate filled composites. According to the
table, the thickness of the interlayer increases with the
extent of deformation applied in the determination of
the property from which the layer thickness was derived.
2.2. Modification
Surface modification also has some general aspects.
One of them is the fact that a specific strategy must be
developed for each individual set of materials, general
solutions do not exist. The goal of modification must
be decided on first of all. If we want to decrease the
aggregation of fillers, non-reactive treatment must be
used, which decreases interactions. The phases are cou-
pled chemically in fiber reinforced composites, because
proper stress transfer can be achieved only in this way.
In this case surface chemistry must be adjusted to the
system, i.e. to the chemical character of the components.
It is rather surprising that such a strategy frequently is
missing and a treatment is expected to work in one sys-
tem, because it was efficient in another. Silanes are the
best examples; they are used for all kind of material
combinations irrespectively of the chemical composition
of the components. However, with the proper approach,
experience obtained in a system can be transferred to
others. The amount of surfactant or coupling agent must
be optimized in all composites. Organophilization of
layered silicates is carried out basically according to
the same principles as the coating of CaCO3. Specific
interactions are used in both cases, the ionic interaction
of chalk surface with the acid group in one case, or that
of the ammonium group with the negatively charged
surface of the silicate, in the other.
Besides these general aspects each group of materials
have specific features as well. In subsequent paragraphs,
we discuss the main groups of heterogeneous polymer
systems with regard to interfacial interactions and inter-
phases developing in them. We try to demonstrate issues
important for further development and questions to be
solved in the future.
3. The role of interphases in various multicomponent
materials
Multicomponent materials are arbitrarily divided
into four groups: fiber reinforced composites including
glass, carbon, aramid and natural fibers; particulate
filled composites and blends; nanocomposites and bio-
related materials. As mentioned previously, we do not
give a detailed survey of the various areas and do not
even try to be comprehensive, just demonstrate our ideas
with a few selected references.
3.1. Fiber reinforced composites
3.1.1. General considerations
The basic condition of the application of fiber rein-
forced composites is perfect adhesion between the com-
ponents. Already this statement is a much discussed
650 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
question, but perfect adhesion is absolutely necessary to
transfer load from the matrix to the fiber. Without adhe-
sion the principle of fiber reinforced systems would not
work, i.e. the strong fiber carries the load, while the ma-
trix distributes it and transfers from one fiber to the
other. The opinion is often expressed that an excessively
strong interface leads to a rigid composite, while in the
case of weak adhesion the above mentioned principle
does not work, thus the strength of adhesion must be
set to an optimum value. However, a clear distinction
must be made here between interface and interphase.
In composites an interphase forms spontaneously even
in the absence of surface treatment. However, treatment
is always used in continuous fiber reinforced composites,
which invariably leads to the formation of an interphase
with a very complex structure [9,26]. As explained
above, the thickness and properties of this interphase
have crucial impact on composite properties. As a con-
sequence, adhesion must be perfect but the properties
of the interphase optimized in order to achieve advanta-
geous or desired properties. The correlations among the
chemistry, processing conditions, composition, structure
and properties of the interphase have not been fully
understood yet, they need further extensive study.
The fibers are usually treated, i.e. sized during their
preparation. In order to achieve high productivity, they
must be processed at a high rate. This requires special
sizings, which prevent fiber breakage and facilitate pro-
cessing. As a consequence, surface coating of all fibers
usually contain a number of additives, of which the cou-
pling agent comprises only a small part. Only limited
number of studies have been carried out on the analysis
of the composition of the sizing and its effect on compos-
ite properties [27,28]. Nevertheless, surface coating of
the fiber determines the structure and properties of the
interphase, as well as the quality of coupling.
The very strong adhesion necessary from efficient
stress transfer is usually achieved by the chemical cou-
pling of the fiber and the polymer matrix. Organofunc-
tional silanes are used the most often for all kind of
fibers. The chemistry and physics of coupling in glass
fiber reinforced thermosets is sufficiently known [9,29],
but there is much to be done in the case of carbon, ara-
mide and PE fiber reinforced composites. Efficient cou-
pling is usually not very simple, the lack of reactive
groups on the polymer prevent the direct coupling of
the components, or limit the number of covalent bonds
formed [30]. Often the modification of the matrix is re-
quired or a modified polymer is introduced into the
composite in order to achiever a high level of adhesion
[31]. Stress transfer is often achieved through a combina-
tion of several mechanisms, e.g. by chemical coupling
and interdiffusion like in glass fiber reinforced PP com-
posites. We must emphasize here again that chemical
coupling is system specific, the coupling agent and the
treatment technique must be selected according to
the characteristics of both components, i.e. fiber and
matrix.
An often neglected question is the amount of cou-
pling agent used. The treatment is usually done by the
producer of the fiber according to a proprietary tech-
nique which is not disclosed to the customer. The treat-
ment (sizing, coupling agent, composition) might be
optimized for a certain fiber/matrix combination, but it
does not necessarily work in other systems. It has been
shown many times that the structure and properties of
the interphase change with the amount of coupling agent
used [9], thus optimization is necessary in order to
achieve maximum efficiency.
The structure of the interphase is usually very com-
plicated. The most often used silanes chemically couple
to the surface of the fiber and through their free func-
tional group form a polysiloxane layer. Depending on
the composition of the matrix and the interphase they
may interdiffuse into each other forming a physically
bonded network [9,26]. The structure and composition
of the interphase can cover a very wide range, they de-
pend on the chemical composition of the components
(fiber, matrix, coupling agent), but they are strongly
influenced also by the composition of the sizing.
Depending on the organofunctional group of the silane
even a very hard interlayer may form on the surface of
the fiber preventing coupling as shown in Fig. 2 in which
interfacial shear stress (IFSS) of polycarbonate micro-
composites is plotted against the amount of coupling
agent used for the treatment of the fiber. The degree
of curing in the matrix close to the fiber is often smaller
than in the bulk material, which leads to a weak inter-
layer [32]. The application of an elastomeric interlayer
Fig. 2. Effect of various coupling agents on interfacial interac-
tion in PC/CF microcomposites. Symbols: (h) isocyanurate,
(}) isocyanate, (s) epoxy silane, (n) anhydride silane forming
a rigid, non-reactive polysiloxane layer.
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
was also suggested to decrease stress concentration
around the fibers [3]. Although this might be advanta-
geous because it decreases stress concentration, the tech-
nique is rarely (or never) used in industrial practice. The
correlation between the structure and properties of the
interphase and the properties of the composites are not
known yet, much more research must be done in this
field. Experience indicates that a thin rigid interphase
leads to low fracture resistance, while a thick soft inter-
phase results in better fracture resistance, but lower com-
posite stiffness. However, quantitative correlations to
transfer these observations into practice are still lacking.
3.1.2. Traditional fibers
The general observations presented above are valid
for all fiber reinforced composites. The interest in these
materials, especially in carbon fiber reinforced compos-
ites decreased somewhat in recent years. The price of
carbon fibers did not decrease to the extent expected,
the aviation industry went through a crisis and some
accidents could undoubtedly be related to the failure
of composite parts. Nevertheless, research continues.
Review papers were published on carbon fibers [33]
and also on surface modification used to improve the
properties of their composites [34]. New methods of sur-
face modification are tried or even introduced into prac-
tice. One of the techniques which is already discussed for
years as a possible means to modify the surface proper-
ties of fillers [35], glass [36,37] and carbon fibers [38] is
plasma treatment, but its introduction into industrial
practice is still outstanding. Ultrasonic treatment is also
used to improve the homogeneity of the treatment and
interphase properties [39]. Although continuous study
and development may lead to further improvement of
existing technologies, revolutionary changes are not ex-
pected to occur in this area in the near future.
3.1.3. Natural reinforcements
Instead of traditional fibers, recently attention is fo-
cused much more on natural reinforcements. A very
large number of papers are published on the advantages
and potential applications of wood flour, as well as all
kinds of natural fibers and several reviews are also avail-
able [40–43]. These materials are claimed to have numer-
ous advantages, they come from renewable resources,
are environmentally friendly, light and strong, etc. On
the other hand, these fibers also have some disadvan-
tages, the properties change from season to season, the
fibers are sensitive to water and their transverse strength
is rather poor. Interfacial adhesion must be very good
also in natural fiber reinforced polymers thus many of
the papers mentioned above focus attention on surface
modification and coupling. Besides surface treatment,
chemical modification of the fiber by impregnation is
also carried out to improve fiber properties especially
to decrease water adsorption. In spite of the enormous
651
interest in natural fibers and in their modification, male-
inated polymers are used for coupling in most cases, at
least in polyolefin composites [42]. More research is
needed to develop practically viable methods for the
modification of these fibers in order to decrease water
sensitivity and improve reliability. In spite of the difficul-
ties, a large increase is expected in the use of such mate-
rials in the future.
3.2. Particulate filled polymers and blends
3.2.1. Particulate filled polymers
Particulate filled polymers and blends represent two
mature areas in the field of heterogeneous polymers.
The use of fillers dates back for a long time. Fillers and
reinforcements were and are used in thermoset matrices,
but also in all kinds of thermoplastic polymers. Particu-
late filled polymers are used in large quantities in many
fields of application from household appliances to auto-
motive parts. This well established position in the plastics
industry creates the impression that all problems of the
production and application of particulate filled polymers
have been already solved, but in reality many questions
need further investigation. Although research on blends
and composites is not in the main streamline of interest
any more, a steady number of publications indicates
the importance of the field. This interest is demonstrated
well by the recent publication of two large monographs
on particulate filled polymers [44,45]. One, Ref. [44] is
rather poor in quality, a mere compilation of informa-
tion collected by online computer search. Its main merit
is the list of references, which can be used for the detailed
study of a specific question of interest. The other is the
second edition of a successful book edited by one of
the experts of the field, Rothon [45], professionally
sound, a book which offers valuable information in all
questions related to particulate filled polymers. The con-
tinuous interest in the area is sufficiently proved also by
Table 1; the number of papers on blends and particulate
filled polymers remained at a relatively high level.
Most of the unresolved questions in blends and com-
posites are related to interactions. In particulate filled
polymers two types of interactions may be distinguished.
Particle–particle interactions lead to aggregation, while
matrix–filler interactions determine micromechanical
deformation processes as well as the macroscopic behav-
ior and performance of the material. Relatively few
papers are published recently, which are related to
aggregation [46,47]. The detection and quantitative
characterization of aggregation is difficult, unambiguous
methods do not exist yet. Although general tendencies,
i.e. the increase in the extent of aggregation with
decreasing particle size and increasing filler content,
are known, exact correlations do not exist in spite of
the fact that aggregation is one of the major issues in
the production of particulate filled polymers.
652 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
A large number of the papers published in this field,
maybe even their majority, are related to the modifica-
tion of interfacial interactions, specifically to the surface
treatment of the filler. A considerable number of these at-
tempts describe surface modifications through the use of
reactive compounds, mainly silanes and titanates [48–
50]. Often considerable improvement in properties is re-
ported, even when the data presented in the paper do
not support the statement. In the majority of the cases
the philosophy of the treatment is unclear and the
amount used is arbitrary, is not adjusted to the surface
characteristics as well as area of the filler and to the
chemistry of the coupling agent. Although silanes were
shown to increase interaction also in PP/filler composites
[51,52], one cannot expect chemical interaction from a fil-
ler not containing active—OH groups on its surface (talc,
CaCO3) or from polymers not having reactive groups at
all (PP, PE). Apart from the fact that coupling agents
often are not adjusted properly to the system, they are
also expensive and not worth to use in an application,
the goal of which in not to increase, but decrease interac-
tion. The usual purpose of the surface treatment of par-
ticulate fillers is to decrease their surface free energy in
order to hinder particle/particle interactions and aggre-
gation. The best way to achieve this goal is the use of long
chain fatty acids. On the other hand, the development of
proper surface treatment technology and the optimiza-
tion of the type and amount of surfactant require knowl-
edge and skill, as well as further studies.
An increasingly important question, which is not ad-
dressed sufficiently, is the study of the micromechanical
deformation processes occurring in particulate filled
polymers, in fact in all heterogeneous polymer systems.
Under the effect of external load stress concentration
develops around the inclusions, which induces local
deformations. In particulate filled polymers the domi-
nating micromechanical deformation process is thought
to be debonding, but considerable shear yielding also
takes place. Other deformations like matrix cracking
or crazing may also occur in these systems. Although a
model developed earlier predicts well the conditions of
debonding [53], it does not give information about the
relative significance of various deformation processes.
Debonding is a process which is used in industrial prac-
tice to produce breathable films [54]. Polyethylene films
are prepared with large amounts of CaCO3 filler, the
films are stretched producing voids, which permit the
passage of vapor, but are not permeable to liquids (see
Fig. 3). The extent of debonding determines moisture
vapor transport (MVTR) through the film, thus the
quality of the product. Interfacial adhesion is one of
the factors determining debonding and its control makes
possible the improvement of product quality in an
important and rapidly developing field. Breathable films
serve as a good example for the importance and poten-
tials of particulate filled composites, which allow the
Fig. 3. Structure of a breathable film prepared from PE/CaCO3
composite. The SEM micrograph taken from the fracture
surface of a broken film shows the voids around the particles
throughout the entire cross-section.
production of high-tech products from simple materials
with a delicate technology.
3.3. Wood flour, hybrids
Two other areas must be mentioned which are in the
center of interest or deserve more attention. A large
number of papers are published on fillers or reinforce-
ments obtained from renewable resources. Wood flour
filled polymers are typical particulate filled polymers,
in which interactions are of utmost importance, espe-
cially if we consider the large size of the wood particles.
These materials were mentioned already in the previous
section. On the other hand, hybrid composites contain-
ing two different fillers or a filler and an elastomer need
more attention [55,56]. These materials also have practi-
cal importance, e.g. PP containing a filler and an elasto-
mer is extensively used for the production of automotive
bumpers. Such hybrids are continuously studied since
the 70s, but general correlation between their structure
and properties are still not known. It has been shown
that two boundary structures may develop in such mate-
rials. The filler and the elastomer may be dispersed sep-
arately in the polymer matrix or the elastomer may
encapsulate the filler and the inclusion formed in this
way is dispersed in the continuous phase. Detailed study
of a PP/EPDM elastomer/CaCO3 filler composite system
proved that that the prevailing structure is determined
by the relative magnitude of adhesion and shear forces
[57]. In practice always mixed structures form. In
Fig. 4 the YoungÕs modulus of three-component PP
composites of various compositions is plotted against
the relative amount of filler embedded by the elastomer.
According to the figure the stiffness of the material is
determined by the extent of embedding. On the other
hand, fracture resistance is influenced also by other fac-
tors (Fig. 5) [58]. In practice high stiffness and toughness
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
Fig. 4. Dependence of the stiffness of three-component PP/
EPDM/CaCO3 composites on embedding expressed as a
percentage of total filler content. YoungÕs modulus decreases
significantly as the number of embedded particles increases;
embedding dominates stiffness.
Fig. 5. Correlation between the extent of embedding and
impact resistance in three-component PP/EPDM/CaCO3 com-
posites. Deviation from the linear correlation indicates the effect
of other factors than encapsulation.
are required simultaneously from these materials, which
is very difficult to achieve. Only further study can lead to
a knowledge, which makes possible the design of com-
posites with optimum or required properties.
3.3.1. Blends
Similarly to particulate filled composites, interactions
are the dominating factors also in polymer blends. Inter-
action or the lack of it determines miscibility, phase
structure and properties of the blends. In spite of the fact
653
that blends are routinely and extensively used in indus-
trial practice, a large number of papers are still being
published in this area, as well. These focus on miscibil-
ity, structure, compatibilization and properties. Misci-
bility of the components is predicted with various
models and theories [59] and the development of more
and more sophisticated methods make possible the
proper characterization of phase structure [60–64]. Sim-
ulation methods are used for the prediction of miscibility
and structure of polymer pairs with increasing frequency
[65,66]. Other papers focus on structure and properties,
while a major issue both in academia [67] and in industry
[68] is the compatibilization of blends.
Unfortunately, the field, and also the papers pub-
lished, can be divided into two well defined groups with
very little connection between the two groups. This divi-
sion is well demonstrated by the two volume book pub-
lished recently on blends in the edition of Paul and
Bucknall [69]. The first volume gives a comprehensive
account of the latest developments in all aspects of poly-
mer miscibility from statistical thermodynamics through
hydrogen bonding systems to polyolefin blends, dis-
cusses characterization techniques and the factors affect-
ing structure formation. The second volume deals with
the performance of the blends, mechanical properties
and fracture characterization, fatigue, toughening mech-
anisms, specific properties like light transmission and
permeability, as well as reinforced and elastomeric
blends. However, in this second volume any thermody-
namic parameter related to miscibility appears only once
or twice, i.e. general correlation between miscibility,
structure and properties is not mentioned, or not
known. However, most of the blends are used in struc-
tural applications and the prediction of mechanical
properties would help very much the development of
new and better materials. An attempt was made earlier
to develop a simple model, which relates miscibility
and mechanical properties [70]. Its application led to a
relatively good correlation between a parameter derived
from mechanical properties, from the effective load bear-
ing capacity or the dispersed phase, and the Flory–Hug-
gins parameter determined by solvent diffusion (Fig. 6)
[71–73]. In spite of the surprisingly good general ten-
dency and validity for the most different polymer pairs,
the model is very simple, applies numerous simplifying
conditions and neglects important factors, thus it needs
considerable improvement and refinement.
Bio-related materials gain increasing importance also
in the research and technology of polymer blends. Poly-
mers from renewable resources, e.g. starch and cellulose,
are used as components of blends or composites and at-
tempts are made to produce biologically degradable
polymers by the combination of such materials and poly-
esters produced by synthetic or natural processes. Results
are still reported on thermoplastic starch/polyolefin
blends in spite of the fact that such materials were already
654 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
Fig. 6. Correlation between the Flory–Huggins parameter for
polymer–polymer interaction determined form solvent diffusion
and parameter C derived from the tensile strength of the blends,
which is related to the load bearing capacity of the dispersed
phase.
produced in industrial scale already 15 years ago [74–76].
Moreover, the ban of such materials is considered in
some countries because they fear that the fine polyolefin
powder forming during the degradation of such materials
blocks the soil and hinders the penetration of water, or
covers lakes ruining living environment. Blends contain-
ing starch or cellulose and aliphatic polyesters either
from synthetic or microbial sources seem to have more
potential in the future [77,78]. However, considerable re-
search must be done to improve their properties and de-
crease price. All cellulose composites may also develop to
materials of some practical importance in the future,
although the technology needs further development [79].
3.4. Nanocomposites
One of the buzz words in the technical world includ-
ing polymer science is nano with all the positive and
negative consequences. In recent years practically every-
thing became ‘‘nano’’ even materials which are around
for more than a hundred years like carbon black used
for the reinforcement of rubbers. Many laboratories
launched projects on composites containing particles in
the nanometer scale with variable extent of success.
The general idea of nanocomposites is based on the con-
cept of creating a very large interface between the nano
sized building blocks and the polymer matrix. However,
the properties of nanocomposites are not determined
only by the size of the interface, interaction is a crucial
factor again. Very often already the homogeneous distri-
bution of the nanosized particles is problematic, i.e. the
expected large surface cannot be always created, but the
adjustment of the proper interaction or coupling of the
components presents further problems. The coupling
agent or surface modification is often not properly se-
lected, it is not adjusted to the system, and thus the
material does not possess the expected property combi-
nation. Nanocomposites can be classified in many ways;
we discuss them here according to the dimensionality of
the nanosized heterogeneity.
3.4.1. Spheres
Spherical or nearly spherical particles have all three
dimensions in the nanometer range. Numerous attempts
have been made to distribute such particles in a polymer
matrix with the most different methods. One approach is
the use of traditional thermoplastic or thermoset technol-
ogies to homogenize the previously prepared particles
into the matrix polymer. Carbon black, precipitated cal-
cium carbonate and silica are the most frequently used
representatives of this class of materials. They were
around before the nano era and are used in specific appli-
cations. Interaction and its control is the key for success
also in the application of these materials, but particle–
particle interactions are usually more important than
polymer–filler adhesion. It has been shown earlier that
the occurrence and extent of aggregation depends on
the relative magnitude of adhesion and shear forces
[80]. The ratio of the two forces depends on interfacial
adhesion, shear forces and the size of the particles; the
aggregation tendency of fillers increases strongly with
decreasing particle size. Since in nanocomposites parti-
cles are very small, aggregation is practically unavoidable
and the formed structure governs the properties. The size
and interaction of the particles determine also the
strength of the aggregates. Although attempts have been
made to describe aggregation strength, further research
must be done in this area. The consequence of insufficient
aggregate strength is demonstrated by Fig. 7 showing the
failure of a large CaCO3 aggregate formed in a PP ma-
trix. Under the effect of external force the aggregate frac-
tures leading to the premature failure of the entire
composite. Shear forces can be changed in a limited range
thus the main factor to control aggregation is the surface
modification of the filler. Various treatments and modifi-
cation techniques are used, e.g. surface grafting of the sil-
ica [81,82], but aggregation can be rarely avoided. We can
hope only for a decrease in its extent at most. This ap-
proach, i.e. the distribution of preformed particles in a
matrix with traditional techniques, must improve consid-
erably in order to produce nanocomposites with the
expected and forecasted exceptional properties.
The simultaneous formation of the particles and the
polymer matrix, usually in sol–gel technology, seems
to have much more potentials. The interest in organic–
inorganic hybrids dates back to the 80s and several re-
views are available in this field summarizing the tech-
nical possibilities, structure, properties and potential
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
Fig. 7. Inferior strength and fracture of a CaCO3 aggregate
consisting of 0.08 lm large primary particles under the effect of
external load.
applications of these materials [83–85]. Usually silicate
chemistry is used to produce particles of different sizes
[86] or organic–inorganic networks [87]. The size of the
particles can be changed from 500 to 10 nm by modify-
ing the conditions of the polymerization, hydrolysis and
condensation of the silica precursors [86]. The homoge-
neity of the composite is much better in these materials,
although depending on chemistry aggregates can form
even in this case [86]. Interfacial interactions can be also
adjusted by using the proper reactants to introduce func-
tional groups to the surface of the filler. These groups
can react with the polymer during polymerization or
cross-linking. This technology may lead to nanocompos-
ites with controlled structure and interfacial adhesion,
thus materials with tailor made properties can be pro-
duced for the most diverse applications.
Another class of materials which created much inter-
est recently and appear to have great potentials in vari-
ous fields of application is polyhedral oligomeric
silsesquioxane (POSS). Possible applications are cataly-
sis, precursors to silicates, preparation of copolymers
and hybrid networks. Interest and the intensity of re-
search increased further by the commercial availability
of the material. POSS cages (Fig. 8) can be functionalized
by various methods like grafting groups on preformed
clusters or particles, or by the formation of functional
groups during particle formation [85]. One way of mod-
655
Fig. 8. An acrylate functionalized POSS cage.
ification is the hydrosilylation of SiH groups present on
the surface of the POSS cube with any unsaturated bond
in the presence of a catalyst. Various functional groups
like epoxy, styril, norbornyl, methacrylate, etc. can be
formed on the surface of the POSS compound [88,89].
The reactive groups available encompass a wide range
offering a large number of possibilities for further modi-
fication and the control of the structure and/or chemistry
of the compounds. Nanocomposites with a wide variety
of structures can be formed in this way. POSS can be
build into the chains, can be attached to them by a
spacer, can form networks, etc. Moreover, besides POSS
other hybrid organic–inorganic supermolecular assem-
blies can be also prepared e.g. from butyltin oxo–hydro-
xo nanobuilding blocks and dicarboxylates, as well as by
related chemistry [90]. By changing structure and func-
tionality, the properties of the composites can also be
modified according to requirements. Although the chem-
istry is not simple, the potentials of the approach are
large and homogeneity, as well as interactions, can be
kept under control relatively easily, at least compared
to traditional homogenization technology.
3.4.2. Fibers and tubes
Similarly to POSS, carbon nanotubes are also in the
focus of attention for some time. Nanotubes and nano-
fibers have two dimensions in the nanometer range; they
are usually micrometer or even millimeter long. They at-
tracted the interest mainly because of their exceptional
mechanical [91] and electrical properties [92]. Theoretical
and experimental investigations proved that carbon
nanotubes have a YoungsÕs modulus in the range of
1.2 TPa, but they are also flexible [93]. The extremely
high stiffness would make these materials ideal reinforce-
ments for composites. The ultimate goal of composite
preparation, i.e. producing materials with high stiffness
and toughness at low reinforcement content, could be
achieved with the nanotubes. However, effective rein-
forcement has two conditions: alignment parallel with
the direction of the load, and good stress transfer from
the matrix to the fibers. Unfortunately, both are difficult
to achieve in this case. Carbon nanotubes form bundles
and they are usually twisted. Separation of the individual
tubes, their homogeneous distribution and parallel align-
ment are problems to be solved in the future. Moreover,
656 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
similar difficulties arise with stress transfer controlled by
interfacial adhesion. Although experiments directed to-
wards the determination of interfacial fracture energy
in multiwalled carbon nanotubes reinforced composites
indicated the existence of a ‘‘relatively’’ strong interface
[94], interfacial adhesion is insufficient in most cases in
spite of the small diameter of the fibers.
Carbon nanotubes have a very regular structure al-
most exclusively consisting of carbon atoms. The surface
free energy of the tubes is low and they do not contain
reactive groups necessary for coupling. The importance
of interfacial interactions in the preparation of carbon
nanotube reinforced composites was recognized by some
groups, Gong et al. [95] declared it as one of the most
critical issues. They used a surfactant processing aid to
improve the properties of a carbon nanotube/polymer
composite, they could increase the Tg of the polymer
and its stiffness in this way. Although a surfactant may
improve homogenization, it is difficult to see how it
can improve interfacial adhesion. Other attempts were
also made to improve interfacial adhesion by the func-
tionalization of the tubes; an improvement of properties
was reported invariably as an effect of modification
[96,97]. In spite of the huge effort and intensive study,
carbon nanotube reinforced composites do not meet
expectations yet, their performance is moderate at most,
especially if we compare it to their price. A possible way
to overcome the difficulties caused by the shape and con-
formation of nanotubes is the use of nanofibers pro-
duced by electrospinning. According to Dzenis [98]
these fibers are superior to nanotubes in many respects,
although the way to control interfacial interactions is
unclear also in this case. Although these fibers have
much potential in nanofabrication processes [99] and
they may have numerous advantages including price,
much has to be done before they can be used as rein-
forcements at industrial scale.
3.4.3. Layered silicates
Nanoreinforcements with only one dimension in the
nanometer range can be achieved by platelets, usually
single silicate layers. Layered silicate polymer nanocom-
posites also created much interest especially since the
results of the Toyota laboratory have become public
[100,101]. Intensive research has been carried out in this
area by many laboratories since then on all kinds of poly-
mers incorporating layered silicate particles. Several re-
view papers and books were also published about the
preparation, structure, properties and possible applica-
tions of these materials [102–106]. Montmorillonite or
hectorite is used the most often as reinforcement. Inter-
actions play a crucial role also in layered silicate nano-
composite preparation. The negative surface charge of
the silicate layers is compensated by solvated cations in
the space confined between two layers, called also the gal-
lery, which can be and are exchanged to organic ions,
mostly by ammonium ions having one or more long ali-
phatic tails. Ion exchange leads to an increase of gallery
distance and to a decrease of attractive forces between
the layers. The decrease of intergallery forces makes
exfoliation possible, which is basically the separation of
the silicate layers. Delamination, or exfoliation, can be
initiated by in situ polymerization or by shear in a con-
ventional processing machine. Practically all the papers
published in this field emphasize the advantages of nano-
composites and often claim complete or at least extensive
exfoliation. Unfortunately, it is rather difficult to achieve
complete exfoliation and usually a complex structure
forms containing large particles, tactoids with extended
gallery distances and individual exfoliated silicate layers.
The determination or estimation of the extent of exfolia-
tion is difficult; drawing conclusions from WAXS pat-
terns [107] may be very misleading. Properties often do
not improve to the extent as expected [108,109] or even
deteriorate [110,111]. Naturally very few papers report-
ing negative results are available although such informa-
tion would also help to increase our knowledge about
factors controlling nanocomposite properties.
The reason for the difficulties to reach complete exfo-
liation can be traced back to interactions. Beside organ-
ophilization, very often additional swelling agents, or
compatibilizers, must be used to increase the extent of
exfoliation and to improve homogeneity [106,107,112].
However, interactions are equally important also for
the determination of properties. A generally accepted
and frequently published view is that the hydrophilic sil-
icate layers are not compatible with the hydrophobic
polymers. Organophilization makes the silicates also
hydrophobic thus compatibility and interaction improve
[104]. In our view this approach, explanation or inter-
pretation is not true and completely misleading. It is
common knowledge that polyethylene and polystyrene
are not miscible or compatible. Why do we expect the
compatibility of a silicate layer to increase in any poly-
mer except PE, if we cover its surface with aliphatic
chains? Moreover, it has been shown a long time ago
that the non-reactive coating of a mineral filler with a
surfactant leads to a decrease in its surface tension and
also in matrix/filler interaction [113]. High energy sur-
faces, like that of the silicates in question are always wet-
ted by low surface energy liquids like a polymer melt
[114]. Obviously the necessity to increase the distance be-
tween the layers of the silicate and to decrease intergal-
lery bonding forces to achieve exfoliation is confused
with its effect on polymer/silicate interaction. As a final
example, we present two figures showing the transpar-
ency and tensile strength of PVC/silicate composites.
The optical transparency of the composite containing
the organophilic silicate is significantly larger than that
of the material prepared with the neat filler (NaMMT),
which indicates at least partial exfoliation (Fig. 9). On
the other hand, its strength is lower because surface
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
Fig. 9. Dependence of the transparency of PVC/MMT com-
posites on silicate content: (h) NaMMT and (n) OMMT.
Fig. 10. Effect of interfacial interaction on the tensile yield
stress of PVC/MMT composites: (h) NaMMT and (n)
OMMT.
modification decreases the matrix/silicate interaction
(Fig. 10). Weak interaction led to decreased strength in
spite of the large contact surface [111]. In conclusion,
much has to be done to properly understand the role
of interfacial interactions in these layered silicate nano-
composites in spite of the fact that some compounds find
already industrial application [115].
3.5. Bio-related materials
The incentive to use biologically active materials is
increasing by the day. As mentioned earlier, materials
657
from renewable resources are used as natural reinforce-
ments or components in polymer blends. The abundance
and low price of natural polymers, like starch and cellu-
lose, make them attractive for industrial applications.
Considerable effort is done to replace synthetic poly-
mers, or fibers, with these materials. We pointed out
the importance of interfaces and interphases also in
the development of bio-related blends and composites.
Surface modification and adjustment of interfacial inter-
actions is the necessary and proper way to control struc-
ture and properties of such materials.
A partly similar and partly different area is the devel-
opment of biomimetic polymers for various applications
in the human body. Basically the same, or very similar
materials, are used for such applications as for blends
and composites. Polyethylene hip joints are used for a
long time and experiments are done to use injection
molded biodegradable starch-based polymeric scaffold
in tissue engineering [116]. Interfacial interactions are
equally, or even more, important in these materials than
in other multicomponent systems. Materials in the
human body interact with cells and tissues and the
chemistry of the material must be selected accordingly
to initiate the proper response from the living cells. Fur-
thermore, the formation of new tissues must be mediated
by biomolecular recognition. Such a response from cells
is achieved by the surface or bulk modification of bio-
materials by chemical or physical methods with bio-
active molecules like proteins or peptides. A recent
review gives a detailed account about the surface and
bulk modification of biomaterials with cell recognition
molecules to design biomimetic materials for tissue engi-
neering [117]. The criteria of design including the con-
centration and spatial distribution of modified
bioactive materials are also evaluated in the paper.
Other review papers [118] and books [119] are also avail-
able discussing tissue engineering as well as synthetic
biodegradable polymer scaffolds and the Journal Bioma-
terials dedicated a complete issue to such materials [120].
All these papers send the message that surface modifica-
tion is the key issue to the success of the preparation of
biomimetic polymers, but modifying molecules must be
adjusted even more precisely in the living environment
than in engineering materials, because of the specific rec-
ognition capability of living organisms. Although all
surface modifications are system specific, in biomimetic
materials this reaches the highest level possible.
4. Technological consequences and future prospects
Development in the areas discussed in previous sec-
tions is driven only partially by the curiosity of the sci-
entific community. Possible application areas are
always kept in mind and a large part of the research is
focused on the development of new materials with a
658 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
lower price or better properties. In traditional areas like
fiber reinforced composites, particulate filled polymers
and blends development is directed towards price de-
crease, improved technology and advanced properties.
Recently a survey was published on the internet present-
ing growth opportunities in the carbon fiber market
[121]. The analysis predicts more then 10% growth per
year in certain application areas of carbon fibers and a
significant decrease in their price. Although such a de-
crease in price has been forecasted for some time, it
has never occurred; this may happen in the near future.
Similarly, a higher than average growth rate is fore-
casted in other areas of heterogeneous polymeric materi-
als, e.g. the market of compatibilizers is expected to
grow by 5.4% per year by 2005 [68]. The interest and in-
crease in the use of wood/plastic, natural fiber reinforced
and natural composites is demonstrated by several re-
ports and surveys [122–124], according to one of which
the growth rate of these materials is 12% per annum in
the US [122]. These reports clearly show that the pro-
duction of multicomponent multiphase materials is
increasing continuously and we can expect the tendency
to continue.
We hoped to show in previous sections that one of
the key factors in the development of new technologies
for the production of these materials and new combina-
tion of materials is the proper adjustment of interfacial
interactions. The importance of interactions is proven
by the numerous attempts to modify them. Some kind
of surface modification is used practically in all hetero-
geneous systems. The goal, method and solution are dif-
ferent in all cases and must be adjusted to the
components. Surface modification by non-reactive treat-
ment, coupling or any other technique is in the focus of
attention. In the case of particulate filled polymers devel-
opments in grinding and separation technology should
result in fillers with controlled particle size (contact sur-
face, deformation mechanism), while surface modifica-
tion controls the aggregation tendency of the filler.
Further progress is expected, for example, in the devel-
opment of breathable films and other high-tech prod-
ucts. Practically the same applies to polymer blends in
which compatibilizers or blending agents are used to im-
prove processability, the stability of the developed struc-
ture and properties. Better stability of the blend
structure leads to a simpler technology, single screw
extruders may be used instead of twin screw machines
[68]. Interfaces and coupling are crucial for fiber rein-
forced plastics as well. As shown above, the fastest
development is expected from natural fiber reinforced
polymers and blends containing natural polymers.
The technological relevance of controlling interac-
tions is even more important for nanocomposites. The
use of these materials is often hindered by the inade-
quacy of technology. Although layered silicates are used
in several application areas, mostly in the automotive
industry [115], the total amount used is low. General
Motors, a pioneer in the use of thermoplastic olefin
(TPO) nanocomposites, uses about 250 tons of compos-
ites per year in its various models [115]. Before a consid-
erable breakthrough is reached, better understanding of
interactions must be achieved in order to control exfoli-
ation, and generally structure. This also requires the
development of principles and methods for the proper
characterization of the multilevel structure of these
materials from the extent of exfoliation to the determi-
nation of the presence of non-exfoliated particles or clay
scaffolds. The adjustment and design of the strength of
interaction, as well as the structure and properties of
the interphase formed need further research in this area.
Interactions and their control are equally important in
carbon nanotube and nanofiber reinforced polymers.
However, the development of proper technology to align
the fibers might largely facilitate the introduction of
these composites into practice. Before this problem is
solved such composites may find application only in lim-
ited areas. The very specific role of interactions in biomi-
metic materials, as well as their particular use, requires a
completely different approach and philosophy. Never-
theless, traditional technologies may play also a role
here shown by the attempt to produce biodegradable
scaffolds for tissue engineering by injection molding
[116].
It is very difficult even to try to envisage future trends
and tendencies in this rapidly developing area. However,
a breakthrough may occur at any time in most fields as a
result of the intensive research pursued currently. Fur-
ther growth may be forecasted in traditional heteroge-
neous muticomponent materials like particulate filled
polymers, blends and fiber reinforced composites. The
application of nanocomposites might be restricted to
specific fields until a better understanding of structure–
property correlations are obtained and the improvement
of processing technology leads to lower price and better
control of properties. These materials cannot compete
with particulate filled and fiber reinforced composites
in bulk applications, like household appliances or build-
ing materials. On the other hand, their barrier properties
and improvement of flammability may find application
in several areas. Nanotechnology might be used also in
the preparation of special films and coatings. Carbon
nanotubes and nanofibers may find application in the
electric or electronic industry, or in places where anti-
static properties are needed. Carbon nanotubes improve
conductivity already at a very low concentration because
of the low percolation threshold of the thin fibers. We
expect continued interest in raw materials from renew-
able resources, and in fact in all bio-related materials.
Better understanding of interfacial interactions and the
development of proper surface modification will be a
central question as well as the driving force of develop-
ment in all of these areas.
 B. Pukánszky / European Polymer Journal 41 (2005) 645–662
5. Conclusions
Interfacial interactions and interphases play a key
role in all multicomponent materials irrespectively of
the number and type of their components or their actual
structure. Recognition of the role of the main factors
controlling interfacial adhesion and proper surface mod-
ification may lead to significant progress in many fields
of research and development, as well as in related tech-
nologies. It may be the key to reach the breakthrough in
nanocomposites the industry is waiting for, but it may
bring progress also in other areas. Although the role
and importance of interfaces and interphases are the
same for all multicomponent materials, surface modifi-
cation must be always selected according to the objec-
tives targeted, as well as to the characteristics of the
particular system. Efficient surface treatment or cou-
pling alone might not achieve the desired goal, we must
always keep in mind that an interphase forms always in
such materials and the control of interphase properties
must be part of the modification philosophy. The use
of multiphase, multicomponent materials is expected
to grow with a larger than average rate also in the fu-
ture. It is important to keep the interdisciplinary nature
of the area, since principles and techniques developed by
one field may find application also in other areas.
Acknowledgments
The author is indebted to all his colleagues, to Ágnes
Ábrányi, Lı́via Dányádi, Erika Fekete, Szilvia Klébert,
János Móczó, Péter Müller, András Pozsgay and László
Százdi, who supplied information to this publication.
The help and support of the editor of EPJ, Julius Vancsó
is also acknowledged. Research on the interfaces and
interphases of heterogeneous polymer systems going
on for many years in our laboratory is partly supported
by the National Scientific Research Fund (OTKA Grant
No. T043517).
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