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Polymer nanocomposites: Why their mechanical performance does not justify

the expectation and a possible solution to the problem?
Article in eXPRESS Polymer Letters · May 2020

DOI: 10.3144/expresspolymlett.2020.36
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eXPRESS Polymer Letters Vol.14, No.5 (2020) 436–466
Available online at www.expresspolymlett.com
https://doi.org/10.3144/expresspolymlett.2020.36
Polymer nanocomposites: Why their mechanical

performance does not justify the expectation and a possible
solution to the problem?
S. Fakirov*
The University of Auckland, Department of Mechanical Engineering, 314 Khyber Pass Road, Newmarket,
1142 Auckland, New Zealand
Received 25 September 2019; accepted in revised form 18 December 2019
Abstract. The expected order-of-magnitude enhancement in modulus (at loadings less than 1%) of polymer nanocomposites
has proven elusive – the observed improvements are 10–35% only. The failure of the concept has been attributed to poor
dispersion, poor interfacial load transfer, process-related deficiencies, and others.
Due to the inherent property of the nano-size materials, their extremely high specific surface, they tend to agglomerate, and
their further dispersion in the matrix component is practically impossible. For this reason, the composites prepared via blend-
ing a polymer with a nano-size material are microcomposites instead of nanocomposites, as demonstrated by light scattering
studies. So long as reliable tools and/or techniques for proper dispersion of nanomaterials are missing, we must use methods
free of the dispersion step in the manufacturing process.
The relatively new ‘concept of converting instead of adding’ offers two such techniques – instead to take the matrix and the
reinforcement in their final form and blend them, one takes one component only and during the processing creates the missing
second component. Both approaches result in true nanocomposites with superior mechanical performance – the improvements
of the tensile strength for nanofibrillar polymer-polymer and single polymer composites are up to 200 and 440%, respectively,
(or even up to 650% if trans-reaction catalyst is used).
Keywords: polymer nanocomposites, mechanical performance, dispersion problem, concept ‘converting instead of adding’,
nanofibrillar polymer-polymer composites
1. Introduction one or more external dimensions is in the size range

Nanomaterials are generally considered as a discov- 1–100 nm …’ [2].
ery of modern science. In fact, they have a very long A common characteristic feature of all nano-sized
history – nanoparticles have been used by artisans as materials, regardless of their chemical composition
far back as the ninth century in Mesopotamia for gen- and method of manufacturing, is the extremely in-
erating a glittering effect on the surface of pots. The creased ratio of surface area to volume. For example,
peculiarities of nanomaterials arise mainly from their 1 kg of particles of 1 mm3 has the same surface area
sizes, which are usually defined as smaller than one- as 1 mg of particles of 1 nm3. The natural tendency to
tenth of a micrometer in at least one dimension [1]. reduce this free surface is the driving force for ag-
In 2011 the European Commission adopted the fol- glomeration of nanoparticles in larger formations.
lowing definition of a nanomaterial: ‘… 50% or Discovery with a revolutionary effect in the nano-
more of the particles in the number size distribution, science was that of Iijima [3] who prepared carbon
*
Corresponding author, e-mail: s.fakirov@auckland.ac.nz
© BME-PT
436
Fakirov – eXPRESS Polymer Letters Vol.14, No.5 (2020) 436–466
nanotubes (CNTs). It turned out that this all-carbon polymers to improve the interfacial adhesion. They
material is the most ideal material ever created – it reported mechanical properties (Young’s modulus
has the highest heat conductivity, highest electrical and tensile strength) only 20–25% higher than those
conductivity, the highest mechanical properties, etc. of the neat PP [7].
and thus attracted the attention of researchers from The above conclusions were supported by the state-
various fields, including polymer science and tech- ments of Schaefer and Justice in their review ‘How
nology. For example, with tensile moduli in the ter- Nano Are Nanocomposites?’ [4]: ‘Composite mate-
apascal range and lengths exceeding 10 μm of car- rials loaded with nanometer-sized reinforcing fillers
bon nanotubes, simple composite models predict are widely believed to have the potential to push
order-of-magnitude enhancement in modulus at polymer mechanical properties to extreme values.
loadings less than 1%. For this reason, a couple of Realization of anticipated properties, however, has
decades ago, it was believed that the most common proven elusive’.
polymer composites comprising about 30% glass Finally, let me mention in this respect the statement
fibers will be replaced by the nanocomposites having in a recent review on the practical applicability of
only 2–5% nano-sized filler as reinforcement! polymer nanocomposites [8]: ‘Initial developments
Unfortunately, this expectation turned out to be elu- of nanocomposite thermosets focused on high aspect
sive. ratio nanoparticles such as nanoclays, carbon nano-
tubes and more recently graphene. Generally, these
2. The reality regarding the mechanical systems showed 10–35% improvement in mechanical
performance of polymer nanocomposites properties with 0.2–5 wt% filler. However, the trans-
As mentioned above, such systems have attracted lation of these improvements to prepregs or lami-
enormous interest from the materials community be- nates proved to be difficult due to processing issues,
cause they theoretically promise a substantial im- including extremely high viscosity, nanoparticle fil-
provement of mechanical properties at very low tration, nanoparticles agglomeration, and void for-
filler loadings. Besides, polymer nanocomposites are mation.’
compatible with conventional polymer processing, It seems rather realistic to assume that polymer
thus avoiding costly layup required for the fabrica- nanocomposites prepared via melt blending of the
tion of conventional fiber-reinforced composites. two basic components, the matrix, and the reinforce-
‘Introductory paragraphs similar to the above can ment, are characterized by a maximum improvement
be found in hundreds of nanocomposite papers. With of their mechanical properties by 30–35% as com-
the exception of reinforced elastomers, nanocompos- pared with the respective neat isotropic matrix. Such
ites have not lived up to expectations. Although claims a result is quite far from the expected 10-fold (at
of modulus enhancement by factors of 10 exist, these least!) improvement.
claims are offset by measurements that show little or An interesting question regarding the reasons for this
no improvement… The lacklustre performance of drastic discrepancy arises.
nanocomposites has been attributed to a number of The concept of polymer nanocomposites, that is, the
factors including poor dispersion, poor interfacial expectation that using 1–5 wt% of nanofiller instead
load transfer, process-related deficiencies, and oth- of the common 30–40 wt%, it will be possible to re-
ers’ [4]. alize improvements of an order of magnitude as
Discussing the mechanical behavior of polymer compared with the traditional composites materials
nanocomposites it should be stressed that an im- as well as to enhance the environmental impact of
provement of 20% (for tensile strength) and 50% these materials failed for the following reasons [4]:
(for the modulus of elasticity) is quite typical for all (i) Poor dispersion
polymer nanocomposites [5]. According to Bousmi- (ii) Poor interfacial load transfer
na [6], only in exceptional circumstances can one (iii) Process-related deficiencies
observe an improvement greater than 30% in the me- (iv) Poor alignment
chanical performance of nanocomposites. More (v) Poor load transfer to the interior of filler bundles
specifically, Zhang et al. [7] studied thoroughly the (vi) The fractal nature of filler clusters.
case of polypropylene (PP)/SiO2 nanocomposites in Nowadays, a rather large number of nano-sized ma-
which the nanoparticles have been coated by various terials are available, and nevertheless, the preparation
437
of true nanocomposites is not an easy task. The basic instead of blending the polymer with nanofillers. In
problem in the manufacturing of polymer nanocom- this way, avoiding the practically non-soluble prob-
posites is the dispersion in the matrix material of the lem of proper dispersion the SEM observations
reinforcing component to single nanoparticles. Due demonstrate that in the nano-fibrillar polymer-poly-
to the inherent property of the nano-sized materials, mer and single polymer composites, the reinforcing
namely, the extremely high specific surface, they nanofibrils (with diameters between 50 and 250 nm!)
tend to agglomerate and their further dispersion in are dispersed to single nanoparticles – no aggregates
the matrix component is practically impossible. In of them are observed.
this respect, it seems useful to cite here the opinion As a matter of fact, the single polymer and polymer-
of Greiner and Wendorff [9] expressed in their ex- polymer composites are favoured since they offer the
cellent review on electrospinning as a method for the opportunity for demonstration of how we can solve
preparation of ultrathin fibers and their application the currently non-soluble problem regarding the prop-
as reinforcing material for nanocomposites. After er dispersion of the reinforcing nanomaterials in the
listing the advantages of the electrospun nanofibers polymer matrix. It is to be stressed that the suggested
as reinforcement over macroscopic fibers as owing approach for avoiding the dispersion step in the prepa-
to their extremely high aspect ratio, little refraction ration of polymer nanocomposites is currently appli-
of light (due to the small diameters) resulting in cable to single polymer and polymer-polymer com-
transparent reinforced matrices, the authors [9] con- posites only.
clude: ‘Given the advantages of nanofibers for rein-
forcement, the number of investigations on this topic 3. Do polymer nanocomposites prepared via
is rather small. The main problems, to which there is blending a polymer with nanomaterial
no convincing solution, yet, are the dispersion of the really exist?
electrospun nanofiber webs and the control of the Such question sounds rather provocative but if we
nanofiber orientation in the polymer matrix. remember the criteria according to which composite
The felt-mat structure of the nonwoven is, for the materials are categorized, we will see that the ques-
most part, maintained upon the incorporation of the tion is quite reasonable [11]. Depending on the sizes
nanofibers into the matrix. Attempts to disperse sin- of the reinforcing filler we distinguish between
gle nanofibers from the nonwoven mats using ultra- macrocomposites (the common ones), microcompos-
sound, kneaders, or high-speed stirrers have only ites when the sizes are in the micrometer range and
been marginally successful. Very similar problems nanocomposites if the single reinforcing particles are
occurred in matrix reinforcement with carbon nan- nano-size particles, i.e. with dimensions below
otubes and nanofilaments [10]’ [9]. 100 nm or around this size.
Obviously, in addition to the attempts for solving of Dealing with this ‘terminological’ issue, it seems im-
the above-formulated problems, new routes to the portant to be reminded how polymer nanocompos-
same target – the creation of polymer nanocomposites are prepared [12]. The most common practice is
ites – must be researched. The main targets of this to blend a polymer (the matrix) with nano-size ma-
review article are two. The first one is to collect terial (reinforcement) and to use as the title of paper
enough proof from the literature demonstrating that the modern word ‘nanocomposite.’ In rare cases, at-
polymer composites prepared via blending the ma- tempts are undertaken to determine the degree of dis-
trix and the nanomaterials are not NANO- but MI- persion and if this is done, it is by using electron mi-
CROcomposites due to the non-proper dispersion (to croscopy. Usually, 2–3 micrographs are incorporated
single nanoparticles!). For this purpose, only results demonstrating a couple of nano-size particles, which
of scattering techniques being relevant for this task show how these particles look. At the same time,
must be used and not electron microscopic observa- these photographs offer no information about their
tions being an inappropriate technique for this pur- amount in the sample. The question regarding the
pose. The second task is to offer an example of how degree of dispersion is not addressed. Such informa-
one could avoid the difficult step of reinforcement tion can be obtained by using scattering techniques
dispersion. This can be achieved via the application – X-ray, neutron scattering, etc. This important detail
of the new converting instead of adding concept, i.e. is also stressed in the recent review on the practical
converting the bulk polymer into nano-size material applicability of polymer nanocomposites [8].
438
It should be added that electron microscopy also re- is good, i.e., up to single nanoparticles, the transparen-
veals rather large aggregates of nanoparticles with cy should not be different from that of the matrix,
sizes closer to the micrometer range rather than to that is, the transmission of the light must be 100%.
the nanometre size. Their existence is to be expected This situation is due to the known fact that light scat-
considering the extremely strong tendency of nano- tering can be observed only if particles have sizes in
size materials to reduce the surface energy via ag- the range of the size of the wavelength of the used
glomeration. Due to the nanoscale structure and Van light, which for the common light is 500–600 nm.
der Waals forces, nanoparticles have shown a great Let look at the results of such studies summarized in
tendency to self-aggregation, self-agglomeration and Table 1. For example, nanocomposites have been
self-assembly making their dispersion into the poly- manufactured from completely transparent at-PMMA
mer matrices very difficult. In contrast, nanoscale (100% transmission of the light) and nano-size ZnO
dispersion is a critical requirement to take the full (particles of 75 nm in concentration 1 wt%). The used
advantage of nanoparticles in polymer nanocompos- light was with wavelength λ = 600 nm. The meas-
ites [13–16]. The question is if these aggregates dom- ured amount of transmitted light is only 2% but it in-
inate in the sample. The answer can be found if we creases up to 50% if the concentration of the filler
return to the scattering techniques, for example, light drops to 0.01% (Sample # 2, Table 1).
scattering. It should be mentioned that in all cited cases (Table 1)
There are polymers that are completely transparent, the thickness of the samples subjected to light trans-
i.e. they let the light trough on 100% as, for example, mission measurement has been between 1 and 4 mm.
atactic poly(methyl methacrylate) (at-PMMA), atac- From the data presented in Table 1 one can conclude
tic polystyrene (at-PS) and, to some extent, polycar- that: (i) the polymers used as matrix are inherently
bonates (PC) and polyarylates (PAr). They can be completely transparent materials, (ii) the reinforcing
used as a matrix for preparation of transparent nano- nanomaterials used have dimensions below 100 nm
composites via blending with nano-size fillers. (typically a couple of nm for the majority of cases),
The nanomaterials of inorganic origin have typical and (iii) for the light transmission measurement a light
sizes below 100 nm and, in many cases around 2– with a wavelength between 500 and 600 nm has been
5 nm. If the dispersion during mixing with the matrix used. If the studied composites are really polymer
Table 1. Examples of light transmission of polymer nanocomposites where the matrix is inherently transparent material (light
transmission of 100%) (Adapted from Fakirov S.: Nanofibrillar polymer–polymer and single polymer composites
via the ‘converting instead of adding’ concept – examples of true polymer nanocomposite. Advanced Industrial and
Engineering Polymer Research, 1, 40–47 (2018), [11]).
# Transmission of light Specimen thickness Filling degree Filler size Ref.
Matrix of at-PMMA
1. 95% (600 nm, 20 wt%) Thin 0–20 wt% ZrO2/SiO2 (<100 nm) [17]
2. 2% (1 wt%, 600 nm) 3.5 mm up to 1 wt% ZnO (75 nm) [18]
50% (0.01 wt%) 0.01 wt%
<90% (0.01 wt%, prepolymer) 0.01 wt%
3. 80% (600 nm, 15 wt%) – 0–15 wt% ZrO2 (4 nm) [19]
4. 90% (600 nm) 4 mm 0.5 wt% ZnO (2.3 nm) [20]
5. >85%, above 400 nm 0.127 mm 0.26 wt% SWNT [21]
6. Increased absorb. >600 nm – 100–300 μm – Fe2O3 (8–200 nm) [22]
Matrix of at-PS
7. Good, brown coloured, 550 nm 1 mm 3–15 wt% Fe3O 410×50 nm [23]
8. ‘Quite’ transparent, >550 nm 100 μm 5–15 wt% Fe3O 410×50 nm [24]
9. Decreases to 75% (20 wt%) 2.5 μm up to 95 wt% CeO (20 nm) [24]
10. High 20 nm (LED) Zn: 8.2, Cu: 0.12 wt% ZnS:Cu (3 nm) [25]
Matrix of other transparent polymers (PC, PAr)
11. 80% (2 wt%, 600 nm) 0.15 mm 2 wt% AlO2 (whisker) [26]
12. 52% (1 wt%, 600 nm) 2 mm 1 or 2 wt% Al2O3 (96 nm) [27]
13 87% (600 nm, 15 wt%) 0.12–0.29 mm 0–15 wt% Al2O3 [28]
439
nanocomposites, i.e. materials in which the reinforc- others). The other peculiarity is that contrasting the
ing component is dispersed to single nanoparticles, studies summarized in Table 1, where the trans-
these composites should have the same transparency parency for one wavelength only is studied, in [29]
as the neat matrices since the single particles are too the cases cover quite a large interval of wavelengths
small to scatter. The reduction in transparency and for this reason, the transparency is presented also
(Table 1) means that the particles in the matrix are as an interval usually between 5–40 and 70–95% [29].
much larger, approaching the size of the wavelength In Table 2 are listed some examples of transparent
of the light used (500–600 nm), i.e. one deals prac- nanocomposites with various matrices and nano-
tically with large aggregates of nanoparticles. fillers indicating the size of the used nanoparticles
The described situation was also discussed in a very as fillers as well as the interval of transparency meas-
recent review [29] on transparent polymer nanocom- ured with lights of a different wavelength. In addi-
posites with emphasis on their synthesis and ad- tion to the completely transparent matrices as PMMA,
vanced properties. The review comprises the follow- PS, and PC the poly(ethylene terephthalate) (PET)
ing text as a general statement: ‘The dispersion of is included.
particles and their affinity with the matrix are cru- It is quite evident from Table 2 that the transparency
cial parameters that closely control global proper- capacity of the polymer nanocomposites covers a
ties of nanocomposites. For optimal transparency, rather wide percentage interval depending on the
nanocomposites require particles with dimensions D wavelength of the used light. This dependence is
very small compared to the wavelength λ (D/λ << 1). much better expressed in Figure 1 where the trans-
This condition can only be respected if primary par- parency is plotted as a function of the wavelength of
ticles are synthesized in such dimensions and if ag- the light used.
gregation is avoided. A challenge for nanocomposite As seen in Figure 1, generally, the transmittance in-
fabrication is to incorporate well-dispersed isolated creases with the rise of the wavelength. It is the small-
particles into the polymer matrix and to improve in- est for the shortest wavelengths (below 350 nm). The
terfacial interactions between matrix and fillers. PC-R-Al2O3-2% nanocomposite film with PC ma-
However, due to their high specific surface area and trix and 2 wt% of nano-size Al2O3 (Figure 1, curve f)
surface interactions often involving polar groups lo- is less transparent over most of the wavelength range
cated at the surface, nanoparticles have a strong ten- for visible light. The authors [26] explain this obser-
dency to aggregate’ [29]. vation by the presence of large agglomerates of raw
A peculiarity of this review article [29] is that the alumina nanowhiskers in the composite film, result-
transparent nanocomposites are categorized according from poor compatibility with PC matrix. These
ing to the other targeted property (mechanical per- large aggregates have comparable sizes to the wave-
formance, thermal stability, barrier properties, and length of visible light (380–750 nm), which would
Table 2. Transparent polymer nanocomposites.
Nanoparticles size Transparency (UV–Vis) NP content
# Polymer matrix Thickness Ref.
[nm] [%] [wt%]
1. PC Coated Al2O3 (96 or 30 nm) From 5 to 60 2 mm 1 to 2 [27]
2. PC Al2O3 (dia. 2–4 nm, l = 2800 nm) From 50 to 80 0.15 mm 2 [26]
3. PET TiO2 From 5 to 40 80 μm 1 to 5 [29]
4. PMMA Clay From 78 to 90 100 μm 1 to 5 [30]
5. PMMA ZrO2 (3.8 nm) From 70 to 85 1 mm Up to 7 [31]
6. PMMA ZnS (3 nm) From 25 to 90 4 mm 5 to 15 [32]
7. PMMA SiO2 From 30 to 90 ~1 mm 4 to 8 [33]
8. PS (grafted) From 20 to 70 70 μm Up to 1.05 [34]
9. PS TiO2 From 5 to 80 100–200 μm 5 to 20 [35]
10. PMMA Clay From 10 to 68 3mm 0.39 to 4.60 [36]
11. PS ZnO (5–35 nm) From 40 to 80 64–68 μm 0 to 9 [37]
12. PS CeO2 (18 nm) From 60 to 80 2.5 μm 5 [38]
13. PMMA TiO2 (33 nm) From 55 to 80 2.35 μm 1 to 5 [39]
14. PS Doped CeF3 (42 nm) From 30 to 75 0.1 mm Up to 20 [40]
440
Figure 1. UV-visible spectra of: (a) extruded plain PC, Figure 2. Light transmittance at various wavelength of the
(b) PC-Al2O3-RT-0.5%, (c) plain PC, (d) PC- light used of melt compounded PC/Al2O3 nano-
Al2O3-RT-1%, (e) PC-Al2O3-RT-2%, (f) PC-R- composites: a) PC neat resin, b) PC with 1 wt%
Al2O3-2% (Adapted from: Hakimelahi H. R., Hu nanoparticles of 96 nm subjected to centrifuge treat-
L., Rupp B. B., Coleman M. R.: Synthesis and ment, as well as PC with 1 wt% nanoparticles of
characterization of transparent alumina reinforced 30 nm subjected to centrifuge treatment, c) PC with
polycarbonate nanocomposite. Polymer, 51, 2494– 2 wt% nanoparticles of 96 nm subjected to cen-
2502 (2010), [26]). trifuge treatment, d) PC with 2 wt% nanoparticles
of 30 nm subjected to centrifuge treatment, e) PC
result in scattering at the interface between alumina- with 2 wt% nanoparticles of 96 nm not subjected to
rich and polymer-rich phases [41]. centrifuge treatment (Adapted from Chandra A.,
The other important conclusion from Figure 1 is that Turng L-S., Li K., Huang H-X.: Fracture behavior
and optical properties of melt compounded semi-
the transparency for the shorter wavelengths is much
transparent polycarbonate (PC)/alumina nanocom-
lower. This means that in the nanocomposite mate- posites. Composites Part A: Applied Science and
rials are dominated by particle aggregates with di- Manufacturing, 42, 1903–1909 (2011), [27]).
mensions between 100 and 300 nm, which do not
scatter anymore if the wavelengths increase to 500– 30 or 96 nm and depends on their concentration only
800 nm, and the transparency increases drastically (Figure 2, curves b–e).
too (above 70%) (Figure 1). At the same time, the It seems important to mention that the transparent
typical sizes of the inorganic nanomaterials are of a nanocomposites discussed in [29] are prepared using
couple of nm (Tables 1 and 2) and the aggregates different fabrication methods aiming at proper nano-
with sizes of 100–300 nm should comprise many particle dispersion as well as perfect matrix-filler ad-
tens of nanoparticles, which means, the composite hesion. The methods used are: (i) blending method-
material does not consist of individual nanoparticles. ology (melt blending or solution blending) [27, 30,
This situation is illustrated in Figure 2 as well, where 35, 42–66]; (ii) in situ polymerization in the pres-
PC is melt-blended with nano-sized Al2O3 with sizes ence of inorganic particles [67–81]; (iii) in situ par-
of 96 or 30 nm, and the used light is of wavelength ticle formation in preformed polymer matrix [82–
in the interval 300 and 700 nm. 112]; (iv) simultaneous in situ particle and polymer
From Figure 2 it is easy to see that at a wavelength matrix formation [113–124]; (v) casting of polymer
shorter than 400 nm the transparency is extremely solution loaded with core-shell nanoparticles [52,
small (up to 25%, Figure 2 curve b) or approaching 120, 121, 125–132]. However, these techniques are
zero (Figure 2, curves c, d, e). Even for λ = 500– very complex. They use solvents, high temperatures,
700 nm it approaches 35–40% transparency only additional chemicals, and others, making the control
(Figure 2, curves c, d, e). These observations indi- of particle sizes and their distribution uneasy. For ex-
cate that the nanoparticles do not exist anymore in ample, the very promising and attractively looking
the PC matrix as individual particles but as their ag- method of simultaneous in situ particle and polymer
gregates with sizes of a couple of hundreds of nm. matrix formation used for the preparation of trans-
Possibly, this is the reason why the transmittance parent PMMA/SiO2 nanocomposites via polymer-
does not depend on the size of individual nanoparti- ization of w/o microemulsions [121] did not justify
cles. The transmittance is the same for particles of the expectations. It has been reported [121]: ‘…. that
441
the transmittance of the composite (1.33 wt% SiO2)

is very close to that of pure PMMA. A significant
loss in transparency is detected only below λ =
500 nm. For higher filler contents, a loss of trans-
mittance is also observed in the visible region (at
6.67% filler, the transmittance is only 33% and the
products are turbid). The sharp drop in transmit-
tance is due to the instability of the particle-contain-
ing microemulsion at higher filler contents and the
formation of agglomerates during the polymeriza-
tion and hydrolysis of the precursor. The reduced
transmittance is also observed in MMA-based sili-
Figure 3. Tensile strength of injection molded samples from
ca-free microemulsions after polymerization. The recycled PET (bottles) and LDPE as compared to
microemulsion used for the generation of a 4% neat LDPE and LDPE reinforced by short-glass
SiO2-containing composite has a transmittance of fibers (GF) or glass spheres (GSph) [136].
only 78% after polymerization, whereas the poly-
merized microemulsion corresponding to the 6.67% in this way nanoparticles are always isodiametric
SiO2-containing composite only has a transmittance and never fiber-like [42–132].
of 50% (600 nm)…’ [121]. Summarizing, we conclude that to observe a rein-
In addition to the dispersion problem, let us not for- forcing effect, we must use reinforcing material in
get some basic knowledge of composite science re- the form of fibers. For manufacturing of polymer
garding the effect of reinforcing particle shape on nanocomposites good candidates in this respect are
the enhancement of mechanical properties of com- the electrospun fibers or, even better, the carbon
posite materials. Some of the properties, e.g. elastic- nanotubes (CNTs), or nanowhiskers but in these
ity modulus E, microhardness H [133] of polymers, cases, we face again the non-soluble problem of the
and their composites obey the Rule of mixture. proper dispersion, dispersion in the matrix to single
Contrasting E and H, the tensile strength σ does not individual nanoparticles without any agglomera-
obey the Rule of mixture. What is more, its enhance- tion! However, dispersion of non-spherical nano-
ment can be observed only if the reinforcing particles particles is a very challenging issue and sometimes
are strongly anisometric, that is, their aspect ratio may lead to deterioration of nanoparticles during
must not be smaller than 6, as demonstrated by mod- the mixing process. For instance, as-synthesized
eling [134, 135] and experimental [136, 137] studies. CNTs form agglomerates consisting of severely en-
This situation is illustrated in Figure 3 for low density tangled nanorods which should be fully disentan-
polyethylene (LDPE) reinforced with glass fibers gled during the mixing process, that is not easily
(Figure 3, second column) or glass spheres (Figure 3, met for polymer-CNT nanocomposites. It was shown
third column) used in equal amounts [136]. that the dispersion of CNT is achieved by fragmen-
From these considerations follows a quite interesting tation of bigger agglomerates to smaller agglomer-
conclusion regarding the reinforcing potential of ates mainly through the rupture mechanism during
nano-size materials whose particle have an aspect melt mixing process [138]; however, the shear
ratio close to 1, i.e., their length and thickness are al- stresses exerted on CNT agglomerates cause a sig-
most of the same size. Considering that practically all nificant fiber breakage during the rupture of ag-
inorganic nanomaterials (rare exceptions are the nano- glomerates which seriously decreases the effective-
whiskers) are isodiametric (with aspect ratios close ness of CNT [138, 139]. Moreover, in many systems,
to 1, Tables 1 and 2), it follows that this fact only is a at high nanotube concentrations, where the aggre-
good reason for their modest mechanical performance gation is developed, the effects of poor dispersion
experimentally observed. Obviously, this is the main are generally accompanied by a decrease in strength
reason for the poor mechanical properties of trans- and modulus [140].
parent nanocomposites prepared via methods avoid- Coming back to the terminological issue it should be
ing mechanical blending of the matrix polymer and noticed that it is hardly correct to classify the above-
the reinforcing nanomaterial [42–132] – the created discussed composites as ‘nanocomposites’ because
442
they, in fact, belong to the category of microcompos-

ites. If we agree with such a statement, a quite im-
portant conclusion can be derived regarding the an-
swer to the very basic question about the drastic
difference between expected and observed mechan-
ical properties of the polymer nanocomposites pre-
pared via blending matrix and reinforcement. These
materials do not justify the expectations derived for
nanocomposites concept because they are not nano-
composites – they are microcomposites. The situa-
tion is quite interesting because it could be consid-
ered from its reverse side – the lack of agreement
Figure 4. Schematic: a) good distribution, poor dispersion,
between observed and predicted mechanical prop-
b) good dispersion, poor distribution, c) stabiliza-
erties support the conclusion that these composites tion. (Adapted from a) and b) Celzard A., McRae
are not of nano-type. Moreover, this can be proven E., Deleuze C., Dufort M., Furdin G. Mareche J. F.:
if we succeed to prepare real polymer nanocompos- Critical concentration in percolating systems con-
ites and measure their mechanical properties as it taining a high-aspect-ratio filler. Journal of Phys-
will be demonstrated in the further paragraphs of this ical Review B, 53, 6209–6214 (1996) ; c) Wu L.,
Glebe U., Boeker A.: Surface-initiated controlled
review.
radical polymerizations from silica nanoparticles,
gold nanocrystals, and bionanoparticles. Polymer
4. The dispersion – a global problem in Chemistry, 6, 5143–5184 (2015), [142]).
chemistry and in material science
The practical needs of materials with new or im- should be avoided as many particles would be use-
proved properties lead to blending two or more dif- less because behaving as dead ends for the conduct-
ferent materials in order to drastically improve the ing path.
properties of one of the components or to obtain a Regardless of how the dispersed system is prepared,
blend with new properties. For a long time this ap- it needs to be stabilized since the dispersed particles
proach has been used in metallurgy and since the tend to agglomerate. How the stabilization could be
middle of the last century, it has been introduced to done is shown in Figure 4c.
polymer material science. The stability of a polymer dispersion is its most im-
Usually, the matrix component is dominating in portant property. There are three different mecha-
amount, and it is presented in a continuous form while nisms that impart stability to polymer dispersions:
the other minor component(s) is in form of small (i) the electrostatic stabilization with either positive
(micro- or nano-range) particles or fibers. Such a dis- or negative charges on the particle surface arising
persed system has three fundamental aspects: (i) dis- from the initiator or ionic comonomers, (ii) the
persion, (ii) distribution, and (iii) stabilization. steric stabilization with adsorbed or tethered poly-
Distribution is the way the particles fill the space, mers that are soluble in the dispersion medium, and
whereas dispersion is the way these particles are ag- (iii) the electrosteric stabilization that is either a
glomerated or not. With a good distribution, each par- simple combination of electrostatic and steric stabi-
ticle is as far as possible from its nearest neighbor, so lization or a stabilization with adsorbed or tethered
that space is homogeneously filled with particles. polyelectrolytes. The search for new stabilizers is
With a good dispersion, all particles have the same an important area in colloid research. A hairy parti-
shape and size, as small as possible, as no agglomer- cle stabilized by polymeric surfactants (Figure 4c)
ates exist. Therefore, it is quite possible to have good is illustrating a topic of such research. The prepara-
distribution but poor dispersion, or poor distribution tion of model particles with only one kind of stabi-
and good dispersion, as schematically demonstrated lization – exclusively steric or exclusively electro-
in Figure 4. If particles are conducting and if you static stabilized particles – is another goal of these
want a high conductivity, you should indeed prefer activities [143].
the situation in which particles can make a conduct- Let us remember what thermodynamics says about
ing path by touching each other, but agglomeration dispersed systems.
443
It is well-known that dissolution is one of the cases of entropy of mixing, Sid. For an ideal solution, the
dispersion, that is, the dispersing of one component change in isobar-isothermal potential ∆G (called
into another one. The multi-component systems, in also free energy at constant pressure or Gibbs free
which some of the components are in a dispersed energy, on whose change depends the possibility for
state, are dispersed systems. Depending on the de- realization of the process) can be expressed as
gree of dispersion, they can be colloid systems or (Equation (2)):
true solutions. True solutions are dispersed systems
in which the components are dispersed as molecules, DGmix = RT R n1 ln x1 + n2 ln x2 W (2)
atoms, and ions. Consequently, the true solution rep-
resents a molecularly dispersed system distinguished where R is the gas constant, T is absolute tempera-
by a couple of characteristic features such as affinity ture, n1, and n2 are the number of moles of the com-
of components, constant concentration in the time, ponents 1 and 2, respectively, and x1, and x2 are
homogeneity (one-phase systems!), and thermody- molar parts of components 1 and 2, respectively
namic stability. [e.g., x1 = n1/(n1 + n2)]. Using the last equation, it is
Dissolution as a self-running equilibrium process is easy to express the change in the ideal mixing en-
possible only if its progress is paralleled by a de- tropy ∆S considering that ∆G = ∆H – T∆S and that
crease in the free energy F (at V: constant and T: H = 0 (ideal solution, i.e., ∆Q = 0) (Equation (3)):
constant) or by reducing the isobar-isothermal po-
tential G (at p: constant and T constant). DSmix =- R R n1 ln x1 + n2 ln x2 W (3)
The change in free energy ∆F at T: constant obeys the
Equation (1): Since the molar parts x are always smaller than 1,
their logarithms are negative. Consequently, the ex-
DF = DH - TDS (1) pression in the bracket in Equation (3) remains neg-
ative in all cases, and ∆Smix is always positive. This
According to this equation, dissolution is possible at means that mixing always results in entropy in-
constant temperature both when the enthalpy of the crease, that is, an increase of degrees of freedom. In
system ∆H decreases and when the entropy ∆S in- other words, the entropy change during mixing is
creases. such that it always results in the spontaneous mixing
It is known that the dissolution of polar polymers in of components in any ratio.
polar solvents takes place with heat development, While the change of ideal mixing entropy can be cal-
that is, the heat effect (Q) is positive. From the other culated also by means of a statistical approach using
side, ∆H = –Q, consequently ∆H < 0 and ∆F < 0. a lattice model, Flory and Huggins suggested simul-
The heat development during dissolving is associat- taneously and independently (in 1942) another, some-
ed with the formation of strong bonds between mol- what different (but not free of some empiricism) ap-
ecules of solvent and those of polymer (for example, proach for solving the same problem. The Flory-
due to the formation of H-bonds). By the way, this Huggins theory has great importance for explaining
positive heat effect can explain the spontaneous dis- the severe deviations of polymer solutions from the
solution of polar polymers into polar solvents. ideal laws [144].
The experiments on solutions of non-polar polymers Unfortunately, the above thermodynamic consider-
in non-polar solvents demonstrated that the degree ations cannot be applied to polymer dispersions being
of solvation is negligibly small, and the heat effect of interest for material science because they are com-
tends to be zero. In case of such solutions ∆H = 0 posed of components that are not thermodynamical-
(Q = 0). Dissolution with zero or negative heat effect ly miscible, i.e. they are not molecularly dispersed
can be explained only by an increase in the entropy systems. For this reason, contrasting the true solu-
of the system during the mixing of solution compo- tions, they are characterized by the following char-
nents and their mutual diffusion. acteristic features:
In the case when the solution is ideal, that is, when – lack of affinity of components resulting in the lack
the molecules of a dissolved substance do not inter- of self-dispersing process,
act, it is possible to calculate the entropy increase – lack of constant concentration in the time due to
of the system as a result of mixing getting the ideal the continuous dephasing and/or sedimentation,
444
– lack of homogeneity (not being one-phase sys- [145]. In a study on understanding the microstruc-
tems!) leading to dephasing, and ture of particle dispersion in confined copolymer
– lack of thermodynamic stability resulting in the nanocomposites [146] it has been shown that, under
need of stabilization. the condition of confinement, particles display dif-
The preparation of dispersed systems for the needs ferent distributions near the solid surfaces, in the mi-
of polymer material science and technology is a task crodomains of two blocks, and at the microphase in-
somewhat different from the preparation of polymer terfaces. The final dispersion depends on the balance
solutions – work is needed to convert the bulk ma- between the enthalpic contribution arising from the
terial into micro- or nano-sized particles, additional particle-segment attraction as well as the entropy-
work has to be invested for dispersing these particles driven depletion attraction induced by the polymer
into polymer matrix, and finally, a stabilization is conformation and the confinement environment. For
needed to keep the desired dispersity. These tasks the systems in which particles weakly attract one
have been attacked since the emergence of colloid block but repel another block, particle dispersion can
chemistry (middle of the 19th century). In fact, the be enhanced by the increasing confinement effect,
areas of ‘understanding the governing parameters and the enhancement becomes more evident as the
that control particle dispersion’, ‘synthetic method- size asymmetries of particles and two blocks in-
ologies to modify particle interfaces’, the ‘role of increase. If the attraction increases, however, particle
terface chemistry on particle dispersion’, ‘transpar- dispersion declines as the confinement effect in-
ent nanocomposites’. etc. have seen tremendous creases [146]. At the same time, as stated in the same
advancements during the recent decades. Examples publication [146], confinement induced particle dis-
of these advances include Flory lattice models and persion in copolymer films is far from being under-
computer simulations that have an advanced under- stood. For a confined copolymer nanocomposite, be-
standing of the role of structural and interaction pa- cause of the microphase separation of the copolymer
rameters on the stability of particle-in-polymer dis- and the physically confined environment, the state of
persions. Surface-initiated controlled polymerizations particle dispersion becomes more complex [146].
have shown to facilitate stable dispersions and trans- In the attempts for synthetic modification of particle
parent materials. This is not to say that all problems interfaces, the emulsion polymerization is the most
have been solved; however, the purpose of this sec- widely used synthetic technique [147]. Emulsion
tion is to provide readers with state-of-the-art and polymerization, as a traditionally leading synthesis
more nuanced overview of the advances and limita- technique, has been widely used for the synthesis of
tions of this field. polymeric particles [148]. However, spherical parti-
The superior properties of nanoparticles themselves cles are often formed because of interfacial tension
do not assure high-performance polymer nanocom- [149], which limits flexibility in tuning the topology
posites at all; however, morphological characteristics and chemistry of the particles. Achieving large-scale
of corresponding polymer nanocomposites have also synthesis of uniform Janus particles with tunable
a prime impact on the final properties. Basically, the topology and surface chemistry by emulsion poly-
dispersion state of nanoparticles in polymer matrices merization remains a great challenge [147].
is dominated primarily by mixing processes; how- Dispersion polymerization is a convenient procedure
ever, surface characteristics of nanoparticles can also to form larger solid particles. Uniform-sized polymer
facilitate the breakdown of the agglomerates result- beads with diameters between 0.1 and 10 µm are find-
ing in better dispersion. Surface characteristics can ing an ever-increasing role in several coatings, elec-
be tailored basically by suitable surface modification tronics, microelectronics, biomedical, and information
of nanoparticles which can be helpful to overcome technology applications. Particle size control and nar-
its incompatibility with hosting polymer and to ob- row size distribution are critical parameters for most
tain strong polymer/nanoparticles interfacial inter- of these applications. Dispersion polymerization is
action [16]. generally recognized as a type of precipitation poly-
Nowadays it is well recognized that the mixing of merization, conducted in the presence of a polymeric
polymers and nanoparticles is paving the way for en- stabilizer that is soluble in the reaction medium [150].
gineering flexible composites that exhibit advanta- As already mentioned, because of their unique size-
geous electrical, optical, or mechanical properties dependent electrical, magnetic, mechanical, optical,
445
and chemical properties, which widely differ from radical polymerization techniques [142] is highlight-
those of the bulk materials, nanoparticles have al- ed that in recent years, core/shell nanohybrids con-
ready become an indispensable material for many in- taining a nanoparticle core and a distinct surrounding
dustrial fields. Nanoparticles have different surface shell of polymer brushes have received extensive at-
structures and surface interactions from those of the tention in nanoelectronics, nanophotonics, catalysis,
sub-micron sized particles; in particular, they show nanopatterning, drug delivery, biosensing, and many
a much stronger aggregation tendency. For applica- others. From the large variety of existing polymer-
tions in functional materials and products, it is im- ization methods on the one hand and strategies for
portant to develop techniques for controlling the dis- grafting onto nanoparticle surfaces, on the other
persion and aggregation of nanoparticles. Dispersion hand, the combination of grafting-from with con-
of nanoparticles in aqueous media can well be mod- trolled radical polymerization techniques has turned
eled with the theory by Deryagin, Landau, Verwey out to be the best suited for synthesizing these well-
and Overbeek (DLVO). However, it is still a chal- defined core/shell nanohybrids and is known as sur-
lenging task to manage high-concentration nanopar- face-initiated controlled radical polymerization.
ticle suspensions in organic media. Surface modifi- Most common among these are surface-initiated
cation of nanoparticles is one of the most common atom transfer radical polymerization (ATRP), sur-
methods to improve the dispersion stability of nano- face-initiated reversible addition-fragmentation
particles. It requires a design of the surface structure chain transfer (RAFT) polymerization, and surface-
based on the type of nanoparticles and the liquid initiated nitroxide-mediated polymerization (NMP)
media. [142]. An example of such a process is schematically
In a review of new methods of surface chemical mod- shown in Figure 4c.
ification, dispersion and electrophoretic deposition In a publication on high-transparency polymer nano-
of metal oxide particles [151] it is reported that pol- composites enabled by polymer graft modification
yaromatic dyes can be used as efficient co-dispersants of particle fillers [153] it is stated that the ability to
for oxide materials, carbon nanotubes and graphene augment the physical properties of polymer materi-
for the fabrication of composite films by electro- als while maintaining their advantageous process-
phoretic deposition. The use of new dispersants with ability characteristics has rendered polymer nanocom-
strong interfacial adsorption and multifunctional posites one of the most actively researched areas in
properties has driven the development of advanced the field of polymer materials [154–158]. One rea-
composites, containing metal oxide nanoparticles, son for the interest in nano-sized filler particles is
conductive polymers, carbon nanotubes, graphene, the opportunity to achieve desired property enhance-
polyelectrolytes and other materials. Colloidal and ments without compromising auxiliary characteris-
interface chemistry of new dispersing agents is emerg- tics such as optical transparency [154]. In the absence
ing as a new area of technological and scientific in- of optical absorption, the transparency of composite
terest [151]. materials is determined by the scattering of light
Surface modification using polymer brushes has be- from dielectric (i.e., structural or compositional) het-
come a powerful approach to tailor the chemical and erogeneities. For the particular case of nanocompos-
physical properties of interfaces. It has given rise to ites based on transparent polymer host materials
great advances in surface and interface engineering (e.g., amorphous thermoplastics or resins) the optical
[152]. In the most general sense, polymer brushes are transparency is hence determined by the light scat-
defined as thin polymer films, in which the individ- tering of particle inclusions [154].
ual polymer chains are tethered by one chain end to The role of polymeric ligands on the optical trans-
a solid interface. Depending on the density at which parency of polymer–matrix composites is analyzed by
polymer chains are anchored to the surface and their evaluating the effect of surface modification on the
molecular weight, surface-anchored polymer chains scattering cross-section of particle fillers in uniform
can adopt various conformations, from the so-called particle dispersions. For the particular case of poly
‘mushroom’ or ‘pancake’ regime at low grafting den- (styrene-r-acrylonitrile)-grafted silica particles em-
sities to the high density ‘brush’ regime [152]. bedded in poly(methyl methacrylate), it is shown that
In a review on the state of the art of growing polymers the tethering of polymeric chains with appropriate
from nanoparticles using surface-initiated controlled optical properties (such as to match the effective
446
refractive index of the brush particle to the embed- photoluminescence, and high/low refractive index
ding matrix) facilitates the reduction of the particle polymer materials [160].
scattering cross-section by several orders of magni- In the end let me mention a review article on devel-
tude as compared to pristine particle analogs [153]. opments in 4D-printing covering current smart ma-
A challenge for the generation of transparent nano- terials, technologies, and their applications [165] as
composites is to develop an integrated synthesis a demonstration of the achievements of polymer ma-
strategy adapting particle generation, surface modi- terial science and technology. Recent advances in ad-
fication, and integration inside the polymer. Surface ditive manufacturing, commonly known as three-di-
grafting using polymerizable surfactants or capping mensional 3D-printing, have allowed researchers to
agents allows for linking the particles to the polymer. create complex shapes previously impossible using
Novel techniques such as in situ polymerization and traditional fabrication methods. A research branch
in situ particle processing are beneficial to avoid ag- that originated from 3D-printing called four-dimen-
gregation of inorganic particles inside the polymer sional 4D-printing involves printing with smart ma-
matrix [159]. terials that can respond to external stimuli. 4D-print-
The fabrication of transparent nanocomposites has ing permits the creation of on-demand dynamically
been the subject of many efforts to develop methods controllable shapes by integrating the dimension of
to limit aggregation. To address this challenge, sev- time. Recent achievements in synthetic smart mate-
eral methods have been implemented to control the rials, novel printers, deformation mechanisms, and
polymerization process, the nanoparticle synthesis, mathematical modeling have greatly expanded the
and the polymer-nanoparticle interface together with feasibility of 4D-printing [161].
the polymer casting or processing. The main method-
ologies developed to fabricate transparent nanocom- 5. Manufacturing of polymer nanofibers
posites are discussed according to four main cate- Since the beginning of the last century exists a tech-
gories: the blending of nanoparticles and polymer, nique for converting many polymers into nanofibril-
the in-situ polymerization in the presence of pre- lar state using their solutions or melts. Electrospinning
formed nanoparticles, the in-situ nanoparticle syn- was first observed by Rayleigh in 1897, studied fur-
thesis in a pre-formed polymer matrix, and finally ther by Zeleny and patented by Formhals in 1934
the simultaneous polymerization and in-situ nano- [162]. Electrospinning has been widely used in the
particle synthesis. past decades to produce nanofibres from a variety of
Polymer nanocomposites for optical applications re- different polymers [9, 163] with application in re-
quire high optical transparency at high filling ratios generative medicine [164].
of nanoparticles. The nanoparticles provide optical Nowadays, electrospinning is used in hundreds of labs
functionality but unfortunately have a strong tenden- worldwide because of its elegance, not expensive set-
cy to aggregate in polymer matrices leading to strong up and the fascinating electron microscopic images
turbidity and reduced optical transmission, particu- of the nanofibers obtained, which can be seen in some
larly at high filling ratios. A general route to non-ag- 2000 papers published per year. At the same time,
gregated highly filled, optically transparent polymer this attractive technique has the disadvantage that not
nanocomposites based on using nanoparticles was so much can be done practically with the fine nano-
reported in [164]. The particles have been coated with fibers because of the not easy handling of the spun
polymers forming spherical brush-like layers, as material. Even more complicated is the situation if
schematically shown in Figure 4c, providing thermo- one tries to use the nanofibers as reinforcement for
dynamic miscibility with the polymer matrix over the polymer nanocomposites – the dispersion problem is
complete range of nanoparticle volume fractions. becoming practically non-soluble not only because of
The polymers are attached via a versatile ligand ex- the difficulties stemming from the nano-sizes but
change procedure which enables us to prepare a wide also due to the network character of the mat.
range of optically transparent polymer nanocompos- Using various techniques, the local molecular orien-
ites up to weight fractions of 45%. This is demonstrat- tation of the polymer chains within the fibers has been
ed for a broad range of metal and semiconductor measured and found that the degree of orientation of
nanoparticles in optically transparent polymer ma- the polymer chains with respect to the fiber axis in-
trices relevant for selective light/UV absorption, creases with decreasing fiber diameters [165–169].
447
Although it has been shown by various researchers extended macromolecules aligned parallel to each
that electrospinning can induce some level of chain other. Such a molecular structure results in superior
orientation in fibers based on flexible chain poly- mechanical properties as compared with the same
mers, these levels are often rather low [165]. Of par- polymer being in an isotropic non-oriented state. The
ticular importance for the issue discussed are the re- lack of molecular orientation in the electrospun ma-
sults of small-angle neutron scattering (SANS) terial is obviously the main reason for its poor me-
studies on chain extension in electrospun poly- chanical performance as discussed below.
styrene fibres [170]. These results are summarised Regardless of the existence of the problem with the
in [165] in the following way: ‘…The SANS was proper dispersion, electrospun nanofibers are hardly
used to quantify the size and shape of the chain con- suitable reinforcing material because of their inferior
formation in electrospun fibers of deuterated atactic mechanical properties. As stated in [163], the me-
polystyrene prepared from solutions. Although the chanical properties of most electrospun polyamide
orientation parameter <P2> was found to increase and polyester fibers are not comparable with con-
with increasing collecting speed, the maximum value ventional microfibers manufactured by melt-spin-
of about 0.15 was well below the orientation param- ning, which again can be ascribed to the low degree
eter expected for high-performance polymer fibers of chain orientation in these as-spun nanofibers and
with values typically approaching 1. When the tan- the absence of a post-drawing step in the electrospin-
gential velocity of the rotating collector was greater ning process. In fact, in many cases, the properties
than the flight velocity of the fibers some degree of of electrospun fibers are even inferior to that of the
orientation of the polymer coils was induced. How- bulk polymer, as can be concluded from the data dis-
ever, even at the highest collector speeds the ratio of played in Table 3. This situation can be attributed
the radii of gyration increased only by 20% from for also to factors, such as residual solvent, plasticiza-
bulk (17 nm) to fibers (20 nm), showing limited coil tion, and porosity [165].
deformation. As the diameters of these fibers were In conclusion, the electrospun polymer nanofibers
much greater than the polystyrene radius of gyration cannot be used as reinforcement for the manufactur-
these effects can be solely contributed to flow-in- ing of polymer nanocomposites because their me-
duced orientation, excluding size or confinement ef- chanical properties are worse than those of the poly-
fects as a result of nano-sized fiber diameters’. mer matrix (Table 3). It turned out that ‘nano-sized’
These results are of paramount importance. They does not mean necessarily ‘superior mechanical per-
demonstrate that the electrospun extremely fine cylin- formance’. The size alone is not enough, something
drical formations with diameters in the nano range more is needed!
are comprised of isotropic material and they even What is more, it follows that these famous electrospun
hardly could be called polymeric fibers. The polymer nanofibers do not belong to the family of the real
fibers, e.g. the synthetic ones, comprise highly polymeric fibers, that is to the family of the cylindrical
Table 3. Mechanical properties of electrospun polyamide (PA) and poly(ethylene terephthalate).
Modulus Strength
# Polymer Sample Ref.
[MPa] [MPa]
1. PA 6 Nonwoven nanofiber mat 34±2 7.2±0.5 [171]
2. PA 6,6 Nonwoven nanofiber mat 21±1 6.5±0.8 [171]
3. PA 6 Nonwoven nanofiber mat 19 10.5 [172]
4. PA 6 Single nanofiber 902 304 [172]
5. PA 6,6 Single nanofiber 950±390 150±49 [173]
6. PA 6,6 Nanofiber yarn 1216 120 [174]
7. PA 6 Single nanofiber 1320±152 78.1±6.0 [175]
8. PA 6 Nonwoven nanofiber mat 418±93 57.7±8.9 [176]
9. PET Nonwoven nanofiber mat 60 3.7 [177]
10. PA 6/6,6 Bulk 2 000–2 500 50–80 [178]
11. PET Bulk 2 000–3 000 50–150 [178]
12. PA 6/6,6 Single fiber 6 000 1000 [179]
13. PET Single fiber 15 000 1100 [179]
448
morphological formations characterized by high

molecular orientation resulting in superior mechan-
ical performance. For this reason, possibly, they
have to be called ‘fiber-like nanomaterials’ or ‘fi-
brous nanomaterials’ or ‘nanomakaroni’ as suggest-
ed recently [180].
Opportunities for converting bulk polymers into nano-
sized materials are also offered by the new type of
polymer–polymer composites, the micro- and nano-
fibril reinforced composites (MFCs and NFCs) de-
veloped during the last two decades [181–191].
MFCs and NFCs are comprised of a polymer with a
lower melting temperature (Tm) as a matrix, rein-
forced with extremely thin fibrils of a higher-Tm
polymer. The two basic requirements for the prepa- Figure 5. Schematic the microfibrils formation mechanism
in polymer blends during cold drawing (transfor-
ration of these two types of polymer-polymer com-
mation of the spherical particles into micro- or
posites are: a difference in the Tm of at least 40 °C nanofibrils via coalescence under transverse con-
between the two composite components, and that the traction) [185].
two polymers are not thermodynamically miscible
[183]. An idea about the mechanical properties of fibers takes place in polymer solutions or melts where
MFCs based on LDPE as a matrix and PET as rein- the drawing could hardly result in significant molec-
forcement can be obtained from Figure 3. The tensile ular orientation as demonstrated above [165–170].
strength of the LDPE/PET = 70/30 (by wt) is close The considerations about the weak molecular orien-
to that of LDPE/GF with the same composition. The tation hold also for MFCs prepared similarly but with
LDPE/PET = 50/50 (by wt) has a tensile strength hot-stretching directly from the melt at a temperature
higher than that of LDPE/GF = 70/30 (by wt) as well far above both polymers’ glass transition temperatures
as 3 times higher than that of the neat matrix (Fig- [193–201]. It is well-known that drawing of polymer
ure 3) [182]. melts does not induce molecular orientation.
Detailed studies on the formation of the individual Neat polymer nanofibrils (Figure 7b) can be easily
micro- and nanofibrils led to the conclusion that it prepared to apply the MFC concept comprising the
takes place during the cold drawing via coalescence steps of melt blending of the two polymers, extru-
of the elongated droplets [185], as schematically il- sion, cold drawing and extraction of the matrix com-
lustrated in Figure 5. ponent (e.g. [202, 203]. The last step could be per-
‘Cold drawing’ in this case means drawing at temper- formed immediately after the cold drawing or after
atures being close to the glass transition temperature the compression molding needed for isotropization
(Tg) of the reinforcing polymer. For polymer blends of the matrix component. The common solvent for
comprising PET as reinforcement, the drawing usu- removing the matrix polymer is xylene but if the neat
ally is performed at 70–80 °C. During this treatment, nanofibrils are needed for biomedical purposes, for
in addition to the transformation of spherical particles
into fibrils via coalescence (Figure 5), a drastic mo-
lecular orientation takes place since, at such temper-
atures, the drawing goes via necking [192]. The per-
fect molecular orientation during the cold drawing is
shown on the wide-angle X-ray scattering (WAXS)
patterns displayed in Figure 6 taken from extruded
PP/PET bled before and after cold drawing.
This perfect molecular orientation represents one of
the basic differences between the electrospun fibers Figure 6. WAXS patterns of PP/PET blend bristle: (a) after
and those prepared using the concept of microfibril- extrusion (no drawing) and (b) after extrusion and
lar composites [183] – the formation of electrospun cold drawing [184].
449
Figure 7. Blend of PP/PET = 70/30 (by wt) subjected to conventional melt spinning: (a) photograph of yarn of filaments
with diameters of 30 μm, (b) SEM micrograph of neat PET nanofibrils isolated from the yarn (a) via removing of
PP with boiling xylene using the modified Soxhlet apparatus [206].
example, scaffolds for regenerative medicine, water The two dispersion-free approaches are the essence
is the preferred solvent as well as a respective water- of the relatively new ‘concept of converting instead
soluble polymer as a matrix [204, 205]. of adding’ [184]. This means that instead of taking
the two basic composite components, the matrix and
6. The solution of the dispersion problem in the reinforcement, in their final form and blend them,
the preparation of polymer one takes one component only and during the pro-
nanocomposites via the concept of cessing creates the missing second component. Ba-
‘converting instead of adding’ sically, there are two approaches in this respect – cre-
Currently, we do not have reliable tools and/or tech- ating the originally missing reinforcing, and creating
niques for proper dispersion of nanomaterials in the originally missing matrix:
polymer melts to reach the dispersion degree of sin- – creating the reinforcement: starting from a blend
gle nanoparticles what is the requirement for having of two thermodynamically non-miscible poly-
true nanocomposites. So long as the respective tools mers, we can convert the minor blend component
and techniques are missing, for the preparation of such into nanofibrils and thus prepare a nanofibrillar
composites, one must use methods free of the dis- polymer-polymer composite (PPC), and
persion step in the manufacturing process. Besides, – creating the matrix: if we have neat polymer
the reinforcing component must be fibrous, i.e. for nanofibrils, by means of thermal treatment close
manufacturing of polymer nanocomposites one must but below the temperature of complete melting,
use nanofibers characterized by superior mechanical we can produce a small amount of isotropic matrix
properties. of the same polymer (playing the role of binder of
Do dispersion-free methods for the preparation of nanofibrils) and in this way to prepare a nanofib-
polymer nanocomposites exist? There are currently rillar single polymer composite (SPC).
at least two techniques allowing to avoid the disper- Both techniques are free of the dispersion step and,
sion problem in the preparation of polymer nano- what is more important, one always observes a per-
composites. Both result in true nanocomposites, fect distribution of the reinforcing nanomaterial in
where the nano-size reinforcing component reaches the polymer matrix, that is, each nanofibril is indi-
dispersion to single nanoparticles. It is important to vidually surrounded by the matrix polymer and no
note here that these two methods concern the prepa- aggregation is observed on the scanning electron mi-
ration of polymer-polymer nanocomposite only. As croscopy micrographs.
demonstrated above [42–132], all attempts to avoid The manufacturing process of nanofibrillar PPCs and
the dispersion step in the preparation of polymer SPCs is schematically shown in Figure 8. It should
nanocomposites comprising inorganic nanoparticles be noted that this process could be performed on
as reinforcement failed for various reasons. standard equipment for polymer processing. The two
450
Figure 8. Manufacturing of nanofibrillar composite (NFC), (Route A), and nanofibrillar SPCs, (Route B), via the ‘concept
of converting instead of adding’ [11].
thermodynamically non-miscible polymers in a temperature is by 20 °C lower than the temperature

usual ratio matrix/reinforcement = 70/30 (by wt) are of complete melting.
melt blended, extruded and cold drawn. Thereafter, Information regarding the sizes of the reinforcing
depending on the target, one goes Route A or Route B nanofibrils and their distribution in the matrix we
(Figure 8). can obtain from the SEM analysis. Such results for
If a nanofibrillar polymer-polymer composite is the two types of nanocomposites under discussion
needed, the drawn bristle is wound on a metal plate are shown in Figures 10 and 11.
and subjected to compression molding at the melting
temperature of the matrix polymer A, which must be
at least 40 °C below the melting of the reinforcing
polymer B (Figure 8, Route A).
For the preparation of nanofibrillar single polymer
composites, one must select Route B (Figure 8), ac-
cording to which from the drawn bristles must be re-
moved the matrix polymer A using a selective sol-
vent. The rest of nanofibrillar reinforcing bunch of
B must be wound on a metal plate and compression-
molded at a temperature at least 20 °C below the
melting temperature of B (Figure 8, Route B). In this
way, due to a partial surface melting, a small amount
of isotropic matrix (binder of nanofibrils) is created Figure 9. Differential scanning calorimetry curve of PVDF
(Figure 8, Route B). The hot-compaction has been demonstrating the melting interval, the true melt-
carried out at temperature corresponding to the start ing temperature (166 °C) and the selection of the
of the melting process as shown for poly(vinylidene proper hot compaction temperature (148 °C) below
fluoride) (PVDF) in Figure 9. In many cases, this enough the true melting temperature [189].
451
Figure 10. SEM micrographs of polyethylene/poly(vinylidene fluoride) (PE/PVDF = 70/30 by wt) nanofibrillar polymer-
polymer composite (a and b) and PET nanofibrillar single polymer composite (c and d): a) and c) represent cry-
ofractures perpendicular to the nanofibril orientation, b) is cryofracture parallel to the nanofibrils orientation, and
d) is the surface of the SPC film shown in c) [11].
Figure 11. SEM micrographs of (a) PBT nanofibrils isolated from PP/PBT (80/20 by wt) drawn blend and used for prepara-
tion of SPC via hot compaction, (b) cryofracture cross-section surface of a nanofibrillar SPC prepared from
nanofibrils of (a), (c) the top surface of compression-molded ‘film’ of PET nanofibrils (as those in Figure 7b),
and (d) cryofracture cross-section surface of a nanofibrillar SPC shown in (c), which demonstrates the adhering
of nanofibrils as a result of surface pre-melting [184].
452
An even better idea about the preparation of the nano- non-miscible polymers. In addition to this, there are
fibrillar SPCs could be obtained from micropho- other three key requirements that must be satisfied,
tographs displayed in Figure 11 where are shown the namely: (i) the blended polymers must have suffi-
starting nanofibrils as well as the structure of the ob- cient draw ability to allow the formation of reinforc-
tained film after compression molding. It is well ing fibrils to occur, (ii) the two partner polymers
demonstrated the fact that the thermal treatment of must be able to be processed at a single temperature
the aligned nanofibrils does not result in complete without the onset of degradation in either polymer
melting but only in adhering to the contacting nano- and (iii) the melting temperature of the reinforcing
fibrils (Figure 11d). component must exceed that of the matrix polymer
The photographs taken from the cryofractures per- by at least 40 °C, to allow fibril retention during ma-
pendicular to the nanofibrils orientation (Figures 10a trix consolidation and isotropization. Once these re-
and 10c, Figures 11b and 11d)), as well as from cry- quirements have been satisfied, the process can be
ofracture parallel to the nanofibrils orientation (Fig- run using standard industrial polymer processing
ure 10b) in both types of nanocomposites, the poly- equipment as shown in Figure 12.
mer-polymer ones as well as the SPCs, demonstrate
rather homogeneous distribution of the reinforcing 7. Mechanical properties of the true
nanofibrils in the polymer matrix, i.e. practically no nanofibrillar polymer-polymer and single
aggregates of nanofibrils can be observed. Such a polymer composites
situation is quite different from the case of polymer Let me remind the readers that the first task of this
nanocomposites prepared via the blending of the two review article is to try to answer the question of why
starting components as demonstrated in the previous the polymer nanocomposites prepared via blending
paragraphs. the polymer matrix with the reinforcing nanomaterial
Coming back to the preparation of these true nano- do not justify the expectations regarding their me-
fibrillar polymer composites it should be stressed chanical performance. Instead of the expected at least
that the formation of the reinforcing nanofibrils pos- ten times higher improvements as compared with the
sibly starts during the melt blending and extrusion common polymer composites, the reported values of
but takes place mostly during the ‘cold’ drawing (in improvements (if any!) are not higher than 30–35%
the slightly heated chamber – up to the Tg-value of [4–8].
the blend component B), as schematically shown in What about the mechanical performance of the true
Figure 12. nanofibrillar polymer-polymer and single polymer
The basic requirement for the preparation of nanocomposites? In Table 4 are shown the tensile prop-
fibrils is again to use blends of thermodynamically erties of some nanofibrillar polymer-polymer com-
posites prepared according to the concept of convert-
ing instead of adding [184]. These properties are com-
pared with those of the neat isotropic matrix polymer
prepared in the same way (compression molding).
The superior mechanical performance of the nano-
fibrillar polymer–polymer composites, prepared
Table 4. Improvements in tensile modulus, E, and tensile

strength, σ, of nanofibrillar polymer–polymer com-
posites (comparison with an isotropic matrix mate-
rial, as well as with PP/glass fibers (GF) composite).
Composition E σ
Figure 12. Schematic the setup for the manufacturing process # Components Ref.
[wt%] [%] [%]
of polymer nanofibrils in polymer blends, used
1. PP/PET 80/20 50 22 [187]
for the preparation of polymer-polymer nanofib-
rillar composites. It comprises two distinct steps: 2. LLDPE/PVDF 70/30 165 230 [189]
(i) melt blending and extrusion, and (ii) cold draw- 3. PP/PBT 70/30 45 190 [191]
ing with fibrillation (S1 and S2 are the rotating ve- For comparison
locities of the pairs of rolls, where S1 < S2) [11]. 4. PP/GF 80/20 100 200 [181]
453
according to the ‘concept of converting instead of fibers of the same polymer. For example, the PET
adding’ (Table 4) originates from the very high as- nanofibrillar SPCs prepared according to the one con-
pect ratio of nanofibrils, their better adhesion to the stituent approach (Table 5, sample 3) are character-
matrix as compared with their mineral counterparts ized by an average modulus value of 6.85 GPa and
and mostly because the perfect distribution of nano- a maximum one of 10.57 GPa. This value surpasses
fibrils in the matrix. Each nanofibril is individually all previously reported values for SPCs based on PET
surrounded by matrix material with absolute lacking [212–215] and approaches even the stiffness of the
any aggregates as demonstrated in Figures 10 and 11 glass fiber reinforced PET composite (with an E mod-
and discussed above. These favorable characteristics ulus of 11 GPa for 40 wt% glass fibers [207, 208]).
are the reason for an interesting observation during Discussing this remarkable mechanical performance
the tensile testing – the accuracy (error bar) for the of the nanofibrillar single polymer composite based
polymer–polymer composites (Table 4, samples 1, 2 on PET (Table 5, sample 3), whose SEM micrographs
and 3) represents 5–10% only of the measured value, are shown in Figures 10c and 10d, we need to com-
while for the PP/GF (Table 4, sample 4) – it is be- ment on another detail. Accounting the fact that the
tween 50 and 100% [181]. This observation indi- sample consists of PET nanofibrils only (Figures 10c
cates the high uniformity (in any aspect) as com- and 10d) and that the mechanical testing has been
pared with glass fiber composites. performed in the fiber axis direction only, one can
In Table 5 are listed data regarding the reinforcing assume that the obtained values for E and σ are char-
effect in tensile experiments of the true nanofibrillar acteristic for the single nanofibrils also (or, possibly,
(diameter of nanofibrils between 10 and 250 nm) even higher for them). As a matter of fact, the E-val-
SPCs, prepared via one- or two-constituent approach- ues between 7 and 10 GPa for the PET nanofibrils
es. The comparison is done with an isotropic film of prepared using concept converting instead of adding
the same polymer prepared via compression molding are in vicinity of the E-value for the melt-spun PET
with a thickness like that of the composite samples. fibers (Table 3, sample 13) of 15 GPa. This similar-
Considering the differences in the mechanical per- ity demonstrates that in the manufacturing of these
formance of the SPCs prepared using the one- or two types of fibers participates the step drawing,
two-constituent approach (Table 5, samples 2, 3, 5, which creates a strong molecular orientation leading
6, 7 and 1, 4, respectively) one has to take into ac- to superior mechanical performance. Such a step is
count the drastic difference in the structure of the missing in the manufacturing of electrospun fibers
two types of materials. While the one-constituent ap- as it follows from their mechanical properties –
proach results in a more homogeneous distribution E-value of around 1 GPa for single PA-66 and PA-6
of the reinforcing fibrils in the matrix, the two-con- nanofibers (Table 3, samples 4, 5 and 7).
stituent approach (Table 5, samples 1 and 4) leads to Quite similar is the situation with the tensile strength
a typical layered structure comprised of film(s) and where improvements of about 300% are achieved in
contrast to all other SPCs found in the literature [209–
Table 5. Improvement in tensile modulus, E, and tensile 215], including the PET/glass fiber composite, for
strength, σ, of true nanofibrillar SPCs (comparison which the improvement is 100–150 % [206]. The ten-
with isotropic matrix material, i.e. isotropic film of sile strength of the same type SPC based on PVDF,
the same polymer).
LLDPE and PP (Table 3, samples 2, 6 and 7) also are
Constituent E σ
# Polymer
(one/two) [%] [%]
Ref. very impressive.
1. PET Two Up to 100 Up to 140 [190] Single polymer composites have an inherent advan-
2. PVDF One 40 330 [189] tage compared to all other polymer composites re-
350 (for garding the adhesion quality between matrix and re-
3. PET One 300 [188]
E = 10.57 GPa) inforcement, which has a fundamental role in the
4. PBT Two 35 5 [191] formation of mechanical properties. Strong interfa-
5. PBT One 31 35 [191] cial interaction between reinforcing particle and
6. LLDPE One 112 325 [209]
polymer matrix is crucial to achieving a desirable
7. PP One 70 440 [209]
level of reinforcement in polymer composites [216,
For comparison
217]. Otherwise, insufficient interfacial interactions
8. PET/GF Two Up to 100–150 – [206]
cause weak load transfer from the polymer matrix to
454
the reinforcement which promotes significant stress (depending on the moisture content) for the samples
concentration at the interface region deteriorating the without catalyst and by 500–650% when catalyst is
performance of polymer composites [217]. Basical- added [222].
ly, the influence of interface region and the degree The improvements in the tensile mechanical proper-
of interfacial interaction would be much pronounced ties of all SPCs so far studied [209–215] and partic-
in polymer nanocomposites, because of the extreme- ularly the superior mechanical properties of the new
ly large specific surface area of nanoparticles com- nanofibrillar SPCs prepared by hot compaction
pared with conventional microparticles. However, to using only one constituent are evident (Table 5).
take the full advantage of such a large specific sur- What could be the reason for this impressive me-
face area of nanoparticles in polymer nanocompos- chanical performance? There are at least four rea-
ites, the nanoparticles should be dispersed in the sons: (i) in the current SPCs the reinforcing nanofib-
polymer matrix in nanoscale which should normally rillar constituent dominates strongly and has much
be achieved during the mixing/dispersion step of better mechanical properties when compared with
nanocomposite fabrication, as discussed in preced- the isotropic matrix of the same polymer, (ii) perfect
ing sections. The interfacial adhesion in polymer/ adhesion between matrix and reinforcement because
nanoparticle composites is basically developed via they have the same chemical composition, (iii) better
the interaction of polymer macromolecules with the orientation of the macromolecules in nanofibrils as
surface of nanoparticles through physical interaction, compared to that in microfibrils and textile filaments
e.g. Van der Waals forces, or chemical bonding such of the same polymer, and (iv) in the test specimen of
as covalent bonding. Normally, chemical bonding SPCs the nanofibrils are uniaxially aligned and the
provides strong interfacial adhesion which is often testing has been performed so far in the drawing di-
achieved with chemically surface-modified nanopar- rection only.
ticles. Nevertheless, interfacial adhesion alters sig- To the factors contributing to the superior mechani-
nificantly the dynamics and conformation of macro- cal properties of the nanofibrillar SPCs (Table 5) and
molecules [218] or promotes the crystallinity of the nanofibrillar polymer-polymer composites also
macromolecules [219, 220] in the vicinity of the belongs the fact that they are manufactured not via
outer surface of nanoparticles leading to distinct layer blending the matrix and reinforcement but using a
in the interface region, referred to as interphase, with technique which excludes the dispersion step in the
transitional properties from the nanoparticle proper- processing. This technique results in a perfect distri-
ties at the interface to the polymer matrix itself [221]. bution of nanofibrils in the matrix where each nano-
The thickness of the interphase layer is often in the fibril is individually surrounded by the matrix, that
order of the radius of gyration of macromolecules. is, one deals with true polymer nanocomposites.
It seems interesting to note here that the problem of In addition to the perfect distribution of the rein-
adhesion quality in the case of SPCs does not exist forcement in the matrix, one has to mention that the
since the two basic composite components, the matrix reinforcing component is distinguished by extremely
and the reinforcement, are of the same chemical com- high aspect ratio values since it represents nanofibers
position. Nevertheless, even higher values for the me- (diameters between 50 and 250 nm). What is more,
chanical properties are achievable if additional spe- these nanofibers demonstrate excellent mechanical
cial care will be taken for further improvement of the properties contrasting, for example, the elctrospun
adhesion quality between the matrix and reinforce- nanofibers (Table 3).
ment via establishing chemical bonds between them. Summarizing, it should be noted that there is no sur-
What is more, the chemical interactions (the addition- prise in these superior mechanical properties (im-
al condensation and trans-reactions in case of conden- provements of 200, 300, or 400%!) of the nanofib-
sation polymers) could be further enhanced using rillar polymer-polymer and the nanofibrillar single
trans-reaction catalysts (e.g. Sb2O3) as recently polymer composites prepared via the concept of con-
demonstrated for Nylon 6 (PA-6) [222]. While the im- verting instead of adding because: (i) they are true
provement of the tensile modulus is almost the same nanocomposites where (ii) the reinforcing agent is
for the cases without and with catalyst, the tensile of high aspect ratio, and (iii) the adhesion quality
strength of the single polymer composites as com- (particularly for the SPCs) is perfect. For such sys-
pared with the isotropic PA-6 improves by 300–400% tems, the expectations about a ten-fold increase of
455
mechanical properties are justified contrasting the The properties of these polymer nanocomposites can
polymer nanocomposites prepared via the blending be further improved attacking the rest of their draw-
of the polymer with the inorganic nanomaterials, backs as poor interfacial load transfer, process-relat-
where the improvements of mechanical properties ed deficiencies, poor alignment, poor load transfer
are up to 30–35%! [4–8]. to the interior of filler bundles. Besides, the author
believes that the efforts of researchers must continue
8. Conclusions and outlook in this direction [12], instead of preparation of ‘new’
Concluding, it should be mentioned that nowadays, polymer nanocomposites via blending of nano-size
there are enough indications (e.g. [4–8]) that the con- materials with polymers and finally getting materials
cept of polymer nanocomposites does not meet the with poor improvement (if any) in their mechanical
expectations – a drastic difference between the the- performance. Alternatively, one could make use of
oretically derived and the experimentally obtained the presence of the nano-size filler having a specific
results regarding the mechanical properties of these effect on polymer behavior as the case is with poly-
materials is observed. Among the many reasons for propylene comprising surface-treated nano-silica.
this unexpected situation, the most important seems
to be the poor dispersion, in other words, we hardly Acknowledgements
deal with true nanocomposites. This is because in the The author would like to thank Dr VB Mohan for his valu-
composites prepared via the blending of polymer able technical help during the preparation of the manuscript
and A/Prof. CJR Verbeek for careful reading and suggesting
matrix with the reinforcing nano-size material the re-
improvements of the manuscript, as well as Revs P. and S.
inforcing elements are not the single nanoparticles Stewart for the polishing of the revised version of the con-
but their aggregates with sizes in the micrometer tribution. Thanks go also to the Publishers Elsevier, Royal
range. The reason for this situation is the current lack Society of Chemistry and Taylor & Francis Inc. for adapting
of reliable techniques for proper dispersion of nano- figures with the respective text from their publications (refs.
material aggregates into the polymer matrix [9] and [11, 26, 27], and [184] of Elsevier, ref. [142] of Royal Soci-
ety of Chemistry as well as ref. [185] of Taylor & Francis
so long such techniques are missing we must avoid
Inc.). Appreciations are also due for their warm hospitality
the dispersion step in the preparation of true polymer to the Centre for Advanced Composite Materials as well as
nanocomposites as the ‘concept of converting in- to the Department of Mechanical Engineering of The Uni-
stead of adding’ does. The essence of this concept is versity of Auckland, where this project was completed.
in not taking the matrix and reinforcement in their
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Polymer nanocomposites: Why their mechanical performance does not justify

Article in eXPRESS Polymer Letters · May 2020

Adhesion Improvement in Polypropylene-Natural Fibre Fabric Sandwich Structures View project

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Polymer nanocomposites: Why their mechanical

Received 25 September 2019; accepted in revised form 18 December 2019

1. Introduction one or more external dimensions is in the size range

the transmittance of the composite (1.33 wt% SiO2)

they, in fact, belong to the category of microcompos-

morphological formations characterized by high

thermodynamically non-miscible polymers in a temperature is by 20 °C lower than the temperature

Table 4. Improvements in tensile modulus, E, and tensile

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