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2015 Eur. J. Phys. 36 063001
(http://iopscience.iop.org/0143-0807/36/6/063001)
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Review
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At the macro scale, the material properties of a polymer composite are determined
primarily by the dimensions of the reinforcement and how it is distributed in the matrix. For
example, carbon bre composites in which the bres are orientated in different directions in
successive laminates, has different mechanical properties to a unidirectional composite in
which all the bres are oriented in the same direction (Matthews and Rawlings 1999).
Likewise, two otherwise identical composites prepared with carbon bres of different diameters will exhibit different properties. At the sub-micron scale, the dimensions of the
reinforcement and the interface formed between the reinforcement and the matrixknown as
the interphaseare the dominant inuence on the material properties (Thostenson
et al 2005). In contrast, as one or more dimensions of the reinforcement approaches the nano
scale, it is increasingly the diameter and surface chemistry of the reinforcement that determines the material properties of the nal composite material, which is now referred to as a
nanocomposite. The difference in length scales between conventional polymer composites
and nanocomposite is signicant; for example, the interphase between the bre and matrix of
a typical carbon bre reinforced polymer composite is larger than an entire nanoparticle.
1.1. Why use nanocomposites?
Though they have come to prominence in recent years, engineered nanomaterials are not
actually new. Materials such as zeolites, pigments, carbon black, synthetic amorphous silica,
and smectic layered clays, which are nowadays considered to be nanomaterials, are well
known commodity materials (Smart and Moore 1995a). The unique properties of metal
colloids have long been known; for example, the vibrant ruby red colours in stained glass
windows such as that shown in gure 2 are obtained by adding either copper or gold to the
glass during manufacture, which forms colloids in the glass. A remarkable example of such
glassmaking is the dichroic glass used to make the Lycurgus Cup, dating from the 4th century
A.D. (Freestone et al 2007). This has an opaque greenyellow hue in direct light, but appears
ruby red when transmitted light shines through the glass. This effect has been attributed to the
presence of nanoparticles of silvergold alloy in the glass, typically 50100 nm in diameter; it
is believed that these nanoparticles formed in situ in the glass during heat treatment following
addition of metal salts to the molten glass.
Compared with conventional polymer composites, polymer nanocomposites display
improved mechanical and tensile strength, reduced scratch and mar resistance, higher heat
distortion temperature and noise dampening. Problems normally associated with high reinforcement content in composites such as decreased toughness, poor optical clarity and higher
melt viscosity are less of an issue in nanocomposite production because a nano-reinforcement
loading of less than 10 wt% is sufcient to produce high performance polymer
nanocomposites.
Nanocomposites may be processed using the same well-established standard methods
used to process virgin polymers, such as extrusion, injection moulding, thermoforming, blow
moulding and compression or transfer moulding (Bower 2002, Ashby and Jones 2006a).
These methods also allow for high throughput which is vital for economic production, e.g.
polymer or glass bre reinforced automotive parts must be produced at a rate of more than
one part per minute if they are to be competitive with traditional materials and technologies
(Bakewell 2014). Considering that processing accounts for between 2/3 and 3/4 the cost of
engineered composite materials, easier processing gives lower overall costs that offsets the
higher material costs that may be incurred using nano-reinforcements.
However, nanocomposites are not without their disadvantages too. Compared to virgin
polymers, they typically exhibit decreased toughness and poorer optical clarity due to the
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Figure 2. Stained glass window, Cathedral of the Nativity of the Blessed Virgin Mary,
Juneau, Alaska. The colours in the glass arise from the presence of metal colloids in the
glass from metal oxides added during its manufacture. At diameters below 100 nm,
such colloids may be considered as nanoparticles (Photograph courtesy: Kate
Murphy.)
presence of the nano-reinforcement. They also have signicantly higher melt viscosity than
virgin polymers, which presents processing difculties. Nonetheless, manufacturing polymer
nanocomposites remains simpler than manufacturing high-performance composite materials
using techniques such as autoclave processing or resin transfer moulding with conventional
carbon bre reinforcements. Depending on the nano-reinforcement and matrix used, it is
possible to obtain a remarkably wide range of materials properties from polymer nanocomposites; a representative range of these that have already been exploited in commercial
applications are presented in table 1, overleaf.
Nanocomposites are now widely used for applications in packaging, automotive, aerospace, electronics and semiconductors, energy, construction and cosmetics, and the global
polymer nanocomposites market is expected to reach a value in excess of $5100 million by
2020 (Markets and Markets 2015). For comparison, the global market for all nanotechnology
4
Property improvement
Application
Polyamide 6
Exfoliated nanoclay
Stiffness
Exfoliated nanoclay
Carbon nanotubes
Carbon nanotubes
Stiffness/strength
Strength/stiffness
Strength/stiffness
Polyisobutylene
Exfoliated nanoclay
Permeability barrier
SBR rubber
Not disclosed
Natural rubber
Various
Silver
Silica
Exfoliated nanoclay
Polymer matrix
Electrical conductivity
Antimicrobial
Barrier
Improved tyre performance
in winter
Antimicrobial
Viscosity control, thixotropic agent
Barrier
Table 1. Examples of commercial applications of polymer nanocomposites (reprinted from Paul and Robeson (2008), Copyright (2008), with
Toyota/Ube
General Motors
Babolat
Montreal: Nitro
Hybtonite
InMat LLC
Various
Hyperion
Curad
ImpermTM: Nanocor
Pirelli
Latex gloves
Various
Auto fuel systems
Ube
Note. Information from company web pages and industry journal reviews.
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Figure 3. (a) TEM image of silver nanoparticles (image: Tanushree Bala, University of
Limerick); (b) solutions of silver nanoparticles of average diameter 50 nm; the colour
of the nanoparticles varies depending on their shape, which is determined by the
conditions under which they are prepared.
products was valued at about $26 billion in 2014 and is expected to reach about $64.2 billion
by 2019 (BCCresearch 2014).
The nanomaterial most widely used to prepare nanocomposites on a commercial scale is
nanoclay (Uddin 2008). Therefore, the discussion throughout the remainder of this review
will take polymer/nanoclay composites as a starting point, and discuss other polymer
nanocomposites such as CNT and nanoparticle reinforced composites by reference to them in
the next section.
1.2. Three categories of nano-reinforcement
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Density (g cm )
Elastic modulus (TPa)
Tensile strength (MPa)
Electric current carrying capability
(amp cm2)
Thermal conductivity at room
temperature (W m1 K1)
Thermal stability (C)
SWCNT
Comparison value
Material
1.331.40
1.2
2000
1109
2.7
1.2
2762000
1106
Aluminium
Diamond
Steel
Copper wire
6000
3320
Diamond
2800 (vacuum)
750 (air)
6001000
Metal wires in
microchips
1.2.3. Nanotubes. CNTs exhibit remarkable electrical and mechanical properties, and have
become key components in advanced sensors, electronic and optical devices, catalysts,
batteries and fuel cells, and high-strength composite materials (Coleman et al 2006).
Arguably, in their purest formsingle-walled carbon nanotubes (SWCNTs)CNTs offer a
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Figure 6. How the structures of graphite, graphene and carbon nanotubes are related.
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This was the approach used to prepare the rst commercial polymer nanocompositesnylon/
nanoclay composites used to manufacture timing belt covers for the 1994 model year Toyota
Camry (Patel and Mahajan 2014). The nano-reinforcement is introduced to the monomer
precursor for the desired polymer matrix in the liquid state, dispersed thoroughly, then the
monomer is polymerized with the nano-reinforcement in situ to make the nal nanocomposite. The experimental approach is similar to surfactant modication of nanoclays,
discussed above, and is illustrated for the preparation of a nylon 6,10/nanoclay nanocomposite in gure 8.
2.2. Nanoclays: surfactant modification
The nylon/nanoclay example above is unusual in that both the nano-reinforcement and
monomer are hydrophilic, and therefore mix readily, whereas most commodity and engineering polymers and monomers are hydrophobic. Naturally occurring nanoclay has positively charged cations (usually sodium or calcium) on the surface of the clay platelets. This
makes it hydrophilicit will not mix with hydrophobic polymers. In this instance, we must
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Figure 7. The material properties of any nanocomposite vary with respect to the loading
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modify the clay platelet surface to make it hydrophobic. Typically, the clay is modied with a
quaternary ammonium surfactant. The surfactant ions exchange with the sodium ions on the
clay platelet surface, as shown in gure 9, so that the resulting organically modied nanoclay,
or organoclay, becomes hydrophobic. The length of the surfactants hydrophobic alkyl
chain, or tail, is chosen to make the organoclay more or less hydrophobic, to better match
the hydrophobicity of the organoclay with that of the polymer it is to be combined with.
Longer alkyl tails give a more hydrophobic organclay (Alexandre and Dubois 2000, Sinha
Ray and Okamoto 2003).
When the platelets are completely separated and dispersed in the matrix, the nanocomposite is referred to as exfoliated. Exfoliation requires high shear and high temperatures,
which can present processing difculties as degradation of the organic treatment may occur at
these higher temperatures. Sometimes, the platelets are not fully exfoliated, but rather, the
polymer enters between the surfactant-modied clay platelets, forcing them apart; such
nanocomposites are referred to as intercalated. The process of intercalation and exfoliation
of nanoclay platelets is illustrated in gure 10 and discussed further in case study A, section 3.
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Figure 12. Typical industrial scale procedure for melt processing of a polypropylene/
organoclay nancomposite. Although the nanoclay is chemically modied with
quaternary ammonium surfactant, an additional compatibiliser additivemaleic
anhydrideis required to achieve complete exfoliation of the nanoclay in the matrix.
Especially at laboratory scale, solution processing is the easiest approach if both the polymer
and nano-reinforcement can be dispersed in a common solvent. A typical procedure is illustrated in gure 11, and is essentially the same as the method followed for surfactant modication of nanoclays. Preferably, the nal nanocomposite should not be miscible in the
solvent used, so that the product is easily recovered by ltration or precipitation from the
solvent. At larger scale, the main disadvantage of this method is that it is slow, and requires
large amounts of solvent and energy.
Melt processing is most appropriate for insoluble or immiscible polymers and nano-reinforcements, and for high-throughput manufacturing. The methods most widely used are
comparable to those employed for preparing polymer composites using micron-sized particulate and short-bre reinforcements (see, for example, Ashby and Jones 2006b). Typically,
high shear mixing, (i.e. a twin screw extruder) and a careful choice of polymer resin and
compatibiliser is required to achieve adequate dispersion of the nano-reinforcement in the
matrix. This is because the nano-reinforcement increases the viscosity of the polymer in the
melt signicantly compared to the virgin polymer. In fact, achieving complete exfoliation of
nanoclay composites by melt mixing, rather than intercalation, poses a signicant formulation
challenge. A typical procedure to prepare a polypropylene/nanoclay composite is shown in
gure 12.
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In summary, the properties of nano-reinforcements can vary depending on how they are
synthesized (morphology and surface/volume ratio), and how they are functionalized (surface
chemistry). Also, the properties of polymer nanocomposites can vary depending on how the
nano-reinforcement is functionalized, whether a compatibiliser is used, and how well the
nano-reinforcement disperses in the polymer matrix. All these factors must be optimized to
formulate a high-quality nanocomposite from a given nano-reinforcement and polymer
matrix. The formulation and processing requirements to formulate nanocomposites from the
three main types of nano-reinforcementnanoparticles, nanotubes and layered materials
are compared and summarized in table 3. How these requirements are balanced in practice to
achieve a successful nanocomposite, and how to characterize them, is the subject of the case
studies presented next in section 2. These offer examples of how to functionalize nanoreinforcements and achieve good dispersion in a chosen polymer matrix, how to choose
suitable analytical techniques to conrm dispersion of the nano-reinforcements in the polymer, and how to characterize the nished nanocomposites.
15
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3. Case studies
3.1. Case study A: comparison of melt processing and supercritical carbon dioxide (ScCO2)
methods to prepare polyethylene oxide (PEO)/MMT nanocomposites
As it is extracted from the quarry, MMT nanoclay is polar, and therefore is only compatible
with polar solvents and polymers. Hence, nanoclay generally undergoes an organic treatment
to make the clay miscible with organic solvents and non-polar polymers of technological
interest. The treatment must the chosen to suit to formulation that the nanoclay will be
used in.
It can be difcult to achieve a consistent end product when modifying nanoclay via melt
processing, especially at laboratory scale where it is difcult to achieve complete mixing of
the nanoclay with the polymer or surfactant used to chemically modify it. Chemically
modifying nanoclay via solution processing is effective, but slow, and requires a large volume
of solvent and is energy-consuming to heat the mixture during processing.
In this case study, the aim was to compare ScCO2 uid treatment with conventional melt
processing methods (Armstrong and Fortune 2007). Supercritical uids are highly compressed gases which combine properties of gases and liquids (Brazhkin et al 2012). They are
used as a substitute for organic solvents in a range of industrial and laboratory processes.
PEO and sodium MMT nanoclay are widely used as a model nanocomposite, because
these are both polar; this avoids complications in interpreting results from experiments caused
by incompatibility between the polymer and nanoclay used. It is known from previous studies
that, when PEO/MMT nanocomposites are formulated, once the PEO content of the formulation exceeds 17 wt%, a bilayer of PEO polymer chains forms in the gallery space
between the clay platelets, and these chains adopt a helical structure. Each bilayer of PEO
polymer chains increases the height of the MMTs gallery spacing by 17 , so powder XRD
may be used to determine the extent of intercalation achieved by determining the increase in
the gallery spacing from Braggs law (Smart and Moore 1995b, Cullity and Stock 2001). If
the MMT were exfoliated completely, there would be no measurable gallery spacing between
adjacent nanoclay platelets, so transmission electron microscopy (TEM) analysis (Williams
and Carter 2009) would be required to conrm the nanocomposite was formulated as
expected. Also, these helical bilayer structures remain unchanged until the PEO loading
exceeds 30 wt%, so a formulation of 4:1 MMT:PEO (by weight) was used for each experiment to allow direct comparisons between varying molecular weights (40010 000) and
grades of PEO used, and both processing methods.
1.00 g PEO and 4.00 g MMT were mixed by grinding in a mortar and pestle. For melt
processing, this MMT/PEO mixture was pressed into pellets and heated in a laboratory oven
at 70 C for 6 h. For ScCO2 processing, the was placed in a gastight pressure chamber, then
pressurized to 2 800 psi with CO2 gas, heated to 60 C, and stirred for 24 h. After cooling to
room temperature, all samples were ground to pass through a 180 m sieve.
XRD was conducted on each sample prepared to determine the change in gallery spacing,
which may be seen as an increase in the d-spacing between the MMT platelets compared to
the unmodied MMT, as shown in gure 13(a). The gallery spacing for nanocomposites
prepared by ScCO2 processing were lower than those prepared by melt processing because
the PEO polymer chains did not coil in the same manner when plasticized as in the molten
state. Thermogravimetric analysis (TGA) showed that samples prepared by the ScCO2
method had lower polymer loading than the equivalent sample prepared by melt processing,
as shown in gure 13(b), and the difference in polymer loading (ScCO2 versus melt)
decreased with increasing PEO molecular weight. No melting transition was observed by
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100
95
A
A
Weight % (%)
90
85
80
B
75
70
30 50
100
150
200
300
250
350
Temperture(C)
400
450
500
550
600
Figure 13. (a) X-ray diffraction patterns for uorinated PEO/MMT composite (A) and
unmodied MMT(B). (b) Comparison of TGA traces showing weight loss due to water
and polymer content for unmodied MMT (A), ScCO2 processed PEO/MMT (B) and
melt-processed PEO/MMT (C). (C) Comparison of properties observed for melt- and
ScCO2-processed samples by XRD and TGA. (Reprinted from Armstrong and
Fortune (2007), with kind permission from Springer Science and Business Media.)
differential scanning calorimetry (DSC) for all samples prepared by the ScCO2 method, i.e. all
the PEO present in these samples was amorphous, rather than crystalline. This indicated that
the PEO was fully intercalated in the MMT galleries. It was concluded that, rather than acting
as solvent for the polymer, ScCO2 plasticized the polymer, allowing it to intercalate into the
MMT galleries in a similar way to melt processing. Any polymer not intercalated into the
nanoclay would have been removed from the samples during ScCO2 processing when the
chamber was vented at the end of the procedure, whereas it would have remained as part of
the melt-processed samples.
Overall, the results obtained using either methodas compared in gure 13(c)were
broadly consistent for each molecular weight of PEO studied, although ScCO2 processing
yielded more homogenous samples. The ScCO2 technique was found to be most effective
when used with PEO of higher molecular weight (10 000) or uorinated EO, which is
otherwise difcult to process using conventional techniques at laboratory scale.
3.2. Case study B: functionalized MWCNTs for improved performance epoxy nanocomposites
The aim of this study was to develop a process which allowed CNTs to be chemically bonded
to a polymer, instead of attempting to disperse surfactant-modied nanotubes in the polymer
matrix. Here, CNTs were chemically modied to act as initiators to polymerize a bisphenol A
type epoxy resin, as illustrated in gure 14; the objective was to formulate a lightweight, high
strength composite nanomaterial (Armstrong et al 2009).
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Figure 14. Polymerization of epoxy monomer in the presence of functionalized multiwall carbon nanotubes (MWCNT) to form a nanocomposite.
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masterbatch methods.
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the epoxy nanocomposites. Thermal stability of the nanocomposites was assessed by TGA
(Bottom 2008, pp 98110). Storage modulus (E) and exural modulus (EB) was determined
by dynamic mechanical analysis (Duncan 2008, pp 127128) and tensile testing (Ashby and
Jones 2005), respectively. Ball indentation tests were conducted to determine hardness and
rotating disc tests to determine wear resistance. The trends observed for the one-pot and
masterbatch methods are presented in gures 16 and 17 respectively.
For the standard method, it was concluded that the functionalized MWCNT did not form
covalent chemical bonds with the epoxy as desired (hence the Tg decreased), but the nanotubes acted as a plasticiser or impurity in the 3D epoxy network. No signicant change
occurred in the thermal stability of the nanocomposites, as expected. Improvements in E, EB,
wear resistance and hardness were observed, but no uniform trend emerged in these changes.
The masterbatch method gave broadly similar results upon addition of functionalized
MWCNT. Here, covalent bonding was achieved between the nanotubes and epoxy (Tg
increased slightly), but the samples did not cure fully. The N3H hardener and triethylamine
accelerator used appeared to have a negative inuence on the nanocomposites performance
and the samples were too soft for wear and hardness testing.
In conclusion, it was possible to improve the epoxy resins mechanical and thermal
properties by adding 1 wt% of functionalized MWCNT, but no single best route to preparing
nanocomposite emerged. Rather, the choice of a preferred processing route depends on which
thermal and mechanical properties are considered most important for the application in which
the composite would be used. Though functionalized MWCNT can indeed act as initiators
and become covalently bonded to epoxy, optimization of the nanotubes, accelerator and
hardener is required to obtain improved physical properties.
3.3. Case study C: alternative approaches to formulating functional antimicrobial
nanocomposites
The rationale behind this study was to functionalize commercially available nano-reinforcements that could add antimicrobial properties to a nanocomposite. Antimicrobial properties
20
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density (OD600) of broth measured over 24 h. Higher values of OD600 indicate more
microbe growth occurred. Control; , AgMMT as-prepared; AgMMT annealed.
(b) Nanoclay samples after 24 h. (Reprinted from Armstrong et al (2012), with kind
permission from Springer Science and Business Media.).
are required in a wide range of applications such as consumer products, medical devices,
textiles, and engineering materials. From a practical point of view, it is important that the
nano-additives can be well dispersed in the polymer matrix using conventional equipment and
processes, so that it is suitable to scale up towards commercial production afterwards. Also,
the nal nanocomposites should demonstrate antimicrobial activity under real world conditions that are representative of the intended applications for the material.
Increasing resistance of microbes to antibiotics is a growing problem in areas such as
healthcare and food production, so it was decided to use silver as the antimicrobial agent in
formulating the nano-additives because it is effective against both primary classes of microbes
Gram positive and Gram negativeand exhibits antimicrobial activity in a variety of
physiological settings (Lansdown 2002). The strategy was to incorporate an antimicrobial
agent containing silver into contact surfaces to break chain of infection. The antibacterial
activity of discs of the materials formulated was evaluated against Gram negative Escherichia
coli (E. coli) and Gram positive Staphylococcus epidermidis (S. epidermidis) using the wellestablished agar disc-diffusion method (Cappuccino and Sherman 2008, p 294) Two alternative approaches were studied, i.e.:
approach 1: formulation of epoxypolyester powder coatings containing silver-modied
nanoclays (Armstrong et al 2012)
approach 2: synthesis of titaniasilver and aluminasilver composite nanoparticles and
formulation into silicone and epoxy nanocomposites (Bala et al 2011).
3.4. Approach 1: formulation of epoxypolyester powder coatings containing silver-modified
nanoclays
Sodium MMT nanoclay was modied with both silver nitrate and quaternary ammonium
surfactant (following the approach described in gure 9) to achieve antimicrobial properties
and mixing with epoxy matrix. The resulting nanoclay was then characterized by XRD to
assess the change in gallery spacing (Smart and Moore 1995b) and x-ray photoelectron
spectroscopy (XPS) (Moulder et al 1992) to determine whether there were silver ions present
on the nanoclay surface as desired. The gallery spacing was found to have decreased from
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11.72 to 10.44 , and elemental analysis of the nanoclay by XPS conrmed that 2.0 at%
Ag ion was present. To conrm that the nanoclay would not be affected by typical processing
conditions, samples of AgMMT were annealed at 180 C for 10 min under ambient atmosphere. No thermal degradation was observed. The antimicrobial efcacy of neat and
annealed AgMMT was tested against E. coli over 24 h (gure 18), and was found to exhibit
comparable antimicrobial performance before and after annealing.
A commercial formulation containing equal parts epoxy and polyester resins was used to
prepare the powder coatings. 2 wt% of antimicrobial nanoclays was incorporated in each
coating, both with and without titanium dioxide (TiO2). TiO2 is typically added to coatings
and paints to make them white; it can also act as an antioxidant. Control coatings that did not
contain nanoclay or TiO2 were also prepared. The powder coatings were applied to a mild
steel substrate using an electrostatic spray-gun and oven-cured at 180 C for 10 min XRD and
TEM of these coatings showed the nanoclay to be mostly exfoliated in the epoxy/polyester
matrix. From XPS analysis of the coatings, it was calculated that, at 2 wt% loading of Ag
MMT, the Ag+ content of the coatings was approximately 8.83103 ppm; the minimum
concentration of Ag+ required for antimicrobial efcacy has been reported as 0.1 ppb.
The antibacterial performance of the coatings was evaluated against both Gram negative
E. coli and Gram positive S. epidermidis using the agar disc-diffusion method. Three discs of
6 mm diameter of each material embedded into the surface of agar plates on which the
microbes had been grown, to assess how the nanocomposites would perform as surface
coatings if these microbes came into contact with the coated surfaces. Unexpectedly, no
inhibition of the microbes growth was seen, except for a control sample of 10 L chloroamphenicol antibiotic solution applied to the unlled coating. Further testing revealed that,
even when the coatings were immersed in broth solution containing microbes, no antimicrobial effect was seen even though the AgMMT itself had proven effective against Gram
positive and negative microbes. The coatings exhibited limited wettability, and it was concluded that this restricted the ability of Ag+ to diffuse from the coating, such that it was not
bioavailable to inhibit microbial growth. (Subsequently, the same nanoclays did show good
inhibition of microbial growth when added to hydrogels made with poly(vinyl alcohol),
which is hydrophilic and, therefore, readily wettable.)
The key conclusion from this case study was that achieving a satisfactory dispersion of
the nanoadditive in the polymer matrix is not enough to prepare a successful material. Rather,
the formulation must be chosen and optimized to give the properties and performance
necessary for the intended target applications.
3.5. Approach 2: synthesis of titaniasilver and aluminasilver composite nanoparticles and
formulation into silicone and epoxy nanocomposites
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Figure 19. (a) TEM images of Ag nanoparticles on titania surface; inset: magnied
Figure 20. Modes of assembly compared for (a) Titaniasilver (TiO2Ag) and (b)
aluminasilver (Al2O3Ag) composite nanoparticles. The coordination of oleic acid
followed different modes on both surfaces: it formed a single layer on titania under
acidic conditions (a), but formed a bilayer on alumina under basic conditions (b). The
binding strength of the oleic acid layersand hence the silver nanoparticlesto the
oxide surfaces was not equal in both cases. The Ag nanoparticles on titania surface
were found to be more site specic and more strongly bound. In contrast, though the
inner layer of oleic acid illustrated in (b) was bonded to alumina strongly, the outer
layer was less strongly bound. Thus Ag nanoparticles which were anchored to the
oxide surface via this outer layer detached easily.
assembly because of differences in the surface chemistry of the titania and alumina particles.
These differences are summarized in gure 20. Here, the key point is that following the same
formulation steps using different starting materials does not always necessarily give the same
outcome, but rather the end product can be affected by variations in morphology and surface
chemistry.
Polymer nanocomposites were formulated with TiO2Ag and Al2O3Ag composite
nanoparticles by dispersing these composite nanoparticles in silicone and epoxy resin at
1 wt% and 10 wt% loading, following a similar approach to the standard method described
in case study 2. Formulations containing 30 and 50 wt% nanoparticles were also prepared, but
these proved too stiff and brittle to use in subsequent testing for antimicrobial activity. In
addition, control samples containing 150 wt% pristine titania or alumina were prepared. At
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Figure 21. Examples of disc diffusion assays against Gram negative Escherichia coli
and Gram positive Staphylococcus epidermidis. (a) Al2O310 wt% Ag at 50 wt%
loading in epoxy; (b) control: 50 wt% alumina in epoxy.
Table 4. Results of disc diffusion assays for epoxy composites against Gram positive
Staphylococcus epidermidis and Gram negative Escherichia coli. The diameter of zone
of inhibition measured serves as a relative measure of antimicrobial activity between
assays conducted under identical conditions.
S. epidermidis
E. coli
Alumina
Al2O310 wt% Ag
Titania
TiO210 wt% Ag
6.97
12.25
7.03
10.00
None observed
10.76
7.65
9.04
all loadings prepared, the composite nanoparticles were found to be well-dispersed in the
polymer matrices, and the distribution of Ag nanoparticles on the titania and alumina surfaces
was unchanged after processing.
Disc diffusion assays against Gram negative E. coli and Gram positive S. epidermidis using
discs of the nanocomposites were conducted as described in approach 1; an example of these is
shown in gure 21. Preliminary results suggested that these TiO2Ag and Al2O3Ag composite
nanoparticles have potential as antimicrobial materials suitable for use on contact surfaces; the
samples tested and zones of inhibition observed are compared in table 4. Comparing these
outcomes with approach 1, we can conclude that there is no one size ts all solution to
preparing functional nanocomposites. Rather, the antimicrobial agent chosen must be tailored to
suit the polymer matrix, composite formulation, target microbes and intended application.
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reinforcements in the polymer matrix is the rst step in the processing of nanocomposites, and
we have discussed in section 2 how it can be very difcult to align nanotubes using same
processing techniques applied to conventional polymer composites. Finding an efcient, costeffective, production route is vital if the nanocomposite is to be used in manufacturing, and it
should be clear from the case studies that it is necessary to be able to measure the dispersion
and alignment of the nano-reinforcement, and the material properties of the nished nanocomposite, consistently.
The eld of polymer nanocomposites is still very new, with rapid progress being made in
both technical and commercial aspects. At the time of writing, there are, however, several
emerging issuescommercial, technical and regulatorythat have the potential to affect the
future direction of the eld signicantly. In the nal section of this topical review, we will
consider some of these in more detail.
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Figure 22. TGA mass loss and its derivative for three separate specimens of (a) puried
SWCNT and (b) corresponding raw nanotubes. To is the peak temperature at which
maximum weight loss of the sample occurs, and Mres is the residual mass remaining at
the end of the experiment, i.e. the ash content at 600 C. (Reprinted from Arepalli
et al (2004), Copyright (2004), with permission from Elsevier.)
4.2. Safety and toxicity of nanomaterials and nanocomposites
In discussing the technical aspects of polymer nanocomposites, we have already seen that the
term nanotechnology can be misleading since it is not a single technology or scientic
discipline, but a group of processes, materials, applications and concepts dened by size. We
have already seen that the physical properties of the same material (e.g. carbon, silicon,
metals) are not the same at the nanoscale as at the macro scale. This may apply equally to
their behaviour in the body as well as to their materials properties!
At the time of writing, the health and safety effects of new nanomaterials are mostly
unknown. Therefore, the risk of accidental exposure to nanomaterials in the workplace is of
growing concern as they become more widely used in industry (ISO 2008, HSE 2013).
Accidental occupational exposure to nanomaterials can occur:
during manufacture
through incorporation in other materials (e.g. polymer nanocomposites)
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The United Kingdom is among the rst countries to regulate the usage of nanomaterials.
For example, the UK Health and Safety Executives guidelines on risk management of CNTs
(HSE 2013) state:
Since there is uncertainty about the risks of being exposed to CNTs, the
regulatory and safe response is to take a precautionary approachKthe toxicity
of CNTs has not yet been fully investigatedKHowever it is clear that Safety
Data Sheets for CNTs that are based on conventional graphite or graphene will
NOT provide suitable adequate information to assess the risk from CNTs.
Emerging data indicates that when CNTs are breathed in they can cause lung inammation and brosis. Inhaled CNT may have adverse effects at other sites in the body, and
CNTs may be able to provoke inammatory reactions in the skin. The type, shape and surface
chemistry of CNT may inuence the severity of the response. The UK HSE notes that:
Kmore information is required to properly understand the conditions of
exposure that are required to produce such effectsKin view of the evidence for
lung damage and lack of information on the effects of long-term repeated
exposure a high level of control is warranted for CNTs.
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Similar regulations to those in force in the UK are now emerging in other countries now.
For example, the French Institut National de Recherche et de Scurit have published a guide
to nanomaterials risk prevention in laboratories (INRS 2012). Also, the European Commission has published two detailed guidance documents on protecting the health and safety of
workers who are exposed to nanomaterials (PROGRESS 2013, 2014). These state that
because of the uncertainty in relation to manufactured nanomaterials (MNMs), the approach
to prevention is based on the precautionary principle. The point is made that new information
is becoming available and that those using the guides must take new information into account.
A strong emphasis is placed on consideration of exposure, while still trying to prioritise
attention paid to MNMs. Inhalation of nanomaterial is regarded as the route of exposure of
greatest concern, followed by respiratory and dermal exposure. Exposure by ingestion is
considered to be of lower concern.
Another health and safety regulation that may have far-reaching implications for the
future use of nanomaterials is Europe is the Registration, Evaluation, Authorization and
Restriction of Chemical substances (REACH) regulation (European Commission 2015).
REACH is a European Community Regulation, EC 1907/2006, on chemicals and their safe
use. Under REACH, manufacturers and importers of chemical substances are required to
gather information on the properties of the chemical substances they sell, which will allow
their safe handling. This information is registered in a central database run by the European
Chemicals Agency (ECHA) in Helsinki. REACH entered into force on 1 June 2007, and its
provisions are being phased-in over 11 years. At the time of its launch, nano-scale forms of
existing materials were not deemed to be new substances; therefore a separate REACH
registration was not required for them (Gergely 2012). A key question for nanomaterials is
whether nanomaterials will be considered separately to their micro-scale equivalents (e.g.
graphite versus graphene)?
4.3. Reuse and recycling of nanocomposites
In all areas of industry and business, there is an increasing emphasisboth from consumers
and regulatory authoritieson reducing waste and reuse or recycling of raw materials and
nished products at the end of their useful life. Let us consider two examples of markets
where polymer nanocomposites are currently used: electronics and automotive.
Across the European Union, the Waste Electrical and Electronic Equipment (WEEE)
directive, 2002/96/EC, requires that producer s of electrical and electronic equipment must
arrange to collect and reuse or recycle these products at the end of their life (EUR-Lex 2014a).
The WEE directive applies to household appliances, IT and telecommunications equipment,
consumer goods, lighting equipment, electrical and electronic tools, toys, leisure and sports
equipment, medical devices, monitoring and control instruments, and automatic dispensers.
For the automotive industry, European Parliament and Council Directive 2000/53/EC
addresses recovery and recycling of end-of-life vehicles. Under this directive, each EU
Member State must achieve 95% reuse/recovery by average weight per vehicle by 1 January
2015, to include 85% materials recycling (EUR-Lex 2014b). The car must be recycled in a
manner that does not cause environmental pollution, and the vehicles owner must not be
charged for the cost involved. In addition, under the directive, the use of specied hazardous
substances in new vehicles must be minimized.
In both cases, the question for future use of nanomaterials in industry is: how can we
develop strategies to recover, separate and recycle polymer nanocomposites in an environmentally sound manner and in compliance with both waste management directives and the
emerging health and safety regulations we have already discussed. How will we safety recycle
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(SWCNT).
Property
Graphene
SWCNT
3
Thermal stability
0.004 g cm
Up to 2630 m2 g1 (theoretical limit)
1 TPa
130 GPA
6000 S cm1
5000 W m1 K1 at room
temperature
<200 C (after functionalization)
Gas permeability
Bulk density
Surface area
Elastic modulus
Tensile strength
Electrical conductivity
Thermal conductivity
1.331.40 g cm3
2400 m2 g1
1.2 TPa
2 GPa
Varies with chirality
6000 W m1 K1 at room
temperature
2800 C (vacuum)
750 C (air)
MMT resistant to O2, hydrocarbons
4.4. Graphene
Review
preparing analogous nanoclay composites that the three principal processing routes available
to us are dispersion in solution, in situ polymerization, or melt processing.
In solution, GO exfoliates easily in water and protic solvents, so it becomes possible to
blend GO with a polymer solution. GO can also be exfoliated in aprotic solvent if it is
modied with an amine or isocyanate, making it compatible with polymers such as polystryene, polyurethane and poly(methyl methacrylate). It is possible to remove the solvent after
exfoliating the GO, but compared to exfoliated nanoclays, graphene platelets are more prone
to re-aggregation due to the formation of hydrogen bonds between the graphene sheets (Kim
et al 2010).
As with nanoclays, in situ polymerization processing of graphene may be achieved by
intercalating a liquid monomer between the graphene layers, then polymerizing it to yield the
nished polymer composite. Alternatively, as we saw for the example of an epoxy/CNT
composite (case study B), monomer or reactive functional groups may be grafted to the
graphene sheets, then undergo a cross-linking reaction to form the polymer. Melt processing
is also feasible, using the approaches already discussed; for example, PET/graphene melt
processed nanocomposite containing 0.07 wt% graphene have been reported (Paton
et al 2014). Even compared to other nano-reinforcements, graphene has very low bulk density
(see table 5) and leads to high viscosity melt mixtures, making it difcult to disperse and mix
with polymer via melt processing. A detailed review of methods to functionalize graphene
surfaces and prepare polymer/graphene nanocomposites in a wide range of polymer matrices
was undertaken by Kuilla et al (2010).
Review
to handle neat nanomaterials for this reason. Alternative approaches include masterbatches of
high loadings of nanoclay, nanotube or nanoparticle already dispersed in a range of engineering polymers, or off-the-shelf polymer nanocomposites ready for processing into nished
articles (e.g. PLASTICYL masterbatches of 15%20% CNTs dispersed in thermoplastic
resins (Nanocyl 2015) or nanoMax nanoclaypolyolen resin masterbatches (Nanocor 2015) which contain contains 50 wt% organically modied montomorillonite.)
Though it is now twenty years since the rst polymer nanocomposites found commercial
application, the eld continues to grow at a remarkable rate, with the combination of new
nanomaterials, processing methods and characterization techniques leading to higher performance materials, new applications and lower costs. Even as this review was being prepared, the UKs rst graphene-enhanced consumer product was launcheda lightbulb
containing a lament-shaped LED coated with graphene (Stoye 2015). This is produced by
Graphene Lighting, a company formed by the University of Manchester and the UKs
National Graphene Institute. Almost simultaneously, researchers based in South Korea and
the USA published reported bright visible light emission from single-monolayer-thick graphene devices suspended between electrodes (Kim et al 2015, Wogan 2015)effectively
these are graphene light-emitting diodes. The authors also created arrays of graphene light
emitters by CVD, which may provide a starting point to develop graphene-based on-chip
optical communications. It is worth noting that these applications made use of graphene
nanoplatelets, whereas many of the laboratory-scale prototype applications reported for
graphenes to date have made use of graphite oxide (Potts et al 2011).
By analogy to nanoclays, graphite oxide may be thought of by as intercalated graphene
platelets rather than fully exfoliated graphene. At the time of writing, Haydale Composite
Solutions have announced that they are working with Alex Thomson Racing to investigate
adding functionalized graphene nanoplatelets into carbon bre reinforced plastics, polyester
and epoxy resins for use in ocean racing yachts. Potential applications include reducing
weight in hulls and structural components, bearings and friction points, protecting against
delamination of composite materials and thermal heat management (Haydale 2015). With the
potential to incorporate such novel functionality into polymer matrices waiting to be
exploited, the future for polymer nanocomposites certainly looks bright!
Acknowledgments
The author acknowledges support from the Erasmus+ teacher mobility programme, which
facilitated the series of guest lectures at lEcole Nationale Suprieure dIngnieurs de
Limoges, on which this review is based.
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