Manufacturing Rev.

2014, 1, 11
 C.A. Charitidis et al., Published by EDP Sciences, 2014
DOI: 10.1051/mfreview/2014009
Available online at:
http://mfr.edp-open.org

REVIEW ARTICLE OPEN ACCESS

Manufacturing nanomaterials: from research to industry

Costas A. Charitidis*, Pantelitsa Georgiou, Malamatenia A. Koklioti, Aikaterini-Flora Trompeta,

and Vasileios Markakis
National Technical University of Athens, School of Chemical Engineering, Department III: Materials Science and Engineering, Research
Unit of Advanced, Composite, Nano-Materials and Nanotechnology, 9 Heroon Polytechniou St., Zografos, Athens GR-157 73, Greece

Received 1 July 2014 / Accepted 25 July 2014

Abstract – Manufacturing of nanomaterials is an interdisciplinary field covering physics, chemistry, biology, mate-
rials science and engineering. The interaction between scientists with different disciplines will undoubtedly lead to
the production of novel materials with tailored properties. The success of nanomanufacturing depends on the strong
cooperation between academia and industry in order to be informed about current needs and future challenges, to de-
sign products directly transferred into the industrial sector. It is of paramount importance the selection of the appropri-
ate method combining synthesis of nanomaterials with required properties and limited impurities as well as scalability
of the technique. Their industrial use faces many obstacles as there is no suitable regulatory framework and guidance
on safety requirements; specific provisions have yet to be established in EU legislation. Moreover, regulations related
to the right of intellectual properties as well as the absence of an appropriate framework for patent registration are
issues delaying the process of products’ industrial application. The utilization of high-quality nanomaterials is now
growing and coming to the industrial arena rendering them as the next generation attractive resources with promising
applications. Undoubtedly, the existing gap between basic research relating nanomaterials and their application in real
life will be overcome in the coming decade.

Key words: Nanomaterials manufacturing, Large-scale synthesis methods, Industrial applications of nanomaterials,
Carbon-based nanomaterials, Metallic nanoparticles, Metal CNTs hybrids, Metal oxides nanomaterials, Metal
oxides/CNTs hybrids, Quantum dots, Quantum dots/CNTs hybrids

1. Introduction Better synthetic methods to build and control particle morphol-

ogy, in large-scale manufacturing, will be needed to broadly
At European level, the manufacturing industry is facing allow the penetration of nanomaterials (NMs) into industrial
today a growing pressure derived from competitive economies. sector.
Especially in the high-technology area, there are already devel- One of the most promising fields in the manufacturing sec-
oped economies, such as China, which are threatening Europe’s tion is NMs manufacturing. ‘‘Nanomanufacturing’’ is now a
primacy [1]. To date, manufacturing sector consists of the 1/4 of growing economy [2]. There are estimations that NMs’ sales
the EU’s gross domestic product (GDP), while it offers millions will reach the 14 billion Euros by 2015, while reliable estima-
of jobs, in times that unemployment is consistently growing. tions cannot be conducted beyond 2020. However, while NMs
Despite the uprising economies, the EC industrial sector is enter early in the value chain, they are often not visible in the
dominating in international level, consisting of the flagship in final product. Thus, nanotechnology should be considered as
areas such as automotive, and machinery. a developing scientific field for the most of the industrial sectors
In order for Europe to maintain this status, a new strategy with uncalculated profits by the end of this decade. Taking that
needs to be implemented from cost-based competition to a into account, it is oxymoron the fact that nowadays there are
new approach based on the creation of high added value relatively few companies in Europe working exclusively on
products. Such a strategy should aim in more environmental- NMs manufacturing. At a European level, nanomaterials’ man-
friendly and high quality products. Additionally, new produc- ufacturing does not reflect the global emphasis on carbon-based
tion methods have to be developed in order to combine greater nanomaterials, such as fullerenes, carbon nanotubes (CNTs) and
production volumes with less energy and material consumption. carbon nanofibres (CNFs). Most of the manufacturers that
use nanomaterials in their production line do not use them in
*e-mail: [email protected] significant quantities.

This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0),
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

The scientific community turned their research efforts in the chlorides by flame pyrolysis. Also, optical fibres are manufac-
development of novel production methods of NMs in order to tured by similar process [7].
make their production more attractive to the industrial sector. Spraying is used either for drying wet materials or for
Most of today’s products involving fabricated nanostructures applying coatings. When the precursor chemicals are sprayed
are produced using top down conventional technologies, while onto a heated surface or into hot atmosphere, a precursor pyro-
the large facilities, needed for large-scale production, have a lysis occurs and particles are formatted. An electro-spraying
huge environmental impact [3]. process in room temperature was developed at Oxford Univer-
Unfortunately, most of the suggested methods fail either to sity for the production of semiconductors and metal nanoparti-
apply to a large scale production, or in succeeding in preserving cles [8]. Spray gun deposition technique was also applied for
the produced NMs, with the desired properties. Another major the deposition of catalysts precursors, such as iron chlorides
issue that scientists deal with is the fact that these novel manu- (III), in order to achieve the growth of CNTs. Such methods
facturing processes should address to be equipped with in situ of catalysts’ deposition as film on various substrates are simple,
monitoring of the whole process in order to deliver high quality cost effective and can be applied on large surfaces [9].
products. One possible solution is the online monitoring of the
whole process which allows a constant feedback from the prod- 2.1.1.2. Atomic or molecular condensation
uct quality, thus minimizing the chances of a product failure. (gas condensation)
Hence, it is critical for the scientific community as well as for The theory of gas-phase condensation process for synthesiz-
the end-users, a strong cooperation to be developed in order ing metal nanoparticles is certainly the oldest, having been first
these obstacles to be overcome. reported since 1930 [10]. The main parts of the gas condensa-
In this sense, European Commission [4] has developed pri- tion system are a vacuum chamber consisting of a heating ele-
vate-public partnerships in order to support research in the field ment, the metal to be evaporized, powder collection equipment
of NMs manufacturing. In the frame of FP6 and FP7 projects, and a pumping system. A bulk material is heated to sufficiently
EC had invested €240.000.000, while in the frame of HORI- high temperature (far above the melting point, but less than the
ZON 2020, over 1 billion Euros will be invested from both boiling point) within a vacuum chamber in order to produce a
the European Commission and manufacturing industries in stream of vaporized and atomised matter, which is directed to a
order to develop and promote key enabling technologies. This chamber filled with either inert or reactive gas atmosphere.
investment will aid the European manufacturing industry and The pressure of the gas is high enough to promote particle for-
especially small and medium enterprises, to successfully corre- mation, but low enough to permit spherical formation of the
spond in this new competitive environment, through the devel- particles. Rapid cooling of the metal atoms, due to their colli-
opment of novel manufacturing methods. sion with the gas molecules, lead to the nucleation and subse-
These newly developed NMs manufacturing methods, quently to the formation of nanoparticles. The introduction of
although still in research labs, are expected to provide with oxygen as reactive gas into the system results in the production
nanoparticles and nanostructures of high process throughput of metal nanoparticles. Attention should be given into the rapid
and low product costs. Rough estimations show that over oxidation, which may result in overheating and sintering of the
100 kg/day of products, ten times higher than today’s volumes, particles. Gas evaporation typically leads to the production of
will be synthesized by using innovative production methods. materials with a broad particle size distribution and agglomer-
It is clear that such methods will dramatically decrease current ates due to the formation of particles being a purely random
nanomanufacturing obstacles, and lead in the creation of process [8, 11].
entirely new applications.
2.1.1.3. Arc discharge generation
Another means of vaporizing metals is the utilization of
2. Methods for large-scale synthesis
an electric arc as a source of energy. This technique is
of nanomaterials based on charging two electrodes made of the metal to be
vaporized in the presence of an inert gas. A large current is
2.1. Bottom-up approaches
applied until the breakdown voltage is reached. The arc created
2.1.1. Vapour phase techniques across the two electrodes leads to the vaporization of a small
amount of metal of one electrode to another. This method pro-
2.1.1.1. Aerosol based processes duces very small amounts of metal nanoparticles, but is charac-
A common method for industrial production of nanoparti- terized by relative reproducibility. Metal-oxides or other
cles is the aerosol based processes [5, 6]. An aerosol can be compounds can be produced by using oxygen or another reac-
defined as a system of solid or liquid particles suspended in tive gas [12]. Even though the arc discharge is a well-known
air or other gaseous environment. Particles can range from mol- method, the process control of the arc’s extremely high temper-
ecules up to 100 lm in size. The use of aerosols was known ature leading to high evaporation rates is of significant impor-
many years before the basic science and engineering of them tance for industrial processing. Moreover, high concentrations
were understood. For example, pigments as carbon black parti- of the vaporized metal in the carrier gas may produce large
cles and titania were used as reinforcements for car tires and for particles [11].
the production of paints and plastics, respectively. Another A European project named BUONAPART-E (Better Up-
example is fumed silica and titania formed from respective tetra scaling and Optimization of Nanoparticle and Nanostructure
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 3

Figure 1. Multiple optimized single units of BUONAPART-E’s project for large scale production of metal nanoparticles by using electrical
discharge methods.

Production by Means of Electrical Discharges) [13] is currently

running and aims at the development of an optimized single
unit (OSU), which is depicted in Figure 1. The latter is the basic
evaporation unit, for large scale production of metal nanoparti-
cles by using electrical discharge methods. The process is sim-
ple, versatile and reliable and the production rate ranges
between 0.1 and 10 g/h, an increase by a factor of 10 to 100
beyond the current state-of-the-art for the single unit. The basic
unit is a pair of electrodes and a large number of these pairs can
be placed in a single housing, resulting in the demonstration of
multiple units of the OSU in parallel, in a closed-loop carrier gas
recycling system, in a production facility yielding 1 kg/day.
The challenge of this project is to show that the product quality Figure 2. Schematic representation of laser ablation process
from multiple parallel OSUs and a single unit are identical. consisting of vacuum chamber, laser beam, target material and
The size of the primary particles is controlled by the carrier gas substrate to be coated [18].
composition and the applied electric current. Nitrogen is the most
economic carrier gas, leaving electric current as the only process
parameter. A higher electric current results in the production of 2.1.1.4. Laser ablation process
bigger particles and thereby to an increased production rate. Laser ablation technique consists of two important
The parallelization of many electrode pairs can optimize both elements: the high-power laser beam with the optical focusing
production rate and particle size <100 nm. Current results of system and the feeding device of the metal-target (Figure 2).
the project include that the production rate of about 0.6 kg/day The laser beam is focused at the surface of the target and a
of the multiple OSU containing 8 OSUs is approximately supersonic jet of evaporated material (known as plume) is
8 times the production rate of the OSU; and the specific electric- ejected perpendicular to the target surface, expanding into the
ity consumption is in the same range for the multiple OSU as it is gas space above the target. The particles formed are transported
for the OSU. To conclude, this is a very important result as it with the carrier gas to the product collector. The use of metals
proves that the scaling-up by multiplying the number of OSU and metal oxides as precursors is the main advantage of this
in one housing is working for large scale production of metal method as well as the production of high crystalline materials.
nanoparticles [14, 15]. The concentration of particles and their size distribution
4 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

Figure 3. Laboratory scale CVD system.

depends on the experimental medium in the ablation chamber 2.1.1.6. Chemical vapor deposition
(ambient air, argon and water), the target material and the laser Chemical vapor deposition (CVD) is referred to activating
operating parameters (wavelength, pulse duration, energy, repe- chemical reactions between a substrate surface and a gaseous
tition time and beam scanning speed). Experimental estimations precursor in order to a thin solid film be deposited onto the sub-
showed that the mass of generated nanoparticles in ambient air strate [22]. Activation can be achieved either with increased
was up to 100 times higher than in water and that in argon gas temperatures (Thermal CVD) or with plasma (PECVD: Plasma
was up to 100 times higher than in ambient air. For example, Enhanced Chemical Vapour Deposition); decreasing signifi-
using nanosecond-laser the generation of Nickel particle con- cantly the process temperature compared to the thermal CVD
centration was estimated up to 1.2 · 105 cm 3 in ambient air process. This technique is a widely used materials-processing
and 1.4 · 106 cm 3 in argon gas flow [16]. However, the high technology due to its low set-up cost, high production yield,
concentration of evaporated material in the plume can lead to and ease of scale-up [23]. Chemical vapor deposition has been
the formation of agglomerates. This process is not often developed as a novel manufacturing process in many industrial
applied, especially in large-scale, due to its low yield and high sectors such as semiconductor and ceramic industry [24]. A typ-
operation cost [11, 17]. ical industrial CVD system includes gas delivery system, reac-
tion chamber or reactor, loading/unloading system (transport of
2.1.1.5. Plasma process substrates), energy system, vacuum system, process automatic
Plasma processes can be divided into two categories, micro- control system, and exhaust gas treatment system (e.g. NaOH
wave plasma process and plasma spray synthesis. In the micro- and liquid N2 traps before by-products being released into the
wave plasma process, particles are originating in the plasma atmosphere). The gases are delivered into a reaction chamber
zone, carrying electric charges. As a result, agglomeration operated at a suitably determined high temperature (500–
and coagulation can be reduced due to the benefits of the 1200 C). Also, inert gases, such as argon and nitrogen, are
charged particles [19, 20]. Because the reactants are ionized usually used as carrier gases. The gases pass through the reactor
and dissociated, lower reaction temperatures can be achieved, coming into contact with the heated substrate; they react and
than chemical vapor deposition, but the electrical charges of form a solid layer deposited onto the substrate’s surface.
the particles remain. Advantages of the method are the high The temperature and pressure system are the critical operation
production rates, the narrow particle size distribution and the parameters of this process [23]. A laboratory scale CVD system
ability of producing unagglomerated particles [21]. Plasma is depicted in Figure 3.
spray synthesis is a method that can be used even in the open CVD is widely used for the production of CNTs and is the
atmosphere for the production of nanoparticles. Because the only promising method for scaling-up compared to arc dis-
flow velocity of the nanoparticles is extremely high, the collec- charge and laser assisted methods [8, 25]. Recently, a swirled
tion of the produced nanoparticles is demanding. Advantages of floating catalytic chemical vapour deposition (SFCCVD)
the method are its simplicity, the low cost and the mass- reactor was developed with the scope of up-scaling the produc-
production that can be achieved. Requirements for safe and effi- tion capacity using a vertical reactor inside a furnace and
cient particle collection restrict the application of the method [8]. cyclones for collecting the final product [26].
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 5

Figure 4. Main stages of sol-gel method [17].

As mentioned, CVD is a powerful method with many

advantages ranging from uniform thickness of coatings,
flexibility of using a wide range of chemical precursors (70%
of elements in the periodic table have been deposited), no
requirement of using ultra-high vacuum environment up to
control of surface morphology and orientation of manufactured
products. However, CVD process invokes safety issues and
health hazards derived from the production of by-products.
Also, despite being a flexible method, CVD requires numer-
ous experiments for standardizing the appropriate growth
parameters [24].

2.1.2. Liquid phase techniques

2.1.2.1. Sol-gel
Sol-gel method is a long established industrial process for Figure 5. SHYMAN’s continuous hydrothermal reactor system
generating colloidal nanoparticles from liquid phase. It has been showing inlets, mixing zone and formulation stages.
further developed in the last years for the production of
advanced nanomaterials and coatings [27, 28]. Sol-gel process
is a chemical method which is based on hydrolysis or conden- The operation temperatures are usually below 100 C and
sation reactions (Figure 4). With the correct amount of reac- the pressure exceeds the ambient pressure.
tants, nanosized particles precipitate. Sol-gel techniques show Hydrothermal synthesis is an enabling and underpinning
many advantages like low temperatures during processing, ver- technology that is ready to prove itself at industrial scale as a
satility and easy shaping and embedding. Common precursors result of recent breakthroughs in reactor design, which suggest
which are used for the production of oxides are alkoxides, that it could now be scaled over 100 tons per annum. Continu-
due to their availability and to the high liability of the M-OR ous hydrothermal synthesis produces nanoparticulate material
bond allowing facile tailoring in situ during processing. This by mixing superheated/supercritical water with a solution of a
method lucks the risk for nanoparticle release after the drying metal salt. That is, rather than slowly heating the entire contents
of the solution [8]. of a batch vessel, the two different fluids are continuously
mixed together. When water is heated towards its critical point
2.1.2.2. Solvothermal method (374 C, 218 atm) the ionic product [H+][OH ] increases and
Solvothermal method is appropriate for the preparation for the superheated fluid is technically supercritical, rather than
both crystalline oxide- and non-oxide materials. Crystalline sol- near-critical.
ids, including silicate materials with high porosity like zeolites Another project named SHYMAN (Sustainable Hydrother-
[29] and oxide or non-oxide nanoparticles [30] can be produced mal Manufacturing of Nanomaterials) [34], funded by Euro-
by this method. Examples from non-oxide nanomaterials that pean Commission, focuses its main goal on finding the
can be produced by solvothermal method and have several optimum reactor design that can manufacture 100 tons/annum
applications are semiconductors (e.g. GaN) [31], carbon nano- (dry weight equivalent) of formulated nanomaterials. The cur-
tubes, diamonds and carbides [32], chalcogenides, nitrides, rent system’s yield is 1 ton/annum with some early indications
phosphides or borides. The main advantage of the method is that 10 tons/annum can be achieved with the same reactor using
that problems like solvents’ toxicity, inability of dissolving salts faster flow rates. The system will be capable of sustaining oper-
and expense, can be overtaken. In the solvothermal method, ation at a range of superheated conditions from sub-critical
solvents are employed well above their boiling point in (starting at 100 C and 10 bar) to near critical and supercriti-
enclosed vessels. By this way, high autogenous pressures can cal conditions (>374 C and >218 atm). In Figure 5 the
be supported. Organic solvents can be used to disperse non- SHYMAN’s continuous hydrothermal reactor system showing
oxide nanocrystallites and to stabilize metastable phases. When inlets, mixing zone and formulation stages is presented. Specif-
the used solvent is water, the method is called hydrothermal. ically, the superheated fluid passes down an inner nozzle pipe
Many times the method includes extra processes as hydrolysis, (A) against an up flow of cold metal salt (B). Nanoparticles
oxidation and thermolysis [33]. The hydrothermal synthesis form at the interface of the two fluids and the buoyancy of
is suitable for the production of fine powders and oxides. the heated flow causes the nanoparticle slurry to be carried
6 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

upwards (downstream). The nanomaterials themselves can then A severe plastic deformation occurs due to mechanical attrition,
be formulated (C) before cooling (D) and collection [35]. so a continuous refinement of the internal structure of the pow-
der particles to nanometer scales is accomplished [39]. Temper-
2.1.2.3. Sonochemical method ature rises during the process over 100 C–200 C [40].
Sonochemistry is the research area in which molecules While mechanical milling is very sensitive to contamination,
undergo chemical reaction due to the application of powerful atmospheric control can be used for chemical reactions between
ultrasound radiation [36]. The driving force responsible for the environment and the milled powders [39]. This has led to the
the sonochemical process is acoustic cavitation, which includes development of a novel, cost effective method of producing a
the formation, growth and collapse of bubbles in an ultrasoni- variety of nanopowders, Mechanochemical Processing (MCP),
cally irradiated liquid. Even though, cavitation is considered which consists the second method of mechanical attrition.
to be avoided in the construction of reactors (erosion damage), In MCP a conventional ball mill can be used as a low temperature
acoustic cavitation is the key to sonochemical processing due to chemical reactor. The ball mill increases the reaction kinetics in
its ability to control and limit its effects to the reaction and not the reacting powder mixture as a result of the intimate mixing and
the reactor [37]. This method has been extensively used to pro- refinement of the grain structure to the nanometer scale. The reac-
duce nanosized materials with unusual properties, since the tion occurs during the actual milling. For this reason, a proper
unique conditions (very high temperatures (5000 K), pressures reactive gas, like O2, N2, atmospheric air, etc. and a suitable
(>20 MPa) and cooling rates (>109 K s 1)) facilitate the forma- precursor are chosen [8]. A variety of metals such as Ti, Fe, V,
tion of smaller particles and different shapes of products com- Zr, W, Hf, Ta and Mo demonstrate the potential of reactive
pared to other methods [38]. The main advantage in conducting milling [41–43]; they can be transformed to nanocrystallines of
sonochemical experiments is that it is very inexpensive. metal nitrides and oxides. Concerning the wet milling, an organic
fluid can also be used. Metal powder can be transformed to
nanocrystalline metal-ceramic composite by this method [39].
2.2. Top-down approaches The resulting product phase is formed as individual single nano-
meter sized grains, in a by-product matrix. For this reason, it is
2.2.1. Solid phase techniques
necessary to confirm that the reaction has finished, so
2.2.1.1. Mechanical attrition (milling/mechanochemical
temperature heat treatment often follows the process.
processing) The reduction of the process cost and the industrialization
Mechanical attrition (MA) is a method that has been devel- of products can be achieved by using a variety of precursors,
oped since 1970, as an industrial process for producing new like oxides, carbonates, sulphates, chlorides, fluorides, hydrox-
alloys and phase mixtures from powder particles. This method ides and others [8]. Different ball mills have been developed for
can overcome the quantity limitations for nanocrystalline prep- mechanical attrition, such as tumbler mills, attrition, shaker
aration, so nanocrystalline powders can be produced in large mills, vibratory mills, planetary mills, etc. [44]. The method
scale. Moreover, it offers many perspectives in preparing a dif- includes shaking or violent agitation. The material powder is
ferent number of structures in nanostructured powders, like placed in a sealed container with coated balls by hardened steel
crystalline/crystalline or crystalline/amorphous and atomic or tungsten carbide. The mass ratio for the ball to the powder
bonding like metal/metal, metal/semiconductor, metal/ceramic, shall be 5:10, with a typical particle diameter 50 lm for the
etc. An important advantage is that mechanical milling process powder. Kinetic energy of balls is a function of their mass
can work at low temperatures, so the newly formed grains can and velocity, as a result, steel or tungsten, which are high den-
grow very slowly [8]. By this method it is possible to prepare sity materials, are preferable as means of milling [39].
advanced materials with particular grain or interface-boundary
design. Because in many cases it is difficult to distinguish a 2.3. Hybrid approach – nanolithography
glassy structure by a nano-crystalline structure, research is ori-
ented to nanocrystalline nanomaterials, in which grain or inter- Nanolithographic techniques (Figure 6) are appropriate for
phase boundaries between the nanophase domains exist [39]. the fabrication of 1D nanostructures [45], nanocatalysts [46],
Two different techniques have been developed for the pro- semiconductors, etc. They include electron-beam or focused-
duction of nanopowders using mechanical milling. The first one ion-beam writing [47, 48], proximal probe patterning [49,
is milling a single phase powder by controlling the balance 50], X-ray lithography [51, 52] and many other methods. Nan-
point between fracturing and cold welding. By this way, parti- olithography also includes dry or wet etching. In the context of
cles larger than 100 nm cannot be excessively cold welded [8]. fabrication of nanostructures the definition of lithography
As a result, a reduction of the average grain size from should be referred not only as a top-down, but also as a
50–100 lm up to 2–20 nm is obtained. The reason that this bottom-up route. By nanolithography, nanostructures or their
reduction of the order of 103–104 for the average grain size arrays can be synthesized, by a directed growth process or by
occurs, is the creation and self-organization of large-angle grain a constrained growth from one to few nanometers. The advan-
boundaries between the powder particles. The mechanism of tage of these methods is that large quantities of 1D nanostruc-
microstructure formation is very different from the other tures can be prepared, using a wide variety of materials, which
synthesis methods, but the final microstructure is very similar. are available [33].
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 7

Figure 6. Scheme of the polymer tip array in patterning instrument

[53].
Figure 7. Vapour and liquid phase techniques are the leaders
2.3.1. Template fabrication for large scale production of inorganic nanoparticles [59]
http://nanoparticles.org/standards/.
One of the most popular and maybe cheapest methods of
nanolithography is the template fabrication, which uses nano-
meter size templates. This method is suitable for the growth These patterns can be transferred onto an underlying substrate,
of nanowires, by electrodeposition, sol-gel or by vapor-phase. in the same way with the other lithography masks in optical or
Nanowires can be decoupled with the templates and can be also e beam lithography. Nanoelectronic devices can be fabricated
independently controlled. First of all, templates of ordered by this method. The main advantage of the SPM-based lithog-
nanopores have to be made. Secondly, the pores should be filled raphy is that the same SPM can be used for writing the pattern
with the chosen materials, using one of the methods referred and for imaging after the writing process.
before. Two ways exist for creating reproducible patterns in nano-
Electrodeposition of metals inside the nanopores is meter scale; ‘‘chemical route’’ which is dip-pen lithography
performed in acidic or basic baths that contain metal salts. (DPN) and SPM, based on anodic oxidation. The central role
A three-terminal potentiostat is used. The metal is deposited in both methods plays the water meniscus between the tip
on the cathode (working electrode) and for this reason, one and the substrate.
end of the porous membrane is metallized with Ti and Au or For the anodic oxidation, meniscus acts like an electro-
Ag by sputtering or evaporation. The anode (counter electrode) chemical cell. The writing operation needs normally ambient
is normally made of graphite or Pt and the reference electrode air with moisture over than 50% RH. The meniscus is formed
can be calomel or Ag/AgCl. The deposition conditions (DC or by the atmospheric moisture capillary which condenses on the
pulsed) affect the polycrystallinity of the nanowires [33]. surface of the substrate. The moisture can be described as a
Sol-gel method can be used as a low temperature synthesis ‘‘nano-reaction vessel’’ for anodic oxidation. A bias is applied
route for complex oxides [54], like functional oxide nanowires. between the tip and the substrate. For oxidation, the substrate
A postdeposition high temperature annealing (>500–600 C) is is at a positive bias with respect to the tip. Its magnitude is
needed to form the required stoichiometric phase. And for this the second important parameter. The applied field accelerates
reason, alumina templates are used. After the required sol is the OH ions to the substrate, which is oxidized, according
prepared, the template is put into the sol for a specific time per- to the Mott mechanism [55]. The oxidation process stops when
iod. The membrane is then taken out from the sol, gets dried the field falls below a critical value (107 V cm 1), as it
and annealed at higher temperature before the required phase decreases. So, the process can be described as self-limiting.
is formed. The width and the height of the oxide grown depend on the
Chemical and physical vapor deposition can be used for the applied bias. The radius of curvature of the tip is also important,
growth of semiconductor nanotubes, including ordered arrays which is made by well-defined and controlled micromachining
of CNTs. CVD process takes place in a three-zone furnace with lithography, in reproducible sizes, shapes and aspect ratios. As a
deposition temperatures varying from 500 to 1000 C. As the result, reproducible lithography of given resolutions can be per-
temperature increases, graphitic content varies, with progressive formed, which is a big advantage [33].
increase in metallic appearance, decrease in resistance and In DPN the water meniscus acts as a medium for molecular
enhanced tube wall structure. CVD techniques, particularly transport. The technique depends on the ability of the deposited
plasma assisted CVD, show many perspectives to grow aligned molecule to be transported in a controlled way from the tip to
nanotubes of complex semiconductor or oxides in alumina the substrate. The molecule is called ‘‘ink’’ and should interact
templates and in future this technique will certainly find more with the substrate for a formation of a chemical bond, to create
applications [33]. a stable structure [56]. An interesting alteration of DPN is to use
the meniscus as an electrochemical cell, by applying a bias
2.3.2. Scanning probe microscopy (SPM) between the two, similar to the anodic oxidation described
before. This electrochemical DPN technique can be used to fab-
SPM-based nanolithography is an established procedure ricate metal and semiconductor nanostructures directly [57].
for creating patterns at nanometer level. Metallic and DPN can also be used for the creation of nanostructures on a
semiconducting surfaces have been patterned using this route. surface for directed assembly of nanoparticles [58] (Figure 7).
8 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

3. Carbon-based materials fullerenes [73]. A variety of stationary phases have been used
so far, such as normal and reversed or charge-transfer stationary
3.1. Fullerenes phases, using LC or HPLC (high performance liquid chroma-
tography) and moreover size exclusion stationary phases in
The most widely studied fullerene is the C60 molecule (also gel permeation chromatography, but most of them are limited
known as Buckminsterfullerene) with a spherical molecular to gram scale separations. Therefore, the research now focuses
structure of ~1 nm in diameter, consisting of 20 hexagonal on finding more selective stationary phases mainly based on
and 12 pentagonal rings [60, 61]. There are also fullerenes with charge-transfer Chromatography. The development of improved
higher mass such as C70, C76, C78 and C80 with different geo- chromatographic methods would provide higher efficacy and
metric structures [62]. The great scientific interest in fullerene better resolution concerning fullerene separation at both analyt-
C60 can be explained by the following reasons: (i) it can be ical and preparative scales, and at the lowest cost [72].
abundantly produced in the carbon soot from carbon evapora- One such economically viable solution [74] is the use of a
tion by arc discharge, (ii) it has high symmetry (icosahedral cheap stationary phase of celite (a naturally occurring, soft,
Ih with all 60 carbons chemically equivalent), (iii) it is less chalk-like sedimentary rock) in combination with activated
expensive, (iv) it is relatively inert under mild conditions and carbon and silica gel.
(v) it is less toxic [63]. Generally, fullerenes possess unique The first commercial usage of fullerenes reported in 2003 in
properties such as super conductivity and anti-oxygen 10-pin bowling balls as a coating of resin containing fullerenes.
activity [61]. Such coating prevents ball from wearing and enhances its con-
The most common laboratory-based methods of synthesis trollability [69]. The authors count today 24 registered fullerene
for fullerenes [64] are the following two methods: the arc dis- suppliers, 19 of which are manufacturers mainly based in the
charge of graphite electrodes in 200 Torr in the presence of United States and the others in Europe and Asia [75]. However,
He (Krätschmer-Huffman method), leading to yields of up to a wide range of fullerene C60 prices still exist beginning from
70% of C60 and 15% of C70 [63, 65] and the gas combustion US $20 per gram and extending to US $180 per gram for
method [66] where a continuous low flow of hydrocarbon fuel 99% purity. Their high cost and small unit sales sizes compared
(e.g. benzene, acetylene) is burned at low pressure in the pres- to other nanoparticles, discourage their widespread usage,
ence of oxygen. The latter method has the advantage of produc- although a large array of potential applications has been
ing large clusters of fullerenes (that are only produced in low identified, including optics [76], electronics/IT (information
yield by the arc-discharge method), whose size distribution technology) devices [77, 78], diagnostics, pharmaceuticals,
can be easily controlled by varying the parameters of combus- environmental and energy industries [69].
tion. Moreover, the doping of clusters is readily achieved by
introducing dopants in the combustion mixture [67]. Those
methods have been successfully adapted to the large-scale pro- 3.2. Carbon nanotube and carbon nanofibres
duction of fullerenes [68, 69].
Particularly the gas combustion method enabled the produc- Both CNTs and CNFs are graphitic filaments with diame-
tion of fullerenes in tonnes-per-year [70]. Furthermore, laser ters ranging from 0.4 to 500 nm and are available in varying
vaporization is also employed for fullerene production, using lengths, up to several hundred micrometers, depending on the
an apparatus of a pulsed Nd:YAG laser as the laser source, production method [79]. SWCNTs are composed of a single
operating at 532 nm and 250 mJ of power and the graphite tar- cylindrical sheet of graphene and MWCNTs several concentric,
get keeping it at 1200 C in a furnace [71]. coaxical rolled up graphene sheets [80]. Specifically, the CNT
Fullerene/fullerene clusters produced with the aforemen- diameters are typically 0.4 to 2 nm and up to 200 nm for single-
tioned methods are in the form of a crude mixture containing walled carbon nanotubes (SWCNTs) and multi-walled carbon
C60 and other Cn (n > 60) as well as conventional hydrocarbon nanotubes MWCNTs), respectively [81]. CNFs are formed by
species. For their isolation from the crude soot, purification graphene nanocones or ‘‘cups’’, sometimes are referred to as
methods are applied such as Soxhlet extraction with toluene ‘‘stacked-cup carbon nanotubes’’ with diameters ranging from
(in which fullerenes are soluble) and with ethers (e.g. diethyl 70 to 200 nm depending upon the carbon nanofibre type [82].
ether) to remove the soluble impurities of hydrocarbons and After the discovery of CNTs by Iijima in 1991 [83], CNTs
accordingly isolation of pure C60 and other individual fullerenes and CNFs have attracted the scientific interest owing to their
employing chromatographic methods [67]. Liquid Chromatog- excellent physicochemical, electrical and mechanical properties.
raphy (LC) has been used since 1990 for the fullerenes’ separa- SWCNTs can be metallic or semiconducting depending on the
tion, isolation and purification. This method is also used to orientation of graphitic filaments; individual SWCNTs can have
control reactions of fullerenes such as nucleophilic additions, a thermal conductivity of 3500 W m 1 K 1 at room tempera-
cycloadditions, hydrogenations and oxidations with electro- ture, exceeding the thermal conductivity of diamond [84]. Their
philes [72]. Typically in chromatographic methods two phases applications in the area of polymer composites as fillers, micro-
are used, a mobile phase and a stationary phase. Here, the electronics, energy storage and sensors have been widely
mobile phase is an aromatic solvent with high fullerene solubil- reported [85]. CNTs and CNFs are usually obtained by CVD
ity, sometimes to which the addition of a non-aromatic solvent method from the decomposition of gaseous hydrocarbon over
with comparatively low fullerene solubility enhances the effi- transition metal-catalyst particles [22]. Other methods such as
ciency of fullerene separation. As a stationary phase different flame synthesis, arc discharge and laser ablation are too
sorbents can be used with relatively high affinity for the energy intensive, expensive and result in less yield compared
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 9

Table 1. Companies producing SWCNTs and MWCNTs [23, 85].

SWCNTs company Production capacity (g/h) Materials
Carbon Nanotechnologies Inc. (USA) 65 Carbon monoxide iron pentacarbonyl
Toray Industries Inc. (Japan) 15 Alcohol
AIST (Japan) 10 Ethylene, Fe thin film (1.5 nm) supported
on an AlOx layer (30 nm)
MWCNTs company Production capacity (kg/h) Materials
Showa Denko KK (Japan) 16 Benzene, metal catalyst
Nanocyl (Belgium) 1 Acetylene
Heperion Catalysis International, Inc. (USA) 8 N/A
Nano Carbon Technologies Co. Ltd. (Japan) 5 N/A
Sun Nanotech Co. Ltd. (China) 0.6 N/A
Shenzhen Nano-Technologies Port 5
Co. Ltd. (China)
Meijo Nano Carbon Co. Ltd. (Japan) 1 Camphor zeolite powder

MWCNTs and SWCNTs, respectively rendering CNT-based

products more expensive up to 10 times than prevalent ones.
SWCNT synthesis by CVD requires much tighter process con-
trol compared to MWCNTs’, rendering their prices orders of
magnitude higher than of MWCNTs’. As mentioned before,
SWCNTs have metallic or semiconducting behavior and their
price depend on this. CoMoCat SWCNTs cost up to €500
for 1 g with 98% of semiconducting SWCNTs. For this reason,
the electronic industry has lost interest for them because it is not
possible to completely control their chirality and it was too dif-
ficult to handle them at low costs. Indeed it is not the more cost-
effective production of SWCNT that it is the real problem; the
Figure 8. Global market for CNTs grades based on committed real problem is focused on controlling their electronic behav-
production, 2011–2016 [90]. iour. Therefore, MWCNTs, being metallic, are preferred for
applications where diameter is not a crucial parameter; the
development of more cost-effective SWCNT production tech-
to CVD [86]. The CVD method is the most dominant technique niques is required in order to obtain industrial entity [85].
for mass production of CNTs due to its easy scaling-up. How- Aixtron company is leader on CNTs market and has developed
ever, the most common problem is focused on their purity, an industrial machinery for CNTs growth. Figure 8 shows the
which decreases with increased yield. Their synthesis routes Global market for CNTs grades based on committed produc-
at laboratory scale can be easily monitored, in order to tailor tion, 2011–2016.
their final properties [23]. Industrial equipment is more sophis- Globally, there are many companies producing CNFs. One
ticated and complex in design, as compared to laboratory CVD of the most known suppliers is Pyrograf Products, Inc. (USA).
equipment due to its accommodation of large-scale deposition Their price depends on their final application from $85/lb (elec-
[22]. trical applications) to $170/lb (thermal applications). There are
The production of both nanomaterials in large scale can also other companies such as: Carbon NT&F 21, Catalytic
result in difficulties as the same technique is applied in large Materials LLC ($40–50/g), Catalyx Nanotech, Inc., Electrovac
reaction vessels decreasing their purity and broadening diameter AG, Espin Technologies, Inc., Graphenano, Nanostructured &
distribution [87–89]. Taking into account their increasing Amorphous Materials Nanofibres Products ($10–20/g), and
demand, a more refined method permitting the control of CoMoCat (Table 1).
parameters and reduction of contaminations is needed to be Summarizing, the industrial production of carbon-based
established in order their mass production to be further devel- materials depends on many parameters such as precursor, cata-
oped with less defects. lyst, catalyst support, and, growth mechanism affecting the final
CNT-related commercial activity has been reported more material’s structure and properties. Minor changes in these
substantially during the past decade. The CNT production parameters lead in products with critically different properties.
capacity as well as annual number of journal publications and The improvement of their production includes future activities
patents follows an increased growth. Globally, the yearly related to the selection of the suitable catalyst diameter, which
CNT production capacity is estimated to be ~300 tons directly affects the diameter distribution for both produced
MWCNTs and ~7 tons SWCNTs, while their anticipated SWCNTs and MWCNTs [91]. The selection of catalyst (e.g.
demand would exceed 1000 tons/year in the near future. Their metals) is directly associated with the final physical, chemical,
commercially available price can reach ~$1/g and ~$500/g for electronic, optical and magnetic properties. Therefore, the
10 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

advantage to understand the correlation between the type of the number of kinks and dangling bonds, offering ability of storing
metal used and the final properties would result in the produc- excess electrons.
tion of carbon-based materials with tailored properties. Also, Bottom-up approaches and especially liquid phase synthesis
the development of a suitable method to separate metallic and is used for the production of metallic nanoparticles [59].
semiconducting CNTs and reduction of catalyst impurities are The general method of synthesis is the reduction of metal com-
other challenges [92]. Recent studies on synthesis of CNTs plexes in dilute solutions [96]. In aqueous systems, the reducing
without metal support and oxygen assisted is breakthrough; agent must be added or generated in situ. However, in non-
future studies should focus on scaling-up this method resulting aqueous systems, solvent and reducing agent can be the same
in the production of CNTs with dramatically reduced impurities [97]. Monosized metallic nanoparticles are formatted by a com-
[93, 94]. Finally, it would be of great importance to explain the bination of a low concentration of solute and polymeric mono-
fundamental growth mechanisms, which would benefit layer adhered onto the growth surfaces. The diffusion of growth
researchers to understand the complicated interdependency species from the surrounding solution to the growth surfaces is
among structural parameters. The detailed understanding of hindered by a low concentration and a polymeric monolayer.
the processes and in situ control would constitute a guide for The diffusion process acts as the rate limiting step and as a con-
the successful mass production of CNTs with tailored sequence, uniform nanoparticles are formed [96].
properties. A variety of precursors, reduction reagents and stabilizers
Carbon nanotube-nanocrystal hetero-structures [95] have are used in the synthesis of metallic colloidal dispersions.
evolved through the years gaining serious interest in recent The most commonly used precursors are elemental metals, inor-
years, due to their impact on a wide range of areas including ganic salts and metal complexes, like Ni, Co, HAuCl4, H2PtCl6,
catalysis, sensing, optoelectronic devices, drug delivery, and bi- RhCl3 and PdCl2. As reduction reagents sodium citrate, hydro-
olabeling or even energy storage and devices as well as alterna- gen peroxide, hydroxylamine hydrochloride, citric acid, carbon
tive power sources (such as efficient solar cells). Based on the monoxide, phosphorus, hydrogen, formaldehyde, aqueous
nature of nanocrystals produced, there are three types of nano- methanol, sodium carbonate and sodium hydroxide are used.
tube-nanocrystal hybrid systems, including CNT-metal nano- Polyvinyl alcohol and sodium polyacrylate are often used as
particles, CNT-metal oxide nanoparticles and CNT-quantum polymeric stabilizers [96]. Easily oxidized solvents like alco-
dots, which will be individually discussed with more details hols can act both as reducing agents and as the colloid diluent.
in the following sections. By this way, the alcohol reduction process has been developed
This field still needs much research since many issues by Hirai and Toshima [97].
remain unresolved. Firstly, it is difficult to control the rate, den- A variety of physical methods of metallic nanoparticles syn-
sity, and spatial localization of functionalization of nanocrystals thesis has been developed, like sonochemical reduction, super-
onto nanotube templates. Secondly, the nature (and adequate critical fluids, pulsed laser ablation, plasma, microwave
detection) of defects in these systems is not well understood. irradiation, gamma radiations and chemical vapour deposition
Thirdly, the exact growth mechanisms are not fully understood, vapour phase synthesis (thermal decomposition of metal salts)
and the role of factors in determining the morphology of the or mechanochemical and thermo-mechanical processes can be
final products such as temperature, heating rates, ionic strength, used for the production of non-precious metals, while silver
solvent viscosity, as well as the presence of organic ligands are and gold can be synthesized only by liquid phase precipitation
only empirically answered. The large-scale synthesis of such to take advantage of inexpensive raw materials and ease of con-
nanomaterial heterostructures has not been developed. Most trol of particle sizes [59].
importantly, health, toxicity, and environmental issues associ-
ated with the various synthetic routes of these composite mate- 4.1.1. Gold nanoparticles
rials need to be promptly dealt with for their general acceptance
and applicability in practice. Gold nanoparticles are usually found as colloidal gold,
namely a suspension of nanometer-sized particles of gold.
4. Inorganic nanomaterials The colloidal gold solutions have properties that differ from
the bulk gold [98, 99]. A colloidal solution has either an intense
4.1. Metals red color, when particles have a size less than 100 nm or a dirty
yellow color, when particles are larger. Gold nanoparticles dem-
Metallic nanoparticles describe nanosized metals with onstrate unusual optical properties, due to their interaction with
dimensions (length, width or thickness) with a size range of electromagnetic field, which causes oscillation of the free elec-
1 to 100 nm. Faraday (1857) first found the existence of metal- trons under a particular frequency of the light [100–104]. This
lic nanoparticles in solutions and Mie (1908) gave a quantitative process is called localized surface plasmon resonance (LSPR).
explanation of their colour. The number of publications dealing The surface plasmon can decay radiatively resulting in light
with metallic nanoparticles increases year by year. The most scattering or nonradiatively by converting the absorbed light
interesting metals being studied are Au, Ag, Pt, Pd, Zn, Cd, into heat. Gold nanospheres with particle size around 10 nm
Cu and Fe. They exhibit a variety of characteristics offering in diameter can absorb around 520 nm in aqueous solution
them special properties; large surface-area-to-volume ratio, due to their LSPR. These nanoshperes can increase in larger
large surface energies, transition between molecular and metal- particles, due to the electromagnetic retardation [105].
lic states providing specific electronic structure, plasmon excita- Properties and applications of colloidal gold nanoparticles
tion, quantum confinement, short range ordering, increased depend on their shape, which can be spherical or rod-shaped.
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 11

Rod-shaped nanoparticles have two resonances, on the long and effort to incorporate silver nanoparticles into a wide range of
on the short axis, which depends on the nanorod aspect ratio medical devices, including bone cement, surgical instruments,
[106]. Rod-shaped particles have both transverse and longitudi- surgical masks, etc. Silver nanoparticles can replace silver sul-
nal absorption peak. The anisotropy of their shape affects their fadiazine for the treatment of wounds. Their physiochemical
self-assembly [107]. Gold nanoparticles’ applications include properties make them suitable for biomedical imaging using
biological imaging, electronics, and materials science [108]. SERS. Molecular labeling can be accomplished due to the sur-
Gold nanoconjugates coupled with strongly enhanced face plasmon resonance and the large effective scattering cross-
LSPR gold nanoparticles have found applications in simpler section of individual silver [117]. These novel biomaterials
imaging techniques such as dark-field imaging, surface were developed for the reduction of the antibacterial infection.
enhanced Raman scattering (SERS), and optical imaging for The methodology allows for the first-time silver impregnation
the diagnosis of various disease states [109]. It has also been (as opposed to coating) of medical polymers and promises to
reported that gold nanoparticles can be used as a probe for lead to an antimicrobial biomaterial [118].
Raman scatters in vivo, for tumor-targeting. The Raman The typical synthesis includes the reduction of a silver salt
enhancement from these tailored particles has been observed with a reducing agent like sodium borohydride in the presence
with electronic transitions at 633 or 785 nm via SERS [110]. of a colloidal stabilizer. Commonly used stabilizers are polyvi-
Moreover, gold nanoparticles in photothermal therapy are one nyl alcohol, poly(vinylpyrrolidone), bovine serum albumin
of the biggest recent successes, due to the invention of gold (BSA), citrate, and cellulose. b-d-glucose can be also used as
nanorods by Murphy and Coworkers, who were able to tune a reducing sugar and a starch as the stabilizer to develop silver
the absorption peak of these nanoparticles, from 550 nm up nanoparticles ion implantation [119]. The size and shape have
to 1 lm just by altering their aspect ratio [111, 112]. Despite been shown to have an impact on its efficacy so all nanoparti-
the incompatibility presented by gold nanorods with Magnetic cles created are equal. Sun and Xia [120] reports the synthesis
Resonance Imaging (MRI) or other high-resolution techniques, of monodisperse silver nanocubes by reduction of silver nitrate
it is a big potential to be used as nanoprobes [105]. with ethylene glycol, which works both as a reducing agent and
The most usual synthetic route for the preparation of gold solvent; poly(vinylpyrrolidone) on the other hand is used as a
nanoparticles is the reduction of a metal salt in solution, with capping agent. Large quantities of high symmetric silver nano-
the help of a stabilizer. A variety of reducing agents and stabi- cubes can be produced, with varying diameters (50–100 nm) by
lizers have been found and as a result, large amounts of nano- controlling the experimental conditions (temperature, metal salt
particles can be produced. According to the method developed concentration, metal/stabilizer ratio, growth time, etc.) [120].
by Brust et al., AuCl4 transfers from aqueous to organic solu- For the preparation of highly monodisperse myristate-capped
tions, while reduction with NaBH4 occurs, in the presence of silver, a suspension of silver myristate in thiethylamine heated
alkanethiols. The achieved sizes of gold nanoparticles are at 80 C for 2 h is prepared. Precipitation of nanoparticles is
between 1 and 3 nm [113, 114]. achieved by acetone and the isolated nanoparticles are obtained
Solvated metal atom dispersion technique (SMAD) [115, in a solid state [121]. Silver nanoparticles, like gold nanoparti-
116] is another method suitable for large quantities synthesis cles are also widely sold in the market. Their prices are similar
of gold nanoparticles. This method involves the vaporization to the price of gold nanoparticles.
of gold under vacuum. Inside the walls of the vacuum chamber,
which is cooled to liquid nitrogen temperature, deposition of the 4.1.3. Platinum nanoparticles
vaporized gold occurs, in the same time with vapors of organic
solvents i.e. toluene. Gold colloids can be easily isolated, Platinum nanoparticles demonstrate catalytic properties for
because there are no by-products. Nanoparticles’ size varies many chemical reactions, such as hydrogen oxidation and oxy-
from 1 to 6 nm and their shape is nearly spherical [114]. gen reduction in fuel cell reactions [122]. Chemical reduction
Gold nanoparticles are widely produced and offered in the techniques have been extensively investigated in the prepara-
market. They can be found in different forms, such as organic tion of platinum nanoparticles because these methods can be
gold, redispersible powders, silica coated or in spheres shaped. implemented under simple and mild conditions, and can be
1 mg of organic gold nanoparticles can be found in the price of used to prepare nanoparticles on a large scale. Platinum nano-
€20–€40 in Europe. However, gold nanoparticles stabilized in particles can be synthesized by chemical reduction of potassium
PVP are much more expensive and 1 mg costs about €160. hexachloroplatinate with trisodium citrate under vigorous stir-
The price does not change in relation to the nanoparticle size. ring and addition of sodium dodecyl sulfate as stabilizer reagent
Generally, gold nanoparticles that are functionalized have an [123]. Except for platinum nanoparticles, 3D platinum nano-
increased price that reaches the price of €200. In USA, gold flowers can be synthesized by a facile and scalable approach.
nanoparticles 90 nm, 99.99% pure, cost $/g350, which is very The ethanol reduction method is used at 85 C in the presence
close to the price that are disposed in Europe. of a capping agent PVP-10. The reaction conditions are con-
trolled so the generation and growth of the Pt nanoflowers
4.1.2. Silver nanoparticles can lead to these ordered structures [124]. Platinum can be used
for the preparation of metal alloys, like FePt; in this case, metal
Particles of silver, with particle size between 1 and 100 nm salts are also considered. The production of monodispersed
are called silver nanoparticles. Most of the time, silver nanopar- FePt nanoparticles includes an organometallic iron (iron
ticles contain large percentage of silver oxide due to their large pentacarbonyl), as iron source precursor. A platinum salt
ratio of surface to bulk silver atoms. Currently, there is also an (platinum acetylacetonate) is used as platinum precursor.
12 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

between metal ions and reduced CNTs. In this case, surface

functionalization of CNTs and use of surfactants in order to
access dispersibility, are not necessary. This electrochemical
method is easily scaled-up and very promising [137]. On the
other hand, Pt nanoparticles can be dispersed in poly(acrylic
acid) modified by MWCNTs, through ethylene glycol reduction
[138]. The electroless deposition presents many advantages,
due to its simplicity and easy scalability. Moreover, thin films
of CNTs decorated with copper can be produced and find use
in photo-electrochemical devices and several nanoscale struc-
tures [139].
These unique materials find application mainly in the field
of catalysis. The unique properties of CNTs, such as the nano-
scale dimensions, the mesoporous structure with the high aspect
ratio and their light weight, render them suitable for catalysts
support. At the same time, they present great catalytic activity
and both reaction selectivity and pathway [140]. Moreover,
Figure 9. CNTs/Metal Hybrids for enhanced electrocatalytic Pt/MWCNTs hybrids show high electrocatalytic activity,
activity. long-term stability and storage property, which make them ideal
for wide use in catalytic applications. Potential applications of
these materials include transportation and portable electronic
Iron pentacarbonyl is added to a 100 C solution containing the devices, as direct methanol fuel cells [138].
platinum acetylacetonate and the reducing agent. A simulta-
neous thermal decomposition of iron pentacarbonyl and the 4.3. Metal oxides
reduction of Pt salt in the present of surfactant, describes the
synthesis of FePt nanoparticles [125, 126]. Platinum nanoparti- Metal oxides such as ZnO, TiO2, CeO2, ZrO2, CuO, Al2O3,
cles are the most expensive; a typical price in Europe is NiO, Fe2O3, Fe3O4, etc. have gained much research attention
€/g1900. owing to their unique chemical, electrical, magnetic, mechani-
cal, optical properties [141], with a broad range of individual
4.1.4. Palladium nanoparticles
applications in various technological fields. They can be used
as semiconductors, pigments in paints, catalysts/photocatalysts,
Large-scale production of palladium and nanoparticles can sensors, piezoelectrics, ferrofluids, luminescents, sun screens
be achieved by thermal decomposition at 300 C of a metal and UV absorbers, in optical devices, piezoelectric devices, sur-
acetate solution in a surfactant, which can be either tri-n- face acoustic wave devices, high-density information storage,
octylphosphine (TOP) or a mixture of TOP/oleylamine. Highly magnetic resonance imaging, solar energy devices, and in
monodisperse palladium nanocrystals with a size distribution of medical field as well, such as in magnetic hyperthermia, bio-
3.5 and 7 nm, can be obtained depending on the surfactant imaging, cell labeling, targeted drug delivery, antibacterial, anti-
mole ratio. Nanoparticles with average size over than 10 nm, oxidant, neutron capture therapy, cancer therapy, etc. As fillers
can be produced using only oleylamine as surfactant. Advanta- in some suitable polymers would yield several novel potential
ges of the technique include the quality of the nanoparticles, the applications including electronic, food packaging, storing, etc.
ease of preparation and the no need of further selective tech- [142–145].
nique [127]. Palladium is also an expensive metallic nanoparti- Based on the vast range of applications of metal oxides,
cle; its price can reach €/g1200. their field has been thoroughly investigated and thousands of
reports are found in the literature. Their synthesis techniques
have grown exponentially in the past years and depending on
4.2. Metal/CNTs hybrids their growth mechanism those techniques can be divided into
the following categories: catalyst-free and catalyst-assisted pro-
Metal nanoparticles can be used in combination with CNTs cedures which can be further distinguished between vapour and
(Figure 9). The metal nanoparticles are attached on the surface solution phase growth i.e. vapour-liquid-solid (VLS), solution-
of the CNTs, either as single-walled or multi-walled. For the liquid-solid (SLS) or vapour-solid (VS) process [146]. Initially,
preparation of the hybrids, several methods have been the most used procedure for metal oxides synthesis was the
employed, such as electrochemical deposition with or without vapour phase but along the way it was realized that solution
reducing agent [128–131], spontaneous reduction [132], physi- phase growth techniques offer more flexible synthesis processes
cal evaporation [133, 134] and solid state reaction with metal with even lower production costs [147]. In the last 1½ decades,
salts at elevated temperatures [135, 136]. the hydrothermal technique which also covers supercritical
Since now, a variety of metals have been tested on CNTs; water or supercritical fluid technology is gaining momentum
gold and palladium have shown high dispersion along the tube owing to its enormous advantages in the yield and speed of pro-
walls. They can be directly produced from a redox reaction duction of nanoparticles, ease of operation, low temperature,
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 13

low cost, environmentally benign process and also it offers high d Hydrothermal and solvothermal methods.
product purity and homogeneity, crystal symmetry, narrow par- d Vapour phase reactions.
ticle size distributions, etc. and it is becoming one of the most d Reactions in confined solids or constrained on surfaces or
important tools for advanced materials processing [142, 148, involving micelles or confined reaction spaces.
149]. The synthesized metal oxides nanostructures have various d Microwave irradiation method [165, 166].
morphologies depending on the production method and its d Ultrasound irradiation [167].
parameters including nanoparticles, nanofibres, nanowires,
nanoneedles, nanorods, nanorings, nanoplates, nanotubes, Theoretical research has been done for the experimental
nanocages, nanospheres, nanohelices (or spirals) hollow synthesis and characterization of graphene quantum dots
spheres, etc. [146, 150–154]. (GQDs). Current synthesis methods including top-down and
According to research undertaken by Abercade Company in bottom-up approaches (e.g. nanolithography or from chemical
2009 [155], metal oxides constituted the 80% of the nanopow- breakdown of the extended planar structure of graphene oxide
der market volume, while the share for fine metal powder was (GO)), are either expensive, very harsh, they do not result in
only 15%. The other 5% was shared between complex metal well-defined particles or they are extremely inefficient [168].
oxides and fine metal powder mixtures. Those percentages were A proposed top-down method has demonstrated a large scale
expected to be increased by 2015. and facile synthesis of GQDs by acidic exfoliation and etching
of pitch carbon fibres, that are cheap and available materials
4.4. Metal oxides/CNTs hybrids (nanocomposites) composed of distributed graphitic domains. Their size distribu-
tion could be tailored by choosing different reaction tempera-
Metal oxides or hydroxides such as MnO2 [156], Fe3O4, tures [167]. In general, an efficacious method that allows for
RuO2, Ni(OH)2 Co3O4, TiO2 [149, 157], MgO [158], etc. have the large-scale synthesis of GQDs of well-defined size and
been successfully deposited on CNTs to fabricate nanocompos- chemical functionality is still lacking. However, their unique
ites, also solving the problem of CNT agglomeration in properties render them an exciting future material with potential
solutions without the use of surfactants [159]. These oxides applications in diverse areas spanning from energy harvesting
can be deposited as a continuous amorphous or single-crystal- and storage to bioanalytics [168] and supercapacitors [170]
line film with controlled thickness, or as discrete units in the would certainly boost research and applications in this area.
form of nanoparticles, nanorods, or nanobeads. The resulting The market of quantum dots still remains small and only
nanocomposites integrate the unique characters and functions few companies sell dots for research purposes. What is more,
of the two types of components and may also exhibit some their extremely high price that fluctuates between US$3000 to
new properties caused by the cooperative effects between the $10,000 per gram restricts their use to highly specialized appli-
two kinds of materials [160]. cations. But this would change over the next years, as it is pre-
The deposition can be carried out either in solution via elec- dicted by industry analysts, since more efficient manufacturing
trochemical reduction of metal salts, electro- or electroless processes are currently sought by scientists [164, 171]. The lat-
deposition, sol-gel processing [161], and hydrothermal treat- ter is driven by their unique size-depended electro-optical prop-
ment with supercritical solvents, or from the gas phase using erties such as sharp and symmetrical emission spectra with high
chemical deposition (CVD or ALD) or physical deposition quantum yield, good photostability and chemical stability, size-
(laser ablation, electron beam deposition, thermal evaporation, dependent emission-wavelength tunability, and exhibition of
or sputtering). Such composites have promising new applica- the localized surface-plasmon resonance (LSPR) phenomenon,
tions in many fields such as mechanics, optics, electronics, catalytic properties for redox reactions, size dependent catalytic
catalysis, gas sensors and chemical sensors, supercapacitors action and controllable charge and electron transfer event [163,
and batteries, field emission devices and in biology [149]. 172]. QDs potential applications in nanomedicine are numerous
spanning the areas of imaging, therapy, drug delivery, and nan-
4.5. Quantum dots (QD) odiagnostic; however their toxicity issues still remain an obsta-
cle for their use in vivo, while their applications in vitro are
Colloidal semiconductor nanocrystals, which are also likely to expand quickly in the coming few years [173].
known as quantum dots (QDs), are monodisperse crystalline QDs toxicity depends on multiple factors derived from both
clusters with physical dimensions smaller than the bulk-exciton inherent physicochemical properties and environmental condi-
Bohr radius [162]. A typical QD has a diameter of about tions; QD’s size, charge, concentration, outer coating bioactivity
2–10 nm. A variety of QDs have been prepared, usually com- (capping material and functional groups), and oxidative, photo-
posed of atoms from groups II–VI, III–V, or IV–VI, which lytic, and mechanical stability [174]. For QDs up-scaling, much
include CdSe, CdTe, ZnSe, CdS, CdSe/ZnS, In, etc. [163]. research should be performed, elucidating the mechanisms of
The following methods have been conducted for the synthesis every individual QD actions as well as its environmental trans-
of semiconductor quantum dots [164]: port and fate covering, also nanotoxicological studies.
d Precipitation method, usually aqueous and at low
temperature. 4.6. Quantum dots/CNTs hybrids
d Reactive methods in high boiling point solvents,
often involving metal organic and/or organometallic CNTs possessing a large chemically active surface
compounds. area are powerful candidates for supporting semiconductor
14 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

nanoparticles, e.g. QDs. The QDs may be linked directly or will be implemented for their mass production. In this point, the
indirectly to the CNT surface by covalent or noncovalent bonds. difficulty in comparing laboratory and industrial data for the
The conjugation of nanomaterials to the CNT via covalent production of the nanomaterials should be mentioned, while
bonding may be achieved using acid solutions that functionalize both laboratory methods and equipment are differentiated
the surface of these materials to provide a suitable platform for [184]. Moreover, the existing life cycle inventory (LCI)
the CNTs to form covalent bonds with QDs. For the indirect databases do not contain datasets for nanomaterials and the only
bonding, an intermediate molecule such as a polymer that has way to proceed to the assessment is to device a custom database
previously been conjugated to either the CNT or the QD is with all data that can be collected. There is also a lack of
needed [95, 175, 176]. emission factors of the nanomaterials into different environ-
QDs/CNTs hybrids are regarded as one of ideal candidate ments (air, water, soil) [187]. Computational methods using
materials for the fabrication of nanoscale optoelectronic several models have been developed to bridge this gap, but
devices, such as photodetector, photoswitch and solar cells the calculated emissions conceal uncertainty. It is obvious that
[169, 177] for medical diagnosis and treatment [175, 178] or the lack of information about the life cycle of nanoproducts
even as catalysts for the oxygen electrodes of low-temperature results in the ignorance towards potential environmental prob-
fuel cells [179]. lems that can be caused during nanomanufacturing.
For the nanoproducts that are already in the market, few
5. Life cycle assessment (LCA) and LCA studies have been conducted and they are related to labo-
nanomanufacturing ratory and pilot synthesis [184]. In most studies, only the
energy usage and chemical consumption are noted [188–190].
With the rapid emergence of materials and products A recent review [191] gathers the environmental impacts that
designed using nanotechnology, concerns have escalated have been reported from several LCA studies for CNTs.
regarding the potential for adverse biological and environmental Meagan et al. investigated three production methods of
effects. Parameters like energy consumption both for the SWCNTs; arc ablation, chemical vapour deposition and high
nanomaterials’ production and the construction of facilities pressure carbon monoxide [192]. An evaluation for environmen-
and equipment [180], water utilisation and long-term impacts, tal impacts of CNFs has also been executed by Khanna and
such as greenhouse gas emissions [181], which are associated Campion [193]. Moreover, FP7 Project named NanoSustain
to nanoproducts should be reassessed during their life cycle. (Development of sustainable solutions for nanotechnology-
Traditional waste management methods should be replaced based products based on hazard characterization and LCA) deals
due to the advances in nano-ecotoxicology that can detect trace with case studies of nanotechnology-based applications, such as
levels of nanowastes [182]. MWCNTs in epoxy plates, nano-TiO2 in paint applications and
Through a life cycle assessment (LCA) a variety of impacts nano-ZnO glass coating as UV-barrier for glass [194].
can be assessed. First of all, environmental problems like global In order to expand the use of LCA to work as a tool for
warming, acidification, eutrophication, ozone depletion and industrially produced NMs, it is necessary to gather data from
ecotoxicity can be determined. Effects on human health can all existing industries which already produce them. In terms
also be assessed; carcinogenesis, respiratory effects, human tox- of research, the toxicity of new developed nanomaterials should
icity, life expectancy are the main fields that are under study. be checked. Experimental data on characteristics and toxicity of
Finally, the use of non-renewable energy, resources as well as nanoparticles can also be collected from recent research projects
the end-of-use of products causing hazardous wastes are that are involved in nanomanufacturing [195]. Complete dat-
investigated [183]. abases need to be developed, which will include each nanoma-
LCA is a tool that has been designed for the quantification terial. All data of the characteristics of nanomaterials,
of the environmental impacts of a system. It can provide a depending on the method of their preparation, can be collected
framework for the identification and measurement of all sources in a European platform. As a result, anyone interested can refer
of nanowaste, while it examines upstream processes (manufac- to it and collect data to perform LCA study, which can be com-
turing of precursors, components, equipment, etc.) as well as bined with adapted exposure and fate modeling, in order to
downstream processes (nanowastes’ capture, recycling, have complete results of nanoproducts during all life cycle
treatment and disposal). The levels of nanowastes tend to vary stages. Finally, LCA results can be combined with risk assess-
in each chain activity; as a result it is important to collect data ment to obtain a comprehension between interactions of
carefully from all stages of life cycle (importing, retailing, prod- nanomaterials and environment and to predict the potential
uct usage, waste treatment, etc.) [182]. LCA can be considered damage on environment and human health due to nanomaterials
as an ecodesign tool, while it can predict the environmental manufacturing and use.
improvements that should be done in a new-designed nano-
product, from the early stages in the laboratory [184]. There- 6. Current applications
fore, it is possible to evaluate the toxicological properties of
nanomaterials before their production stage [185]. The unique properties of nanomaterials have a broad range
However, LCA has to face many challenges, especially of applications in many industries. In 2010, 1317 consumer
when it is applied for decision making in scaling issues, includ- goods were already estimated in the market, which incorporate
ing process selection, design and optimization [186]. Its uncer- nanomaterials, taking advantage of the nanomaterials unique
tainty is associated to the unknown future applications of the properties, while this number is steadily increasing every year.
produced nanomaterials and the unknown industrial scales that Among them, only 313 products use inorganic nanomaterials,
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 15

while the 50% of which (313 products) contain silver nanopar- d Nanoscale electronic and optical instruments
ticles for antibacterial purposes. Carbon in the form of CNTs (nanocables).
and titanium oxide are the second and third most used in these d Environmental protection (dendrimers exhibiting high
313 products. The other remaining 1004 products out of 1317 degree of surface functionality and versatility can act as
contain either non-specific chemicals or nanofilms or nanoscale ‘‘attractors’’ of metal ions.
wax particles. Approximately 450 of the 1317 products are
personal care products including cosmetics and sunscreens
There also some applications of certain nanomaterials under
and textile-related products (~200) [196–200].
investigation:
Some of these available products include the following
[196, 201]:
6.1. Carbon nanotubes
d Non-scratch glasses, on which tissues made of ultra-fine
polymers exist with protective and anti-glare properties. CNTs exhibit extraordinary molecular properties rendering
d Building materials (cement, tiles, grouts, sealants, them applicable to many fields such as fillers in polymer matri-
windscreen glass) that are coated with nanoparticles of ces for better mechanical performance (e.g. for the manufactur-
titanium oxide obtaining advanced functions such as ing of more powerful windmills, in automotive or in
self-cleaning, anibacterial, anti-mould, anti-fungal, anti- construction) [196, 201–203] and improvement of electrical
fouling, anti-fogging and deodorizing. conductivity [204, 205], energy storage (in supercapacitors or
d Clothes with advanced properties such as UV blocking, infra- lithium ion batteries) and energy conservation technology
red reflecting, antibacterial, crease-proof, stain-resistance, [196, 206–208], biotechnology [209], medicine (in bone
water-repellence, moisture-control, flame-retardant, odour replacement), field emission devices (e.g. transistors and
removing, antistatic, electric conductivity, heat retaining, displays), nanosensors, storage of hydrogen and ions, solar
temperature regulating, wrinkle resistance and high mechan- cells [196].
ical strength. Such examples are ties that repel dirt, shirts that
do not need ironing or skiing anoraks that use nanofibres to 6.2. Carbon nanofibres
resist water and wind.
d Automotive and aerospace technology. Nanoparticle A wide spectrum of CNFs includes their use in gas storage,
additives in engine-construction materials for lighter energy storage and energy conservation technology, catalysts’
weight, higher strength, improved temperature/corrosion support, polymer additives and tissue scaffolds [196, 210–214].
resistance and superior wear resistance. Metal oxide
nanoparticles, CNTs and CNFs as additives in polymer 6.3. Fullerenes
nanocomposites for densification, and improved mechan-
ical strength and wear resistance of structural materials, Fullerenes have shown drug targeting capability and exhibit
tyres, etc. Additionally, in sports equipment, such as antioxidant and antimicrobial behavior. They also act as super-
tennis rackets with CNTs to make them more flexible conductors at very low temperatures. Their current applications
and more resistant. include lubricants and solar cells [196, 201, 215, 216].
d More effective and protective cosmetics. Lotions granu-
lated to below 50 nm that let light through, giving a
purer, cleaner feel. Anti-wrinkle creams that use polymer 6.4. Metal and metal oxides nanoparticles
nanocapsules to distribute active agents such as vitamins Metal and metal oxides nanoparticles exhibit size and
more efficiently. Sun creams that use nanoparticles of shape-dependent properties that gain al lot of interest for appli-
titanium dioxide and zinc oxide, so they do not turn white cations ranging from catalysis and sensing to solar cells, optics,
when spread on the skin, while they offer the same degree data storage and as antibacterial agents. Ceramic nanoparticles
of protection against UV light as traditional creams. such as cerium oxide and silicon oxide are enhancing the effi-
d Antibacterial agents. Silver nanoparticles are used as an anti-
ciency of fuel cells in a variety of ways. Many semiconductor
bacterial agent in many consumables ranging from surgical
nanoparticles can act as photocatalysts to split water in hydro-
instruments and household appliances to pet food bowls.
gen generation. Electrochromic windows made with tungsten
oxide nanoparticles exhibit enhanced thermal insulation. Zinc
Some applications of nanomaterials that are close to indus- oxide and titanium oxide as UV-shielders can increase the dura-
trial level include [202]: bility and product lifetime of many organic materials (plastic,
wood, textiles, paints) [196]. The applications of gold nanopar-
d Hydrogen storage (specifically metals or ceramics nano- ticles mainly include imaging [217], cancer diagnosis and drug
structured materials). delivery [218] due to their intriguing optical and physical prop-
d Delivery of pharmaceuticals in nanocapsules (hollow erties. Silver nanoparticles have been extensively used as anti-
nanoparticles). bacterial agents, surface disinfection applications [219–221]
d Catalysts, adsorbents and absorbents as nanoporous mate- and catalysts [222]. A wide range of nanosilver applications
rials (e.g. in vehicles in filters for reducing environmental has emerged in consumer products ranging from disinfecting
pollution and fuel consumption). medical devices and home appliances to water treatments and
16 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11

air purification. Platinum and palladium nanoparticles are organs, transport characteristics, exposure and dose/response
among the most efficient metals used in many catalytic pro- data, their distribution and persistence in the environment
cesses, including fuel cells [196, 223–225]. [228]. As a result, the lack of a suitable regulatory framework
and guidance on safety requirements renders manufacturers
reluctant to develop new products containing nanomaterials
6.5. Quantum dots [227]. The latter can be overcome by a systematic scientific
The quantum dot is defined as a particle of matter so small approach to the study of nanoparticle toxicity that requires
that the addition of a single electron will alter its properties. its correlation with the physical and chemical characteristics
Quantum dots can be manufactured from semi-conducting properties of nanoparticles (such as exact composition, crystal-
material, comprising only a few hundred atoms, and when linity, size, size dispersion, aggregation, ageing). Moreover,
excited they emit light at different wavelengths depending on research should also be directed to the ecological and environ-
their size, which makes them extremely useful as biological mental implications of natural and anthropogenic nanoparticles
markers of cell activity. Therefore their possible applications pollution [229]. To this direction, a number of organizations,
are the following: light emitters, LED lasers in optoelectronics, including federal bureaus such as the EPA and testing stan-
quantum cryptography for invisibly marking documents or dards developers such as ASTM, have begun developing
banknotes, biomarkers and biosensors, quantum computing, methods to assess nanomaterial properties, such as LCA meth-
solar cells [196, 201]. odology [227]. Hopefully, the engineered nanomaterials will
be manipulated with more cautious in the future and new laws
and policies will manage all aspects of nanomaterial manufac-
6.6. Current status turing, industrial use and recycling.
Summarizing, there are five critical success factors for
Many companies are engaged to perform analyses of the nanotechnology growth and development thoroughly explained
current and future market size for nanotechnology. Most of their in literature [230]:
reports predict that nanotechnology markets will be tens of
billions of dollars in the near future. The continuous progress d Product orientation (and not technology admiration)
in product development and market acceptance will spread s This factor should satisfy both of the following needs:
the use of nanoparticle technology further, wider and deeper focusing on the single most viable and attainable
in many industries [196]. application and starting to make an exhaustive list of
potential applications.
d Continuous industry interaction and selection of a beach-
7. Conclusions and perspectives
head application
The existence of nanomaterials has been known for s Focusing on the development of the single most viable
centuries; examples of which are the carbon black, fumed silica, and attainable product opportunity once known, to the
titania; their industrial applications dated since the 1900s [201, exclusion of all else, until it is successfully scaled-up or
226, 227]. Over the years research has provided researchers it fails.
with a better understanding of the mechanisms involved during d Application of spiral product development methodology
the synthesis of nanomaterials, their intrinsic properties affect- s Engaging with lead users and utilizing iterative product
ing from increased surface area and quantum effects, and it still development to increase the probability that the prod-
leads to the development of advanced analytical techniques for uct meets the customer’s wants and needs.
their characterization and their systematic tailored synthesis. d Attraction and retention of industry partners
Since many industrial sectors (such as aerospace, energy, trans- s Attracting and retaining investors and corporate part-
portation, and medicine) are highly benefited and improved by ners through effective sharing of context-rich technol-
the application of nanomaterials, their demand is increasingly ogy knowledge to reduce the risk from an absence of
growing. The available consumer products containing nanoma- universal product development milestones that repre-
terials (as particles or fibres) most commonly carbon, cerium sents an increase in value for the nanotechnology ven-
oxide, silver, silica, titanium dioxide, magnesium oxide and ture to justify.
zinc oxide now exceeds the number of 1000 and is still raising d Mitigation of nanotechnology – specific technology risks
[196, 227]. However, apart from the advantages that nanotech- s Identifying and addressing technical risks which may
nology offers to society, it may also have negative impacts on exist in relation to cost, quality control and tolerance
human health and the environment which are not yet under- of the nanotechnology in the manufacture, including
stood, since the quantum mechanics which regulate nanomate- occupational and environmental health and safety
rials’ interactions with other substances also make their considerations.
toxicological behavior difficult to predict [227].
Although the existing regulations appear adequate to man- Acknowledgements. The support from the EU FP7 Project ‘‘Func-
age the risks of nanotechnology at its current stage of devel- tionalized Innovative Carbon Fibres Developed from Novel Precur-
opment, further research is needed concerning the sors with Cost Efficiency and Tailored Properties’’ (FIBRALSPEC)
toxicological and ecotoxicological properties of nanoparticles, under Grant Agreement no. 604248 is greatly acknowledged by
their uptake in the body, accumulation in the tissues and CAC, PCG, MAK, AFT and VK.
 C.A. Charitidis et al.: Manufacturing Rev. 2014, 1, 11 17

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Cite this article as: Charitidis CA, Georgiou P, Koklioti MA, Trompeta A-F & Markakis V: Manufacturing nanomaterials: from
research to industry. Manufacturing Rev. 2014, 1, 11.